DK152589B - Free-flowing, particulate detergent-emollient and production process thereof - Google Patents

Description

DK 152589B

The present invention relates to a free-flowing particulate detergent plasticizer prepared by means of an agg 1 grinder in process and having a weight of at least o, 6 g / cm 3 and particle sizes in the range of 0.42 to 4.76 mm, and a process for the preparation thereof.

Agents which combine detergent action and fabric softening effect are known. Nonionic detergents are known to be useful components in detergents, and quaternary ammonium halide 2

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Genides, which have a long-chain lipophilic moiety on their nitrogen atom, have been successfully used as textile softeners and antistatic agents. Inorganic buffer salts such as phosphates, carbonates and silicates have long been used as builders for organic detergents, and zeolites such as sodium aluminosilicates have also been used for this purpose. Although most particulate detergents have low bulk, it is also known to produce high bulk particulate detergents. Prior to the present invention, however, it was not known to produce a high bulk weight particulate detergent fabric softener and with the desired properties of the products described herein, and the processes for producing such products have also not been known or obvious. from the prior art.

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The free-flowing particulate detergent softener-containing composition of the present invention is characterized in that it comprises core or base particles of an alkali metal builder salt selected from sodium carbonate mixed with sodium bicarbonate, sodium carbonate, sodium bicarbonate, pentane sodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate, borax, similar potassium salts and mixtures thereof, which contain a normally liquid or paste-like nonionic detergent on the interior of these particles and on the surfaces thereof and coated with a calcium ion-exchanging zeolite particle particle diameter in the range of 0.005 - 20 mm, which adheres to the buildup of the nonionic detergent in the salt surface of clear surfaces, and a waxy quaternary ammonium compound as emollient placed externally on or inside said particles, wherein said zeolite has the following chemical formula: (M 2 O) {Al 2 O 3) y (SiO 2) z x W H2 O where M is sodium or potassium, y is 0.8 - 1.2, z is 1.5 - 3.8 and W represents the water content of approx. 1.5 to 36% by weight of said zeolite and the weight percent of said builder salt, said nonionic detergent, said zeolite and said plasticizer are in the range of 20 - 40%, 12 - 30%, 30 - 60% and 4 - 12 respectively. %.

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The products of the invention are excellent high performance detergent textile softeners with suitably high room weights to enable the use of small volumes thereof, e.g. 50-150 cm, for an average of 5 washes in an automatic washing machine (which has a drum volume of approx.

30 to approx. 65 liters and wash a portion of approx. 4 kg of contaminated garments, etc.). Thus, smaller packages can be used for similar effective amounts of detergent-softener, and shelf space can be saved in the supermarket and at home. Of course, it is also easier to handle the smaller packages and to pour from them, resulting in easier use and less waste.

The core particles: or the base particles into which and to which nonionic detergent is added can be any suitable builder salts sufficiently absorbent for the nonionic detergent when in liquid state. Typically, it is desirable for the builder particles to have rounded shapes, preferably spherical shapes, with passages through the particles to the interior thereof, allowing absorption of at least 10%, preferably 20% and most preferably 30% by weight 20 or more of the nonionic detergent. in the builder particle. Suitable builders which can be used include a preferred mixture of sodium carbonate and sodium bicarbonate (including Wegscheider's salt), which will be described in more detail, sodium carbonate, sodium bicarbonate, pentane sodium tripolyphosphate, tetrasodium pyrophosphate, Na = 25 ratios ranging from 1: 1.6 to 1: 3) and borax. Such products which can be spray-dried, agglomerated or prepared by another suitable process will preferably have particle sizes just like the particle size of the preferred carbonate bicarbonate mixture to be described. Mixtures of various builders can of course be used, as is the case for mixtures of various other components of the present compositions. In addition to the sodium salts, other alkali metal salts, primarily potassium salts, can be used, but these are usually not preferred.

Instead of some of the inorganic builder salt, organic builders such as sodium citrate, trisodium nitrilotriacetate, CMOS (sodium carboxymethyloxysuccinate), sodium gluconate and sodium EDTA may be used. The overall content of such organic builders will usually-

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4 only constitute a minor part of the total builder content, preferably less than 25% thereof. Furthermore, some of the builder salt may be replaced by sodium sulfate or another compatible filler salt, but such filler will also usually constitute a lesser amount and preferably less than 25% of the total amount of builder plus the filler salt content.

The preferred mixture of alkali metal carbonate and alkali metal bicarbonate is very advantageously a mixture thereof, in which both types of compounds are present in the same individual grains or particles. For purposes of the present invention, such particles should suitably have sizes in the range of 0.149 to 0.84 mm, preferably 0.250 to 0.59 mm, and most preferably about 0.42 mm.

Larger particles of up to approx. 2.38 mm can be used, provided that the size of the resulting final product is in the desired range. In some such cases, efforts will be made to prevent any agglomeration or appreciable size growth from occurring during the absorption of nonionic detergent, otherwise the final particle sizes will usually become too large. When sizes smaller than those specified in the desired range are used, an unacceptable paste-like product is sometimes produced instead of individual free-flowing grains.

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The alkali metal carbonates and bicarbonates (sodium or potassium preferred), most preferably the sodium salts, will be substantially anhydrous in the preferred embodiments of the invention, but partially dehydrated builder salts of this type may be acceptable. Usually, the moisture content will be less than 9%, preferably less than 7%. The weight ratio of alkali metal carbonate to alkali metal bicarbonate will generally be in the range of 1:10 to 10: 1, preferably in the range of 1: 5 to 1: 1, most preferably in the range of 1: 3 to 1: 1 and most preferably be about 1: 3 to 1: 1. 1: 2. Preferably, the mixed product is prepared by a process which results in a substantial content, e.g. 10 to 100% of Wegscheider's salt, the rest being sodium bicarbonate. Such a product has excellent absorbency for liquid nonionic detergents and can easily be converted into a suitable

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send basic material for a zeolite builder powder coating. A process for preparing a mixed carbonate bicarbonate product that has been successfully used is disclosed in U.S.A. No. 3,944,500, which is incorporated herein by reference. A useful mixed car = 5 bonate bicarbonate of the type described can be obtained from Allied Chemical Corporation under the designation "Snowlite". Although the method of the patent is a preferred method, the mixed carbonate / carbonate grains can be prepared by other techniques. Instead of the carbonate and bicarbonate being intimately linked to each other in single grains, separate amounts of carbonate and bicarbonate according to one aspect of the invention may be used, preferably of the same sizes and quantities as the products described above, provided the is sufficiently absorbent to absorb the nonionic detergent in sufficient quantity to produce the desired final products. More finely divided carbonate and bicarbonate powders, such as those with particle sizes below 0.149 mm, e.g. 0.053 to 0.88 mm, and agglomerate them, either separately or in admixture, taking care to preserve the porosity of the product, using only minimal amounts of a binder such as starch 20 or other agglomerating agent. Wegscheider's salt can also be added to such products.

The softening compounds which can be used to soften laundry and help to give it resistance to curling as well as to free it from static electricity include a wide variety of compounds containing significant amounts of positively charged molecules. Such compounds will generally include hydrophobic groups as parts of the positively charged moieties, and such groups will often be relatively long chain groups such as higher hydrocarbyl groups or alkyl groups. Although amines, imidazolines, pyridines, guanidines and salts and derivatives thereof are useful, especially if they contain relatively long chain hydrophobic groups, the most preferred plasticizers will usually be quaternary ammonium compounds containing one or two long chain hydrophobic groups and two or three short chain 35 groups together with a solubilizing cation or a salt-forming group, usually either halide, sulfate, acetate, hydroxide or another inorganic or organic solubilizing mono- or dibasic group. Various cationic compounds useful in the invention are also described in U.S.A. Patent Specification No. 3,227,614 6

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In the quaternary ammonium compounds and salts, the nitrogen atom is longer chain substituents, preferably higher alkyl groups having 12 to 18 carbon atoms, more preferably 16 to 18 carbon atoms, and most preferably stearyl, and the shorter hydrophobic groups being alkyl groups 5 having 1-4 carbon atoms. preferably with 1 to 2 carbon atoms and most advantageously the methyl group. Similar long chain substituents are found on the imidazolines and imidazoles, pyridines and piperidines, as well as the guanidines and amines. Specific examples of preferred cationic conditioning agents used in the present invention include dimethyl distearyl ammonium chloride, trimethyl stearyl ammonium bromide, cetyltrimethylammonium chloride, di-higher alkyl dimethyl ammonium chloride, wherein the higher alkyl benzyl chloride is obtained from hydrogen alkyl, monium chloride, di-isobutylphenoxyethoxyethyldimethylbenzylammonium chloro = 15 rhide and laurylisoquinolinium bromide. While these are preferred compounds, the higher alkyl amines and other cationic conditioning agents known to be useful for softening various fabrics and fibers and making them shrink-resistant or static-free may also be used instead. Such compounds will be very important to textiles, especially those of cotton or cellulose materials and synthetic organic fibers. Furthermore, the disclosed softening compounds containing higher alkyl groups are usually waxy or paste-like solids and can be melted at elevated temperatures so that they are useful for coating 25 particles of the invention. Such a coating may be obtained by mixing relatively soft plasticizer compound particles with material to which they must be adhered, such as carbonate-bicarbonate non-ionic detergent zeolite particles, or the softener may be melted and sprayed onto seed particles or may be mixed with nonionic -30 tergent and simultaneously sprayed on such particles. In large part due to the use of nonionic detergent instead of anionic detergent, with which cationic plasticizers often react, the softening compound retains its use efficiency in the products in question.

35

The nonionic detergents include those described in detail in McCutcheon's Detergents and Emulsifiers, 1973, and in Surface Active Agents, Volume II, by Schwartz, Perry, and Berch (Interscience Publishers, 1958), the disclosures of which are incorporated herein by reference. .

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Such non-ionic detergents are usually paste-like or waxy solids at room temperature (20 ° C) which are either sufficiently water-soluble to immediately dissolve in water or which will rapidly melt at the temperature of the wash water, such as when the temperature is above 40 ° C. The non-ionic detergents used will usually be those which are liquid or paste-like at room temperature, but are preferably usually paste-like or semi-solid products because they are less likely to form a sticky product with poor flow properties and tendency to clump or coagulate. baking at storage. They are also less prone to moisture sweating and release of their "attachment" to the zeolites. Furthermore, normally liquid nonionic detergents can be used, and used nonionic detergents will be dropletable so that they can be sprayed at reasonable temperatures, such as temperatures below 45, 50 or 60 ° C. Typically useful non-ionic detergents are the poly (lower alkenoxy) derivatives usually prepared by condensing lower (2-4 carbon atoms) alkylene oxide, e.g. ethylene oxide, propylene oxide (with sufficient ethylene oxide to form a water-soluble product), with a compound having a hydrophobic hydrocarbon chain and containing one 9Q or more active hydrogen atoms such as higher alkyl phenols, higher fatty acids, higher fat mercaptans, higher fat amines and higher fat polyols and alcohols, e.g. fatty alcohols having 8-20 or 10-18 carbon atoms in an alkyl chain and alkoxylated with an average of approx. 3 to 30, preferably 3 to 15 or 6 to 12 lower alkylene oxide units.

Preferred nonionic surfactants are those of formula R0 (C2H40) nH wherein R is the residue of a linear saturated primary alcohol (an alkyl alcohol) having 10 or 12 to 18 carbon atoms and n is an integer from 3 or 6 Typical commercially available nonionic surfactants suitable for use in the invention include "Neodol" ® 45-11, which is an ethoxylation product (with an average of about 11 ethylene oxide units) having a fatty alcohol containing a 14 to 15 carbon atoms chain (average) (manufactured by Shell Chemical Company), "Neodol" ® 25-7, a fatty alcohol having a chain containing 12 to 15 carbon atoms, which is ethoxylated 35 with an average of 7 ethylene oxide units, and "Alfonic" ® 1618-65, which is an alkanol having 16 to 18 carbon atoms ethoxylated with an average of 10 to 11 ethylene oxide units (Continental Oil Company). Also applicable are "Igepals" ^ from GAF Company Incorporated. Such materials are usually the polyethoxylated (3 to 30 ethylene oxide = 8

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units) intermediate alkyl (6 to 10 carbon atoms) phenols such as "Igepal® CA-630, CA-730 and CO-630." Pluronics1 (manufactured by BASF-Wyandotte), such as "Pluronic1® F-68 and F- 127, which are condensates of ethylene oxide with hydrophobic base materials formed by condensation of propylene oxide with 5 propylene glycol / and which usually have molecular weights in the range of 5000 to 25,000 / can also be used, as is the case for the various "Tween" ® (ICI products) in America), which are polyoxy = ethylene sorbitan higher fatty acid (12 to 18 carbon atoms) esters, such as those containing solubilizing amounts of ethylene oxide. Various other nonionic detergents described in the descriptions previously described incorporated herein by reference thereto may also be used, but preferably the amount of nonionic detergent or surfactant present, other than the higher fatty alcohol polyoxyethylene ethanols, will be less and rarely more than 50 % and preferably not more than 25% of the total non-ionic detergent content. In the above description, higher, such as in higher alkyl, higher fat, etc., means from 8 to 20 and preferably from 10 or 12 to 18.

The zeolites which can be used in the practice of the present invention include the crystalline, amorphous and mixed crystalline-amorphous zeolites of both natural and synthetic origin, which zeolites are sufficiently fast and have sufficiently effective effects to counteract hardness ions such as calcium ions. wash-25 water. Such materials are preferably capable of reacting rapidly enough with hardness cations, such as calcium, magnesium, iron and the like, or any of them to soften wash water before adverse reactions resulting from such hardness ions with other components of the sintering material take place. The zeolites used can be characterized as having a high exchange capacity against calcium ion, which is usually from approx.

200 to 400 or more mg equivalents of calcium carbonate hardness per grams of the aluminum silicate, preferably 250 to 360 mg equivalents / gram, and a residual hardness reduction rate of 0.02 to 0.05 35 mg CaCO 3 / liter over one minute, preferably 0.02 to 0.03 mg / l , and less than 0.01 mg / l over 10 minutes, all based on anhydrous zeolite.

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Although other ion-exchange zeolites may also be used, the finely divided synthetic zeolite builder particles used in the practice of the present invention will usually have the formula 5 (Na 2 O) x · (Al 2 O 3) y · (SiO 2) z * w H 2 O wherein X is 1 , y is from 0.8 to 1.2, preferably approx. 1, z is from 1.5 to 3.5, preferably 2 to 3 or approx. 2, and w is from 0 to 9, preferably 2.5 to 6.

10

The water-soluble crystalline aluminum silicates used are often characterized in that they have a network of pores of substantially uniform size in the range of from ca. 3 to approx. 10 Angstroms, often approx. 4 Angstrom (normal), such size being uniquely determined by the unit structure of the zeolite crystal. Of course, zeolites containing two or more such networks of different pore sizes can also be used satisfactorily, as is the case for mixtures of such crystalline materials with each other and with amorphous materials, etc ..

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The zeolite should be a monovalent cation exchange zeolite, i.e. it should be an aluminum silicate of a monovalent cation such as sodium, potassium, lithium (when practicable) or another alkali metal, or ammonium or hydrogen. The monovalent cation in the zeolite molecular sieve is preferably an alkali metal cation, especially sodium or potassium, and most preferably is sodium, but various other types are also useful.

Crystalline zeolite types useful as good ion exchangers according to the invention, at least in part, include zeolites of the following crystal structure groups: A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of such molecular sieve zeolites may also be useful, especially when type A zeolite is present. These crystalline zeolite types are well known and are extensively described in the 35 work Zeolite Molecular Sieves by Donald W. Breck, published in 1974 by John Wiley & Sons. Typical commercially available zeolites of the aforementioned structural types are set forth in Table 9.6 on pages 747-749 of the above work, to which Table is hereby referred.

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The zeolite used according to the invention is preferably synthetic and it is also preferred that it is of type A or has a similar structure, especially as described on page 133 of the above work. Good results have been obtained when using a type 4A molecular sieve zeolite, where the monovalent cation of the zeolite is sodium and the pore size of the zeolite is approx. 4 Angstrom. Such zeolite molecular sieves are described in U.S.A. No. 2,882,243, which describes them as zeolite A.

Molecular sieve zeolites can be prepared in either a dehydrated or a calcined form, containing from ca. 0 or approx. 1.5% to approx.

3% moisture, or in a hydrated or aqueous form containing further bound water in an amount of about 4% and up to approx. 36% of the total weight of the zeolite, depending on the type of zeolite used. The aqueous hydrated form of the molecular sieve zeolite (preferably 15 from about 15 to 70% hydrated) is preferred in the practice of the invention when such a crystalline product is used. The preparation of such crystals is well known in the art. For example, in the preparation of zeolite A referred to above, the hydrated zeolite crystals formed in the crystallization medium (such as an aqueous, amorphous sodium aluminum silicate gel) are used, without the high temperature dehydration (calcination to 3% or less water content). ) normally used in the preparation of such crystals for use as catalysts, e.g. cracking catalysts. The crystalline zeolite in either fully hydrated or partially hydrated form 25 can be obtained by titrating the crystals from the crystallization medium and drying them in the air at ambient temperature so that their water content is in the range of from 5 to approx. 30% moisture, preferably from approx. 10 to approx. 25%, such as from 17 to 22%. However, the moisture content of the molecular sieve zeolite used can be much lower, as described above.

The zeolites used according to the invention should usually also be substantially free of adsorbed gases such as carbon dioxide, since such gaseous zeolites can produce undesirable foaming when the zeolite-containing detergent is contacted with water. Sometimes, however, foaming can be tolerated and sometimes desirable.

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The zeolite should preferably be in a finely divided state with final particle diameters up to 20 microns / e.g. 0.005 or 0.01 to 20 microns, preferably from 0.01 to 15 microns and particularly advantageously with an average particle size of 0.01 to 8 microns, e.g. 3 to 7 or 5 12 microns if the zeolite is crystalline and from 0.01 to 0.1 microns, e.g. 0.01 to 0.05 micron if the zeolite is amorphous. Although the final particle sizes are much smaller, the zeolite particles will usually have sizes in the range of 0.037 to 0.149 mm, preferably 0.044 to 0.105 mm. Minor sized zeolites will often become unevenly dusty, and larger-sized zeolites cannot adequately and satisfactorily cover the carbonate-bicarbonate base portion of the nuclei.

Although the crystalline, synthetic zeolites are more common and better known, amorphous zeolites can be used instead and are often superior to the crystalline materials for various important properties which will be described, as is the case for the mixed crystalline-amorphous materials and mixtures of the various zeolite types described. The particle sizes 20 and pore sizes of such materials may be similar to those previously described, but variations from the indicated ranges may be made as described, provided that the materials function satisfactorily as builders and not adversely with white overshadowed colored materials by which they are treated in aqueous media. .

25

A variety of suitable crystalline molecular sieve zeolites are disclosed in DE-A-2,519,815, DE-A-2,538,679, DE-A-2,656,251 and DE-A-2,656,009, which are incorporated herein by reference. the zeolites described therein and other materials used in the present invention. A variety of other such compounds are described in the descriptions of Swedish patent applications SE 74 06 287-A and SE 77 14 495-A, to which reference is also made. Other such useful molecular sieve zeolites are illustrated in German Patent Specifications Nos. 2,412,837 and 2,412,839 as well as in the descriptions of Austrian Patent Applications Nos. A 4484/73, A 4642/73, A 4666/73, A 4717/73, A 4750/73, A 4767/73, A 4787/73, A 4788/73, A 4816/73 and A 4888/73, to which also k η nwt '12

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Preparation methods for amorphous and mixed amorphous-crystalline aluminum silicate ion exchange zeolites are described in the description of a U.S.A. patent application filed July 12, 1974, entitled Detergent Builder Composition (Burton H. Gedge, III and Bryan L. Madison 5 are Inventors). Detergents containing such amorphous materials are disclosed in an application filed by John Michael Corkill and Bryan L. Madison on July 18, 1974, and detergents containing mixed amorphous-crystalline aluminum silicate builder material are disclosed in an application filed July 12, 1974 by the same inventors (application -10 can be identified by the clerk's journal numbers 2001, 2003 and 2002, respectively). A preferred ion exchange zeolite is the amorphous zeolite of Belgian Patent Specification No. 835,351, which has the formula m 2 O-ai 2 O 3 * (sio 2) z * w h 2 o 15 wherein z is from 2.0 to 3.8 and w is from 2.5 to 6 , especially when M is sodium. Reference is only made to said patent specification to avoid the necessity of long enumeration of such materials, methods of manufacture and use, etc.

20

A variety of auxiliaries or additives, both functional and aesthetic, can be incorporated into the present compositions, such as bleaching agents, e.g. sodium umperborate, coloring agents, e.g. pigments and dyes, fluorescent brightening agents, e.g. stilbene detergents, foam stabilizers,

£ O

eg. alkanolamides such as laurylmyristinediethanolamide, enzymes, e.g. proteases, skin protection agents and conditioners such as low molecular weight water-soluble proteins obtained by hydrolysis of protein materials such as animal hair, skins, gelatine and collagen, 3Q foam breakers, e.g. silicones, bactericides, e.g. hexachlorophen, and perfumes. Usually, such auxiliaries and any additional builders will be mixed with the other components at a particular stage in the manufacturing process which is the most suitable and which usually depends on the nature of the auxiliary and its physical condition. Particularly desirable are such additives which aid in stabilizing the excipient or other components of the product, and / or which enhance the ability of the carbonate-bicarbonate mixture to absorb nonionic detergent. Such auxiliaries can thus be sprayed 13

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on the base particles with the non-ionic detergent, or they can be mixed with the zeolite and applied therewith to the base particles treated with non-ionic detergent, or they can be added to such zeolite coated particles, either together with the plasticizer 5 or after the addition of the emollient.

Normally, it is preferred that only nonionic detergents are used (except for the plasticizer which may be considered to have cationic detergent properties), but sometimes nonionic detergents jO can be supplemented with an anionic, organic detergent, an amphoteric organic detergent. or a mixture thereof. However, when such materials are used, they will usually be present in smaller amounts, preferably in an amount of less than 25% of the total non-ionic detergent content and such detergents and more preferably less than 10% of them, and they will be present in the product and incorporated so as to minimize adverse reactions between the emollient and such detergents. Thus, when a cationic plasticizer is added, it will be preferable to have any anionic and amphoteric detergents in the base particles, preferably sprayed onto them and into them together with the nonionic detergent. Similarly, when the cationic plasticizer is sprayed onto the germ or core particles with the nonionic detergent or separately from it, it would be preferable to incorporate any anionic and amphoteric detergents on the surface of the zeolite coated grains, or may optionally be mixed with the zeolite and applied to the cationic plasticizer and nonionic detergent-treated particles.

Among the useful anionic detergents are the sulfates and sulfonates of lipophilic moieties, especially those containing longer carbon atom chains, such as chains having 8 to 20 or 10 to 18 carbon atoms. Such compounds include the linear higher alkylbenzenesulfonates, ole = 35

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finesulfonates, paraffin sulfonates, fatty acid soaps, higher fatty alcohols = sulfates, higher fatty acid monoglyceride sulfates, sulfated condensation products of ethylene oxide (3 to 30 moles per mole), and higher fatty alcohols, higher fatty acid esters of isethionic acid, and other known anionic detergents which are also mentioned previously incorporated herein by reference thereto. Most of these products are usually in solid form, usually as alkali metal salts, e.g. sodium salts, and can be spray dried with conventional builders. The spray-dried particles including such builders can be used as seed or base particles in the composition of the invention. Agglomeration technique, size reduction, "pilling1" and other methods may be used to prepare such intermediate products of sizes corresponding to the size of the carbonate-bicarbonate particles. A few examples of suitable anionic detergents include sodium linear tridecylbenzenesulfonate, sodium = cocosmonoglyceride sulfate, sodium paraffin and olefin sulfonates, each having an average of about 16 carbon atoms. Amphoteric compounds such as the sodium salt of "Miranol" ® C2M and “Deriphat” ® 151 can also be used in the detergents of this invention. the amphoteric detergents are spray-dried or otherwise molded with a builder or they can be dispersed in the liquid, nonionic detergent or appropriately mixed with other powders during the preparation of the products in question, although both anionic and amphoteric detergents can be 25 present in the products of the invention is preferred to a large extent, the only purifying component other than the cationic plasticizer is a nonionic detergent or a mixture thereof.

Quantities of core or base particles (preferably car = 30 bonate bicarbonate), nonionic detergent, zeolite and plasticizer should be selected, resulting in the desired free flowing detergent softener particles of satisfactory high room weight when prepared by the process. according to the invention. Such amounts are 20 to 40% core or base particles, 10 or 12 to 30% nonionic detergent, 30 to 60% zeolite and 4 to 12% plasticizer, with the preferred ranges being 23 to 33%, 13 to 23%, respectively. 40 to 52% and 5 to 10%. The weight of the product will be at least 0.6 g / cm 2, preferably

ISLAND

in the range of 0.75 to 0.95 g / cm and most preferably in the range

ISLAND

range from 0.8 to 0.9 g / cm. The particle sizes of the product will usually range from 4 to 40 mesh, preferably from 4

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15 to 12 mesh and most preferably approx. 6 or 8 mesh. The particle sizes of the carbonate-bicar = bonate starting material or the particle sizes of other basic particles will usually be in the range of from about 1 to about 5 hours before any treatment. 20 to approx. 100 mesh, preferably 5 from 30 to 60 mesh and most preferably approx. 40 mesh. However, finer carbonate and bicarbonate powders and other builders may be used initially, and may be agglomerated up to said sizes. Generally, the materials within the stated mesh ranges will form a mixture of particles of different sizes within such ranges. This is also the case for the various other particulate materials described herein.

In the preparation of the preferred carbonate-bicarbonate blend particles in the form of starting particles, the method of U.S.A.

Patent No. 3,944,500 is used and the product thus obtained, designated by the trade name "Snowlite", which is available from Allied Chemical Corporation, is preferably used. A typical analysis of "Snowlite" I is 35% Na 2 CO 2, 58.5% NaHCO 3, and 6.5% 30, whereas the analysis for another such product, "Snowlite" II, is 20 30.0%, 66 5% and 3.5%. Sieve analyzes (percent of targets with numbers 10, 40, 60 and 100 according to US Standard) are 0.2, 67.6, 96.9 and 99.0 for "Snowlite" I and 0.7, 60.7, 90 respectively. , 7 and 97.0 for "Snowlite" II. The space weights (g / cm3) are 0.51 and 0.48 (packed) as well as 0.42 and 0.38 (unpackaged). The brittleness is particularly low for "Snowlite" I (2.5% according to Allied Chemical Corporation, experiments Na 17-35) and such a product is preferred. Low brittleness and particle strength are also important for other types of ground particles that can be used to prevent them from over-powdering and to form pastes instead of individual coated particles when nonionic detergent is added. In some cases, the other components of the final product may be incorporated into the mixture of bicarbonate and Wegscheider's salt (sesguicarbonate may also be present) prepared according to the method disclosed in the patent provided that they are stable and do not adversely react or generate the preparation. of the carbonate-bicarbonate product.

Typically, the carbonate-bicarbonate particles will contain at least 60%, preferably 70%, and most preferably 70 to 85% or more of the carbonate and bicarbonate when such other excipients are present, such as 10 to 20% sodium silicate and / or 0.1 to 5% fluorescent

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16

The free-flowing, high-density particulate plasticizer according to the invention can be prepared by a variety of methods. In one such method, the described sodium carbohydrate sodium bicarbonate particles or other builder particles are mixed with liquid non-ionic detergent, which detergent is preferably applied by spraying, but which in some cases can also be added as a material stream. The detergent penetrates the carbonate bi-carbonate particles, but also coats the surfaces of such particles so that the zeolite applied thereafter adheres thereto. It is important to apply sufficiently high non-ionic detergent so that in addition to that absorbed in the interior of the builder particles, no detergent will be left on the particle surfaces. During the mixing after the addition of non-ionic detergent, the particles resemble wet sand and have a greasy or waxy appearance. The nonionic detergent is usually liquid paste or semi-solid and preferably pasty or semi-solid to minimize any tendency of the product to become sticky or form lumps upon storage, although normally liquid nonionic detergents can also be used with satisfactory results. . After coating the 2Q base particles with nonionic detergent, these particles are mixed with zeolite powder, which thereby adheres or adheres to the nonionic detergent on the particle surfaces. The particles formed are essentially spherical and have sizes in the range of 0.42 to 4.76 mm. In this embodiment of the process according to the invention, plasticizer is mixed in the agent, usually in the form of rather small granules, scales, grains or powder particles to end with the nonionic basic zeolite grains. The plasticizer will usually be a waxy or greasy or low-melting solid material having 3Q particle sizes in the range of 80 to 160 mesh, corresponding to approx. 0.095 - 0.177 mm, whereby these particle sizes are preferably approx. 0.149 mm. It will be physically and / or electrostatically retained on the surfaces of the zeolite coated particles. The amounts of the materials used, the mixing times, the temperatures and the mixing technique used will, of course, be such that the product will have the desired composition and properties described above.

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17

The initial spraying or other mixture of nonionic detergent with carbonate bicarbonate or other builder particles is usually carried out with the particles at approx. room temperature (20 to 25 ° C), but the temperature can vary over the range of 10 to 40 or 50 ° C.

The spraying and mixing can last as little as 1 to 5 minutes and mixing can be continued for up to 10 minutes after completion of spraying, preferably from 1 to 5 minutes. The higher fatty alcohol polyethylene oxide condensation product sprayed onto the surfaces of the grains in motion is usually liquid or heated to an elevated temperature so that it is liquid and is sprayed onto the surfaces in motion or otherwise applied thereto. so that it is distributed over it and absorption of the liquid product into the porous particles is promoted. Furthermore, some agglomeration may be carried out during the initial mixing apparently as a result of adhesion or cohesion between some of the finer particles present which have "excessive" amounts of liquid nonionic detergent on their surfaces. During such agglomeration, such particles may increase in size to sizes approximately in the range of the final product, although the subsequent adhesion of 20 zeolite particles further increases particle sizes. The mixing and spraying of the nonionic detergent on the moving particles is preferably carried out in a rotating drum or rotating tube inclined at a slight angle such as 5 to 15 °. The rotation speed can be any suitable, such as 5 25 to 50 rpm. minute. The spraying of the nonionic detergent will usually be such that fine droplets of the detergent are formed, such as droplets having diameters in the range of 40 to 200 microns, preferably 50 to 100 microns, but other suitable spray droplet sizes may also occur, and in some cases, the nonionic detergent may be mixed with the builder particles after being applied or poured onto its surfaces during movement. In such cases, a higher speed or higher mixing force mixer may be used, such as a "Low" blender operating at a relatively low speed, or a double sheath mixer or similar type to prevent excessive agglomeration. of particles caused by the addition of the larger droplets or streams of nonionic detergent. Although not preferred, absorbent carbonate-bicarbonate particles, as previously mentioned, 18

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are prepared by methods other than those described herein to obtain more sharp-edged products, but it is highly desirable for the particles to be flowable and it is most preferred that they be somewhat rounded.

5

Upon completion of the absorption of the nonionic detergent, the zeolite powder is mixed with the product, usually in the course of 1 to 10 minutes, preferably in about 10 minutes. 5 minutes, and it is maintained there to form free-flowing grains of particle sizes in the range of 0.42 to 4.76 mm. At this stage, the product will usually have a moisture content of 2 to 20%, preferably of 5 to 15% including hydrate water. The plasticizer, which has the shape and particle sizes previously mentioned, is then "powdered" on the surfaces of the particles, and in about 1 to 10 minutes, preferably approx. 5 minutes, it will be glued to it. Due to the relatively small amount of cationic plasticizer used, the particle sizes are not greatly increased and the plasticizer particles are sufficiently firmly adhered to the builder nonionic detergent zeolite particles to form a stable, non-segregating and non-dusting final product. As previously mentioned, various adjuvants may be incorporated into the product by introduction together with suitable components, or they may be added thereto at appropriate process steps during the preparation of the free flowing grains or after such preparation is substantially complete. The total excipient content, other than water, will rarely exceed 20% of the product and will usually be less than 10%. Of course, if a perborate bleach is used, the percentage thereof may be increased to an effective bleaching amount which may be as high as 30% of the product, the amounts of the other important components usually being proportionally reduced accordingly. The perborate may be mixed with the carbonate / carbonate mixture or added to the nonionic detergent-treated mixture or to the final product. Dyes, perfumes and other excipients may be mixed with the various components and mixtures during manufacture or even after completion thereof.

19

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By modifications of the manufacturing method which result in the preparation of materials of the same composition but with further improved properties, the cationic plasticizer is melted and applied to the nonionic detergent at an increased temperature at which they are both liquid. Alternatively, the emollient and the nonionic detergent are applied sequentially to the base particles. In such cases, the particles will usually be kept at a sufficiently high temperature so that the liquids do not solidify prematurely, which could prevent further adsorption of such materials. When liquid quaternary plasticizer is initially applied prior to the nonionic detergent, it tends to penetrate the interior of the base particles, so that when the nonionic detergent is added, a greater amount thereof, although some penetrate the interior of the particles than the amount of plasticizer present on the surfaces of the materials where the detergent will adhere to the then applied zeolite powder.

In further embodiments of the process according to the invention, amounts of the nonionic detergent and of the zeolite will be kept outside and used for product coating again. Thus, from approx. 5 to approx. 50%, preferably from approx. 10 to approx. 30% of the nonionic detergent and of the zeolite are applied to the product, first the nonionic detergent and then the zeolite, thereby forming an additional protective shell around the product and allowing 25 more of the nonionic detergent to be incorporated. than would otherwise be possible, still forming a free-flowing, particulate detergent softener. Usually, as many as six coating operations can be used, but it is preferable to limit them to three (two gene coatings).

30

The products of the invention have significant advantages over other detergent softeners. They can be prepared as either phosphate-containing or low-phosphate or no phosphate-containing agents. The phosphate-free agents have satisfactory washing properties against a variety of debris normally found on household laundry and yet comply with the regulatory and administrative provisions limiting the use of phosphates in detergents. The manufactured products can therefore 20

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is marketed nationwide and there is no need for a variety of product compositions and for limitation to certain shipments of detergent compositions to specific geographical areas. The satisfactory purity of the product is due to the presence of the nonionic organic detergent and the mixed water-soluble inorganic builders and zeolite builders. Although the product has satisfactory purity, it also contains enough softener which is essential for the laundry so that the finished laundry is considerably softer and to a greater extent free of static electricity than laundry washed with control materials which does not contain such a plasticizer. Usually, relatively high amounts of nonionic detergent and plasticizers, which are usually usually liquid, paste, semi-solid or waxy, would cause the product to become "lazy" or poorly flowing with a tendency to bake together upon storage, but due to the application of the nonionic detergent to the base particles in liquid form and its penetration into the interior of such particles with only a relatively thin coating thereof on their surfaces which are then coated with zeolite powder (and sometimes some soft casting). 20), a very free flowing and non-caking product is obtained. The preferred mixture of carbonate and bicarbonate in the base grains provides a highly desirable basis for absorption of the nonionic detergent and provides sufficient builder or pH-regulating effects so that the product is a satisfactory detergent. However, other base materials can also be used provided they are similarly absorbent, e.g. spray dried pentane sodium tripolyphosphate or sodium carbonate. When the bicarbonate is present, it usually reduces the high pH value that would otherwise be obtained from the use of the carbonate alone, making the product safer to use than a carbonate based detergent.

It also significantly improves the ability of the agent to absorb nonionic detergent, especially when the bicarbonate is largely in the form of Wegscheider's salt. The zeolite powders on the surfaces of the particles will, in addition to prevent the nonionic detergent from causing stickiness or poor flowability, also protect the interior of the product from the effect of external moisture and moisture conditions. Thus, the agents can be marketed without the use of special wax-coated protective layers on the cartons.

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21

Due to its affinity for moisture, the zeolite absorbs such moisture before it can penetrate into the interior of the particles where it could have an adverse effect on the bicarbonate or carbonate, or as a result of the formation of moist, alkaline substances. 5 conditions may adversely affect some of the other product ingredients, such as the plasticizer or any of the various adjuvants. > The ion-exchanging zeolite present on the exterior of the particles and rapidly effective in removing calcium ions from the wash water removes any harmful calcium ions (and other hardness ions) before reacting with some of the other detergent emollients , such as auxiliaries, and before they can adversely react with laundry or dirt thereon, which could cause the laundry to hold the dirt more effectively against the action of the detergent. Also, because zeolites are intimately associated with the nonionic detergent, they are better kept in suspension of the nonionic detergent during the initial period of contact with the wash water, at which point they would normally have a significantly larger particle size than their final particle size and therefore, would be more likely to be trapped in laundry textiles. Such an interception would be unfortunate as it could cause a light staining of the appearance of dark colored laundry pieces. The nonionic detergent helps keep the zeolite particles suspended until they decompose into smaller particle sizes that are less likely to be deposited on the laundry.

The relatively large particle size in the products of the invention and in the starting materials is somewhat unusual, but results in very free-flowing particles, which still dissolve rapidly and have high room weight. Due to the relatively large particle size of the builder salt, better absorption of non-ionic detergent, along with desirable coating effect, no undesirable paste formation is obtained, and the surfaces of the particles contain enough non-ionic detergent to retain the desired coating of zeolite powder.

By holding the plasticizer in the interior of the product, such as when added to the base particles as a liquid prior to the application of zeolite or, when present in a post-coating particle, 35 »

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22 is initially prevented from contacting the plasticizer with the laundry, which is desirable as the fabric softening compound could otherwise be deposited on the fabrics and also cause a reaction between the plasticizer and the dirt on the laundry or with the laundry itself, which would interfere with the cleaning thereof. . In some cases, when "outer" plasticizer is added to the laundry and begins to melt, it forms greasy stains on the laundry, which counteracts the cleansing effect of the stains. In that the zeolite and at least some of the nonionic detergent first come into contact with the laundry, the agent of the invention assists in preventing such undesirable staining. Similarly, when various auxiliaries are retained in the interior of the subject particles, their initial contact with laundry is prevented, which is often desirable. Thus, in the case of fluorescent detergents, such as those of the stilbene detergent type, contact of detergent particles with the laundry is initially prevented by incorporation of the detergent into the interior of the particles, thereby preventing excessive bright spots on the laundry.

The following examples illustrate various embodiments of the invention, but this is not to be construed as being limited thereto. Unless otherwise noted, all parts are parts by weight and all temperatures are given in ° C.

Example 1.

Percentage

Mixed sodium carbonate-sodium bicarbonate builder particles ("Snowlite" I, about 1: 2 weight ratio of Na2CC> 3 to NaHCO3, with particle sizes in the range of 20 to 100 mesh, U.S.A.

s recycle 27.8 "Neodol" 25-7 (non-ionic detergent, condensation product of higher fatty alcohol with an average of 7 moles of ethylene oxide, available from Shell Chemical

Company 18.5 23

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Crystalline zeolite of type 4A with high ion exchange capacity ("Zeolite" CH-252-91-1 with particle sizes in the range of 170 to 270 mesh, with final particle sizes in the range of 3 to 7 microns with an average of about 5.2 microns, is available from JM Huber

Corporation) 46.3

Distearyl dimethyl ammonium chloride ("Arosurf" TA-100, 95% active ingredient as a particle size powder in the range of 80 to 160 mesh, available from Ashland

Chemical Company) 7.4

The carbonate-bicarbonate builder grains are filled at room temperature (25 ° C) on a sloping drum of 8 ° inclination, which drum rotates at a speed of approx. 40 rpm and within 5 minutes, the nonionic detergent at 30 ° C is sprayed onto the moving surface of the particles, after which mixing in the drum is continued for an additional 5 minutes, and then the zeolite powder is mixed with the product, also for an additional 5 minutes. . The non-ionic detergent is sprayed in the form of small droplets having a diameter mainly in the range of 0.149 to 0.297 mm, and during the spraying and subsequent mixing the particle sizes of the contents of the mixer increase somewhat and all fine material present is agglomerated to lie. in the range 0.149 25 to 0.84 mm. The zeolite addition is performed over approx. 5 minutes (times from 1 to 10 minutes are typical), and at the end of this time, the intermediate particles are spherically in range from 0.42 to 4.76 mm. Then, the powdered fabric softener is mixed with the builder non-ionic detergent-zeolite intermediate, and mixing is continued for 8 minutes, during which the softener particles adhere to the larger particles.

2

The resulting product has a non-stamped room weight of approx. 0.8 g / cm and is free flowing. It is packaged and stored, and there is no unfortunate baking or lumping on storage under usual storage conditions during normal storage times. When a package thus stored is opened, the detergent softener can be easily poured and the room weight is approx. 0.8 g / cm.

24

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When subjected to real laundry or practical laundry tests, the product is found to be non-dusting, free-flowing, non-caking and has acceptable cleaning and softening properties for commercial applications, as compared to tri = 5 polyphosphate-containing detergent emollients with similar contents of active ingredient. The zeolite is not adversely deposited on laundry and does not brighten the colors of dark colored laundry, and the carbonate has no adverse effect on the cotton, polyester and acrylic materials which are washed, due to the presence of the bicarbonate which results in the the wash water has a pH of approx. 9.8. Also, no accidental greasy stains appear on the laundry resulting from the melting of the plasticizer thereon, apparently due to the fact that the plasticizer is largely protected from initial contact of the bulk with the laundry 15 by the zeolite on the particle surfaces.

In a comparison experiment, finely divided powders of sodium carbonate and sodium bicarbonate are used with particle sizes in the range of 0.053 to 0.88 mm, which particles are agglomerated to a particle size in the range of 0.149 to 0.84 mm in preliminary treatment with 5 wt% of a 20 % aqueous cornstarch paste sprayed onto the moving particles of the powdered carbonate and bicarbonate in the same mixing drum as previously described in about

3 minutes, with the drum rotating at low speed, e.g. 10 rpm minute. The resulting product is a useful detergent softener at the same concentration used in the previous experiment (1/4 to 1/2 cup or about 45-90 g / ml).

65 liters of wash water), where portions of approx. 4 kg of contaminated garments, but it is not as free flowing as the detergent plasticizer described above. When only sodium bicarbonate is used as the starting builder salt, the product does not wash as well as the preferred product described, and when the carbonate is used alone, the product is more alkaline than desirable and not as free flowing. However, the carbonate-containing agent is useful as a detergent softener in applications where higher pH values can be tolerated, although it will not be as acceptable in the retail market as the preferred products of the present invention as available from its relatively poor stretching characteristics.

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In a modification of the above example, the "Arosurf" particles are melt agglomerated to sizes in the range of 4.76 to 0.42 mm before adding the remainder of the agent. Due to the similar particle sizes, there is no segregation of softener from the pre-made rounded grains, but in some cases a slight "fatness" can be observed on washed laundry, although some such is usually not considered severe enough that it average consumer will find it unfortunate.

In another modification of the example, the plasticizer is fused with the nonionic detergent and sprayed onto the base grains so that it is absorbed in the interior thereof and receives a minor portion thereof on the surfaces of such grains before coating them with zeolite particles.

The product produced has the same desirable high room weight and particle sizes as previously described and is an effective detergent softener in which the softener is protected from initial contact with the laundry, thereby avoiding unwanted staining.

Similar results are obtained when the molten quaternary ammonium halide softener softener is sprayed onto the ground particles during drumming followed by spraying of nonionic detergent as well as "powdering" of the zeolite powder. In this latter embodiment, fluorescent stilbene-type brightener ("Tinopal" 5BM) mixed with "Tinopal" RBS (0.5% and 0.05%, respectively) is mixed with the zeolite before being applied to ionic detergent coated grains. Thus, the fluorescent clarifier is effectively prevented from coming into substantial contact with the quaternary ammonium compound and all adverse reactions between these two are inhibited.

30 When used for washing laundry, both the fluorescent detergent and the non-ionic detergent function effectively in the wash water before releasing potentially annoying plasticizer from the particles.

In other modifications of the procedure, a quaternary ammonium = compound is sprayed in liquid form on the surfaces of the zeolite particles before such particles are applied as coatings to the non-ionic detergent coated carbonate-bicarbonate mixture. The resulting product is in properties comparable to those previously mentioned. This is also the case

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precipitated when the powdered quaternary ammonium compound of the above particle size is admixed with the zeolite and such mixture is applied as a coating to the waxy greasy surface of the non-ionic detergent coated base particles. In yet another embodiment of the process, the powdered quaternary compound is adhered to the coating of nonionic detergent on the germ or core particles and zeolite powder is applied as a coating on the outside. Thus, a useful detergent plasticizer having the above described properties is obtained.

10

Example 2.

Percent "Snowlite" In 19 2g "Britesil" ®, hydrate-containing silicate particles (18% H2O, Na2O: Si02 ratio of 1: 2 available from Philadelphia

Quartz Company 9 "Neodol" 25-7 14 20 Type 4A zeolite ("Zeolite" CH-252-91-1) 50

Distearyl dimethyl ammonium chloride ("Arosurf" TA-100) 8 The "Snowlite" particles are filled at room temperature on the sloping drum of Example 1, rotating at 12 rpm. minute. The hydrate-containing silicate, which conveniently has approx. The same particle size is added to the drum under mixing over approx. 2 minutes, and the mixture is continued for a further 3 minutes until uniform 3Q mixing of the silicate with the carbonate-bicarbonate particles. For a further 5 minutes, the nonionic detergent, mixed with the emollient, is sprayed at a temperature of ca. 50 ° C on the moving surfaces of the particles preheated to 40 ° C. From this point on, the procedure is the same as in Example 1. The resulting product is an excellent, concentrated, high performance

ISLAND ISLAND

the non-phosphate detergent softener useful for washing laundry at a concentration of 0.1 to 0.2% 27

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in the wash water (0.15% is most frequently used in top-loading washing machines. The product has a weight of about 0.7 to 0.8 g / cm and it is free flowing after normal storage without the use of a protective carton. of hydrate-containing silicate helps to enhance the builder effects of the detergent and also improves the anti-corrosion effect thereof compared to the products of Example 1, although these products are also satisfactory in both of these respects.

Example 3

10 Percent "Snowlite" I 27 "Neodol" 25-7 19.5 "Neodol" 25-3S (sodium polyethoxy higher fatty alcohol = hollow sulfate [C12-15 alcohol and 3 moles ethylene oxide per mole], 60% active ingredient, 25 % 1 50 and 15% C 2 H 2 OH, available from Shell Chemical Company) 4 20 Zeolite of type 4A ("Zeolite" CH-252-91-1) 40

Distearyl dimethyl ammonium chloride 10

The preparation procedure of Example 1 is followed where applicable, except that "Neodol" 25-3S is mixed with "Neodol" 25-7 and the two are sprayed on the "Snowlite" particles. The resulting product is an excellent high performance detergent softener which is free flowing, non-sticky, non-sticky upon storage and * 3 has a desirable high room weight (0.6 to 0.8 g / cm). Due to the content of the additional anionic detergent, this product is slightly better as a detergent than the product of Example 1. No adverse interaction between the anionic and cationic materials present arises from storage due to the separation of the two material types and particles. In a modification of the procedure of the example, the cationic plasticizer for the base particles is combined with the nonionic detergent, and the anionic detergent is mixed with the zeolite and added to the principal particles.

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similar to non-ionic detergent coated particles. In another modification, "Neodol" 25-3S together with some of the "Neo-dol" 25-7 is first added to the carbonate-bicarbonate particles / and further nonionic detergent is then added as a coating for such 5 particles to isolating the anionic detergent from the quaternary ammonium compound added. In yet another modification of the experiment, 0.5% "Tinopal" ® 5BM fluorescent brightener replaces a similar amount of "Neodol" 25-3S and mixes with the "Snow-lite" amount before applying "Neodol" 25-7 and "Neodol" 25-3S thereon.

It is thus isolated from the quaternary compound applied.

All such products have the desired particle sizes, bulk weights and other previously mentioned product characteristics.

Example 4

15

This example describes a further change to the products and methods of the invention whereby additional amounts of nonionic detergent are capable of being incorporated into the product using sequential coating technique. In the foregoing Examples 1-3, the liquid nonionic detergent is applied in sufficient quantity to penetrate the interior of the "Snowlite" particles or other base particles, with an excess such that it wets the surfaces of the the particles in order to cause the zeolite powder to adhere to such surfaces. In some cases, when it is desirable to use a greater amount of non-ionic detergent in the product, thereby producing a more concentrated detergent and following the procedures of Examples 1-3, the excess liquid will cause or promote the formation of an agglomerate or a pasta. By the method of this example, such an undesirable result is avoided and further nonionic detergent is satisfactorily incorporated into the product which is still free flowing and has high room weight. By this method, particle size can also be increased in the desired manner.

The procedures of Examples 1-3 are followed, but in each case an additional 5 parts of the nonionic detergent, based on 100 parts of product obtained by performing the procedures of said Examples, are sprayed onto the product and a further 10 parts of zeolite are mixed .29

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then with the product to be adhered to the nonionic coating thereon (using the spray and mixing procedures described in Examples 1-3). The particle size increases approx. 5% (diameter), but the product still has approx. the same bulk density as previously obtained and is still free-flowing and without clumping.

5

In further tests, an additional 5 parts of the nonionic detergent is sprayed onto the two-stage product and another 10 parts of the zeolite is powdered on this product with similar desirable results (using the same spray and mixer methods).

10

In carrying out the described sequential concentration and coating operations, the "Snowlite" amount or other ground particles as well as the softening quaternary ammonium compound will usually not be reapplied, but this may occur when advantageous. Usually as many as six coating operations can be used, but it is preferred that they be limited to three such operations, as described in the "further experiment" described herein. It is also preferred that, in the coating operations following the first coating, the total amount of nonionic detergent and zeolite be limited to the amounts used in the first coating, and preferably 20 to half such amounts, the amounts of the nonionic detergent and the zeolite are within the amounts indicated by the percentages mentioned above.

Example 5

25 -

The procedures of Examples 1-4 are repeated, using "Snowlite" II instead of "Snowlite" I, and the crystalline zeolites of types X and Y of similar particle sizes and amorphous zeolites are used instead of the type 4A zeolite and "Neodol" 23-6,5 and 30 "Neodol" 45-11 and "Alfonics" 1618-65 and "Alfonics" 1412-60 are used instead of "Neodol" 25-7, and "Aliquat" H226 and 400, "Arquad" 2HT -100, "Culversoft" WS paste as well as "Varisoft" 100 replaces "Arosurf" TA-100, thereby obtaining similar free-flowing detergent softeners with high room weight. The only changes in the preparation technique consist in maintaining the temperature of the nonionic detergent at a sufficiently high level to ensure that the detergent is present.

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30 is in liquid state when sprayed onto the surfaces of the ground particles. Furthermore, the quantities of the various components are modified - 10% and - 30%, being kept within the percentages and quantities mentioned above. Care is taken to ensure that the amount of nonionic detergent used is such that an unabsorbed amount is obtained on the surface of the base grains in the form of an adhesive coating capable of retaining the zeolite particles. When the nonionic detergent is normally a solid, the temperature of the detergent at the time of application of the zeolite is kept sufficiently high so that the 10 zeolite particles will adhere thereto and to the base particles. Also, when the cationic plasticizer is a solid and must be applied to the interior of the base particles. the temperature thereof is sufficiently increased to melt it for such application, either alone or together with the nonionic detergent.

15

The particularly desirable results obtained in the above examples and by following the procedures of the invention for the preparation of the present compositions are unexpected. Although the use of mixed carbonate bicarbonate products (each particle contains such a mixture) of the type described in U.S.A. No. 3,944,500, as absorbents for non-ionic detergents had been proposed, there was no mention that high volume weight products similar to those of the invention could be prepared using such core or base particles. In fact, Wegscheider's salt in the form of carbonate-bicarbonate materials, which often also contains sesquicarbonate, is described as having low bulk weight (range ranges from about 0.4 to about 0.5 g / cm). Although 0.6 g / cm is considered to be a high bulk weight (stamped) for detergent softener products in the present case, the products made in accordance with the present invention will usually have even higher bulk weights, usually about 0.7 g / cm or higher. The presence of the zeolite particles and their adherence to the base particles is not disclosed in any known printing press, and the use of sufficient liquid nonionic detergent to maintain a coating of zeolite particles on the base particles is also not a known feature, despite 31

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of the high liquid absorption of such base particles. Also, the incorporation of a cationic plasticizer into such agents in the various ways described and their protection from reactive materials in the agent and from initial contact with the laundry being washed is also a novel feature. By the method of the invention, a non-segregating free-flowing product of desirable relatively large particle size containing even more non-ionic detergent is prepared than the base particles can normally retain. During application of the nonionic detergent 10 to the core particles which absorb much of the nonionic detergent, the "excess" amount of nonionic detergent forms a coating on the surfaces of the particles, which coating has a greasy or waxy appearance, and the particles. does not agglomerate adversely, but retains the smaller zeolite particles which are then applied. The mixture prior to the addition of the zeolite is not paste-like, but is reminiscent of moist sand, where each particle is not attached to other such particles or is loosely attached thereto. The final products produced are free flowing despite the presence of 10 to 100% of Wegscheider's salt in the form of needles in the base particles, partly because the coating of more finely divided zeolite helps to round them and make the particles spherical. Furthermore, the relative locations of the various components of the product grains are desirable in a functional manner and the buffering effect of the base particles when using carbonate-bi = carbonate is useful during washing (the pH in a 0.1% aqueous solution of "Snowlite"). types are about 9.8).

It is believed important that the finished product particles be in the range comprising the relatively large sizes given to the particles, but when the conditions of the above examples change (usually using smaller base particles) so that less particles, e.g. such as in the range of 8 to 100 mesh, higher room weights are obtained than the room weights of conventional detergent plasticizers, and the products manufactured are useful for various detergent plasticizers applications, although not as free flowing or attractive as the preferred embodiments. for the products of the invention.

The invention has been explained in connection with exemplary embodiments and illustrations thereof, but is not to be limited thereto, since it is clear that the person with the right to the object in the description given

Claims (11)

A free-flowing part in a kel-shaped detergent plasticizer, one prepared by an agglomeration process and having a weight of at least 0.6 g / cm 3 and particle sizes in the range of 0.42 to 4.76 mm, characterized in that it comprises - 10 ter core or base particles of an alkali metal builder salt selected from sodium carbonate blended with sodium bicarbonate, sodium carbonate, sodium bicarbonate, pentane sodium tripolyphosphate, tetrasodium pyrophosphate, sodium silicate, borax, and similar mixtures of potassium salts, liquid or paste-like non-ionic detergent in the interior of these particles or on their surfaces and coated with calcium ion-exchanging zeolite particles with a final particle diameter in the range of 0.005 - 20 µm, adhering to the non-ionic detergent's surface salt particles, and a waxy quaternary ammonium compound as plasticizer placed externally on or inside said particles wherein said zeolite has the following chemical formula: 25 (M 2 O) (Al 2 O 3) γ (SiO 2) z xw 20 20 where M is sodium or potassium, y is 0.8 - 1.2, z is 1.5 - 3.8 and W represents the water content of approx. 1.5 to 36% by weight of said zeolite and the weight percent of said builder salt, said nonionic detergent, said zeolite and said plasticizer 30 are in the ranges of 20 - 40%, 12 - 30%, 30 - 60% and 4 - respectively. 12%. An agent according to claim 1, characterized in that the base salt base particles comprise alkali metal carbonate and alkali metal bicarbonate in a weight ratio in the range of 1:10 to 10: 1 and have particle sizes in the range of 0.149 to 0.84 mm, the zeolite being selected from crystalline, amorphous and mixed crystal 1 insect-amorphous zeolites of types A, X and Y, that the nonionic detergent is a higher fatty alcohol polyethylene of Uwam JJ ama a 1 1 U »m 1 Λ _ 1 O aam. DK 152589B bon atoms, and the polyethylene oxide has 3 to 15 moles of ethylene oxide per and that the softening quaternary ammonium compound is a normal solid quaternary ammonium in umha 1 and i in d in particulate form, which adheres to the outer surface of the resulting particles. in An agent according to claim 2, characterized in that the alkali metal bicarbonate is sodium carbonate, the alkali metal bicarbonate is sodium bicarbonate, that the mixture of sodium carbonate and sodium bicarbonate includes Wegscheider's salt and that the weight ratio of Na 2 CO 3 to NaHCO 3 is in the range: 1 that the zeolite is a type A zeolite with a finite particle size in the range of 3-12 microns and a moisture content of 10-25%, that the nonionic detergent is a condensation product of a higher fatty alcohol of 10-18 carbon atoms and 6 to 12 moles of ethylene oxide per mole, that the softening quaternary ammonium compound is a di-higher-alkyl, di-lower alkyl quaternary ammonium chloride, and that the finished product has mainly spherical particles. 20 An agent according to claim 2, characterized in that the resulting particles are coated with a normally liquid or paste-like nonionic detergent coated with ion-exchanging zeolite particles. An agent according to claim 1, characterized in that the major part of the plasticizer is located in the interior of the outer surface of the base particles. An agent according to claim 1, characterized in that the plasticizer and the nonionic detergent are found within and on the surface of said base salt base particles. Process for the preparation of a free flowing particulate detergent plasticizer having a weight of at least 0.6 g / cm 3 and particle sizes in the range of 0.42 to 35 4.76 mm according to claim 1, characterized in that a) nonionic liquid detergent is mixed with builder salt base particles so that said detergent is absorbed into and supernatant of said builder salt particles, b) the product of step a) is mixed with zeolite particles, whereby the zeolite particles adhere to the surface of the resulting particles, and c) the product according to step b), it is mixed with plasticizer particles having a size in the range of 0.095 - 0.177 mm, whereby said plasticizer adheres to the surfaces of said zeolite coated particles. Process according to claim 7, characterized in that a) the liquid softener is mixed with said builder-salt base particles so that the majority of the softener is absorbed into said builder salt particles, b) the particles obtained in step a) are mixed with said non-ionic liquid. 15, liquid detergent is absorbed so that the detergent is absorbed into and coated with said particles, and c) the product of step b) is mixed with said zeolite particles, whereby the zeolite particles adhere to the surface of the resulting particles. 20 Process according to claim 7, characterized in that a) said plasticizer and said nonionic detergent are mixed together at a temperature sufficient to form a liquid mixture, b) the liquid mixture according to step a) is mixed with the builder base particles. so that said liquid mixture is absorbed into and coating the builder salt particles, and c) the product of step b) is mixed with said zeolite particles, whereby the zeolite particles adhere to the surface of the resulting particles. 30 Process according to any one of claims 7, 8 and 9, characterized in that the obtained product is coated with additional non-ionic liquid detergent, and that this detergent coating is coated with additional zeolite particles with 35 final particle diameters in the range 0.01 - 20 pm. Process according to claim 10, characterized in that the additional detergent is a normal liquid or solid condensate of higher fatty alcohol and polyethylene oxide, wherein the higher fatty alcohol has 10-18 carbon atoms and the polyethylene oxide content is 3-15 mol of ethylene oxide. per. and that the additional zeolite is selected from crystalline, amorphous and mixed crystalline and amorphous zeolites of types A., X and Y, and that the amounts of such nonionic detergent and zeolite subsequently applied does not exceed half the total content of said nonionic detergent and said zeolite in said product. 10 15 20 25 30