DE2753053C2 - - Google Patents

Description

The invention relates to free-flowing granular washing and Plasticizer according to the preamble of the main claim and processes for their production.

Compositions with combined washing and softening effects are known. The person skilled in the art also knows that nonionic Surfactants as useful components in detergents and quaternary ammonium halides with a long chain Lipophilic molecule residue on nitrogen as a fabric softener and can serve as antistatic agents. Inorganic builder salts such as phosphates, carbonates and silicates have long been used as builders for organic surfactants, more recently you have zeolites such as Sodium aluminosilicates used for this purpose. Although most granular detergents have low bulk densities you already know granular detergents with high Bulk density.

In particular, DE-OS 25 38 755 zeolite molecular sieve and quaternary ammonium compounds as laundry softeners containing detergents known. These detergents, which also includes nonionic detergents and inorganic Builder salts such as borax, alkali silicates and carbonates and contain polyphosphates are available as powder, in which the zeolite as a carrier for the plasticizer and u. a. acts to improve fluidity and are obtained by dry mixing the particulate Components manufactured. These dry mixtures out differentiate individual particulate components differ significantly from the Means of the invention.

Detergent compositions are also known from DE-OS 25 19 815 based on spray-dried particles containing anionic surfactant and zeolite, to which a nonionic surfactant can be applied as well from US-PS 38 68 336 substances to improve the Flowability of detergents in the presence of oily Detergent boosters.

It is the object of the invention to be a free flowing granular detergent and softener with a bulk density of at least 0.6 g / cm³ and particles in sizes in the range of 0.42 to 4.76 mm (4 to 40 stitches, US standard sieve range) and a process for Making them available.

A washing and softening agent is used to solve this problem according to the characterizing part of the main claim suggested. Claims 2 to 6 contain preferred Embodiments claims 7 to 10 the method for production in its various variants.

In particular, the invention provides a detergent and plasticizer, the core particle from an alkali builder salt namely from separator salt, sodium bicarbonate, sodium carbonate, Pentasodium tripolyphosphate, tetrasodium pyrophosphate, Sodium silicate, borax and / or the corresponding Has potassium salts, inside and on their Surfaces are usually liquid or pasty non-ionic surfactant is present and the surfaces the builder particles have a coating on the have non-ionic surfactant-adhering zeolite particles and in and / or on these particles one of a waxy quaternary ammonium compound of existing plasticizers is available. The invention also includes several Coated products and manufacturing processes.

The detergents and plasticizers according to the invention are ideal for coarse, white and colored laundry.

Due to the high bulk densities, they enable washing in a conventional automatic washing machine (capacity from approx. 30 to 65 l, approx. 4 kg wash load per wash cycle) a lower volume of detergent, e.g. B. 50 to 150 cm³, to be used with the result that one with the same effect Amounts of plasticizer smaller packages of washing and Can use softening agents, so less Storage space in the supermarket and household needed. Naturally it’s also easier to handle smaller packages and to pour out the agent from it; it is more convenient work, the risk of spillage is reduced.

The core and base particles in and on which one is non-ionic Surfactant out there can be made from any builder salt exist that have a sufficient sorption capacity for the non-ionic surfactant, if this is is in a liquid state. Usually it is desirable that the builder particles are rounded, preferably spherical are present and passages through the particles in their Inside there are sorption of at least 10%, preferably 20% and in particular 30% or more based on weight, of non-ionic surfactant in the builder particles enable. Mixtures of are preferred Sodium carbonate and sodium bicarbonate (including Wegscheider's salt), Sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, Tetrasodium pyrophosphate, sodium silicate, (Na₂O to SiO₂ ratios in the range of 1: 1.6 to 1: 3) and Borax. Such products that are spray dried, agglomerated or can otherwise be made preferably in particle sizes that correspond to the particle size of the preferably used carbonate-bicarbonate mixture (specified later). Man can also be mixtures of different builder substances and mixtures with numerous others in the compositions of the invention use existing components. In addition to the Sodium salts can Potassium salts are used.

Instead of part of the inorganic builder salts organic builder salts, such as sodium citrate, Trisodium nitrilotriacetate, CMOS (sodium carboxymethyloxysuccinate), Sodium gluconate and sodium EDTA are used, but the Total content of such organic builders usually only a small proportion of the total builder content accounts for, preferably less than 25% thereof. It is also possible to use sodium sulfate or another compatible one Filler instead of part of the builder salt to be used, again the filler should only be present in small parts and preferably less than 25% of the total amount of builder plus filler is.

As a mixture of alkali carbonate and alkali bicarbonate is appropriate used such a mixture in which the two types of components in the same individual particle shape or grain shape are available. For the purposes of the present invention should these particles have sizes between 0.149 and 0.84 mm, preferably 0.250 to 0.59 mm, in particular approximately 0.42 mm (40 mesh US standard sieve row). You can also use larger particles [up to approximately 2.38 mm (8 mesh)], provided that the finished end product then in the above desired particle range. Sometimes you have to Take precautions, agglomeration or other particle growth during the absorption of the non-ionic surfactant or on to avoid another procedural body, otherwise the end product could be too large a particle size. If you have smaller particle sizes than those given in the the desired area, the finished falls Product sometimes free instead of in the form of individual flowable beads undesirably pasty at.

The alkali carbonates and bicarbonates, which in particular as sodium salts are used in the preferred embodiment of the present invention is essentially anhydrous a; partially hydrated builders of these However, species are also tolerable. In general the moisture content is less than 9%, preferably lower than 7%. The percentage ratio of alkali carbonate to alkali bicarbonate is usually in the range of 1:10 to 10: 1, preferably in the range from 1: 5 to 1: 1 and in particular between 1: 3 to 1: 1, with the ratio 1: 2 especially is preferred. The mixture is appropriately prepared so that it has a substantial content, e.g. B. 10 to 100% of Wegscheider's salt, Balance sodium bicarbonate. Such a product is characterized by excellent sorption power for the liquid non-ionic surfactant and can easily a suitable basis for a coating of powdered zeolite builders be made. A Method of making a mixed carbonate-bicarbonate product is in U.S. Patent 3,944,500 described. The method described in the patent is preferred; the mixed carbonate-bicarbonate particles can also be made according to other known Manufacture techniques. Instead of the intimately mixed in the individual particles You can also use carbonate and bicarbonates separate batches of carbonate and bicarbonate, appropriate in the same grain sizes and in the same proportions, use, provided the sorption force is sufficient to absorb large amounts of non-ionic surfactant. You can also use finer carbonate and use bicarbonate powder, for example with particle sizes below 0.149 mm (100 mesh), e.g. B. 0.053 to 0.088 mm (170 to 270 stitches), and these separately or agglomerate in a mixture, taking care care must be taken to maintain the porosity of the product will, d. H. only a minimal amount of binder, such as starch or another agglomerating agent, can also be used. Mn can also add Wegscheider's salt to such products admit.

The compounds used as plasticizers, which the Give textiles a soft feel and make them wrinkle-resistant and antistatic a variety of compounds in their molecules contain essential parts with positive charge. Generally such compounds have in the positively charged Part of their molecule hydrophobic groups, and often acts it is a relatively long chain remnants such as higher hydrocarbyls or alkyls. Although amines, imidazolines, Pyridines, guanidines and their salts and derivatives useful, especially if they are relatively long chain hydrophobic Groups included, but the am most preferred plasticizers are usually quaternary Ammonium compounds that have one or two long chain hydrophobic Groups and two or three short chain groups included and a solubilizing anion or a salt-forming Possess group, usually either halide, sulfate, acetate, Hydroxide or another inorganic or organic solubilizing monobasic or dibasic residue. For the purposes of the present invention Ammonium compounds with higher alkyl groups with 12 to 18, especially 16 up to 18 carbon atoms used as longer-chain substituents on nitrogen. The stearyl radical is particularly preferred. The shorter hydrophobic residues are alkyl residues with 1 to 4, preferably 1 to 2 carbon atoms. Particularly preferred is the methyl residue.

Specific examples of preferred cationic Conditioning agents are dimethyldistearylammonium chloride, Trimethylstearylammonium bromide, cetyltrimethylammonium chloride, Di-higher-alkyldimethylammonium chloride, where the higher alkyl residues from hydrogenated tall oil alcohols come. These connections are strong substantive for the fabrics, especially for cotton or cellulose materials and synthetic organic fibers. The described softening compounds that have higher alkyl groups are usually waxy or pasty Solids and can melt at elevated temperatures or be liquefied so that they can be coated the base particles are useful. Such coatings can be made by comparative soft particles of the softening compound with the substances to which they adhere, such as carbonate-bicarbonate-non-ionic-surfactant-zeolite particles mixes, or you can use the emollient Melt or spray the compound onto the core particles, or you can mix them with the non-ionic surfactant and spray it with the particles. In the products according to the invention, the softening retains Compound while using these products their effectiveness, and this is largely due to the fact that instead of anionic surfactant, with to which the cationic softening substances often react, non-ionic surfactant is present.

Usable non-ionic surfactants are described in detail, for example, in McCutcheon's Detergents and Amulsifiers, 1973 Annual and in Surface Active Agents, Volume II, by Schwartz, Perry and Berch (Interscience Publishers, 1958).

Nonionic surfactants of this type are generally pasty or waxy solids at room temperature (20 ° C), which are either sufficiently water-soluble that they dissolve quickly in water, or at the temperature of the wash water if these are above 40 ° C quickly become molten. The nonionic surfactants used according to the invention are normally liquid or pasty at room temperature. The usually pasty or semi-solid substances are preferably used, because when they are used, a sticky product with poor flow properties is less likely to form, which tends to cake and solidify during storage. Such products also tend to become less moist and give up their "coating" to the zeolites. Nevertheless, liquid non-ionic surfactants can also be used. Nonionic surfactants are appropriately liquefied so that they can be sprayed at reasonable temperatures, such as below 45, 50 or 60 ° C. Typical useful non-ionic surfactants are polyalkenoxy derivatives, which are usually obtained by condensation of lower alkylene oxide (with 2 to 4 carbon atoms), e.g. B. ethylene oxide, propylene oxide (with a sufficient amount of ethylene oxide to make the substance water-soluble) with a compound containing a hydrophobic hydrocarbon chain and one or more active hydrogen atoms, such as higher alkylphenols, higher fatty acids, higher fatty mercaptans, higher fatty amines and higher fatty polyols and Alcohols, e.g. B. fatty alcohols having 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. Preferred nonionic surfactants are those of the formula RO (C₂H₄O) _n H, where R represents a residue of a linear saturated primary alcohol (an alkyl) having 10 or 12 to 18 carbon atoms and n is an integer from 3 or 6 to 15 . Examples of useful, typical, commercially available nonionic surfactants are oxyethylated products (with an average of about 11 ethylene oxide units) of 14 to 15 carbon atoms (on average) in the chain containing fatty alcohol; Products from a fatty alcohol containing 12 to 15 carbon atoms in the chain, which is oxethylated with an average of 7 ethylene oxide units; and products from an alkanol containing 16 to 18 carbon atoms, which is oxethylated with an average of 10 to 11 ethylene oxide units. The polyoxethylated (3 to 30 ethylene oxide units containing) middle alkyl (6 to 10 C atoms) phenols are also useful. Useful products are also condensation products of ethylene oxide with hydrophobic bases, which have been prepared by condensation of propylene oxide with propylene glycol, usually with molecular weights in the range from 5000 to 25,000. Furthermore, the various products can be used, which are polyoxyethylene sorbitan esters of higher fatty acids (12 to 18 carbon atoms), such as those which contain solubilizing amounts of ethylene oxide. Numerous other non-ionic surfactants, as described, for example, in the references mentioned above, can also be used for the purposes of the invention, the proportion of non-ionic surfactants other than higher fatty alcohol polyoxyethylene ethanols preferably being low and possibly not more than 50%, preferably not more than 25% of the total non-ionic surfactants present. When "higher" is used in the present description, for example higher alkyl compounds, higher fatty acid compounds and the like, it is understood to mean those which contain 8 to 20, preferably 10 or 12 to 18, carbon atoms.

According to the invention, crystalline, amorphous and / or crystalline-amorphous natural or use synthetic zeolites that are quick enough and effectively the hardness formers like calcium ions in the wash water counteract. Materials are preferred those causing the hardness quickly enough Cations like calcium, magnesium, Iron or the like react to the wash water to soften before such hardness ion builds up the other components of the detergent act undesirable. Suitable zeolites can be identified by high Characterize ion exchange capacity for calcium ions. It is 200 to 400 mg Equivalent calcium carbonate hardness per g of aluminosilicate, preferably at 250 to 350 mg equivalent / g. The rate of softening supposed to be within one Minute a residual hardness of 0.02 to 0.05 mg CaCO₃ / l, preferably 0.02 to 0.03 mg / l, and in 10 minutes a residual hardness of less than 0.01 mg / l (based on anhydrous zeolite).

Man used finely crushed particles of zeolite following formula

(M₂O) _x · (Al₂O₃) _y · (SiO₂) _z · w H₂O,

where M is sodium or potassium, x is 1, y = 0.8 to 1.2, preferably about 1, z = 1.5 to 3.5, preferably 2 to 3 or about 2 and w = 0 to 9 , preferably 2.5 to 6.

The soluble soluble for the purposes of the invention crystalline aluminosilicates are often replaced by a Network of essentially uniformly large pores in the area from about 3 to 10 Å, often characterized about 4 Å (normal); these pore sizes are by structure of the zeolite crystal. It can such zeolites are also used, the two or more such networks of different pore sizes have, as well as mixtures of such crystalline Materials with each other or with amorphous materials.

To the invention usable at least proportionally crystalline zeolites belong to the zeolites following crystal structure groups: A, X, Y, L, mordenite and Erionite, preference is given to types A, X and Y. give. Mixtures of such molecular sieve zeolites can also be used use, especially if a type A zeolite is present is. The crystalline zeolites are known to the person skilled in the art well known and in detail for example in the treatise "Zeolite Molecular Sieves" by Donald W. Breck, published in 1974 by John Wiley & Sons. Examples for typical commercially available zeolites The types of structure mentioned are in Table 9, 6 on the pages 747 to 749 of the Breck treatise.

Synthetic is preferably used for the purposes of the invention Zeolites and advantageously also those of type A or a similar structure (on page 133 of the treatise mentioned). You can do good Results with a type 4 A molecular sieve zeolite whose monovalent cation is sodium, and its pore size is about 4 Å. Such zeolite molecular sieves are in US Pat. No. 2,883,243 and described there as zeolites A designated.

The molecular sieve zeolites can be dehydrated or calcined form (about 0 or about 1.5 to 3% moisture), or one uses them in hydrated or water-laden form, so that they contain additional bound water in an amount of about 4 to about 36% based on the total weight of the zeolite, obtained depending on the type of zeolite used. The Hydrated water-containing Form of molecular sieve zeolites (preferably about 15 up to 70% hydrated) is preferable if crystalline Product is used. The production of such crystals is known. For example, at Production of the mentioned zeolite A the hydrated Zeolite crystals that form in the crystallization medium (e.g. water-containing amorphous sodium aluminosilicate gel) used without being at high temperature dehydrated (calcined to 3% or less water content), as is normally the case when manufacturing such crystals for use as catalysts, e.g. B. cracking catalysts, happens. The crystalline zeolite can be both complete hydrated as well as partially hydrated by Filter off the crystals from the crystallization medium and Dry in air and at room temperature can be obtained so that the water content ranges from about 5 to 30% Moisture, preferably about 10 to 25%, such as about 17 to 22%. However, the moisture content of the for Molecular sieve zeolite used according to the invention as described, also be much lower.

The zeolites used should be practically free of adsorbed gases, such as Carbon dioxide, because gaseous zeolites tend to undesirable foaming when containing zeolite Detergent comes into contact with water; but for some Foaming purposes are tolerated, and sometimes is you specifically wished.

The zeolite material is used in finely crushed Condition with extreme particle diameters from 0.005 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 for example 3 to 7 or 12 microns if it is crystalline Product, and 0.01 to 0.1 micron, e.g. B. 0.01 to 0.05 micron if it is an amorphous product. Even though the outermost particle size is much lower the zeolite particles usually have particle sizes in the range of 0.037 to 0.149 mm (100 to 400 mesh), preferably 0.044 to 0.105 mm (140 to 325 mesh, US standard sieve range). Zeolites with smaller particle sizes are often undesirable dust-forming, and those with larger ones Particle sizes are not sufficient Coverage for the carbonate-bicarbonate base particles.

Crystalline synthetic zeolites are more common and better known, but you can also use amorphous instead Use zeolites and these are the crystalline materials often superior in many properties, as will be described later. One can also mixed crystalline amorphous materials and mixtures of different Use types of the described zeolites. The Particle sizes and pore sizes of the materials are similar those previously described, with the specified Areas can be changed, provided that the material has sufficient scaffold function and colored Detergent and cleaning agent, so in an aqueous medium is treated, does not brighten undesirably.

The production of amorphous and mixed amorphous-crystalline Aluminosilicate ion exchange zeolites are described in a U.S. patent application filed on July 12, 1974, with the Title "Detergent Builder Composition" (Burton H. Gedge, III and Byran L. Madison, inventor). Detergent compositions with Amorphous materials are in one of John Michael Corkill's and Bryan L. Madison, filed on July 18, 1974 described, and mixed with detergent compositions amorphous-crystalline aluminosilicate framework material are in one application filed by the same inventors on July 12, 1974 described. A preferred one Ion exchange zeolite is the one in the BE-PS 8 35 351 described amorphous zeolite of the formula

M₂O · Al₂O₃ · (SiO₂) _z · w H₂O,

where z is 2.0 to 3.8 and w is 2.5 to 6, especially when M is sodium.

There can be various adjuvants with functional like aesthetic effect can also be used, for example Bleach, e.g. B. sodium perborate, colorants, for example Pigments and dyes, optical brighteners, for example Stilbene brighteners, foam stabilizers, e.g. B. Alkanolamides, such as laurin, mysterin, diethanolamide, enzymes, for example proteases, skin protection agents and conditioning agents, for example water soluble proteins with low molecular weight, which can be obtained by hydrolysis of proteinaceous materials such as animal hair, hides, gelatin and has received collagen, foam-destroying agents, such as Silicones, bactericides, e.g. B. hexochlorophene, and perfumes. in the in general, such adjuvants and other additional Framework substances in a special, depending on Adjuvant and its physical condition, best appropriate stage of the manufacturing process the other components added. It is particularly desirable that Addition so that the adjuvants or other components of the product are stabilized and / or the absorbency of the carbonate-bicarbonate mixture is increased for the non-ionic surfactant.

Such adjuvants can be added to the base particles spray on the non-ionic surfactant, you can use the Mix the zeolite and together with the non-ionic Abandon surfactant treated base particles, or you can add them to the zeolite coated particles, either together with the plasticizer or after adding the plasticizer.

Preferably only non-ionic surfactant is used (apart from the plasticizer, which acts as a cationic surfactant exhibiting connection), but in some In some cases, the non-ionic surfactant can also be combined with an anionic surfactant, an amphoteric Use surfactant or mixtures thereof. If however, such substances are normally only used 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 it, and you locate it in the product so that disruptive reactions between the plasticizer and kept such detergents low and prevented will. For example, if a cationic plasticizer is subsequently added, it is recommended to add about with built-in anionic or amphoteric surfactant in the base particles to be provided, preferably together with non-ionic Spray on the surfactant and let it penetrate. On the other hand, when the cationic softener is combined with the non-ionic surfactant or separately thereof on the Core particles is sprayed on, one is preferably one about with anionic and amphoteric surfactant used Apply the surface of the beads coated with the zeolite or first mix with the zeolite and then open those with the cationic softener and non-ionic Apply surfactant treated particles.

Examples of useful anionic surfactants are the sulfates and sulfonates with lipophilic moieties, for example those with 8 to 20 or 10 to 18 carbon atoms Carbon chain. These include, for example linear higher alkyl benzene sulfonates, 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, higher fatty acid esters of isethionic acid and other known anionic surfactants, such as, for example also in the aforementioned publications are mentioned. Most of these substances are under normal conditions in solid form, for example as alkali salts, e.g. As sodium salt, before and can be with conventional frameworks spray dry. The spray dried particles that these builders can contain core or base particles be used for the purposes of the invention. To Manufacturing of such preliminary products can be done in any known manner Agglomeration techniques, crushing methods, accumulation processes or other working methods to use these primary products in the carbonate-bicarbonate particles of similar particle size to manufacture. Some examples of suitable anionic Surfactants are the sodium salt of linear tridecylbenzenesulfonic acid, the sodium cocomonoglyceride sulfate, the sodium lauryl sulfate and the sodium paraffin and olefin sulfonates with each an average of about 16 carbon atoms. One can also use amphoteric Substances as sodium salt deploy. Similar to the anionic surfactants you can use the spray-dry amphoteric surfactants together with a builder substance, or you can disperse these surfactants in the liquid non-ionic surfactant or otherwise suitable Way with for the production of the washing according to the invention or detergent needed other powdery Work in mixed substances. Basically, though both anionic and amphoteric surfactants be present in products according to the invention, but it is much more advantageous if, apart from the cationic softening substance, as the sole wash-active Component a non-ionic surfactant or mixture of non-ionic Surfactants is used.

The proportionate amounts of core particles (preferably carbonate-bicarbonate particles), non-ionic surfactant, zeolite and softening agent are chosen so that the free-flowing, containing plasticizers Detergent particles with a sufficiently high bulk density result. Suitable proportions are 20 to 40% core or base particles, 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 to 23% or 40 to 52% or 5 to 10%. The bulk density the product is at least 0.6 g / cm³; it lies preferably in the range of 0.75 to 0.95 g / cm³ and in particular in the range of 0.8 to 0.9 g / cm³. The particle size of the product is generally in the range of 0.42 to 4.76 mm (4 to 40 Mesh US standard sieve row) and is suitably 1.68 to 4.76 mm (4 to 12 stitches) and in particular about 2.38 to 3.36 mm (6 to 8 stitches). The particle size carbonate-bicarbonate starting material or other base particles generally lie before their treatment in the range of approximately 0.149 to 0.84 mm (20 to 100 mesh US standard sieve row), preferably at 0.250 to 0.59 mm (30 to 60 stitches) and in particular at about 0.42 mm (40 stitches). You can also start with finer carbonate and bicarbonate powder and use other builders and agglomerate them to the specified particle sizes. As a general rule 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 ones mentioned in this description Materials).

In the production of the starting particle mixture from carbonate and bicarbonate can be described in US Pat. No. 3,944,500 Operate the way of working and preferably the one there mentioned Substances use. A typical analysis for such framework substance I is 35% Na₂CO₃, 58.5% NaHCO₃ and 6.5% H₂O, and another framework substance II this type consists of 30.0, 66.5 and 3.5%. The following sieve analyzes showed these substances (Percentages in mm: 2.00, 0.42, 0.250 and 0.149); 0.2, 67.6, 96.9, 99.0 and 0.7, 60.7, 90.7 and 97.0 and respectively Bulk densities (g / cm³) of 0.51 or 0.48 (shaken) and 0.42 or 0.38 (loose). The tendency to disintegrate or crumble is particularly low for framework substance I (2.5% according to Allied Chemical Corporation Exam Na 17-35), and this product is preferred. Low fragility and firmness The particle is also found in other types of base particles one can use it, important to prevent it from being too are very powdery and instead of single coated particles Pastes are created when adding non-ionic surfactant. In In some cases, additional components of the end product can be used into the mixture of bicarbonate and Wegscheider's salt (sesquicarbonate can also be present) incorporated and together with this according to the method described in the patent processed, provided that they remain stable and the manufacture of the carbonate-bicarbonate product do not undesirably influence or thus do not react. Usually is in the carbonate-bicarbonate particle mixture Proportion of at least 60%, preferably 70% and in particular 70 to 85% or more of carbonate and bicarbonate present, provided such other abjuvants, for example 10 to 20% Sodium silicate and / or 0.1 to 5% optical brightener, sometimes 5 to 15% water are also present.

Free-flowing, granular, Detergent and softener with high bulk density can be created using one of several process methods manufacture. One of these methods uses the methods described Sodium carbonate-sodium bicarbonate particles or other builder particles with a non-ionic used in liquid form Mixed surfactant. The surfactant is preferably sprayed on, in some cases it can also be infused will. The surfactant penetrates the carbonate-bicarbonate particles one, but a part remains on the particle surface, so that subsequently admixed zeolite adheres to it can It is important that the non-ionic surfactant be so sufficient amount is applied that in addition to that in the Part of the surfactant absorbed inside the builder particles Surfactant remains on the particle surfaces. While the mixing process after adding the non-ionic surfactant the particles appear like damp sand and have a greasy texture or waxy appearance. The non-ionic surfactant is usually liquid, pasty or semi-solid and becomes used advantageously pasty or semi-solid, which reduces the risk the product becomes sticky when stored, or clumped. However, in principle you can also normally liquid non-ionic surfactants with a satisfactory result to use. After the base particles with the non-ionic The zeolite powder is coated with surfactant admixed, and this adheres to that on the particle surfaces located non-ionic surfactant. The particles are being essentially spherical, and the particle sizes are in the range of 0.42 to 4.76 mm (4 to 40 stitches, US standard sieve row), In this embodiment of the manufacturing process the plasticizer is usually in the form of rather small ones Granules, flakes, grains or powders to finish with the formed from base material, non-ionic surfactant and zeolite Ball particles mixed. The softener is usually a waxy or fatty low melting solid material in particle sizes from about 0.094 to 0.177 mm (80 to 160 mesh), preferably about 0.149 mm (100 mesh, US standard sieve series). It becomes physical and / or electrostatic on the surfaces of those coated with the zeolite material Particles held. The used Material quantities, the mixing times, the temperatures and the mixing techniques are chosen so that the finished Product the desired specified composition and has the described properties.

The initial spraying or other mixing of non-ionic surfactant with the carbonate-bicarbonate particles or other builder particles are usually done at room temperature (20 to 25 ° C); the However, temperature can generally be in the range between 10 vary up to 40 or 50 ° C. For spraying or mixing you need a period of only 1 to 5 minutes, and after spraying on completely you can still 0 to 10 Mix for more minutes, preferably 1 to 5 minutes. The Fatty alcohol polyethylene oxide condensation product that one on sprayed on the surface of the moving particles, is usually liquid or is heated to a higher temperature, so that it is liquid and when sprayed on the moving surfaces or other application to it can spread well over it and so the absorption of the liquid is facilitated in the porous particles. It can be during the initial mixing stage some agglomeration of the Particles take place. This is apparently due to the adhesion or cohesion between part of the existing fine powder Particle material, on the surfaces of which "excess" There are quantities of liquid nonionic surfactant, attributed. During such agglomeration takes the particle size of the individual particles to approximately the size in the size range for the particles of the final product, although also by the subsequent adhesion of zeolite particles the particle size increases a little further. Appropriately the non-ionic is mixed and sprayed on Surfactant on the moving particles in one Rotary drum or at a small angle, such as 5 to 15 ° C inclined pipe. It can be with anyone any suitable speed of rotation, for example 5 to 50 rpm, can be worked. The non-ionic Surfactant is usually in the form of fine droplets of surfactant, for example with a diameter in Range from 40 to 200 microns, preferably 50 to 100 microns sprayed on. You can also use other suitable spray droplet sizes work, and in some cases you can non-ionic surfactant in the builder particles even further mix after you put it on its moving Dripped or poured on surfaces. You bet expediently high-performance mixing devices, such as one Lodige mixer one that operates at a comparatively low speed works, or you use a twin drum mixer or a similar mixer to add by of larger drops or liquid jet of non-ionic Surfactant caused the particles to agglomerate too much to prevent. As said before, one can, although this is not the preferred way of working, absorbent carbonate bicarbonate particles also in other ways than explained here in Manufacture shape of more angular particles, but it is more advantageous that they be a little rounded, so the particles have good fluidity.

After complete absorption of the non-ionic surfactant the zeolite powder is usually during 1 to 10 minutes, preferably about 5 minutes long mixed with the product and is adhered to. Make it up free-flowing grains with a particle size in the range from 0.42 to 4.76 mm (4 to 40 stitches, US standard sieve range). At this stage of the process is the moisture content of the product usually 2 to 20%, preferably 5 to 15%, inclusive Hydrated water. The plasticizer is then in the mentioned particle sizes within a period of time from 1 to 10 minutes, preferably 5 minutes on the Surfaces of the particles "dusted" and attached to them brought. Since the cationic plasticizer is only available in relative uses a smaller proportion, the particles not much bigger. The plasticizer particles stick on the particles of builder, non-ionic surfactant and zeolite so firm that a stable, non-dusting end product arises. As mentioned, different Adjuvants can be incorporated into the product. You can add suitable components or in a suitable work stage during the manufacturing process of free-flowing grains or add after the manufacturing process essentially ends is. The total adjuvant content, exclusive Water, rarely amounts to more than 20% of the product and lies generally below 10%. When using a perborate bleach can be its percentage however, to be effective to be up to 30% of the product turn off. The additional quantities are then usually used of the other essential components proportionately lower. The perborate can be mixed with the carbonate-bicarbonate mix or in 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.

In a modified embodiment of the manufacturing process, with the compositions of the same formulation but can be produced with improved properties the cationic softener melted and together with the non-ionic surfactant at elevated temperature at which both substances are liquid, applied. Alternatively, you can the plasticizer and the non-ionic surfactant in succession give up on the base particles. Recommended in these cases the particles at such a high enough temperature to keep the liquid substances from solidifying prematurely which could result in further sorption of the Substances is disabled. If liquid quaternary softener as the first substance earlier than the non-ionic surfactant is applied, it tends to be inside the base particle penetrates, and then when the non-ionic Surfactant is added, although some of it inside the particle can penetrate, but a larger proportionate Amount compared to that of the emollient remains on the surfaces of the material and there with the following arrested zeolite powder arrested.

In a further modified embodiment of the invention Processes are aliquots of the non-ionic surfactant and zeolite initially held back 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 afterwards on the Give up the product, first the non-ionic surfactant and then the zeolite. Additional protective covers are used around the product. That way you can get one Apply more non-ionic surfactant than this is possible in another way, and yet a free-flowing, granular detergent and softener to produce. It is possible to have six coating treatments to make; it is preferably limited to three coating treatments (two additional covers).

The products of the invention have significant advantages compared with other detergent compositions containing plasticizers. They can be low in phosphates Formulated phosphate or phosphate-free compositions be. The phosphate-free compositions have very good ones Washing power for many things with common household laundry occurring pollution, and they correspond to the legal and administrative regulations that limit the use of Prohibit phosphates in detergents and cleaning agents. One can accordingly use the products worldwide, and they are no more multiple formulations and attention certain restrictions on the use of detergent compositions required in different areas. The excellent washing power of the products is due to the existing non-ionic 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 detergent on the Laundry can be drawn up so that the finished laundry is noticeable is softer and more antistatic than with Comparative products washed without plasticizer Laundry. One should expect in itself that due to the comparatively high concentration of non-ionic surfactants and plasticizers, which as such are usually liquid, are pasty, semi-solid or waxy, the product be "sluggish" or poorly flowable and when stored for Should tend to cake; but it is found how surprising was, instead, a very free-flowing, not received baking product, which may be due to this is that you have the non-ionic surfactant in liquid Form on the base particles and penetration into the inside of these particles allows only one relative leaves a thin coating on their surfaces, which then with zeolite powder (and sometimes some powdered fabric softener) is covered. The preferred mixture of carbonate and bicarbonate in the base particles has a sufficient framework function and pH regulating effect that the product is a very good detergent. However, it can also be other Basic substances can be used, provided that they are similar are good sorptive, such as spray-dried Pentasodium tripolyphosphate, sodium carbonate. If bicarbonate is present, the pH is usually very high is obtained when carbonate is used alone, and this makes the product more fuel-efficient than one with Carbonate detergent built up as a structural substance. It will thereby also the sorption power of the composition for non-ionic Surfactant significantly improved, especially if that Bicarbonate is largely in the form of Wegscheider's salt. The zeolite powder on the surface of the particles also serves its effect of preventing stickiness or worse Flowability of the non-ionic surfactant also as protection for the inside of the product against exposure to external moisture under ambient conditions with high humidity. Man can therefore detergent compositions according to the invention market without the use of cardboard boxes with special wax coatings as a barrier layer.

Due to its affinity for moisture, the zeolite material can absorb the moisture from the ambient air, before it can penetrate the interior of the particles, such as the bicarbonate or carbonate may be affected or where, due to the presence of moist alkaline conditions, possibly on some other product components, such as plasticizers or any of the various adjuvants, has harmful influence. The one on the outside surface of the particle-based ion exchange zeolite, with which quickly and effectively calcium ions from the wash water Removed has the effect that possibly harmful calcium ions (and other water hardness Ions) must be removed before using any other component of the laundry and plasticizers, such as an adjuvant, in Reaction can occur, and before using the laundry or react to the pollution present thereon; Such reactions can potentially cause the dirt on the laundry is stubborn and against washing of the surfactant becomes more resistant. Furthermore the zeolite material remains because it closely adheres to the non-ionic Surfactant is bound by the non-ionogenic substance during the first contact period with the wash water in Suspension. The particles usually take on one their original particle size significantly larger Particle size, which leads to them being trapped in the laundry remain. Such inclusions are disadvantageous because this causes lightening symptoms in dark-colored laundry can be. So the non-ionic surfactant contributes help to keep the zeolite particles in suspension until they fall apart into smaller size particles that focus on do not put the laundry down.

The comparatively large particle size of the product and the Starting material is a bit unusual, but you can handle 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 is the absorption of non-ionic surfactant and at the same time the desired coating effect better, it does not find any undesirable paste formation instead, and the particle surfaces contain such a sufficient one Amount of non-ionic surfactant that the desired Zeolite powder coating adheres to and is held.

By placing the plasticizer inside the product holds by making it the base particle as a liquid added before zeolite is applied, or by incorporates it into a particle that is subsequently added Is provided, you avoid initial Contact of the fabric softener with the laundry. This is desirable because otherwise the softening compound could settle on the tissue, causing a reaction the softener with the dirt on the laundry or could come from the fabric of the laundry itself and that would the cleaning process is affected. In some cases, if "external" plasticizer is added to the laundry and starts to melt, grease stains can appear on the laundry form, and at these points is then the cleaning process inhibited. According to the invention, such undesirable staining prevented that first the zeolite material and at least a portion of the nonionic surfactant in contact comes with the laundry. If different adjuvants in the Inner base particles can be kept in the same Prevent their initial contact with the laundry, which is often desirable. It can also be avoided that Particles of optical brighteners, for example stilbene brighteners, come into contact with the laundry immediately. One works the brightener so that it trapped particles inside is. This avoids the training of particularly shiny spots on the laundry.

In the following examples of some embodiments inventive washing and softening agents mean all parts unless otherwise stated Parts by weight and all temperature values Temperatures in ° C.

example 1

%

Mixture of sodium carbonate-sodium bicarbonate framework particles I
Weight ratio of Na₂CO₃ to NaHCO₃ about 1: 2, particle sizes in the range
0.149 to 0.84 mm (20 to 100 stitches, US standard sieve range) 27.8

Non-ionic surfactant, condensation product from C _12-15 fatty alcohol with
an average of 7 moles of ethylene oxide18.5

Type 4 A crystalline zeolite with high ion exchange capacity in particle sizes
from 0.053 to 0.088 mm (170 to 270 mesh, US standard sieve range) with extreme
Particle size in the range of 3 to 7 microns, with an average of about 5.2 microns46.3

Distearyldimethylammonium chloride, 95% active ingredient, powder of particle size
in the range of 0.094 to 0.177 mm (80 to 160 mesh, US standard sieve series) 7.4

The carbonate-bicarbonate backbone particles were at Room temperature (25 ° C) filled in an inclined Drum with 8 ° inclination at a speed of rotation of about 40 rpm. was driven, and during a The nonionic surfactant was added for 5 minutes 30 ° C sprayed on the moving surfaces of the particles. After that there was another 5 minutes in the drum mixed, followed by another 5 minutes the zeolite powder mixed with the material. The spraying of the non-ionic surfactant was in the form of droplets that largely a diameter in the range of 50 to 100 microns had, and during the spraying process and after that Mixing increased the particle size of that in the mixer Material slightly, and the existing fines agglomerated to particles with a size in the range from 0.149 to 0.84 mm (20 to 100 meshes, US standard sieve series). The zeolite addition was during about 5 minutes (time spans from 1 to 10 minutes are typical), after that it was that far manufactured, intermediate product still spherical in particle sizes of about 0.42 to 4.76 mm (4 to 40 mesh). After that was the powdered plasticizer with that from Builder, intermediate non-ionic surfactant and zeolite mixed, continued mixing for 8 minutes, and during At that time, the plasticizer particles adhered to the larger particles. The resulting product had poured loose a bulk density of about 0.8 g / cm³ and was free-flowing. It was packed and stored, and found that when stored under normal storage conditions no significant caking during normal storage and clumps arose. If such a stored pack was opened, the plasticizer-containing Pour out detergent well and the bulk density was still always about 0.8 g / cm³.

Cleaning tests with the manufactured Product revealed that it was not dusty, freely flowable was not prone to caking and for commercial use Suitable washing power and softening properties possessed that with those of with tripolyphosphate constructed as a structural substance, containing plasticizers Detergents with comparable active ingredients are good let compare. The zeolite did not settle worth mentioning on the laundry and bleached dark colored Wash out, and the carbonate had due to the presence of the bicarbonate and the resultant in the wash water pH of about 9.8 no harmful effects the cotton, polyester and acrylic material Laundry. There were also no greasy stains in the laundry caused by melted plasticizer, apparently not because the softener is through the zeolite material on the particle surface largely against initial strong contact with the laundry is protected.

In a comparison test were powder of finely divided sodium carbonate and sodium bicarbonate with particle sizes in the range of 0.053 to 0.088 mm (170 to 270 Meshes) and used to form a material with a particle size in the range of 0.149 to 0.84 mm (20 to 100 mesh, US standard sieve range) agglomerated. For this purpose, a 20% solution was initially used with 5% by weight treated aqueous cornstarch paste, and this was during over a period of about 3 minutes in the same as previously described mixing drum kept moving particles sprayed on, the drum at a speed of, for example, 10 rpm. was moved. The resulting Product was a very usable one Detergent and softener that when used in the same Concentration as in the previous example (¼ to ½ measuring cup or about 45 to 90 g each 65 l wash water filling) for washing washing machine fillings of about 4 kg soiled clothing was sufficient, but its free flowability was not was as good as that previously described Detergent and softener. If you use as the starting scaffold salt only used sodium bicarbonate Product does not have as good a washing power as the one before product described and if the carbonate alone is used, the product has one compared to the desired one Alkali content higher alkali content and is not free flowable. However, one can use the carbonate-containing composition as a detergent and softener in such Use applications where higher pH values can be tolerated, yet this product is for the Retail because of its worse Flow properties and the higher pH are less interesting than the products according to the invention.

The above example was repeated in a modified form. Here were the plasticizer particles together to particle sizes in Range from 0.42 to 4.76 mm (4 to 40 mesh, US standard sieve series) melt agglomerated, before the remaining ingredients of the composition were added. As a result of the same particle sizes the softener was not rounded off from before manufactured particles, but sometimes it could happen that a hint of "fat" is observed on the washed laundry has been; however, such appearances were not serious hindering and being used by the average consumer Not criticized.

In another embodiment of this example, this was Plasticizer fused with the non-ionic surfactant and sprayed onto the base grain particles (base core particles) so that they enter the Particles have been absorbed and even less Portion remained on the surfaces of these grain particles before these were coated with zeolite particles. The product failed with the same high bulk density and as described above Particle sizes and was a very effective detergent and softener, in which the plasticizer is so protected that it initially has no contact with the laundry; thereby unwanted stains avoided.

Similar good results were obtained when the melted one quaternary ammonium halide (plasticizer) sprayed onto the circulated base particles, then the non-ionic surfactant is sprayed on and then the zeolite powder was dusted. With this latter Embodiment became the zeolite before application on the spherical particles coated with non-ionic surfactant an optical brightener of the stilbene type mixed with another (0.5% or 0.05%) added. On this prevents the optical brightener in significant contact with the quaternary ammonium compound comes and between these any disadvantage of either ingredient Reactions can take place. When you wash the product used by laundry in the washing machine, both can Components, the optical brightener and the non-ionic Surfactant, active in wash water before acting out of the particles Plasticizer is released, which may interact with it could kick.

In further modifications of this method according to the invention became a quaternary ammonium compound in liquid form the surfaces of the zeolite particles are sprayed on before these Particles as a coating on that with the non-ionic surfactant coated carbonate-bicarbonate mixture were applied. The resulting product had similar properties to the previously mentioned products. This is also the case when the powdered quaternary ammonium compound in the specified Particle size mixed with the zeolite and this mixture as a coating on the wax-like, fat-like surface of base particles coated with the non-ionic surfactant is applied. According to yet another version of this The powdered quaternary compound the non-ionic coating on the core particle Surfactant adhered, and over it is zeolite powder applied as a coating. That way too is a good detergent and softener available with the properties described above.

Example 2

%

Sodium carbonate-sodium bicarbonate builder I from Example 119

Aqueous silicate particles (18% Water, Na₂O: SiO₂ ratio of 1: 2 9

Nonionic surfactant from Example 114

Type 4A zeolite from Example 150

Distearyldimethylammonium chloride from Example 1 8

The sodium carbonate sodium bicarbonate backbone particles were at room temperature in the as in Example 1 inclined drum (Rotation speed of 12 rpm). The hydrous silicate, which is about the same particle size had been during 2 minutes added to the drum contents with constant mixing, and then was mixed for another 3 minutes and so the silicate with uniformly mixed the carbonate-bicarbonate particles. Subsequently was at another temperature for 5 minutes of about 50 ° C mixed with the non-ionic surfactant the fabric softener on the moving surfaces the particles that had been preheated to 40 ° C sprayed on. Thereafter, as in Example 1 continued to work. The resulting product was excellent concentrated, phosphate-free Detergents and softeners for coarse, white and colored laundry, that in a concentration of 0.1 to 0.2% in the wash water was good for washing dirty clothes (in general are used in washing machines that are filled from above, 0.15%). The product had a bulk density of about 0.7 to 0.8 g / cm³ and was free-flowing after normal storage without that a protective cardboard with barrier properties is necessary was. The addition of water-containing silicate improved the builder effect of the detergent and the corrosion preventing activity compared to that Product according to example 1, although these products too satisfied in this regard.

Example 3

%

Sodium carbonate-sodium bicarbonate builder I of Example 127

Nonionic surfactant from Example 119

Sodium polyethoxy fatty alcohol sulfate, anionic surfactant from C _12-15

-Alcohol and
3 moles of ethylene oxide per mole, 60% of active ingredient, 25% H₂O and 15% C₂H₅OH 4

Type 4A zeolite from Example 140

Distearyldimethylammonium chloride from Example 110

The procedure was as in Example 1, with the difference that the anionic surfactant with the nonionic surfactant mixed and both sprayed together on the sodium carbonate-sodium bicarbonate framework particles were. The resulting product was an excellent one free-flowing, non-sticky and during storage non-clumping detergent and softener for coarse, white and colored laundry with the desired one high bulk density (0.6 to 0.8 g / cm³). Because this product is additional still contained anionic surfactant as a detergent a little better than the product according to Example 1. There were no impairments during storage Interactions of the existing surfactants through separation of these two substances and the particles. With a modified one Embodiment of the method described in this example became the cationic plasticizer with the non-ionic Surfactant added to the base particles, and the anionic surfactant was mixed with the zeolite and to the almost complete particles coated with non-ionic surfactant. Another modification was the non-ionic surfactant together with some anionic surfactant, the carbonate-bicarbonate particles then added as a coating for these particles added further non-ionic surfactant and so that anionic surfactant from the quaternary ammonium compound added later kept separate.

With a further modification of the described 0.5% of the optical brightener (syllable type) used anionic surfactant instead of an equal percentage and mixed with the sodium carbonate-sodium bicarbonate builder before the nonionic surfactant and the anionic surfactant was applied to it. That way the brightener from the later applied quaternary compound kept separate. All of these products were in the desired particle sizes and bulk densities before and also had the stated other properties.

Example 4

In this example, a further modification according to the invention is made Detergents and softeners and the process their manufacture explained, after which using a gradual coating technique additional amounts of non-ionic Surfactant can be incorporated into the product. As in the Examples 1 to 3 became liquid, non-ionic Enough surfactant applied, that it gets inside the sodium carbonate sodium bicarbonate builders or other base particles could penetrate and that was still a sufficient Excess remained with which the surfaces of the particles so were wetted that the subsequently applied zeolite powder stuck to the surfaces. If a larger amount of non-ionic Desires surfactant in the product, making it more concentrated Detergent composition is obtained, and if then according to that described in Examples 1 to 3 Procedure works so excess can Liquid to form an agglomerate or paste lead between favor this education. This undesirable result can be avoided and additional non-ionic surfactant work into the product in a satisfactory manner, that it is still free-flowing and retains a high bulk density, if, as described in this example below, is working. With this procedure you can also change the particle size increase.

First, the procedure was as in Examples 1 to 3, however, an additional 5 parts non-ionic surfactant per 100 parts of the according to these examples resulting product sprayed on, and additional 10 parts of zeolite were then mixed with the product and adhered to the non-ionic surfactant coating (The spraying and mixing was carried out as in the examples 1 to 3). The particle size increased by about 5% (diameter), but the product had still the same bulk density as before and was also free flowing and not clumping. In others Another 5 parts of non-ionic could be tried Surfactant on that obtained in the two-step process Spray on product and another 10 parts of zeolite material dust on it, whereby (with the same spray and Mixing methods) similar good results were obtained.

When performing the gradual enrichment described and build-up usually become the builder (sodium carbonate-sodium bicarbonate) particles or other base particles and as plasticizers existing quaternary ammonium compound is not again additional sprayed on, however you can also do this if it is is advantageous. It is possible to have six coating treatments but only three such operations are preferred, as described in the "further experiment" here, executed. It is also appropriate that Total amount of non-ionic surfactant and zeolite in the following applied coating treatments to the amount to limit who have been applied in the first treatment is. Half of those in the first treatment are expedient used amount, the percentage of non-ionic surfactant and zeolite within the percentage range given above should lie.

Example 5

As in Examples 1 and 4, however, instead of the framework substance I from Example 1, the sodium carbonate-sodium bicarbonate framework substance II was used instead of the type 4 A zeolite crystalline type X zeolites and Y uses the same particle size and amorphous zeolites, instead of the nonionic surfactant from Example 1, C₁₂ to C₁₃ alkanol ethoxylates with 6.5 E 0 and C₁₄ to C₁₅ alkanol ethoxylates with 11 E 0 and C₁₆ to C₁₈ alkanol ethoxylates with 10 to 11 E 0, and instead of Distearyldimethylammonium chloride plasticizer from Example 1 were C₈ to C₁₈ alkyltrimethylammonium chlorides used. There were free-flowing Get detergents and softeners that a similarly high bulk density exhibited. In the manufacturing process was the only one Difference the temperature of the non-ionic surfactant kept sufficiently high that this is in a liquid state when it was sprayed onto the surface of the base particles has been. In addition, the proportionate amounts of the different Components modified to ± 10% and ± 30%, whereby however, the proportions within the above Areas were kept. It is important to ensure that the non-ionic surfactant in such a proportionate amount is used that part of it is not absorbed at the Surface of the base particles in the form of an adhesive coating remains so that the zeolite particles can be retained. If the non-ionic surfactant at the temperature that it has when the zeolite material is applied the temperature must be high enough be adjusted so that the zeolite particles on it and on the Base particles can adhere. If the cationic softener is a solid and inside the base particles the temperature must be sufficient be increased to allow it to be inserted alone or together with the non-ionic surfactant, sufficiently liquefied is.

The carbonate bicarbonates called Wegscheider's salt, which often also contain sesquicarbonates, are products with a low bulk density (in the range from about 0.4 to 0.5 g / cm³). In contrast is already the bulk density specification of 0.6 g / cm³ (shaken) for the inventive detergent and laundry detergent Detergents have a high value, and usually have according to the invention manufactured products even higher bulk densities, usually these are around 0.7 g / cm³ or higher.

Means the process of the invention can be a free-flowing Product from which no components separate out in which produce the desired, comparatively large particle sizes, even higher levels of non-ionic surfactant than the base particles normally hold capital. During the application of the non-ionic surfactant on the core particles, which are a large part of the non-ionic Absorbing surfactant is caused by "excess" non-ionic surfactant a greasy and waxy coating on the surface of the Particles formed, but the particles stick not worth mentioning to each other, rather they keep them afterwards applied smaller zeolite particles firmly. In front when the zeolite is added, the mixture is not pasty, it rather resembles damp sand, with each particle attached the other is non-adhesive or easily removable. The finished products are free-flowing, though they contain 10 to 100% of needle-shaped Wegscheider's salt in the Base material included. This is partly because that the particles were crushed by the coating of fine Zeolite can be rounded off or spherical particles arise. In addition, the different components particularly functional in the spherical product arranged to each other, and that of the base particles, if as such carbonate bicarbonate is present, buffering effect supports the washing process (the pH value of a 0.1% aqueous solution of the sodium carbonate-sodium bicarbonate framework is about 9.8).

It is also important that the finished product in the specified relatively large particle size; but if, as in the examples above, the conditions are changed (if you use smaller base particles, for example) so that the product in the form of smaller particles, e.g. B. in the order of 0.149 to 2.38 mm (8 to 100 stitches, US standard sieve row) is obtained, higher bulk densities are obtained than for detergents containing plasticizers are common.

Claims (11)

1. 1. Free-flowing, granular washing and softening agent containing

• 20 to 40% by weight of alkali builder salt as core particles, namely from separator salt, sodium carbonate, sodium bicarbonate, pentasodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate, borax and / or the corresponding potassium salts,
• 12 to 30% by weight of liquid or pasty nonionic surfactant at room temperature,
• - 30 to 60 wt .-% ion-exchanging zeolite particles with an outermost particle size of 0.005 to 20 microns and a calcium ion exchange capacity of 200 to 400 mg CaCO₃ / g with the formula (M₂O) (Al₂O₃) _y (SiO₂) _z · w H₂O, where M is sodium or potassium means, y stands for 0.8 to 1.2, z stands for 1.5 to 3.5 and w = 0 to 9, as well
• 4 to 12% by weight, as a rule, waxy or pasty quaternary ammonium compound substituted with at least one C₁₂ to C₁₈ alkyl group as a plasticizer,

characterized in that the agent

• - a bulk density of at least 0.6 g / cm³
• - also has particles in sizes from 0.42 to 4.76 mm (4 to 40 mesh, US standard sieve row),
• contain the core particles of the nonionic surfactant in their interior and on their surfaces and have a coating of zeolite particles adhering to the nonionic surfactant and
• - That the plasticizer is located in and / or on these particles.

2. washing and softening agent according to claim 1, characterized in that the builder salt core particles Sodium carbonate and sodium bicarbonate in one Weight ratio of 1:10 to 10: 1 included and Particle sizes in the range of 0.149 to 0.84 mm (20 to 100 mesh, US standard sieve range) possess that crystalline, amorphous and / or mixed crystalline amorphous zeolite type A, X and / or Y is the nonionic surfactant Condensation product from C₁₀ to C₁₈ fatty alcohol and Polyethylene oxide with 3 to 15 moles of ethylene oxide per mole Fatty alcohol is the quaternary, emollient Ammonium compound is a normally solid, quaternary Ammonium halide in granular form is that adheres to the surface of the particles obtained. 3. washing and softening agent according to claim 2, characterized in that the mixture of sodium carbonate and sodium bicarbonate contains Wegscheidersalz, and that the weight ratio of Na₂CO₃ to NaHCO₃ in the core particles is 1: 3 to 1: 1 that the zeolite is of type A. , a particle size in the range of 3 to 12 microns and a moisture content of 10 to 25%, that the nonionic surfactant is a condensation product of a C₁₀ to C₁₈ fatty alcohol and 6 to 12 moles of ethylene oxide per mole that the quaternary ammonium halide is quaternary di-C _12-18 alkyl, di-C _1-4 alkyl ammonium chloride and the end product is present in essentially spherical particles. 4. washing and softening agent according to claim 1, characterized characterized in that the particle according to claim 1 additional coating from the normally liquid or paste-like nonionic surfactant which in turn with additional calcium ion exchangers Zeolite particles is coated. 5. washing and softening agent according to claim 1, characterized characterized in that a small, proportionate amount of Softening agent on the surfaces of the core builder particles is. 6. washing and softening agent according to claim 1, characterized characterized in that the plasticizer and non-ionic surfactant inside and on the surfaces the core builder salt particle is present. 7. A method for producing the detergent and plasticizer according to claim 1, characterized by

• (a) mixing the nonionic surfactant in liquid form with the core particles of the builder salt, the surfactant being absorbed in these particles and coating them,
• (b) mixing the product obtained thereby with the zeolite particles which are held on the surface of the particles obtained and
• (c) mixing the product obtained with plasticizer in particle sizes of 0.094 to 0.177 mm (80 to 160 mesh, US standard sieve series), the plasticizer adhering to the surfaces of the zeolite coated particles.

8. A method for producing the detergent and plasticizer according to claim 1, characterized by

• (a) mixing the plasticizer in liquid form with the builder salt core particles at a sufficiently high temperature that the liquid substances do not solidify prematurely, a smaller proportion of the plasticizer being absorbed on the surface of these builder salt particles,
• (b) mixing the particles obtained with the nonionic surfactant in liquid form, the surfactant being absorbed in the particles and coating them in a larger proportion than that of the emollient,
• (c) mixing the product obtained with the zeolite particles, the zeolite particles adhering to the surface of the particles obtained.

9. A method for producing the detergent and plasticizer according to claim 1, characterized by

• (a) mixing the plasticizer and the nonionic surfactant at a temperature sufficient to form a liquid mixture,
• (b) mixing the liquid mixture obtained with the core particles of the builder salt, the liquid mixture being absorbed in the builder salt particles and coating them and
• (c) mixing the product obtained with the zeolite particles, the zeolite particles adhering to the surface of the particles obtained.

10. The method according to claims 7, 8 and 9, characterized characterized in that the product obtained also with additional non-ionic surfactant in liquid form is coated and that this surfactant coating with additional zeolite particles with extreme particle diameters is coated from 0.01 to 20 microns.