CH633579A5 - Free-flowing granular detergent and cleaning agent of high bulk density containing a fabric softener - Google Patents

Description

The invention relates to a free-flowing granular detergent and cleaning agent containing a fabric softener with a high bulk density and to processes for their production.

Compositions which have a washing and cleaning action in combination and which give the laundry a soft feel are known. The person skilled in the art also knows that components which can be used in non-ionic surfactants in washing and cleaning compositions and quaternary ammonium halides with a long-chain lipophilic moiety on the nitrogen atom present therein can be successfully used as fabric softening agents and for antistatic finishing. Inorganic builder salts, such as phosphates, carbonates and silicates, have long been used as builders for organic surfactants, and zeolites, such as sodium aluminosilicate, have recently been used for these purposes. Most granular detergents and cleaning agents have a low bulk density, but it is also known to produce granular detergents and cleaning agents with a high bulk density. So far, however, it was not known to be a granular one

To produce laundry detergent and cleaning agent containing fabric softener with a high bulk density and the desired product properties described in the present invention, and also production methods for such products are not known from the prior art. The invention relates to a free-flowing, granular washing and cleaning agent containing a fabric softener with a bulk density of at least 0.6 g / m3 and a particle size in the range of 4-40 meshes of the US standard sieve-io series, comprising core particles an alkali metal builder salt selected from the group consisting of Weg-Scheider's salt of the formula Na2C03. 3NaHCOs, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate, borax, and / 15 or the corresponding potassium salts, and mixtures thereof, a nonionic surfactant being contained in the interior and on the surfaces of these particles, and also on non-ionic surfactant adheres to the surface of the builder particle, a coating of calcium ion-exchanging zeolite particles with a 20 extreme particle size in the range of 0.005-20 microns, and a wax-like or solid quaternary ammonium compound as a fabric softener, which has at least one C] 2-C18 alkyl group in the molecule and localized in or on these particles, the zeolite having the following 25 formula:

(MaO) (Al203) y (Si02) z. wH20

wherein

M means sodium or potassium,

y has a value of 0.8-1.2,

30 z has a value of 1.5-3.8, and w has a value of 0-9,

and the percentages by weight of builder salt, nonionic surfactant, zeolite and fabric softener within the ranges of 20-40% by weight, 10-30% by weight, 35-30-60% by weight, and 4-12% by weight .-% lie.

The invention also includes products and methods for producing the detergents and cleaning agents containing granular fabric softening agents according to the invention, provided with several coatings. 40 The products according to the invention are excellent detergents and detergents containing fabric softeners for coarse, white and colored laundry with high bulk densities. This makes it possible, for a laundry of average size in an automatic washing machine (which has a capacity of 45 to about 30 to 65 liters and processes about 4 kg of laundry in soiled clothes in one washing operation), a smaller volume of detergent according to the invention, e.g. 50 to 150 cm3. This has the further consequence that comparatively effective amounts 50 of detergent composition containing fabric softener can be used in smaller packages, which reduces the need for storage space in the supermarket and in the household. Of course, it is also easier to handle smaller packages and pour out or fill up the product from them; it is easier to work with and the risk of spilling is reduced.

The core or base particles, in and onto which the non-ionic surfactant is added, consist of a builder salt defined above, which has a sufficient sorption capacity for the non-ionic surfactant when it is in the liquid state. It is normally desirable for the builder particles to be in a rounded shape, preferably spherical, and to have passages through the interior of the particles that have a sorption of at least 10%, preferably 20% and especially 30% or more, by weight , enable non-ionic surfactant in the builder particles. For the purposes of the present invention, builders are

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dersubstanzen preferably mixtures of sodium carbonate and sodium bicarbonate (including Wegscheider's salt of the formula Na2C03.3NaHCOs) are used, which are described in more detail below. Sodium carbonate, sodium bicarbonate, pentatrium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate (Na20: SiO2 ratios in the range from 1: 1.6 to 1: 3) and borax are also used as builder substances. Such products, which can be spray-dried, agglomerated or manufactured in any other suitable manner, are preferably in particle sizes which correspond to the particle size of the carbonate-bicarbonate mixture used with preference, which is specified later in the description. Mixtures of various builder substances and mixtures with numerous other components present in the compositions according to the invention can also be used. In addition to the sodium salts, potassium salts are also 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 carboxymethyl oxysuccinate), sodium gluconate and sodium EDTA can be used. However, the total content of such organic builder substances will usually only make up a small proportion of the total content of builder substance, preferably less than 25% thereof. For example, it is also possible to use sodium sulfate or another compatible filler substance instead of part of the builder salt, but again the filler substance should only be present in small proportions and preferably less than 25% of the total amount of builder-plus filler salts is.

As a mixture of alkali carbonate and alkali bicarbonate, it is expedient to use a mixture in which the two types of components are present in the same individual particle shape or grain shape. For the purposes of the present invention, these particles should advantageously have sizes between 20 to 100 meshes, preferably 30 to 60 meshes and in particular approximately 40 meshes (US standard sieve limit; in the present case the word “mesh” is synonymous with “No.” used). Larger particles, up to about 8 meshes, can also be used, provided that the finished end product then falls into the desired particle range specified above. Sometimes you have to take precautions to avoid agglomeration or other particle growth during the absorption of the non-ionic surfactant or at another process site, otherwise the end product could be obtained in too large a particle size. If smaller particle sizes are used than those in the specified desired range, the finished product is sometimes obtained as an undesirably pasty product instead of in the form of individual free-flowing beads.

The alkali carbonates and bicarbonates (i.e. the sodium or potassium salts) which are used in particular as sodium salts are used in the preferred embodiment of the present invention to be essentially anhydrous; partially hydrated structural salts 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 and 1: 1, the ratio 1: 2 is particularly preferred. The mixture is appropriately prepared so that it has a substantial content, for. B. 10 to 100% of Wegscheider's salt of the formula Na2COs. 3NaHCOs, balance sodium bicarbonate. Such a product is characterized by excellent sorption power for the liquid nonionic surfactant and can be easily and conveniently placed in a suitable base for a powder coating made of zeolite framework. A successful method for producing a mixed carbonate-bicarbonate product is described in Gancy et al., U.S. Patent 3,944,500, incorporated herein by reference. A mixed carbonate-bicarbonate of the type described can be purchased under 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 produced by other known techniques. For the purposes of the invention, separate batches of carbonate and bicarbonate, which expediently have the same grain sizes and are present in the same proportions, are also used instead of the carbonate and bicarbonate substances intimately brought together in the individual particles, provided that the sorption power is sufficiently strong, that a sufficient amount of nonionic surfactant can be absorbed to produce the desired end product. It is also possible to use carbonate and bicarbonate powders of higher fineness, for example those with particle sizes below 100 meshes, such as 170 to 270 meshes, and agglomerate them either separately or in a mixture, taking care that the porosity of the product is maintained, ie only a minimal amount of binder, such as starch or another agglomerating agent, may be used. Wegscheider's salt of the formula Na2C03 can also be used with such products. Add 3NaHCOs.

The compounds used as fabric softeners, which give the laundry a soft feel and help to make it wrinkle-resistant and antistatic, comprise a large number of compounds which contain a substantial amount of positive charge in their molecules. In general, such compounds have hydrophobic croups in the positively located part of their molecule, and they are often relatively long chain residues, such as higher hydrocarbyls or alkyls. While amines, imidazolines, pyridines, guanidines and their salts and derivatives are generally useful, especially when they contain relatively long chain hydrophobic groups, the fabric softeners used in the invention are quaternary ammonium compounds containing one or two long chain hydrophobic groups and contain two or three short chain groups and have a solubilizing cation or salt-forming group, usually either halide, sulfate, acetate, hydroxide or other inorganic or organic solubilizing monobasic or dibasic residue. Numerous quaternaries can be used for the purposes of the present invention Use ammonium compounds as fabric softeners, as described, for example, in US Pat. Nos. 3,227,614 and 3,442,692.

The longer-chain substituents on the nitrogen in the quaternary ammonium compounds and salts are higher alkyl groups with 12 to 18 carbon atoms, in particular 16 to 18 carbon atoms. The stearyl radical is particularly preferred. The shorter hydrophobic residues are alkyl residues with 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms. The methyl radical is particularly preferred.

Similar long chain substituents can be present in the imide azolines and imidazoles, the pyridines and piperidines, the guanidines and the amines. Specific examples of cationic conditioning agents which can preferably be used for the purposes according to the invention are di-

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methyldistearylammonium chloride, trimethylstearylammonium bromide, cetyltrimethylammonium chloride, di-higher - alkyldimethylammonium chloride, in which the higher alkyl residues are derived from hydrogenated allele oil alcohols, higher alkyl-dimethylbenzylammonium chloride and laurylisoquinoline bromide. Instead of these preferred compounds, it is also possible to use higher alkylamines which are known for their softening action on various fabrics and fibers, give them wrinkle resistance and make them antistatic. These compounds are highly substantive for the fabrics, especially for cotton or cellulose materials and synthetic organic fibers. The plasticizing compounds described, which contain higher alkyl groups, are waxy or pasty solids and can be melted or liquefied at elevated temperatures, so that they are useful for coating the base particles used according to the invention. Such coatings can be made by mixing comparatively soft particles of the softening compound with the substances to which it is to be adhered, such as carbonate-bicarbonate-non-ionic ten-sid zeolite particles, or one The softening compound can be melted or sprayed onto the core particles, or can be mixed with the non-ionic surfactant and sprayed onto the particles together with this. In the products according to the invention, the plasticizing compound remains effective during the use of these products, and this is largely due to the fact that nonionic surfactant is present instead of anionic surfactant with which the cationic plasticizing substances frequently react.

Nonionic surfactants that can be used for the purposes of the invention are, for example, those as described in detail in McCutcheon's Detergens and Amulsifiers, 1973 Annual and in Surface Active Agents, Volume II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). This prior art is assumed to be known for the present invention. Non-ionic surfactants of this type are generally pasty or waxy solids at room temperature (20 ° C), which are either sufficiently water-soluble that they quickly dissolve in water, or at the temperature of the wash water if these are above 40 ° C quickly become molten. The non-ionic surfactants used for the purposes of the invention are those which are liquid or pasty at room temperature, and preferably the usually pasty or semi-solid substances are used, because when they are used there is less tendency for a sticky product to form poor flow properties means that it is sensitive to caking during storage and tends to solidify. Such products usually tend to become less moist and give up their "coating" to the zeolites. Nevertheless, liquid niclit-ionic surfactants are also used, and the non-ionic surfactants used are usefully liquefied in such a way that they can be sprayed at reasonable temperatures, for example below 45, 50 or 60 ° C. Examples of typical useful nonionic surfactants are polyalkenoxy derivatives, which are usually obtained by condensation of lower alkylene oxide (with 2 to 4 carbon atoms), e.g. Ethylene oxide, propylene oxide (with a sufficient amount of ethylene oxide to render the substance water-soluble) with a compound containing a hydrophobic hydrocarbon chain and one or more active hydrogen atoms, such as, for example, higher alkylphenols, higher fatty acids, higher fatty mercaptans, higher fatty amines and higher fatty polyols and alcohols, e.g. Fatty alcohols with 8 to 20 or 10 to 18 carbon atoms in the alkyl chain, which are oxalkylated with an average of about 3 to 30, preferably 3 to 15 or 6 to 12, lower alkylene oxide units. Preferred nonionic surfactants are those of the formula R0 (C2H40) nH, where R is a radical of a linear saturated primary 5 alcohol (an alkyl) having 10 or 12 to 18 carbon atoms and n is an integer from 3 or 6 to 15 means. Examples of typical commercially available nonionic surfactants that can be used 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) ) chain 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 oxethylated 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). The products sold under the trade name “Ige-pals” by GAF Co., Inc. can also be used. These include, for example, the polyoxethylated (3 to 30 ethylene oxide units) middle alkyl (6 to 10 C atoms) phenols, such as Igepals CA-630, CA-730 and CO-630. Another 25 usable 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, which are caused by the condensation of 3o Propylene oxide with propylene glycol have usually been produced with molecular weights in the range from 5000 to 25,000. Furthermore, the various products available under the trade name “Tweens” (products from ICI America) can be used, which are 35 polyoxyethylene sorbitan esters of higher fatty acids (12 to 18 carbon atoms), such as those that provide solubilizing amounts Contain ethylene oxide. Numerous other non-ionic surfactants, as described, for example, in the references mentioned above, can also be used for the purposes according to the invention, preferably the proportion of non-ionic surfactants present which differ from higher fatty alcohol polyoxyethylene ethanols, is small and preferably not more than 50%, preferably not more than 25% of the total of 45 nonionic surfactants present. If "higher" is used in the present description, for example higher alkyl compounds, higher fatty acid compounds and the like, then it is understood to mean those which contain 8 to 20, preferably 10 or 12 to 50, 18 carbon atoms.

Crystalline, amorphous and / or mixed crystalline-amorphous natural or synthetic zeolites can be used for the purposes according to the invention, which are able to counteract sufficiently quickly and satisfactorily effectively the ions which cause water hardening, such as calcium ions, in the wash water. It is preferred to use materials which are able to react sufficiently quickly with the hardness-causing cations, such as calcium, magnesium, iron or the like, 60 in order to soften the wash water before such hardness-forming ions on the other components of the synthetic organic Detergent composition may have an undesirable effect. The zeolites that can be used can be characterized by a high ion exchange capacity for calcium 65 ions; it is normally about 20 to 400 or more mg equivalents of calcium carbonate hardness per g of the aluminosilicate, preferably 250 to 350 mg equivalent / g, and the rate of softening should be

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be so high that a residual hardness of 0.02 to 0.05 mg CaCO3 / l, preferably 0.02 to 0.03 mg / 1, is achieved in one minute, and the residual hardness should be less than 0.01 mg in 10 minutes / 1, all data based on anhydrous zeolite.

Finely chopped particles of synthetic zeolite framework substance are used, which has the following formula:

(M20) x. (Al203) y. (Si02) e.g. w H20,

where M is sodium or potassium, x is 1, y = 0.8 to 1.2, preferably about 1, z = 1.5 to 3.8, preferably 2 to 3 or about 2 and w = 0 to 9 , preferably 2.5 to 6.

The soluble crystalline aluminosilicates which are advantageously used for the purposes of the invention are often characterized by a network of substantially uniformly large pores in the range from about 3 to 10 Â, often about 4 Â (normal); these pore sizes are excellently determined by the structural unit of the zeolite crystal. It is of course also possible to use zeolites which have two or more such networks of different pore sizes, and mixtures of such crystalline materials with one another or with amorphous materials can also be used with advantage.

It should preferably be a univalent cation exchange zeolite, i.e. an aluminosilicate with a monovalent cation, namely sodium or potassium. Preferably, the monovalent cation of the zeolite molecular sieve is sodium.

The crystalline types of zeolites which can be used at least in a proportionate amount for the purposes of the invention as good ion exchangers include, for example, zeolites of the following crystal structure groups: A, X, Y, L, mordenite and erionite, and types A, X and Y are preferred to give. Mixtures of such molecular sieve zeolites can also be used, especially if a type A zeolite is present. The crystalline types of zeolites are well known to those skilled in the art and are described in detail, for example, in the treatise “Zeolite Molecular Sieves” by Donald W. Breck, published in 1974 by John Wiley & Sons. Examples of typical commercially available zeolites of the aforementioned type of structure are listed in Table 9, 6 on pages 747 to 749 of the Breck treatise. This table is assumed to be known in the present description.

For the purposes of the invention, preference is given to using synthetic zeolites and advantageously also those of type A or a similar structure, as described in particular on page 133 of the above-mentioned treatise. Good results can be obtained using a type 4A molecular sieve zeolite, the monovalent cation of which is sodium and whose pore size is approximately 4 Â. Such zeolite molecular sieves are described in US Pat. No. 2,882,243 and are referred to there as zeolites A.

The molecular sieve zeolites can be used in either dehydrated or calcined form, so that they have about 0 or about 1.5 to 3% moisture, or they can be used, for example, in hydrated or water-loaded form, so that they provide additional bound water in an amount of from about 4 to about 36% based on the total weight of the zeolite. included, depending on the type of zeolite used. For the purposes of the invention, the water-containing hydrated form of the molecular sieve zeolites (preferably about 15 to 70% hydrated) is preferred when crystalline product is used. The production of such crystals is known to the person skilled in the art. For example, in the production of the aforementioned zeolite A, the hydrated zeolite crystals which form in the crystallization medium (for example water-containing amorphous sodium aluminosilicate gel) are 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, for example Crack catalysts, happens. The crystalline zeolite can be obtained in both fully hydrated and partially hydrated form by filtering off the crystals from the crystallization medium and drying in air and at room temperature so that the water content is in a range from about 5 to 30% moisture, preferably about 10 to 25%, such as 17 to 22%. However, the moisture content of the molecular sieve zeolite used for the purposes of the present invention, as previously described, can also be much lower.

The zeolites used for the purposes of the present invention should preferably be practically free of ad-20 sorbed gases, such as carbon dioxide, because gas-containing zeolites tend to foam undesirably when detergent containing zeolite comes into contact with water; however, foaming can be tolerated for some purposes and sometimes it is specifically desired

The zeolite material is used in a finely comminuted state with outermost particle diameters from 0.005 to 20 microns, for example 0.01 to 20 microns, preferably between 0.01 to 15 microns and particularly preferably with an average particle diameter of 0.01 to 8 microns, such as 3 to 7 or 12 microns if the product is crystalline, and 0.01 to 0.1 micron e.g. 0.01 to 0.05 micron if it is an amorphous product. Although the outermost particle size is much lower, the zeolite particles usually have particle sizes in the range of 100 to 400 mesh, preferably 140 to 325 mesh (US standard sieve range). Zeolites with smaller particle sizes are often undesirably dust-forming, and those with larger 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 zeolites can be used instead, and these are often superior to crystalline materials in many important ways, as will be described. Mixed crystalline amorphous materials and mixtures of different types of the zeolites described can be used in the same way. The particle sizes and pore sizes of the materials are similar to those described above, although, as stated, the ranges given can be changed, provided that the material has sufficient builder function and colored detergent and cleaning agent which is used to treat it in an aqueous medium will not brighten undesirably.

55 A number of suitable crystalline molecular sieve zeolites are described in Belgian Patent No. 828 753 and the published German Patent Descriptions No. P 25 38 679.2, P 26 58 009.8 and P 26 56 251.6. Various other such compounds are described in British Patent 60 No. 1,429,143. Further such useful molecular sieve zeolites are illustrated in the descriptions of British Patents Nos. 1,473,201, 473,571, 437,512 and 1,464,427.

65 The preparation of amorphous and mixed amorphous crystalline aluminosilicate ion exchange zeolites is described in the description of British Patent No. 1 470 250.

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An ion exchange zeolite which can preferably be used for the purposes according to the invention is the amorphous zeolite of the formula described in BE-PS 835 351

MaO. A1203. (Si02) e.g. w H20,

where z is 2.0 to 3.8 and w is 2.5 to 6, especially when M is sodium. The content of these patents and applications can also be used for the purposes according to the invention; To avoid elongation of the text, reference is made to such materials and methods for their production and use.

Various adjuvants, both functional and aesthetic, can be used in compositions according to the invention, such as bleaches, e.g. Sodium perborate, colorants such as pigments and dyes, optical brighteners such as stilbene brighteners, foam stabilizers, e.g. Alkanolamides, such as laurin, myristine, diethanol amide, enzymes, for example proteases, skin-protecting agents and conditioning agents, such as, for example, water-soluble proteins with a low molecular weight, which have been obtained by hydrolysis of protein-containing materials, such as animal hair, hides, gelatin and collagen, foam-destroying agents , such as silicones, bactericides, e.g. Hexachlorophene, and perfumes. In general, such adjuvants and other additional builder substances are mixed with the other components in a special stage of the production process which is most suitable for the nature of the adjuvant and its physical state. It is particularly desirable to make the addition in such a way that the adjuvants or the other components of the product are stabilized and / or the absorbency of the carbonate-bicarbonate mixture for the nonionic surfactant is increased.

Such adjuvants can thus be sprayed onto the base particles with the non-ionic surfactant, one can mix them with the zeolite and together with it onto the base particles treated with the non-ionic surfactant, or one can add them to the particles coated with zeolite, either together with the softening agent or after adding the softening agent.

Preferably, only ionic surfactant is used (apart from the plasticizer, which can be regarded as a compound having cationic surfactant properties), but in some cases the nonionic surfactant can also be used together with an anionic organic surfactant, an amphoteric organic surfactant or mixtures use from it. If you use such fabrics,

however, they are normally present only in small proportions, preferably less than 25%, based on the total amount of nonionic surfactant and such surfactants, and preferably less than 10% thereof, and are localized and incorporated in the product such that disturbing reactions between the plasticizer and such detergents are kept to a minimum or prevented. If, for example, a quaternary ammonium compound is subsequently added as a plasticizer, it is advisable to provide an anionic or amphoteric surfactant, for example, with built-in anionic surfactants, preferably to be sprayed on and allowed to penetrate together with nonionic surfactant. If, on the other hand, the quaternary ammonium compound is sprayed onto the core particles together with the non-ionic surfactant or separately therefrom, then an anionic and amphoteric surfactant, for example, will be applied to the surface of the beads coated with the zeolite or initially with the zeolite mix and then apply to the particles treated with the cationic softener and the non-ionic surfactant.

Usable anionic surfactants are, for example, the sulfates and sulfonates with lipophilic molecular components, for example those with a carbon chain consisting of 8 to 20 or 10 to 18 carbon atoms. These include, for example, the linear higher alkylbenzenesulfonates, olefin sulfonates, paraffin sulfonates, 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 higher fatty alcohol, hearing fatty acid esters of isethionic acid and other known anionic surfactants as mentioned, for example, in the publications previously cited as references. Most of these substances are in solid form under normal conditions, for example as alkali salts, e.g. Sodium salt, before and can be spray-dried with conventional framework substances. The spray-dried particles which contain these builder substances can be used as core or base particles for the purposes according to the invention. Any known agglomerating techniques, comminution methods, accumulation processes or other working methods can be used to produce such preliminary products in order to produce these preliminary products in the carbonate-bicarbonate particles of similar particle size. Some examples of suitable anionic surfactants are the sodium salt of linear tridecylbenzenesulfonic acid, sodium cocomonoglyceride sulfate, sodium lauryl sulfate and sodium paraffin and olefin sulfonates, each with an average of about 16 carbon atoms. It is also possible to use amphoteric substances, such as, for example, the sodium salt of the products commercially available under the names Miranol C2M and Deriphat 151, as surfactants for the purposes according to the invention. 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 non-ionic surfactant or otherwise incorporated in a suitable manner mixed with other powdery substances required for the production of the washing 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, a non-ionic surfactant or mixed non-ionic surfactants is used as the sole detergent component .

The proportionate amounts of core particles (preferably carbonate-bicarbonate particles), non-ionic surfactant, zeolite and softening agent should be selected so that the desired free-flowing detergent particles containing free-flowing fabric softeners result in a sufficiently high bulk density during manufacture by means of the process according to the invention. The proportions are 20 to 40% core or base particles, 10 or preferably 12 to 30% non-ionic surfactant, 30 to 60% zeolite and 4 to 12% fabric softener, and particularly expedient ranges are 23 to 33% or 13 up to 23% or 40 to 52% or 5 to 10%. The bulk density of the product is at least 0.6 g / cm3; it is preferably in the range from 0.75 to 0.95 g / cm3 and in particular in the range from 0.8 to 0.9 g / cm3. The particle size of the product is in the range of 4 to 40 meshes (US standard sieve series) and is expediently 4 to 12 meshes and in particular approximately 6 to 8 meshes. The particle size of the carbonate-bicarbonate starting material or the other base particles before their treatment is generally in the range from approximately 20 to 100 meshes (US standard sieve series), preferably 30 to 60 meshes and in particular approximately 40 meshes. One can also use finer ones

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First use carbonate and bicarbonate powder and other builders and agglomerate them to the specified particle sizes. In general, the material with particles of the specified size range consists of a mixture of particles of different sizes within this range (this also filters for the various other granular materials mentioned in this description).

In the production of the starting particle mixture from carbonate and bicarbonate, one can use the procedure described in US Pat. No. 3,944,500 and preferably use the substances mentioned there available under the trade name “Snowlite” from Allied Chemical Corporation. A typical analysis for Snowlite I is 35% Na2C03, 58.5% NaHC03 and 6.5% H20, and another product of this type, Snowlite II, consists of 30,0,66,5 and 3,5% respectively. These products showed the following sieve analyzes (percentages on sieves 10, 40, 60 and 100); 0.2.67.6.96.9.99.0 and 0.7.60.7, 90.7 and 97.0 and had bulk densities (g / cm3) of 0.51 and 0.48 ( shaken) and 0.42 or 0.38 (loose). Snowlite I has a particularly low tendency to disintegrate or crumble (2.5% according to Allied Chemical Corporation test Na 17-35), and this product is preferred. Low brittleness 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 to form pastes instead of single coated particles when adding non-ionic surfactant. In some cases, further components of the end product can be added to the mixture of bicarbonate and Wegscheider's salt of the formula Na2C03. 3NaHCOs (sesquicarbonate may also be present) incorporated and further processed together with this according to the method described in the patent specification, provided that they remain stable and do not undesirably influence or do not react to the production of the carbonate-bicarbonate product material. 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 present.

Free-flowing, granular detergents and cleaners containing fabric softeners with a high bulk density can preferably be produced by one of several process methods. In one of these preferred methods, the sodium carbonate-sodium bicarbonate particles or other builder particles described are mixed with a nonionic surfactant used in liquid form. The surfactant is preferably sprayed on, but in some cases it can also be poured on. The surfactant penetrates into the carbonate-bicarbonate particles, but some remains on the particle surface, so that subsequently mixed zeolite can adhere to them. It is important that the nonionic surfactant is applied in such a sufficient amount that, in addition to the surfactant absorbed into the interior of the builder particles, some of the surfactant remains on the particle surfaces. During the mixing process after adding the non-ionic surfactant, the particles appear like wet sand and have a greasy or waxy appearance. The non-ionic surfactant is usually liquid, pasty or semi-solid and is advantageously used pasty or semi-solid, which reduces the risk of the product becoming sticky or clumping when stored. However, normally liquid non-ionic surfactants can generally be used with a satisfactory result. After the base particles have been coated with the non-ionic surfactant, the zeolite powder is mixed in and this adheres to the non-ionic surfactant on the particle surfaces. The particles become essentially spherical and the particle sizes are in the range of 4 to 40 meshes (US standard sieve series). In this embodiment of the manufacturing process, the fabric softener is usually blended in the form of rather small granules, flakes, granules or powders with the spherical particles formed from the base material, nonionic surfactant and zeolite. The fabric softener is usually a wax-like or fat-like low-melting solid material in particle sizes in the range of about 80 to 160 meshes, preferably about 100 meshes (US standard sieve ranges). It is held physically and / or electrostatically on the surfaces of the particles coated with the zeolite material. 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 the properties described above.

The initial spraying or other mixing of non-ionic surfactant with the carbonate-bicarbonate particles or other builder particles is usually done with the particles at room temperature (20 to 25 ° C); however, the temperature can generally vary between 10 to 40 or 50 ° C. Spraying or admixing usually takes only 1 to 5 minutes, and after complete spraying it is possible to continue mixing for 0 to 10 minutes, preferably 1 to 5 minutes. The fatty alcohol-poly-ethylene oxide condensation product that is sprayed onto the surface of the moving particles is usually liquid or is heated to a higher temperature so that it is liquid and when sprayed onto the moving surfaces or otherwise applied can be well distributed over it, thus facilitating the absorption of the liquid in the porous particles. There may be some agglomeration of the particles during the initial mixing stage. This is apparently due to the adhesion or cohesion between a portion of the fine powder material present, on the surface of which there are “excess” amounts of liquid non-ionic surfactant. During such agglomeration, the particle size of the individual particles increases to approximately the size in the size range for the particles of the end product, although the particle size also increases somewhat as a result of the subsequent adhesion of zeolite particles. The mixing and spraying of the non-ionic surfactant onto the particles in motion is expediently effected in a rotating drum or in a tube inclined at a slight angle, such as, for example, 5 to 15 °. Any suitable rotation speed, for example 5 to 50 rpm, can be used. The non-ionic surfactant is usually sprayed on in the form of fine surfactant droplets, for example those with a diameter in the range from 40 to 200 microns, preferably 50 to 100 microns. Other suitable spray droplet sizes can also be used, and in some cases, the non-ionic surfactant can be mixed with the builder particles even more after being dripped or poured onto the moving surfaces thereof. It is expedient to use high-performance mixing devices, such as a Lodige mixer, which operates at a comparatively low speed, or to use a twin-drum mixer or a similar mixing device in order to avoid the addition of larger drops or liquid jets5

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Ionic surfactant caused excessive agglomeration of the particles to prevent them. As previously mentioned, although this is not the preferred method of working, absorbent carbonate-bicarbonate particles can also be produced in the form of more angular particles in a different way than explained here, but it is more advantageous for the particles to have good flowability, that they are somewhat rounded.

After the absorption of the nonionic surfactant is complete, the zeolite powder is usually added to and held on your product for a period of 1 to 10 minutes, preferably about 5 minutes. Free-flowing granules with a particle size in the range of 4 to 40 meshes form (US standard sieve series). In this stage of the process, the moisture content of the product is usually 2 to 20%, preferably 5 to 15%, including water of hydration. The plasticizer, in the form of the aforementioned particle sizes, is then normally "dusted" on and adhered to the surfaces of the particles within a period of 1 to 10 minutes, preferably 5 minutes. Since the cationic plasticizer is only used in a relatively small proportion, the particles do not become much larger. The particles of the plasticizer adhere so firmly to the particles of builder, non-ionic surfactant and zeolite that a stable, non-dusting end product is produced without pressing errors. As previously mentioned, various adjuvants can be incorporated into the product and added to appropriate components or added or added at a suitable stage in the process of making the free-flowing granules after the manufacturing process is substantially complete. The total content of adjuvants, excluding water, is rarely more than 20% of the product and is generally below 10%. However, if a perborate bleaching agent is used, its percentage can be increased to such an extent that effective amounts are available for the bleaching process, and these can make up up to 30% of the product. Usually the additional amounts of the other essential components will then be proportionately lower. The perborate can be mixed into the carbonate-bicarbonate mixture, or it can be added to the mixture treated with the nonionic surfactant in a later process step or added to the finished product. Coloring agents, perfumes or other adjuvants can be mixed with the various components and mixtures during manufacture or even after the manufacturing process has ended.

In a modified embodiment of the manufacturing process, with which compositions of the same formulation but with improved properties can be produced, the cationic softening agent is melted and applied together with the non-ionic surfactant at an elevated temperature at which both substances are liquid. Alternatively, the plasticizer and the non-ionic surfactant can be applied to the base particles in succession. 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 substances being impeded. If liquid quaternary plasticizer is applied as the first substance earlier than the non-ionic surfactant, it tends to penetrate inside the base particles, and if the non-ionic surfactant is added, some of it will also get inside the particle is able to penetrate, but a larger proportion, compared to 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 method according to the invention, portions of the nonionic surfactant and zeolite are initially retained and used to apply additional coatings to the product. For example, 5 to 50%, preferably about 10 to 30%, of the nonionic surfactant and the zeolite can be subsequently applied to the product, first the nonionic surfactant and then the zeolite. Additional protective coverings are formed around the product. In this way, a larger amount of non-ionic surfactant can be introduced than is possible in any other way, and yet a detergent and cleaning agent containing free-flowing granular fabric softener can be produced. It is possible to make six cover treatments; preferably one is limited to three coating treatments (two additional coatings).

The products according to the invention have significant advantages compared to other detergent compositions containing fabric softeners. They can be formulated as phosphate-20-containing, low-phosphate-containing or phosphate-free compositions. The phosphate-free compositions have very good detergency for many types of soiling that occur in normal household laundry, and they comply with the legal and administrative regulations which prohibit the use of phosphates in detergents and cleaning agents. Accordingly, the products can be used worldwide and there are no longer any need for several different formulations and certain restrictions when sending detergent compositions to different areas. The excellent washing power of the products is given by the non-ionic organic surfactant and the mixture of water-soluble inorganic and zeolite scaffolders. In addition to its excellent washing power, the product contains a sufficient amount of fabric softener that can be applied to the laundry, so that the finished laundry is noticeably softer and more antistatic than laundry washed with comparative compositions not containing fabric softener. One should expect 40 due to the comparatively high concentration of non-ionic surfactants and fabric softeners, which as such are usually liquid, pasty, semi-solid or wax-like, that the product is "sluggish" or poorly flowable and baked when stored should tend; but 45, as has surprisingly been found, a very free-flowing, non-baking product is obtained instead, which may be due to the fact that the non-ionic surfactant is applied to the base particles in liquid form and penetrates into the interior of these particles 50 enables, and leaves only a relatively thin coating on their surfaces, which is then coated with zeolite powder (and sometimes some powdered fabric softener). The preferred mixture of carbonate and bicarbonate in the base particles has a sufficient structure and pH-regulating effect that the product is a very good detergent. However, other basic substances can also be used, provided that they are similarly good sorptive, such as spray-dried pentasodium tripolyphosphate, sodium carbonate. 60 If bicarbonate is present, the normally very high pH value that is obtained when carbonate is used alone is reduced, and this makes the product safer to use than a detergent built up with carbonate as a structural substance. This also considerably improves the sorption power of the composition for non-ionic surfactant, especially when the bicarbonate is largely in the form of Wegscheider's salt of the formula Na2C03. 3NaHC03 is present. The zeolite powder on the surface of the

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In addition to preventing stickiness or poor fluidity of the non-ionic surfactant, particles also serve as protection for the interior of the product against the effects of external moisture under ambient conditions with high atmospheric humidity. Accordingly, detergent compositions according to the invention can be marketed without the need to use cartons provided with special wax coatings as a barrier layer.

Because of its affinity for moisture, the zeolite material is able to absorb moisture from the ambient air before it can penetrate into the interior of the particles, where it may interfere with the bicarbonate or carbonate, or where it may affect some others because of the presence of humid alkaline conditions Product components, such as plasticizers or any of the various adjuvants, have a detrimental effect. The ion exchange zeolite material on the outer surface of the particles, which can quickly and effectively remove calcium ions from the wash water, acts to remove potentially harmful calcium ions (and other ions that cause water hardness) before they are mixed with any other component of the fabric softener containing detergents and cleaning agents, such as an adjuvant, can react and before they react undesirably with the laundry or the soiling on it; Reactions of this kind can possibly cause the dirt on the laundry to become stubborn and more resistant to the washing activity of the surfactant. In addition, since it is intimately bound to the nonionic surfactant, the zeolite material remains in suspension during the first contact period with the wash water due to the nonionic substance. The particles usually assume a particle size that is considerably larger than their original particle size, which means that they remain enclosed in the laundry. Such inclusions are disadvantageous because they can cause lightening effects in dark-colored laundry. The non-ionic surfactant thus helps to keep the zeolite particles in suspension until they fall apart into particles of smaller size that do not settle on the laundry.

The comparatively large particle size of the product u. of the starting material is a little unusual, but you get 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 non-ionic surfactant and at the same time the desired coating effect is better, there is no undesired paste formation, and the particle surfaces contain such a sufficient amount of non-ionic surfactant material that the desired coating of zeolite powder thereon is liable and can be held.

This is avoided by keeping the fabric softener inside the product, by adding it to the base particles as a liquid before zeolite is applied, or by working it into a particle that is subsequently given an additional coating initial contact of the fabric softener with the laundry. This is desirable because otherwise the softening compound could settle on the fabric, which could cause the softening agent to react with the dirt on the laundry or the fabric of the laundry itself, and would interfere with the cleaning process. In some cases, when "external" softener is added to the laundry and begins to melt, grease stains can form on the laundry and the cleaning process is inhibited at these points. According to the invention, such is undesirable

Staining is prevented by firstly bringing the zeolite material and at least part of the non-ionic surfactant into contact with the laundry. If various adjuvants are kept inside the base particles 5, their initial contact with the laundry can likewise be prevented, which is often desirable. This also prevents particles from optical brighteners, for example stilbene brighteners, from coming into direct contact with the laundry. The brightener is worked in so that it is enclosed in the interior of the particles. This avoids the formation of particularly shiny spots on the laundry.

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

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example 1

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25 Mixture of sodium carbonate-sodium bicarbonate framework particles (Snowlite I, weight ratio of Na2C03 to NaHCOs about 1: 2, particle sizes in the range from 20 to 100 mesh, US standard sieve series) 27.8

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Neodol 25-7 (non-ionic surfactant, condensation product of C12-i5 fatty alcohol with an average of 7 moles of ethylene oxide, manufactured by Shell Chemical Company) 18.5

35

Type 4A crystalline zeolite 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 outermost particle size in the range from 3 to 7 microns, with average about 5.2 microns, manufactured by JM Huber Corp.] 46.3

Distearyldimethylammonium chloride [Arosurf TA-100 45 95% active ingredient powder having a particle size in the range of 80 to 160 mesh (US standard sieve series) manufactured by Ashland Chemical Company] 7.4

The carbonate-bicarbonate framework particles were placed at room temperature (25 ° C) in an inclined drum with 8 ° inclination, which at a speed of 55 revolutions of about 40 rpm. and the nonionic surfactant was sprayed onto the moving surfaces of the particles at 30 ° C over a period of 5 minutes. The mixture was then mixed for a further 5 minutes in the drum, and the zeolite powder was then mixed with the material for a further 5 minutes for 60 minutes. The spraying of the non-ionic surfactant was in the form of droplets, which largely had a diameter in the range of 50 to 100 microns, and during the spraying process and after mixing 65 the particle size of the material present in the mixer increased slightly, and that Existing fine particles agglomerated into particles with a size in the range from 20 to 100 meshes (US standard sieve series). The zeolite was added

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carried out for a period of about 5 minutes (periods of 1 to 10 minutes are typical), and after that the intermediate product so far produced was spherical in particle sizes of about 4 to 40 meshes. The powdered softener is then mixed with the intermediate consisting of builder, non-ionic surfactant and zeolite, mixing is continued for 8 minutes, during which time the softener particles adhere to the larger particles. The resulting product had a bulk density of about 0.8 g / cm 3 and was easy to pour. It was packaged and stored, and it was found that no significant caking and clumping occurred during storage under normal storage conditions during normal storage periods. If such a stored package was opened, the detergent containing fabric softener could be poured out well, and the bulk density was still about 0.8 g / cm3.

Washing tests or practical cleaning tests with the product produced showed that it was not dusty, was free-flowing, did not tend to cake and had washing power and softening properties suitable for commercial purposes, which were comparable to those of detergents containing fabric softener containing tripolyphosphate as a builder compare comparable active ingredients well Hessen. The zeolite material did not appreciably settle on the laundry and did not bleach dark-colored laundry, and the carbonate had no harmful effect on the product due to the presence of the bicarbonate and the pH value of about 9.8 resulting in the wash water Cotton, polyester and acrylic material existing laundry. There were also no greasy stains in 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.

A comparative study was carried out, using powders of finely divided sodium carbonate and sodium bicarbonate with particle sizes in the range from 170 to 270 meshes and agglomerating to a material with a particle size in the range from 20 to 100 meshes (US standard sieve series). For this purpose, treatment was first carried out with 5% by weight of a 20% strength aqueous corn starch paste, and this was sprayed over a period of about 3 minutes onto particles kept moving in the same mixing drum as described above, the drum being slow at a speed of, for example 10 rpm was moved. The resulting product was a very useful detergent containing fabric softener which, when used in the same concentration as in the previous example (up to H measuring cup or about 45 to 90 g per 65 1 wash water filling), washes for washing machine loads of about 4 kg soiled clothing was sufficient, but it was not as free-flowing as the detergent containing the previously described fabric softener. If only sodium bicarbonate is used as the starting skeleton salt, the product does not have as good a washing power as the product described above, and if the carbonate is used alone, the product has a higher alkali content than the desired alkali content and it is not free-flowing . However, the carbonate-containing composition can be used as a fabric softener detergent in applications where higher pH values can be tolerated, yet this product is less interesting and acceptable to retailers due to its comparatively poorer flow properties and higher pH value the products according to the invention.

The above example was repeated in a modified form. The Arosurf particles were melt agglomerated with one another to particle sizes in the range from 4 to 40 meshes (US standard sieve series) before the remaining constituents of the composition were added. As a result of the same particle sizes, the softening agent 10 did not separate from previously rounded particles, but it could sometimes happen that a touch of "fat" was observed on the washed laundry; however, such phenomena were not a serious hindrance and are not objected to by the average consumer.

15

In a further embodiment of this example, the plasticizer was fused with the non-ionic surfactant and sprayed onto the base grain particles so that they were absorbed into the interior of the particle and a smaller proportion remained on the surfaces of these grain particles before they were coated with zeolite particles . The product could be produced with the same high bulk density and the particle sizes described above and was a very effective detergent containing detergent, in which the detergent is protected so that it initially has no contact with the laundry; this prevents unwanted staining.

Comparably good results were obtained when the melted plasticizer consisting of quaternary ammonium halide was sprayed onto the circulated base particles, the nonionic surfactant was then sprayed on and the zeolite powder was then “dusted”. In this latter embodiment, before the zeolite material was applied to the spherical particles coated on the nonionic surfactant, a stilbene-type optical brightener (Tinopal 5BM) was mixed with Tinopal RNS (0.5% and 0.05, respectively) %) added. In this way it is effectively prevented that the optical brightener comes into significant contact with the quaternary ammonium compound; this prevents any adverse reactions from occurring between these two components. If the product is used to wash laundry in the washing machine, both components, the optical brightener and the non-ionic surfactant, can act actively in the wash water before the fabric releases detergent, which could possibly interact with it.

In further modifications of this method according to the invention, a quaternary ammonium compound in liquid form was sprayed onto the surfaces of the zeolite particles before these particles were applied as a coating on the carbonate-bicarbonate mixture coated with the nonionic surfactant. The resulting product had 55 properties comparable to the aforementioned products. This is also the case when the pulverized quaternary ammonium compound in the particle size specified above is mixed with the zeolite material and this mixture is applied as a coating to the wax-like, fat-like surface of base particles coated with the nonionic surfactant. According to yet another version of this method, the powdered quaternary compound is adhered to the non-ionic surfactant coated on the core particles, and Zeo-65 lith powder is applied as a coating. It is also possible in this way to obtain a readily usable washing and cleaning agent containing fabric softener with the properties described above.

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Example 2

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Snowlite I 19

Britesil water-containing silicate particles (18% water,

Na20: Si02 ratio of 1: 2 made by

Philadelphia Quartz Company) 9

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, which at a speed of rotation of 12 rpm.

ran, filled. The water-containing silicate, which was about the same particle size, was added to the drum contents over a period of 2 minutes with constant mixing, and then mixed for a further 3 minutes, so that the silicate was uniformly mixed with the carbonate-bicarbonate particles. The nonionic surfactant, mixed with the fabric softener, was then sprayed onto the moving surfaces of the particles, which had been preheated to 40 ° C., for a further 5 minutes at a temperature of about 50 ° C. The procedure was then continued as described in Example 1. The resulting product was an excellent concentrated, phosphate-free, fabric softening detergent for coarse, white and colored laundry, which was well suited for washing dirty laundry in a concentration of 0.1 to 0.2% in washing water (generally used one in washing machines filled from above, 0.15%). The product had a bulk density of about 0.7 to 0.8 g / cm 3 and was free-flowing after normal storage without the need for a protective cardboard with barrier properties. The addition of water-containing silicate helped to increase the structure of the detergent and also improved the corrosion-preventing activity compared to the product according to Example 1, although these products were also satisfactory in this regard.

Example 3

%

Snowlite I 27

Neodol 25-7 19

Neodol 25-3S [sodium polyethoxy fatty alcohol sulfate (C12_i5 alcohol and 3 moles of ethylene oxide per mole), 60% of active ingredient, 25% H20 and 15%

C2H5OH manufactured by Shell Chemical Company] 4

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

Distearyldimethylammonium chloride 10

The procedure was as described in Example 1, but 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 and non-clumping detergent and detergent for coarse, white and colored laundry with the desired high bulk density (0.6 to 0.8 g / cm3). 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 it can have no adverse effects on the anionic substances present, as may be the result of the secretion of these two types of substances the particles could occur. In a modified embodiment of the method described in this example, the cationic fabric softener with the non-ionic surfactant was added to the base particles and the anionic surfactant was mixed with the zeolite and applied to the particles almost completely coated with non-ionic surfactant. In a further modification, the Neodol 25-3S was first added to the carbonate-bicarbonate particles together with a little Neodol 25-7, and then further non-ionic surfactant was added as a coating for these particles, and so the anionic surfactant from the quaternary added later Ammonium compound kept separate.

In yet another modification of the experiment described above, 0.5% of the optical brightener Tinopal 5BM was used instead of an equal percentage of Neodol 25-3S and mixed with the Snowlite before the Neodol 25-7 and Neodol 25-3S were applied to it. In this way, the brightener was kept separate from the quaternary compound applied later. All of these products were in the desired particle sizes and bulk densities as described above and also had the other property characteristics stated 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 nonionic surfactant are incorporated into the product using a step-by-step coating technique. As described in Examples 1 to 3 above, liquid, non-ionic surfactant was applied in such an amount that it could penetrate the inside of the Snowlite or the other base particles and that there was still a sufficient excess with which the surfaces of the Particles were wetted in such a way that the subsequently applied zeolite powder adhered to the surfaces. If, in some cases, it is desirable to have a higher amount of non-ionic surfactant in the product, thereby obtaining a more concentrated detergent composition, and then operating according to the procedures described in Examples 1-3, it can happen that excess liquid leads to the formation of an agglomerate or a paste or favors this formation. This undesirable result can be avoided and additional non-ionic surfactant can be satisfactorily incorporated into the product in such a way that it is still free-flowing and maintains a high bulk density if one works as described below in this example. In this way of working, the particle size can also be desirably increased.

The procedure was initially as described in Examples 1 to 3, but an additional amount of 5 parts of nonionic surfactant was sprayed onto 100 parts of the product resulting from these examples, and an additional 10 parts of zeolite material were then mixed with the product and adhered to the non-ionic surfactant coating (spraying and mixing was carried out as described in Examples 1 to 3). The particle size increased by about 5% (diameter)

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on, but the product still had the same bulk density as previously stated and was also free-flowing and not clumping. In further tests, an additional 5 parts of non-ionic surfactant were sprayed onto the product obtained in the two-stage process and another 10 parts of zeolite material were sprayed on, with similarly good results (using the same spraying and mixing methods).

When carrying out the stepwise enrichment and coating formation described, the snowlite particles or other base particles and the quaternary ammonium compound present as a fabric softener are usually not sprayed on again, but this can also be done if it is advantageous. It is possible to carry out six coating treatments, but preferably only three such processes as are described in the “further experiment” here are carried out. It has also proven expedient to limit the total amount of nonionic surfactant and zeolite in the subsequent coating treatments to that which was applied in the first treatment, and it is expedient to add half of the amount applied in the first treatment to be used, the percentage of non-ionic surfactant and zeolite should be within the percentage range stated above.

Example 5

The procedure was as described in Examples 1 to 4, but instead of Snowlite I Snowlite II, instead of zeolite type 4A, crystalline zeolites of types X and Y with the same particle size and amorphous zeolites were used, instead of Neodol 25-7, neodols were used 23-6.5 and 45-11 and Alfonics 1618-65 and 1412-60 were used, and instead of Arosurf TA-100, Aliquats H226 and 400, Ar-quad 2HT-100, Culversoft WS-Paste and Varisoft 100 were used. Detergent compositions containing fabric softener were obtained which were free-flowing and had a comparatively high bulk density. The only difference in the manufacturing process was that the temperature of the nonionic surfactant was kept sufficiently high that it was in a liquid state when sprayed onto the surface of the base particles. In addition, the proportions of the various components were modified to ± 10% and ± 30%, but the proportions were kept within the aforementioned ranges. Care must be taken to ensure that the nonionic surfactant is used in such a proportionate amount that part of it does not remain absorbed on the surface of the base particles in the form of an adhesive coating, so that the zeolite particles can be retained. If the non-ionic surfactant is solid at the temperature the surfactant is at when the zeolite material is applied, care must be taken to set the temperature high enough so that the zeolite particles can adhere to it and to the base particles. If the cationic fabric softener is a solid and is to be introduced into the interior of the base particles, the temperature must be raised to such an extent that it is sufficiently liquefied for introduction, either alone or together with the non-ionic surfactant.

The particularly excellent results that were achieved according to the examples described above when carrying out the process according to the invention for the preparation of the detergent compositions could not be expected. Attempts have already been made to use mixtures of sodium carbonate and bicarbonate (each particle consisting of such a mixture), as described in US Pat. No. 3,944,500, as absorbents for nonionic surfactants, but the skilled worker was unable to do so Lesson and no suggestion that products similar to the washing and cleaning agents according to the invention can be produced with a high bulk density if this mixture is used as core particles. The carbonate bicarbonate materials known as Wegscheider's salt, which often also contain sesquicarbonates, are described as products with a low bulk density (in the range of about 0.4 to 0.5 g / cm3). In contrast, the bulk density specification of 0.6 g / cm3 (shaken) is already high for the detergents and cleaning agents containing fabric softener according to the invention, and the products produced according to the invention usually have even higher bulk densities, which are around 0 , 7 g / cm3 or higher. It is not known from the prior art that zeolite particles can be present and can be held on the base particles, and it is also not known from the literature that liquid, nonionic surfactant is used to adhere a coating to the base 20 particles can use, although such particles have a high sorbability for liquids. Furthermore, it was not known that a cationic fabric softener of the various types described can be incorporated into such compositions and protected against reactive constituents in the composition as well as against initial contact with the items to be cleaned. The process according to the invention can be used to produce a free-flowing 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 non-ionic surfactant to the core particles, which absorb a large part of the non-ionic surfactant, an “excess” non-ionic surfactant forms a coating on the surface of the particles, which is of a greasy or waxy nature and appearance is, but the particles do not adhere to each other appreciably, rather they hold the subsequently applied smaller zeolite particles. Before the zeolite is added, the mixture is not pasty, but rather resembles moist sand, each particle being non-adherent or readily releasably adhered to the other. The end products produced are free-flowing, although they contain 10 to 100% 45 of Wegscheider's needle-shaped salt in the base material, and this is partly due to the fact that the particles are rounded off by the coating of finely ground zeolite or spherical particles are formed. In addition, the various components 50 in the spherical product are arranged particularly functionally with respect to one another, and the buffer effect exerted by the base particles, if present as carbonate bicarbonate, supports the washing process (the pH value of a 0.1% aqueous solution of the Snowlite is around 9.8). 55 Furthermore, it is important that the finished product is in the specified relatively large particle size; but if, as in the examples above, the conditions are changed (e.g. using smaller base particles) so that the product is in the form of smaller particles, 60 e.g. those in the order of 8 to 100 meshes (US standard sieve series) are obtained, then higher bulk densities are obtained than are common for detergent-containing detergent compositions, and the products produced according to the invention are used for many 65 different washing and cleaning processes usable even if they do not have the particularly high flowability and the extremely good properties of the particularly preferred embodiments of the present invention.

Claims (15)

633579 1. Free-flowing, granular washing and cleaning agent containing a fabric softener with a bulk density of at least 0.6 g / cm 3 and a particle size in the range of 4-40 meshes of the US standard sieve series, containing core particles from an alkali metal builder salt, selected from the group consisting of Wegscheider's salt of the formula Na, CO ,. 3NaHCOs, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pvrophosphate, sodium silicate, borax, and / or the corresponding potassium salts, and mixtures thereof, a nonionic surfactant being contained in the interior and on the surfaces of these particles, and further a coating of calcium ion-exchanging zeolite particles with an extreme particle size in the range of 0.005-20 microns adheres to the non-ionic surfactant on the builder particle surfaces, and a wax-like or solid quaternary ammonium compound as a fabric softener, which has at least one C12-Ci8 alkyl group in the molecule and is located in or on these particles, the zeolite having the following formula: (M20) (AI203) y (Si02) 2. wH20 wherein M means sodium or potassium, y has a value of 0.8-1.2, z has a value of 1.5-3.8 and w has a value of 0-9, and the percentages by weight of builder salt, nonionic surfactant, zeolite and fabric softener within the ranges of 20-40% by weight, 10-30% by weight, 30-60% by weight, and 4-12% by weight. -% lie. 2. Detergent and detergent containing fabric softener according to claim 1, characterized in that sodium carbonate and sodium bicarbonate are contained as builder salt core particles in a weight ratio of 1:10 to 10: 1, the particle size of which ranges from 20 to 100 meshes of the US -Standard sieve series is, as zeolite crystalline, amorphous and / or mixed crystalline-amorphous zeolites of the types A, X and Y of the formula defined in claim 1 are present, as a non-ionic surfactant having a condensation product of 10 to 18 carbon atoms Fatty alcohol and polyethylene oxide with 3 to 15 moles of ethylene oxide per mole of higher fatty alcohol is present, the quaternary ammonium compound present as a fabric softener is a solid quaternary ammonium halide in granular form which adheres to the outer surface of the resulting particles. 2nd PATENT CLAIMS 3rd 633579 densationsprod;., vt from a higher fatty alcohol with 10 to 18 carbon atoms and polyethylene oxide with 3 to 15 moles of ethylene oxide per mole of higher fatty alcohol, the additional zeolite from crystalline, amorphous and / or mixed crystalline-amorphous zeolites 1 defined formula of types A, X and Y is selected, and the weight amounts of subsequently applied non-ionic surfactant and zeolite is not greater than half of the total content of non-ionic surfactant and zeolite in said agent. 3. Detergent and detergent containing fabric softener according to claim 2, characterized in that the sodium carbonate / sodium bicarbonate mixture Wegscheider's salt of the formula Na2C03. 3NaHC03, and the weight ratio of Na2COs to NaHC03 in the core particles is in the range from 1: 3 to 1: 1, as zeolite a type A zeolite of the formula defined in claim 1 with an extreme particle size in the range from 3 to 12 Micron and a water content of 10 to 25 wt .-%, as a nonionic surfactant a condensation product from a 10 to 18 C-containing higher fatty alcohol with 6 to 12 moles of ethylene oxide per mole of higher fatty alcohol and as quaternary ammonium halide fabric softener, a quaternary ammonium chloride with two C12-C13-alkyl groups and two C1-C4-alkyl groups are contained therein, and the agent in the form of essentially spherical individual particles are present. 4. Detergent and detergent containing fabric softener according to claim 1, characterized in that the particles are coated again with said non-ionic surfactant, which in turn has a coating of the zeolite particles exchanging calcium ions. 5 5. Detergent and cleaning agent containing fabric softener according to claim 1, characterized in that the main part of the fabric softener is located inside the core builders. 6. Detergent and detergent containing fabric softener according to claim 1, characterized in that the fabric softener is present inside and on the surface of the core builders particles. 7. The method for producing a free-flowing granular washing and cleaning agent containing a fabric softener according to claim 1, characterized in that it comprises the following steps: (a) mixing the non-ionic surfactant in liquid form with the core particles of the builder salt so that the surfactant is absorbed and coats the particles of the builder salt, (b) mixing the product of step (a) with the zeolite particles, the zeolite particles adhering to the surface of the resulting particles, and (c) Mixing the product of step (b) with 80-160 mesh particles of the US standard sieve series of fabric softener, the fabric softener adhering to the surfaces of the zeolite coated particles. 8. The method according to claim 7, characterized in that the particles are coated again with a coating of the non-ionic surfactant in liquid form and on the surfactant in turn a coating of further zeolite particles with an extreme particle diameter in the range of 0.01 to 20 microns is applied. 9. The method according to claim 8, characterized in that the additional non-ionic surfactant is a condensation product which is liquid or pasty at room temperature and consists of a higher fatty alcohol having 10 to 18 carbon atoms and polyethylene oxide containing 3 to 15 moles of ethylene oxide per mole of higher fatty alcohol , the additional zeolite is selected from crystalline, amorphous and / or mixed crystalline-amorphous zeolites of the formula of types A, X and Y defined in claim 1, and the amounts by weight of subsequently applied non-ionic surfactant and zeolite are not greater than half of the total content of non-ionic surfactant and zeolite in said medium. 10th 15 20th 25th 30th 35 40 45 50 55 60 65 10. A method for producing a free-flowing granular detergent and cleaning agent containing a fabric softener according to claim 1, characterized in that it comprises the following steps: (a) mixing the fabric softener in liquid form with core particles from the builder salt, so that a major part of fabric softener in the particles mentioned is absorbed from the builder salt, (b) mixing the particles from step (a) with nonionic surfactant in liquid form so that the surfactant is absorbed and coated in the particles, and (c) Mixing the product from step (b) with zeolite particles so that the zeolite particles adhere to the surface of the resulting particles. 11. The method according to claim 10, characterized in that the particles are coated again with a coating of the non-ionic surfactant in liquid form and on the surfactant in turn a coating of further zeolite particles with an extreme particle diameter in the range of 0.01 to 20 microns is applied. 12. The method according to claim 11, characterized in that the additional non-ionic surfactant is a liquid or pasty liquid at room temperature. 13. A method for producing a free-flowing granular detergent and cleaning agent containing a fabric softener according to claim 1, characterized in that it comprises the following steps: (a) mixing the fabric softener with the nonionic surfactant at a temperature high enough to form a liquid mixture, (b) mixing the mixture from step (a) in the liquid state with core particles from the builder salt so that said liquid mixture is absorbed and coated on said particles of builder salt, and (c) Mixing the product from step (b) with the zeolite particles so that the zeolite particles adhere to the surface of the resulting particles. 14. The method according to claim 13, characterized in that the particles are coated again with a coating of the non-ionic surfactant in liquid form and in turn a coating of further zeolite particles with an extreme particle diameter in the range from 0.01 to 20 microns on the surfactant is applied. 15. The method according to claim 14, characterized in that the additional non-ionic surfactant is a condensation product which is liquid or pasty at room temperature and consists of a higher fatty alcohol with 10 to 18 carbon atoms and polyethylene oxide with 3 to 15 moles of ethylene oxide per mole of higher fatty alcohol the additional zeolite is selected from crystalline, amorphous and / or mixed crystalline-amorphous zeolites of the formula of types A, X and Y defined in claim 1, and the weight amounts of subsequently applied non-ionic surfactant and zeolite are not greater than is half of the total content of non-ionic surfactant and zeolite in said agent.