DE2753053A1 - FREE-FLOWABLE GRINED SOFT SOFT DETERGENT CONTAINING DETERGENT AND CLEANING AGENT WITH HIGH SHOCK DENSITY - Google Patents

Description

description

The invention relates to free-flowing, concentrated, granular laundry softeners containing detergents and cleaning agents with high bulk density as well as processes for their production.

Compositions which, in combination, have a washing and cleaning effect and give the laundry a soft feel, are known. The person skilled in the art also knows that nonionic surfactants are useful components in detergent and cleaning agent compositions and quaternary ammonium halides having a long chain lipophilic moiety on that present therein Nitrogen atom can be used successfully as a fabric softener and for antistatic finishing. Inorganic Builder salts such as phosphates, carbonates and silicates have long been used as builders for organic surfactants has been used, and zeolites such as sodium aluminosilicates have more recently been used for these purposes used. Most granular detergents and cleaning agents have a low bulk density, but it is also known that to produce granular detergents and cleaning agents with a high bulk density. So far, however, it was not yet known a detergent and cleaning agent containing granular fabric softener

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medium with high bulk density and the desired in the present application to manufacture product properties described, and also manufacturing methods for such products are not known from the prior art.

The present invention relates to granular detergent and cleaning agent containing free-flowing fabric softener and having a bulk density of at least 0.6 g / cm and particle sizes in the range from 4 to 40 mesh (US standard sieve series), the core particle of an alkali builder salt, namely with sodium carbonate mixed with sodium carbonate, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate and / or borax, inside and on the surfaces of which a usually liquid or pasty nonionic surfactant is present and the surfaces of the builder particles do not have a coating -ionic surfactant have adhering ion exchange properties possessing zeolite particles and a fabric softener consisting of a waxy quaternary ammonium compound is present in or on these particles. The invention also comprises products provided with a plurality of coatings and methods for producing the granular laundry softener-containing detergents and cleaning agents according to the invention.

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The products according to the invention are excellent detergents and cleaning agents containing fabric softeners for coarse, white and and colored laundry with high bulk densities. This makes it possible for a wash of average size in an automatic Washing machine (which has a capacity of around 30 to 65 liters and around 4 kg of laundry items in one wash processed on soiled clothing) use a smaller volume of detergent according to the invention, e.g. 50 to 150 cm. This further results in detergent compositions containing comparatively effective amounts of fabric softener Can be used in smaller packages, reducing the need for storage space in the supermarket and in the home will. Of course, it is also easier to handle smaller packages and pour or fill the agent out of them; it is more convenient to work and the risk of spillage is reduced.

The core or base particles into and onto which the nonionic surfactant is placed can be any builder salt exist that has sufficient sorption capacity for has the non-ionic surfactant when it is in the liquid state. Usually it is desirable that the builder particles are in rounded shape, preferably spherical, and have passages through the particles in them Inside are present into it that have a sorption of at least

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10%, preferably 20% and in particular 30% or more, based on weight, of nonionic surfactant in the builder particles. Builder substances suitable for the purposes of the present invention are preferably mixtures of sodium carbonate and sodium bicarbonate (including Wegscheider's ¹ s salt), which are described in more detail below, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate (Na ₂ O: SiO ₂ ratios in Range from 1: 1.6 to 1: 3) and borax. Such products, which can be spray-dried, agglomerated or manufactured in any other suitable manner, are preferably present in particle sizes which correspond to the particle size of the preferably used carbonate-bicarbonate mixture, which is specified later in the description. Mixtures of various builders and mixtures of numerous other components present in the compositions of the invention can also be used. In addition to the sodium salts, other alkali salts, primarily potassium salts, can also be used, but this usually has no advantages.

Instead of some of the inorganic builder salts, organic builder salts, such as sodium citrate, Trisodium nitrilotriacetate, CMOS (sodium carboxymethyloxysuccinate), Sodium gluconate and sodium EDTA. However, the total content of such organic structural substances is usually

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only borrowed a small proportion of the total builder content make up, preferably less than 25 of them. It is also possible to use sodium sulfate or another acceptable one To use filler substance instead of part of the builder salt, but again that the filler substance should only be present in small proportions and preferably less than 25% of the total amount of builder-plus-filler salts amounts to.

As a mixture of alkali carbonate and alkali bicarbonate is appropriate uses such a mixture in which the two kinds of components in the same individual particle shape or granular shape are present. For the purposes of the present invention, these particles should advantageously have sizes between 20 to Mesh, preferably 30 to 60 mesh and especially about 40 mesh (US standard sieve limit; the word "mesh" is used synonymously with "No." used). Larger particles, up to about 8 meshes, can also be used, provided that that the finished end product is then obtained in the above-specified desired particle range. Sometimes you have to Take precautions against agglomeration or other particle growth during absorption of the non-ionic surfactant or to avoid another process point, otherwise the end product could be obtained in a particle size that is too large. If one particle sizes smaller than those specified in the

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If a desired area is used, the finished product sometimes falls free instead of in the form of individual ones flowable beads as an undesirably pasty product.

The alkali metal carbonates and bicarbonates (of which the sodium or potassium salts are preferred), which are used in particular as sodium salts, are employed in the preferred embodiment of the present invention in an essentially anhydrous form; however, partially hydrated builder seeds of this type can also be tolerated. Generally the moisture content is less than 9%, preferably less than 7%. The percentage ratio of alkali carbonate to alkali bicarbonate is generally in the range from 1:10 to 10: 1, preferably in the range from 1: 5 to 1: 1 and in particular between 1: 3 to 1: 1, the ratio being 1: 2 is particularly preferred. The mixture is expediently made up in such a way that it has a substantial content, for example 10 to 100%, of Wegscheider ¹ s salt, the remainder being sodium bicarbonate. Such a product is characterized by excellent sorption power for the liquid non-ionic surfactant and can be easily and conveniently brought into a suitable base for a powder coating made of zeolite framework substance. One successful method for making a mixed carbonate-bicarbonate product is shown in U.S. Patent 3,944,500 to Gancy et al.

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referred to herein. A mixed carbonate-bicarbonate of the type described can be found under Acquire the trade name Snowlite from Allied Chemical Corporation. The method described in the patent is a preferred mode of operation; the mixed carbonate-bicarbonate particles can also be manufactured using other known techniques. For the purposes of the invention can instead of the carbonate and bicarbonate substances intimately brought together in the individual particles separate batches of carbonate and bicarbonate, which suitably have the same grain sizes and in the same proportions are available, provided that the sorption power is sufficiently strong that a sufficient quantity of nonionic to produce the desired end product Surfactant can be absorbed by it. It is also possible to use carbonate and bicarbonate powders of higher fineness, for example those with particle sizes below 100 mesh, such as 170 to 270 meshes, and these agglomerate either separately or in a mixture, taking care carefully it must be ensured that the porosity of the product is maintained, i.e. only a minimal amount of binder is allowed, such as starch or another agglomerating agent can also be used. You can also divorce such products Add the salt.

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The compounds used as fabric softeners that give the laundry a soft feel and help that They are crease-resistant and antistatic, include a large number of compounds in their molecules contain a substantial portion with a positive charge. Generally such compounds have in the positively charged Part of their molecule are hydrophobic groups, and often these are relatively long chain residues, such as higher hydrocarbyls or alkyls. It is true that amines, imidazolines, Pyridines, guanidines and their salts and derivatives are useful, especially when they are relatively long-chain hydrophobic Groups contain, but the most preferred fabric softeners are usually quaternary Ammonium compounds that contain one or two long-chain hydrophobic groups and two or three short-chain groups and have a solubilizing cation or salt forming group, usually either halide, sulfate, acetate, Hydroxide or another inorganic or organic solubilizing monobasic or dibasic radical. Numerous cationic compounds, such as, for example, can be used for the purposes of the present invention are described in U.S. Patents 3,227,614 and 3,442,692.

The longer chain substituents on the nitrogen in the quaternary ammonium compounds and salts are preferred

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higher alkyl groups with 12 to 18 carbon atoms, in particular 16 up to 18 carbon atoms. The stearyl radical is particularly preferred. The shorter hydrophobic groups are alkyl groups with 1 to 4 Carbon atoms, preferably 1 to 2 carbon atoms. The methyl radical is particularly preferred.

Similar long-chain substituents are found in the imidazolines and imidazoles, the pyridines and piperidenes, the guanidines and the amines. Specific examples of cationic ones which can preferably be used for the purposes according to the invention Conditioning agents are dimethyldistearylammonium chloride, trimethylstearylammonium bromide, cetyltrimethylammonium chloride, Di-higher-alkyldimethylammonium chloride, where the higher alkyl radicals come from hydrogenated tall oil alcohols, cetylpyridine chloride, higher alkyldimethylbenzylammonium chloride, Diisobutylphenoxyethoxyethyldimethylbenzyl ammonium chloride and laurylisoquinoline bromide. Instead of these preferred compounds, higher alkylamines can also be used and other cationic conditioning agents used for their softening effect on various tissues and Fibers are known to give them crease resistance and to make them antistatic. These connections are strong Noun for the fabrics, especially for cotton or cellulose materials and synthetic organic fibers. The softening compounds described, the higher alkyl groups are usually waxy or paste-like

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shaped solids and can be melted at elevated temperatures or liquefied so that they are useful for coating the base particles used in the invention. Such coatings can be manufactured in such a way that one compares soft particles of the softening compound with the substances to which they are made to adhere is said to, such as carbonate-bicarbonate-non-ionic surfactant-zeolite particles mixes, or you can use the plasticizing Melt or spray the compound onto the core particles, or it can be mixed with the nonionic surfactant and spray it onto the particles together with this. In the products according to the invention, the plasticizing retains Compound while using these products their effectiveness and this is largely due to that non-ionic surfactant instead of anionic surfactant, with which the cationic softening substances often react, is available.

Nonionic surfactants which can be used for the purposes of the invention are, for example, those described in detail in McCutcheon's Detergents and Amulsifiers, 1973 Annual and in Surface Active Agents , Volume II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). This prior art becomes known as for the present invention

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subordinated. Non-ionic surfactants of this type are pasty usually at room temperature (20 ⁰ C), or waxy solids, which are either sufficiently soluble in water that they rapidly dissolve in water, or at the temperature of the washing water when these above 4O ° C quickly become molten. The non-ionic surfactants used for the purposes of the invention are normally those which are liquid or paste-like at room temperature, and the usually paste-like or semi-solid substances are preferably used, because when they are used there is less tendency that a sticky product with bad Forms flow properties, which is sensitive to caking during storage and tends to solidify. Such products also tend to become less moist and give off their "coating" to the zeolites. Nonetheless, liquid non-ionic surfactants can also be used, and the non-ionic surfactants used are expediently liquefied in such a way that they can be sprayed at reasonable temperatures, for example below 45, 50 or 60.degree. Examples of typical useful non-ionic surfactants are polyalkeneoxy derivatives, which are usually produced by condensation of lower alkylene oxide (with 2 to 4 carbon atoms), for example ethylene oxide, propylene oxide (with a sufficient amount of ethylene oxide to make the substance water-soluble) with a hydrophobic Hydrocarbon chain and one or more active hydrogen atoms

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containing compound, such as higher alkylphenols, higher fatty acids, higher fatty mercaptans, higher fatty amines and higher fatty polyols and alcohols, for example fatty alcohols with 8 to 20 or 10 to 18 carbon atoms in the alkyl chain, with an average of about 3 to 30, preferably 3 to 15 or 6 to 12 lower alkylene oxide units are oxalkylated, have been prepared. Preferred nonionic surfactants are those of the formula RO (C ₂ H ₄ O) _n H, where R is a radical of a linear saturated primary alcohol (an alkyl) having 10 or 12 to 18 carbon atoms and η is an integer of 3 or 6 to 15 means. Examples of typical, commercially available nonionic surfactants useful in the context of the present invention are the commercial product Neodol 45-11, which is an ethoxylated product (with an average of about 11 ethylene oxide units) of 14 to 15 carbon atoms (on average) in the Chain-containing fatty alcohol (manufactured by Shell Chemical Company); "Neodol 25-7", which is a fatty alcohol containing 12 to 15 carbon atoms in the chain, which is ethoxylated with an average of 7 ethylene oxide units; and "Alfonic 1618-65", which is an alkanol containing 16 to 18 carbon atoms which is ethoxylated with an average of 10 to 11 ethylene oxide units (Continental Oil Company). Farther

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those sold under the trade designation "Igepals" by GAF Co., Inc. are useful. This includes the polyoxethylated (having 3 to 30 ethylene oxide units) middle alkyl (6 to 10 carbon atoms) phenols, such as Igepals CA-630, CA-730 and CO-6 30. Other useful products are products available under the trade name "Pluronics" (manufactured by BASF-Wyandotte) such as Pluronic F-68 and F-127, which are condensation products of ethylene oxide with hydrophobic bases, the by condensation of propylene oxide with propylene glycol, usually with molecular weights in the range from 5000 to 25,000 have been produced. Furthermore, the various products can be found under the trade name "Tweens" (products from ICI America) which are polyoxyethylene sorbitan esters of higher Fatty acids (12 to 18 carbon atoms), such as those that contain solubilizing amounts of ethylene oxide. Numerous other non-ionic surfactants, such as those described in the aforementioned references can also be used for the purposes of the invention, preferably the proportion of nonionic surfactants other than higher fatty alcohol polyoxyethylene ethanols is low and if possible not more than 50%, preferably not more than

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25% of the total non-ionic surfactants present. If in the present description of "higher" spoken of, for example, higher alkyl compounds, higher fatty acid compounds and the like, then are understood to be those which contain 8 to 20, preferably 10 or 12 to 18 carbon atoms.

For the purposes of the invention, crystalline, use amorphous and / or mixed crystalline-amorphous natural or synthetic zeolites that are sufficiently rapid and satisfactorily effective the water hardening ions such as calcium ions in the washing water able to counteract. It is preferred to use materials that are sufficiently rapid with the hardness causing Cations such as calcium, magnesium, iron or the like are able to react to form the wash water to soften before such hardener ions come on the other components of the synthetic organic detergent composition able to act undesirably. The appropriately usable zeolites can be by high Characterize ion exchange capacity for calcium ions; it is usually about 200 to 400 or more mg Equivalent calcium carbonate hardness per g of the aluminosilicate,

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preferably at 250 to 350 mg equivalent / g, and the softening rate should be so high that a residual hardness of 0.02 to 0.05 mg CaCO ₃ A, preferably 0.02 to 0.03 mg / l, is achieved in one minute , and in 10 minutes the residual hardness should be less than 0.01 mg / 1, all data based on anhydrous zeolite.

In principle, any such ion exchange properties can be used using zeolites, but advantageously uses finely comminuted particles of synthetic zeolite framework, has the following formula:

(Na ₂ O) _x . (Al ₂ O ₃ ). (SiO ₂ ) _e.g. H ₂ O ₁

where χ is 1, y = 0.8 to 1.2, preferably about 1, ζ = 1.5 to 3.5, preferably 2 to 3 or about 2 and w = 0 to 9, preferably 2.5 to 6.

The soluble crystalline aluminosilicates used advantageously for the purposes of the invention are often characterized by a network of substantially uniformly sized pores in the range from about 3 to 10 R, often about 4 Å (normal); these pore sizes are determined by the structural unit of the zeolite crystal. It can be

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Zeolites which have two or more such networks of different pore sizes can also be used with advantage and mixtures of such crystalline materials with each other or with amorphous materials can also be used will.

It should be a monovalent cation exchange zeolite, ie an aluminosilicate with a monovalent cation, such as sodium, potassium, lithium (if practicable) or other alkali, ammonium or hydrogen. Preferably, the monovalent cation of the zeolite molecular sieve is an alkali, especially sodium or
Potassium, and especially sodium; but other types can also be used usefully.

The crystalline types of zeolites which can be used as good ion exchangers at least in a proportional amount for the purposes according to the invention include zeolites of
following crystal structure groups: A, X, Y, L, mordenite and erionite, and types A, X and Y are preferred
give. Mixtures of such molecular sieve zeolites can also be used, especially when a type A zeolite is present. The crystalline types of zeolites are very well known to the person skilled in the art and in detail, for example, in the

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action "Zeolite Molecular Sieves" by Donald W. Breck, published in 1974 by John Wiley & Sons. Examples for typical commercially available zeolites of the aforementioned type of structure are in Table 9, 6 on pages 747 to 749 of the Breck treatise compiled. This table will be known in the present specification as provided.

For the purposes of the invention, preference is given to using synthetic zeolites and advantageously also those of type A or a structure similar to that specifically described on page 133 of the aforementioned paper. One can do good Results using a Type 4A molecular sieve zeolite whose monovalent cation is sodium and its pore size is about 4 Å, achieve. Such zeolite molecular sieves are described in US Pat. No. 2,882,243 and referred to there as Zeolites A. designated.

You can use the molecular sieve zeolites in either dehydrated or calcined form so that they have about 0 or about 1.5 to 3% moisture, or they are used in hydrated or water-laden form, so that they have additional bound water in an amount of about 4 to about 36%, based on the total weight of the Zeo-

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liths, depending on the type of zeolite used. For the The purposes of the invention are the hydrated form of molecular sieve zeolites containing water (preferably about 15 up to 70% hydrated) to be preferred if crystalline product is used. The manufacture of such crystals is known to the person skilled in the art. For example, in the preparation of the aforementioned zeolite A, the hydrated Zeolite crystals that form in the crystallization medium (e.g. hydrous amorphous sodium aluminosilicate gel) used without being dehydrated at high temperature (calcined to 3% or less water content), as is normally the case in the manufacture of such crystals for use as catalysts, e.g. cracking catalysts, happens. The crystalline zeolite can be in both fully hydrated and partially hydrated form Filter off the crystals from the crystallization medium and dry them in air and at room temperature, so that the water content ranges from about 5 to 30% moisture, preferably about 10 to 25%, such as about 17 to 22%, lies. However, the moisture content of the molecular sieve zeolite used for the purposes of the invention, as previously described, it can also be much lower.

The zeolites used for the purposes of the present invention should be practically free of adsorbed gases, such as

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For example, carbon dioxide, because gas-containing zeolites tend to undesirable foaming when zeolite-containing Detergent comes into contact with water; however, foaming can and sometimes be tolerated for some purposes specifically requested.

The zeolite material is preferably used in finely comminuted form State with outermost particle diameters up to 20 microns, e.g. 0.005 or 0.01 to 20 microns, preferably between 0.01 to 15 microns and especially preferably having an average particle diameter of 0.01 to 8 microns, such as for example 3 to 7 or 12 microns if the product is crystalline and 0.01 to 0.1 microns, e.g. 0.01 to 0.05 microns if the product is amorphous. Although the outermost particle size is much lower, have the zeolite particles usually particle sizes in the range of 100 to 400 mesh, preferably 140 to 325 mesh (US standard sieve series) . Zeolites with smaller particle sizes are often undesirably dust-forming, and those with larger ones Particle sizes do not have sufficient and satisfactory covering power for the carbonate-bicarbonate base particles.

Crystalline synthetic zeolites are more common and better known, but amorphous ones can be used instead

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Use zeolites, and these are often superior to crystalline materials in many important properties, as this will be described later. One can mix crystalline amorphous materials and mixtures of different in the same way Use types of the zeolites described. The particle sizes and pore sizes of the materials are similar those previously described, although, as said, the ranges given may be changed, provided that the material Has sufficient structural substance function and colored detergent and cleaning agent that is thus in an aqueous medium is treated, does not lighten undesirably.

A number of suitable crystalline molecular sieve zeolites are described in the following U.S. patent applications to Bao-Ding Cheng, SN ¹ p. 467,688, filed May 7, 1974; 503,734, filed September 6, 1974; and 649,793 and 640,794 filed December 15, 1975; reference is made to these in the present context in connection with the zeolites and with other material which can be used for the detergents and cleaning agents according to the invention. Further components are explained in US patent applications 359 29 3, filed May 11, 1973 and 450,266, a continuation-in-part application thereto, filed March 11, 1974, and knowledge of these two applications is also for the

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present invention provided. Other useful ones Molecular sieve zeolites are explained in DT-OSs 2 412 837 and 2 412 839 as well as in the Austrian patent applications A 4484/73, A 4642/73, A 4666/73, A 4717/73, A 4750/73, A 4767/73, A 4787/73, A 4788/73, A 4816/73 and A 4888/73, knowledge of which is also assumed for the present invention.

The production of amorphous and mixed amorphous-crystalline aluminosilicate ion exchange zeolites is described in a U.S. patent application filed July 12, 1974, entitled "Detergent Builder Composition" (Burton H. Gedge, III and Bryan L. Madison, inventor). Detergent compositions containing amorphous materials are in an application filed by John Michael Corkill and Bryan L. Madison on July 18, 1974 and detergent compositions with mixed amorphous-crystalline aluminosilicate framework material are in one application filed July 12, 1974 by the same inventors. A preferred for the invention Purpose of usable ion exchange zeolite is the amorphous zeolite of the formula described in BE-PS 835 351

. (SiO ₂ ) _e.g.

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wherein ζ is 2.0 to 3.8 and w is 2.5 to 6, especially when M is sodium. The contents of these patents and applications can also be used for the purposes of the invention; to avoid elongation of the text, reference is made to such materials and methods of making and using them are referred to.

Various adjuvants can be used, both functional Type and aesthetic effect, can be used in compositions according to the invention, such as, for example Bleaches such as sodium perborate, colorants such as pigments and dyes, optical brighteners, for example Stilbene brighteners, foam stabilizers, e.g. Alkanolamides, such as laurine, myristic, diethanolamide, enzymes, for example proteases, skin protecting agents and conditioning agents such as water soluble proteins low molecular weight obtained by hydrolysis of proteinaceous materials such as animal hair, hides, gelatin and collagen, foam-destroying agents such as silicones, bactericides such as hexochlorophene, and perfumes. in the In general, such adjuvants and other additional structural substances are used in a special way, depending on the nature the adjuvant and its physical state at the most suitable stage of the manufacturing process the other components mixed in. It is particularly desirable that the

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Make the addition so that the adjuvants or the other components of the product are stabilized and / or the absorbency of the carbonate-bicarbonate mixture for the non-ionic surfactant is increased.

Such adjuvants can therefore be sprayed onto the base particles with the non-ionic surfactant, they can be sprayed with the Mix the zeolite and add it to the base particles treated with the nonionic surfactant, or they can be added to the zeolite-coated particles, either with the plasticizing agent or after adding the softening agent.

Preferably only ionic surfactant is used (apart from the plasticizer, which acts as cationic surfactant properties containing compound can be considered), but in some cases the non-ionic surfactant can also be used together use with an anionic organic surfactant, an amphoteric organic surfactant, or mixtures thereof. if if such substances are used, however, they are normally only in small proportions, preferably less than 25%, based on the total amount of non-ionic surfactant and such surfactants and preferably less than 10% of which exist, and one localizes in the product so and

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a fact that disruptive reactions between the plasticizer and such detergents are kept low or prevented will. If, for example, a cationic plasticizer is added subsequently, then it is advisable to use a to provide built-in anionic or amphoteric surfactant in the base particles, preferably together with non-ionic ones Spray surfactant on it and let it penetrate. On the other hand, when the cationic softener together is sprayed onto the core particles with the nonionic surfactant or separately, it is preferably a Apply for example used anionic and amphoteric surfactant to the surface of the zeolite-coated beads or mix first with the zeolite and then mix with the cationic softener and the nonionic Apply surfactant treated particles.

Usable anionic surfactants are, for example, the sulfates and sulfonates with lipophilic molecular fractions, for example those having 8 to 20 or 10 to 18 carbon atoms Carbon chain. These include, for example, the linear higher alkylbenzenesulfonates, olefin sulfonates, paraffin sulfonates onates, fatty acid soaps, higher fatty alcohol sulfates, higher fatty acid monoglyceride sulfates, sulfated condensation products from ethylene oxide (3 to 30 moles per mole) and

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higher fatty alcohol, higher fatty acid esters of isethionic acid and other known anionic surfactants such as, for example are also mentioned in the publications cited above as references. Most of these substances are under normal conditions in solid form, for example as alkali salts, e.g. sodium salt, and can be combined with conventional structural substances spray drying. The spray-dried particles containing these builder substances can be used as core or base particles can be used for the purposes of the invention. For the production of such preliminary products one can use any known Agglomeration techniques, comminution methods, accumulation methods or use other working methods to convert these precursors into the carbonate-bicarbonate particles of similar particle size to manufacture. Some examples of suitable anionic surfactants are the sodium salt of linear tridecylbenzenesulfonic acid, sodium cocomonoglyceride sulphate, sodium lauryl sulphate and sodium paraffin and olefin sulphonates an average of about 16 carbon atoms each. You can also use amphoteric substances, such as, for example, the sodium salt of the Designations Miranol C ~ M and Deriphat 151 commercially available products for the purposes according to the invention as surfactants insert. Similar to the anionic surfactants, the amphoteric surfactants can be spray-dried together with a builder substance, or these surfactants can be dispersed in the liquid nonionic surfactant or otherwise in a suitable manner

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Incorporate in a manner mixed with other pulverulent substances required for the production of the detergents or cleaning agents according to the invention. In principle, both types, both anionic and amphoteric surfactants, can be present in products according to the invention, but it is considerably more advantageous if, apart from the cationic softening substance, as the sole detergent
Component a nonionic surfactant or mixed nonionic surfactants is used.

The proportionate amounts of core particles (preferably carbonate-bicarbonate particles), non-ionic surfactant, zeolite and softening agent should be chosen so that the desired free-flowing fabric softener-containing detergent particles with sufficiently high bulk density result when manufactured using the process according to the invention. Suitable proportions are 20 to 40% core or base particles, 10 or 12 to 30% non-ionic
Surfactant, 30 to 60% zeolite and 4 to 12% fabric softener, and particularly useful ranges are 23 to 33% and
13 to 23% or 40 to 52% or 5 to 10%. The bulk density of the product is at least 0.6 g / cm; it is preferably in the range from 0.75 to 0.95 g / cm and in particular in the range from 0.8 to 0.9 g / cm. The particle size
of the product generally ranges from 4 to 40

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Mesh (US standard sieve series) and is expediently 4 to 12 meshes and in particular about 6 to 8 meshes. The particle size of the carbonate-bicarbonate feedstock or other base particles prior to their treatment generally lies in the range of about 20 to 100 mesh (US standard sieve series), preferably 30 to 60 mesh and in particular at about 40 stitches. One can also use finer carbonate and bicarbonate powders and other builders initially and these agglomerate to the specified particle sizes. Generally, the material consists of particles of the specified size range from a mixture of particles of different sizes within this range (this also applies to the various other granular materials mentioned in this specification).

In the manufacture of the starting particle mixture from carbonate and bicarbonate, the procedure described in US Pat. No. 3,944,500 can be used and preferably the substances mentioned there under the trade name "Snowlite" available from Allied Chemical Corporation. A typical analysis for Snowlite I is 35% Na ₃ CO ₃ , 58.5% NaHCO ₃ and 6.5% H ₂ O, and another product of this type, Snowlite II, consists of 30.0, 66.5 and respectively 3.5%. These products gave the following sieve analyzes (percentages on sieves no. 10, 40, 60 and 100};

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0.2, 67.6, 96.9, 99.0 and 0.7, 60.7, 9O, 7 and 97.0 and had bulk densities (g / cm) of 0.51 and 0.48 ( vibrated) and 0.42 or 0.38 (loose). The tendency to crumble is particularly low with Snowlite I (2.5% according to Allied Chemical Corporation test Na 17-35) and this product is preferably used. Low fragility and strength of the particles is also important with other types of base particles that can be used, in order to prevent them from being too powdery and from becoming pastes instead of individual coated particles when nonionic surfactant is added. In some cases, further components of the end product can be incorporated into the mixture of bicarbonate and Wegscheider ¹ S salt (sesquicarbonate can also be present) and processed further together with this according to the method described in the patent, provided that they remain stable and do not undesirably influence the production of the carbonate-bicarbonate product material or do not react with it. Normally, a proportion of at least 60%, preferably 70% and in particular 70 to 85% or more of carbonate and bicarbonate is present in the carbonate-bicarbonate particle mixture, provided such other adjuvants, for example 10 to 20% sodium silicate and / or 0.1 up to 5% optical brightener, sometimes 5 to 15% water are also present.

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Free-flowing, granular, fabric softener according to the invention detergents and cleaning agents containing high bulk density can be prepared by one of several process methods manufacture. One of these methods uses the sodium carbonate-sodium bicarbonate particles or other builder particles described mixed with a nonionic surfactant used in liquid form. The surfactant is preferably sprayed on, In some cases, however, it can also be infused. The surfactant penetrates the carbonate-bicarbonate particles One, however, remains on the particle surface, so that subsequently admixed zeolite adhere to it able. It is important that the non-ionic surfactant is applied in sufficient amount that, in addition to that in the Surfactant absorbed inside the builder particles leaves some of the surfactant on the particle surfaces. While the mixing process after adding the non-ionic surfactant, the particles appear like moist sand and have a greasy texture or waxy appearance. The non-ionic surfactant is usually liquid, paste, or semi-solid and becomes used advantageously or semi-solid, which reduces the risk that the product becomes sticky during storage or clumped together. However, in principle, normally liquid non-ionic surfactants can also be used with satisfactory results use. After the base particles are coated with the nonionic surfactant, the zeolite powder becomes

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mixed in, and this adheres to that on the particle surfaces located non-ionic surfactant. The particles become essentially spherical and the particle sizes are in the range from 4 to 40 mesh (US standard sieve series). In this embodiment of the manufacturing process the fabric softener usually in the form of rather small granules, flakes, grains or powders to finish off with spherical particles formed from base material, non-ionic surfactant and zeolite are mixed together. The fabric softener is it is usually a waxy or fat-like low melting solid material in particle sizes in the range from about 80 to 160 mesh, preferably about 100 mesh (US standard sieve series). It becomes physically and / or electrostatically on the surfaces of those coated with the zeolite material Particle held. It goes without saying that the amounts of material used, the mixing times, the temperatures and the mixing techniques are chosen so that the finished product has the desired composition and composition specified above has the properties described.

The initial spraying or other mixing of the nonionic surfactant with the carbonate-bicarbonate particles or other builder particles are usually made with the particles at room temperature (20-25 ° C); the

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However, the temperature can in principle vary in the range between 10 to 40 or 50.degree. For spraying or mixing you need a time span of only 1 to 5 minutes, and after the complete spraying you can still get 0 to 10 Continue mixing for minutes, preferably 1 to 5 minutes. The fatty alcohol-polyethylene oxide condensation product that one has on the surface of the moving particles is sprayed on, is mostly liquid or is heated to a higher temperature, see above that it is liquid and that it settles when sprayed onto moving surfaces or when otherwise applied can be distributed well over it and so the absorption of the liquid in the porous particles is facilitated. It can be during the some agglomeration of the particles take place in the initial mixing stage. This is apparently due to the adhesion or cohesion between a part of the finely powdered particulate material present, on the surfaces of which "excess" Amounts of liquid non-ionic surfactant are to be traced back. During such agglomeration it increases the particle size of the individual particles increases to approximately the size in the size range for the particles of the final product, although the particle size also increases somewhat further due to the subsequent adhesion of zeolite particles. Appropriate is the mixing and spraying of the non-ionic surfactant onto the moving particles in one

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Rotary drum or one at a low angle, such as 5 to 15 inclined tube, causes. It can be at any suitable rotational speed, for example 5 to 50 rpm. The nonionic surfactant is usually in the form of fine droplets of surfactant, for example those with a diameter in the range of 40 to 200 microns, preferably 50 to 100 microns sprayed on. Other suitable spray droplet sizes can be used, and in some cases one can Further blend nonionic surfactant with the builder particles after placing it on its in motion Has dripped or poured onto surfaces. One sets expedient high-performance mixing devices, such as a Lodige mixer, which operate at a comparatively low speed works, or use a twin drum mixer or a similar mixing device, by adding larger drops or a liquid jet of non-ionic Surfactant caused excessive agglomeration of the particles to prevent. As said before, one can, though not the preferred mode of operation is absorbent carbonate-bicarbonate particles also manufactured in other ways than explained here in the form of more angular particles, but it is so the particles have good flowability, more advantageously that they are somewhat rounded.

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After the absorption of the nonionic surfactant is complete, the zeolite powder is usually during a A period of time of 1 to 10 minutes, preferably about 5 minutes, is admixed with the product and kept there. Make it up free-flowing granules with a particle size in the range from 4 to 40 mesh (US standard sieve series). At this stage of the procedure the moisture content of the product is usually 2 to 20%, preferably 5 to 15%, inclusive Water of hydration. The plasticizer is then in the form of the aforementioned particle sizes within a period of time "dusted" and adhered to the surfaces of the particles for from 1 to 10 minutes, preferably 5 minutes brought. Since the cationic plasticizer is only used in a relatively small proportion, the particles are not much bigger. The plasticizer particles adhere to the builder, nonionic surfactant and zeolite particles so firmly that a stable, non-dusty end product is created without pressing defects. As mentioned earlier, different Adjuvants are incorporated into the product, and they can be added to suitable components or in a suitable work stage during the manufacturing process of the free-flowing grains add or add after the manufacturing process has essentially ended is. The total content of adjuvants, excluding water, is rarely more than 20% of the product and lies

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generally below 10%. However, if you use a perborate bleach is used, its percentage can be increased to the point that it is effective for the bleaching process Quantities are available and these can constitute up to 30% of the product. The additional amounts are then usually the other essential components proportionally correspondingly lower. The perborate can be mixed with carbonate and bicarbonate or it can be added at a later stage of the process add to the mixture treated with the non-ionic surfactant or add to the finished product. Colorants, perfumes or other adjuvants can be used with the various components and mixtures during manufacture or after Completion of the manufacturing process are added.

In a modified embodiment of the manufacturing process, with the composition of the same formulation but with improved properties, the cationic plasticizer is melted and applied together with the nonionic surfactant at an elevated temperature at which both substances are liquid. Alternatively, the plasticizer and the nonionic surfactant can be added to the base particles in sequence. In these cases it is advisable to keep the particles at a sufficiently high temperature that the liquid substances do not solidify prematurely, which could result in further sorption of the

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Substances is obstructed. When liquid quaternary emollient as the first substance is applied earlier than the nonionic surfactant, it tends to get inside of the base particle penetrates, and then, when the non-ionic surfactant is added, some of it also penetrates the interior of the particle is able to penetrate, but in a larger proportion as compared with that of the emollient remains on the surfaces of the material and adheres there with the subsequently applied zeolite powder.

In a further modified embodiment of the invention In the process, portions of the non-ionic surfactant and zeolite are initially retained and used to apply additional coatings to the product. So you can for example 5 to 50%, preferably about 10 to 30% of the non-ionic surfactant and the zeolite post-applied to the Give up the product, first the non-ionic surfactant and then the zeolite. There are additional protective covers formed around the product. In this way one can introduce a larger amount of non-ionic surfactant than this is possible in other ways, and yet a free-flowing granular fabric softener containing detergent and cleaning agent to produce. It is possible to have six coating treatments; it is preferred to limit oneself to three coating treatments (two additional coatings).

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The products of the invention have significant advantages when compared with other detergent compositions containing fabric softener. They can be considered to be low in phosphate phosphate-containing or phosphate-free compositions can be formulated. The phosphate-free compositions are very good Detergent power for many types of soiling that occurs in normal household laundry, and they comply with the legal requirements and administrative regulations that prohibit the use of phosphates in detergents and cleaning agents. One can use the products accordingly worldwide, and there are no longer several different formulations and attention certain restrictions are required in shipping detergent compositions to different areas. The excellent detergency of the products is due to the presence of non-ionic organic surfactant and the mixture given to water-soluble inorganic and zeolite framework formers. In addition to its excellent washing power, the product contains a sufficient amount of fabric softener that is able to be absorbed by the laundry so that the finished laundry is noticeable is softer and more antistatic than those washed with comparative compositions not containing fabric softener Laundry. One should expect that as a result of the comparatively high concentration of nonionic surfactants and fabric softeners, which as such are usually liquid, pasty, semi-solid or waxy, the product

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"sluggish" or poorly flowable and in storage for Should tend to bake; but, as was surprisingly found, it does not become a very free-flowing one instead Baking product obtained, which is possibly due to the fact that the non-ionic surfactant in liquid Applies shape to the base particles and allows penetration into the interior of these particles, and only one relative leaves a thin coating on their surfaces, which is then coated with zeolite powder (and sometimes a little powdered fabric softener) is covered. The preferred mixture of carbonate and bicarbonate in the base particles thus has a sufficient framework function and pH regulating effect that the product is a very good detergent. However, others can also be used Basic substances are used, provided that they are as sorptive as, for example, spray-dried Pentasodium tripolyphosphate, sodium carbonate. If bicarbonate is present, the pH will usually be very high if carbonate is used alone, it is lower, and this makes the product safer to use than one with Detergent built up as a structural substance using carbonate. It also significantly improves the sorbent power of the nonionic surfactant composition, especially when that Bicarbonate is largely in the form of Wegscheider's salt. The zeolite powder on the surface of the particles, besides its effect, serves to prevent stickiness or worse Flowability of the non-ionic surfactant also acts as a protection for

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the inside of the product against the effects of external moisture under ambient conditions with high humidity. Man can accordingly detergent compositions according to the invention market without the need to use cardboard boxes provided with special wax coatings as a barrier layer.

As a result of its affinity for moisture, the zeolite material can absorb the moisture from the ambient air before it can penetrate the interior of the particles, where it can the bicarbonate or carbonate may be adversely affected or where they, as moist alkaline conditions arise as a result, possibly some other product ingredients, such as emollients or any of the various adjuvants, has a damaging influence. The ion exchange zeolite material sitting on the outer surface of the particles, with which can quickly and effectively remove calcium ions from the wash water, acts to possibly harmful calcium ions (and other ions that cause water hardness) are removed before they can be treated with any other component of the fabric softener-containing detergent and cleaning agent, such as an adjuvant, in Reaction can occur, and before they react undesirably with the laundry or the soiling on it; Reactions of this kind can potentially cause the dirt on the laundry to be more stubborn and contrary to the washing activity of the surfactant becomes more resistant. Furthermore

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the zeolite material remains, as it is closely related to the non-ionic Surfactant is bound by the non-ionic substance in during the first period of contact with the wash water Suspension. Usually the particles face one another their original particle size to a considerably larger particle size, which leads to them being trapped in the laundry remain. Such inclusions are disadvantageous because they cause lightening phenomena in dark-colored laundry can be. In this way, the non-ionic surfactant helps to keep the zeolite particles in suspension until they fall apart into smaller-sized particles that do not settle on the laundry.

The comparatively large particle size of the product and the starting material is a bit unusual, but it does get on with it Free-flowing particles that dissolve quickly and that have a high bulk density. As a result of the comparatively large particle sizes of the builder salt, the absorption of nonionic surfactant and at the same time the desired coating effect is better, there is no undesired paste formation instead, and the particle surfaces contain sufficient amount of nonionic surfactant material that the desired Zeolite powder coating is able to adhere to it and can be held.

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By keeping the fabric softener inside the product, by having it with the base particles as a liquid added before zeolite is applied, or by incorporating it into a particle that is subsequently added with additional If a coating is provided, initial contact of the fabric softener with the laundry is avoided. This is desirable otherwise the softening compound could settle on the fabric, causing a reaction of the softener could come with the dirt on the laundry or the fabric of the laundry itself, and thereby would the cleaning process is impaired. In some cases, when "external" softening agent is added to the laundry and begins to melt, grease stains can form on the laundry, and this is where the cleaning process begins inhibited. According to the invention, such undesired staining is prevented by first applying the zeolite material and at least a portion of the nonionic surfactant comes into contact with the laundry. When various adjuvants in the Inner base particles are held, their initial contact with the laundry can be prevented in the same way, which is often desirable. This also prevents particles of optical brighteners, for example stilbene brighteners, come into contact with the laundry immediately. The brightener is worked in so that it traps particles in the interior is. This avoids the formation of particularly shiny spots on the items to be washed.

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In the following examples, in which some embodiments of detergents and cleaning agents according to the invention are illustrated without, however, the invention being limited thereby, unless otherwise stated, all parts are parts by weight and all temperature values are temperatures in ⁰ C.

example 1

Mixture of sodium carbonate-sodium bicarbonate structural substance particles (Snowlite I, weight ratio of Na ₃ CO ₃ to NaHCO ₃ approx. 1: 2, particle sizes in the range of 20 to 100 meshes, US standard sieve series)

Neodol 25-7 (nonionic surfactant, condensation product of C ₁₂ _ ₁₅ ~ fatty alcohol with throughput 18.5 average 7 moles of ethylene oxide, manufactured by Shell Chemical Company)

Crystalline zeolite of type 4A with high ion exchange capacity (Zeolite CH-252-91-1, in particle sizes in the range from 170 to 270 mesh (US standard sieve series) with ultimate particle size in the range of 346.3 to 7 microns, with an average of about 5.2 Micron, manufactured by J.M. Huber Corp.)

Distearyldimethylaitunonium chloride (Arosurf TA-100 95% active ingredient powder with a particle size in the range of 80 to 160Ma- 7.4 See (US Standard Sieve Series) manufactured by Ashland Chemical Company)

The carbonate-bicarbonate framework particles were poured into an inclined at room temperature (25 C)

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Drum with 8 ° inclination, rotating at one speed at about 40 rpm, and for a period of 5 minutes the nonionic surfactant was at 30 C sprayed onto the moving surfaces of the particles. Then another 5 minutes in the drum mixed, and then the zeolite powder was mixed with the material for a further 5 minutes. The spraying of the nonionic surfactant took the form of droplets, largely in the range of 50 to 100 microns in diameter and during the spraying process and following mixing, the particle size of that present in the mixer increased Material slightly and the fines present agglomerated to particles ranging in size from 20 to 100 mesh (US Standard Sieve Series). The zeolite addition was during a period of about 5 minutes (periods of 1 to 10 minutes are typical), and then that's it manufactured, still in the intermediate state, spherical product in particle sizes of about 4 to 40 mesh. Thereafter becomes the powdered softener with the builder, nonionic surfactant and zeolite intermediate mixed, mixing is continued for 8 minutes, during which time the fabric softener particles adhere to the larger particles. The resulting product had a loose bulk density of about 0.8 g / cm and was free-flowing. It has been packaged and stored and it has been found that when stored under normal storage conditions

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- 5υ -

No noteworthy caking and clumping occurred during normal storage. If such a stored package was opened, the detergent containing fabric softener poured out well and the bulk density was still always about 0.8 g / cm.

Washing tests or practical cleaning tests with the product produced showed that it did not generate dust, was free-flowing, did not tend to cake and was suitable for commercial use
Purpose of use possessed suitable detergency and softening properties which are similar to those of fabric softeners built up with tripolyphosphate as a builder substance
Detergents with comparable active ingredients work well
let compare. The zeolite material did not settle
noticeably on the laundry and bleached dark colored ones
Laundry does not finish and the carbonate had no damaging effect on the laundry made of cotton, polyester and acrylic material due to the presence of the bicarbonate and the resulting pH of about 9.8 in the washing water. There were also no grease stains on the laundry
caused by melted fabric softener, apparently not because the fabric softener is largely protected against initial strong contact with the laundry by the zeolite material on the particle surface.

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A comparative test was carried out and powder of finely divided sodium carbonate and sodium bicarbonate were obtained with particle sizes in the range of 170 to 270 mesh and to a material with a particle size agglomerated in the range of 20 to 100 mesh (US standard sieve series). To this end, a 20% strength was initially used with 5% by weight aqueous corn starch paste and this was treated for a period of about 3 minutes on in the same as previously described mixing drum sprayed particles kept in motion, the drum slowly at a speed of, for example, 10 rpm. The resulting product was a very useful fabric softener containing detergent, which, if you use it in the same concentration as in the previous example (1/4 to 1/2 measuring cup or about 45 to 90 g per 65 1 washing water filling) used for washing washing machine fillings of about 4 kg was sufficient on soiled clothing, but was not as free-flowing as the fabric softener described above containing detergents. If you only use sodium bicarbonate as the starting framework salt, that has Product did not have as good detergency as the product described above, and when the carbonate alone is used, the product has a higher alkali content than the desired alkali content and it is not free

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flowable. However, one can use the carbonate-containing composition useful as a detergent containing fabric softener in those applications where higher pH values can be tolerated, however, this product is comparatively inferior for the retail trade due to its comparatively poor quality Flow properties and the higher pH value are less interesting and acceptable than the products according to the invention.

The above example was repeated in a modified form. The Arosurf particles were together to particle sizes im Range from 4 to 40 mesh (US standard sieve series) melt agglomerated before the remaining ingredients of the composition were admitted. Due to the same particle sizes, the plasticizer did not separate from previously rounded produced particles, but it could sometimes happen that a hint of "fat" was observed on the washed laundry became; however, such phenomena have not been seriously debilitating and will be appreciated by the average consumer Not criticized.

In another embodiment of this example, the plasticizer was fused with the nonionic surfactant and so sprayed on the base grain particles that they were absorbed into the particle interior and also a smaller one Share on the surfaces of these grain particles remained before

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these were coated with zeolite particles. The product could have the same high bulk density and density as previously described Particle sizes are produced and was a very effective laundry detergent and cleaning agent containing fabric softener, in which the fabric softener is so protected that it initially has no contact with the laundry; thereby becomes unwanted staining avoided.

Comparably good results were obtained when the melted Softening agent consisting of quaternary ammonium halide is sprayed onto the circulating base particles, then the non-ionic surfactant was sprayed on and then the zeolite powder "was dusted on. In this latter case Embodiment was applied to the zeolite material before this on the nonionic surfactant coated spherical particles , an optical brightener of the stilbene type (Tinopal 5BM) mixed with Tinopal RNS (0.5% and 0.05%, respectively). on in this way it is effectively prevented that the optical brightener is in significant contact with the quaternary ammonium compound comes; this avoids any detrimental effect between these two components Reactions can take place. If you use the product to wash laundry in the washing machine, both can Ingredients, the optical brightener and the non-ionic surfactant, act actively in the wash water before breaking out of the particles Fabric softener is dispensed, which could possibly interact with it.

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With further modifications of this inventive method a quaternary ammonium compound in liquid form was sprayed onto the surfaces of the zeolite particles before they Particles were coated onto the carbonate-bicarbonate mixture coated with the nonionic surfactant. That resulting product had properties comparable to the aforementioned products. It is the same when the pulverized one quaternary ammonium compound in the particle size specified above mixed with the zeolite material and this mixture as a coating on the waxy, fat-like surface of base particles coated with the nonionic surfactant is applied. According to yet another version of this process, the powdered quaternary compound is an the nonionic surfactant coated on the core particles is made to adhere, and zeolite powder becomes over it applied as a coating. A laundry detergent and cleaning agent containing fabric softener can be used in this way as well available with the properties described above.

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Example 2

Snowlite I 19

Britesil hydrous silicate particles (18% water, Na-O: SiO ₂ ratio of 1: 2, manufactured by the Philadelphia Quartz Company)

Neodol 25-7 14

Type 4A zeolite (Zeolite CH-252-91-1) 50

Distearyldimethylammonium chloride (Aerosurf

TA-100) 8

The Snowlite particles were at room temperature in the inclined drum, as described in Example 1, with a rotational speed of 12 rpm, ran, filled. The water-containing silicate, which was about the same particle size, was added over a period of 2 minutes with constant mixing added to the contents of the drum, and then mixing was continued for a further 3 minutes and so did the silicate the carbonate-bicarbonate particles are uniformly mixed. This was followed by a further 5 minutes at one temperature from about 50 C the non-ionic surfactant mixed with the fabric softener on the moving surfaces of the particles that had been preheated to 40 C, sprayed on. Then, as described in Example 1, continued working. The resulting product was an excellent

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Nice concentrated, phosphate-free, fabric softener-containing detergent and cleaning agent for coarse, white and colored laundry, which at a concentration of 0.1 to 0.2% in the wash water was well suited for washing dirty laundry (generally used in washing machines that are filled from the top, 0.15%). The product had a bulk density of about 0.7 to 0.8 g / cm and was free-flowing after normal storage without the need for protective cardboard with barrier properties was. The addition of water-containing silicate contributed to increasing and improving the structural effect of the detergent also the corrosion-preventing activity compared with the product according to Example 1, albeit also these products satisfied in this regard.

Example 3

Snowlite I 27

Neodol 25-7 19

Neodol 25-3S (sodium polyethoxy fatty alcohol sulfate (C ₁₉ .., .- alcohol and 3 moles of ethylene oxide per mole), 60% aft active ingredient, 25% H ₃ O and 15% 4 C ₂ H ₅ OH, manufactured by Shell Chemical Company) )

Type 4A zeolite (Zeolite CH-252-91-1) 40

Distearyldimethylammonium chloride 10

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The procedure was as described in Example 1, with the difference that the Neodol 25-3S was mixed with the Neodol 25-7 and both were sprayed onto the Snowlite particles together. The resulting product was an excellent, free-flowing, non-sticky detergent and cleaning agent containing fabric softener for coarse, white and colored laundry with the desired high bulk density (0.6 to 0.8 g / cm), which did not clump when stored. Since this product also had an anionic surfactant content, it was a little better as a detergent than the product according to Example 1. During storage, there were no adverse effects of the anionic substances present, as they may have been due to the separation of these two types of substances from the particles could occur. In a modified embodiment of the process described in this example, the cationic fabric softener with the nonionic surfactant was added to the base particles and the anionic surfactant was mixed with the zeolite and applied to the virtually completely nonionic surfactant coated particles. In a further modification, the Neodol 25-3S was first added to the carbonate-bicarbonate particles together with some Neodol 25-7, and then further non-ionic surfactant was added as a coating for these particles and so the anionic surfactant from the later added quaternary Ammonium compound kept separate.

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In yet another modification of the experiment described above, 0.5% of the optical brightener was Tinopal 5BM instead of an equal percentage Neodol 25-3S is used and mixed with the Snowlite before the Neodol 25-7 and Neodol 25-3S were applied to it. In this way the brightener was removed from the later applied quaternary compound kept separate. All of these products were in the desired particle sizes and bulk densities as previously described before and also had the other characteristics specified above .

Example 4

This example explains a further modification of detergents and cleaning agents according to the invention and the process for their production, according to which additional amounts of non-ionic surfactant are incorporated into the product using a step-by-step coating technique. As described above in Examples 1 to 3, liquid, nonionic surfactant was applied in an amount sufficient that it could penetrate into the interior of the Snowlite or the other base particles and that a sufficient excess remained to protect the surfaces of the particles were wetted that the subsequently applied zeolite powder adhered to the surfaces. If one thing in some

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In cases it is desirable to have a higher amount of non-ionic surfactant in the product, thereby creating a more concentrated one Detergent composition is obtained, and if then according to those described in Examples 1 to 3 Process works, it can happen that excess liquid forms an agglomerate or a paste leads or favors this education. This undesirable result can be avoided and additional non-ionic surfactant incorporate it into the product in a satisfactory manner so that it is still free-flowing and maintains a high bulk density, when operating as described below in this example. In this procedure, one can also check the particle size increase desirable.

First, as described in Examples 1 to 3, worked, however, an additional amount of 5 parts of nonionic surfactant for every 100 parts of that used in these examples resulting product was sprayed on, and an additional 10 parts of zeolite material was then mixed with the product and adhered to the nonionic surfactant coating (spraying and mixing as in the examples 1 to 3 described). The particle size increased by about 5% (diameter), but the product had still the same bulk density as previously stated and was also still free-flowing and non-clumping. In further Another 5 parts could be tried on non-

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ionic surfactant to that obtained in the two-step process Spray on the product and dust another 10 parts of zeolite material on it, using (with the same spray and Mixing methods) similarly good results were obtained.

When performing the step-by-step enrichment described and coating usually become the Snowlite particles or other base particles and the quaternary ammonium compound present as fabric softener not additionally again sprayed on, but this can also be done if it is beneficial. It is possible to have six coating treatments to undertake, but only three such processes are preferred, as they are described in the "further experiment" here, executed. It has also proven to be expedient to reduce the total amount of nonionic surfactant and zeolite in the following coating treatments carried out to the amount that was applied in the first treatment is, and it is advisable to use half of the amount applied in the first treatment, with the percentage of non-ionic surfactant and zeolite within the percentage range given above should lie. ■

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Example 5

The procedure was as described in Examples 1 to 4, but instead of Snowlite I, Snowlite II was used of zeolite type 4A, crystalline zeolites of types X and Y with the same particle size and amorphous zeolites are used, instead of the Neodol 25-7, Neodole 23-6.5 and 45-11 as well as Alfonics 1618-65 and 1412-60 were used, and instead Arosurf TA-100, Aliquats H226 and 400, Arquad 2HT-100, Culversoft WS-Paste and Varisoft 100 were used. There were fabric softener Detergent compositions obtained which were free-flowing and a comparatively high bulk density exhibited. In the manufacturing process, the only difference was the temperature of the nonionic surfactant kept sufficiently high that it was in a liquid state when sprayed onto the surface of the base particles became. In addition, the proportions of the various components were modified to -10% and -30%, whereby however, the proportions were kept within the aforementioned ranges. Care must be taken that the non-ionic surfactant is used in such a proportion that a part of it does not absorb on the The surface of the base particles remains in the form of an adhesive coating so that the zeolite particles can be held in place. If the non-ionic surfactant is at the temperature that

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the surfactant when the zeolite material is applied is solid, it must be ensured that the temperature is high enough is adjusted so that the zeolite particles can adhere thereto and to the base particles. When the cationic fabric softener is a solid and is to be introduced into the interior of the base particles, the temperature must be so sufficient be increased so that it is sufficiently liquefied for incorporation, either by itself or together with the nonionic surfactant is.

The particularly excellent results obtained according to the examples described above when carrying out the invention Processes for the preparation of the detergent compositions achieved could not be expected. Attempts have already been made to use mixtures of sodium carbonate and bicarbonate (each particle being made from such a mixture exists), as described in US Pat. No. 3,944,500, to be used as absorbents for non-ionic surfactants, but the skilled person could not infer any teaching or indication that products were similar to those according to the invention Detergents and cleaning agents with high bulk density can be produced if this mixture is used as core particles used. The carbonate-bicarbonate materials known as Wegscheider's salt, which often also contain sesquicarbonates, are classified as products with a low bulk density (in the range from about 0.4 to 0.5 g / cm). In contrast

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is the specified bulk density of 0.6 g / cm (shaken) for the detergent-containing detergents and detergents according to the invention Detergents are of high value and usually are of the invention manufactured products have even higher bulk densities, usually around 0.7 g / cm or higher. It It is not known from the prior art that zeolite particles are present and that these are held on the base particles can be, and it is also not apparent from the literature that in order to adhere a coating to the base particles can use liquid, non-ionic surfactant, nevertheless such particles have a high sorbent capacity for liquid to have. Furthermore, it was not known that a cationic fabric softener in the various types described in incorporate such compositions and against reactive ingredients in the composition as well as against initial ones Contact with the laundry to be cleaned can protect. By means of the method according to the invention, a free-flowing Manufacture a product from which no components separate, in the desired, comparatively large particle size, which has an even higher content of non-ionic surfactant than the base particles normally hold capital. During the application of the nonionic surfactant to the core particles, which absorb a large part of the nonionic surfactant, "excess"

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non-ionic surfactant a coating on the surface of the Particles are formed which are greasy or waxy in nature and appearance, but the particles adhere not noticeably against each other, rather they hold onto the subsequently applied smaller zeolite particles. before After adding the zeolite, the mixture is not pasty, it rather resembles moist sand, with each particle attached the other non-adherent or the easily detachable adherent. The end products produced are free-flowing, though they add 10 to 100% of needle-shaped Wegscheider's salt Base material included, and this is partly due to the fact that the particles are crushed by the coating Zeolite are rounded or spherical particles are formed. In addition, the various components in the spherical product particularly functionally arranged to one another, and those of the base particles if As such carbonate-bicarbonate is present, the buffering action exerted supports the washing process (the pH of a 0.1% aqueous solution of the Snowlite is about 9.8).

Furthermore, it is important that the finished product in the specified the particle size is relatively large; but when, as in the examples above, the conditions are changed (if one uses, for example, smaller base particles),

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so that the product is in the form of smaller particles, e.g. those on the order of 8 to 100 mesh (US standard sieve series) is obtained, then one obtains higher bulk densities than they are for detergent compositions containing fabric softener are common, and the products made in accordance with the invention are for use in a wide variety of washing and cleaning operations usable even if they do not have the particularly high flowability and extremely good properties of the specifically preferred embodiments of the present He found on white.

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Claims (10)

Claims 1. Free-flowing, granular fabric softener containing Detergents and cleaning agents with a bulk density of at least 0.6 g / cm and particle sizes in the range of 4 to 40 mesh (US standard sieve series), the core particle of an alkali builder salt with sodium bicarbonate mixed sodium carbonate, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, Sodium silicate, borax and / or the corresponding potassium salts, in their interior and a usually liquid or paste-like nonionic surfactant is present on the surfaces of these 809843/0565 INSPECTED and the surfaces of the builder particles have a coating from ion exchange properties adhering to the nonionic surfactant possessing zeolite particles or on these particles one of a waxy quaternary airanonium compound existing fabric softener is localized. 2. Washing and cleaning agent containing fabric softener according to claim 1, characterized in that core particles as builder salt Alkali carbonate and alkali bicarbonate in a weight ratio of 1:10 to 10: 1 are, the particle size of which is in the range of 20 to 100 mesh (US standard sieve series), as zeolite crystalline, amorphous and / or mixed crystalline-amorphous zeolites of type A, X and / or Y are present as non-ionic surfactant a condensation product of 10 to 18 carbon atoms containing fatty alcohol and polyethylene oxide with 3 to 15 moles of ethylene oxide per mole of fatty alcohol is present, the quaternary existing as fabric softener Ammonium compound is a normally solid quaternary ammonium halide in granular form, and the percentages of mixed alkali carbonate and alkali bicarbonate or non-ionic surfactant or zeolite and quaternary ammonium halide in the range from 20 to 20 to 40% or 12 to 30% or 30 to 60% or 4 to 12% lie. 809849/0565 3. A washing and cleaning agent containing fabric softener according to claim 2, characterized in that the alkali carbonate is sodium carbonate, the alkali bicarbonate is sodium bicarbonate, the sodium carbonate / sodium bicarbonate mixture contains Wegscheider's salt, and the weight ratio of Na ₃ CO ₃ to NaHCO _{3 is} in the range from 1: 3 to 1: 1, as a zeolite a type A zeolite with an absolute particle size in the range from 3 to 12 microns and a moisture content of 10 to 25%, as a nonionic surfactant a condensation product of a 10 to 18 Fatty alcohol containing carbon atoms with 6 to 12 moles of ethylene oxide per mole, as a quaternary ammonium halide fabric softener a quaternary ammonium chloride with two higher alkyl groups and two lower alkyl groups and the end product is in the form of essentially spherical individual particles. 4. Detergents and cleaning agents containing fabric softener according to claim 1, characterized in that it is coated with a usually liquid or paste-like, non-ionic surfactant, which in turn has a coating of zeolite particles exhibiting ion exchange properties. 809843/0666 5. washing and cleaning agent containing fabric softener according to claim 1, characterized in that the fabric softener is present in the particles and coated with zeolite particles. 6. washing and cleaning agent containing fabric softener according to claim 1, characterized in that the fabric softener and the nonionic surfactant are present in the same alkali builder salt particles. 7. A process for the production of a free-flowing, granular fabric softener-containing detergent and cleaning agent with a bulk density of at least 0.6 g / cm and particle sizes in the range from 4 to 40 mesh (US standard sieve series) from core particles from an alkali builder salt such as sodium bicarbonate mixed sodium carbonate, sodium carbonate, sodium carbonate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate and / or borax, a normally liquid or pasty non-ionic surfactant contained in the interior of these particles and on their surfaces and coated with zeolite particles having ion exchange properties, which are attached to the non-ionic surfactant adhere derteilchenoberflachen the buil and waxy with a trapped in this particle softeners 809843/0566 in the form of a quaternary ammonium compound, characterized in that the alkali builder salt, the nonionic surfactant and the fabric softener are used quaternary ammonium compound mixed together, the non-ionic surfactant and the quaternary ammonium compound be in liquid form during the mixing process, absorbed by the builder substances and these are coated with it, and that the particles so coated with zeolite of their own particle sizes mixed in the range of 0.01 to 20 microns, these zeolite particles on the surface of the coated Particulate surfactant and quaternary ammonium compound as fabric softener to adhere and makes the particles so free flowing. 8. The method according to claim 7, characterized in that the core particles are alkali carbonate and alkali bicarbonate, including Wegscheider's salt, used as zeolite crystalline, amorphous or mixed crystalline amorphous zeolites of type A, X and / or Y, as a non-ionic surfactant, a usually liquid or paste-like condensation product from a 10 fatty alcohol containing up to 18 carbon atoms and polyethylene oxide with 3 to 15 moles of ethylene oxide per mole of fatty alcohol used, for the quater- 8098U / 056S nary ammonium compound is a quaternary ammonium chloride with two higher alkyl groups and two lower alkyl groups used the non-ionic surfactant and the quaternary ammonium chloride on kept moving Surfaces of the core particles sprayed on, the percentage of core particles composed of mixed sodium carbonate and sodium bicarbonate, nonionic surfactant, zeolite and quaternary ammonium chloride in the range of 20 to 40% or 12 to 30% or 30 to 60% or 4 to 12% selects the proportional amounts of sodium carbonate Sodium bicarbonate is used in the range from 1: 3 to 1: 1, the mixture of sodium carbonate and sodium bicarbonate used in particle sizes ranging from 20 to 100 mesh (US standard sieve series) and the final product in the form of particles with a size in the range from 4 to 40 mesh (US standard sieve series) wins. 9. The method according to claim 7, characterized in that the product obtained according to claim 7 again with a Coating made of non-ionic surfactant in liquid form and on the surfactant in turn a coating Zeolite particles having extreme particle diameter in the range of 0.01 to 20 microns is applied. 809843/0566 10. The method according to claim 8, characterized in that the product produced according to claim 8 with a non-ionic surfactant in the liquid state, which is a normally liquid or paste-like condensation product of a fatty alcohol with 10 to 18 carbon atoms and polyethylene oxide with 3 to 15 moles of ethylene oxide per mole of fatty alcohol is coated and this surfactant in turn receives a coating of crystalline, amorphous and / or mixed crystalline amorphous zeolites of type A, X and / or Y and the Amounts of nonionic surfactant subsequently applied to the product produced according to claim 8 and Zeolite not greater than half the content of nonionic surfactant and zeolite in the one prepared according to claim 8 Product is. 809843/0565