NL8301250A - "HEAVY DUTY" TISSUE SOFTENING DETERGENT. - Google Patents

Description

* 4 VO 4713 "Heavy duty" fabric softening detergent.

The invention relates to detergent mixtures. More particularly, it relates to heavy duty particulate wax and fabric softening detergent compositions hereinafter referred to as "heavy duty" intended for both machine and hand washing use. It also relates to processes for preparing a component of such mixtures (substantially grit-free agglomerated bentonite).

Heavy duty detergent mixtures suitable for machine washing of textile materials are everyday household products 10 which are widely used in house washing all over the world. British patent applications 404,413 and 461,221 disclose that laundry blends for clothing containing bentonite, synthetic anionic detergent and builder salt "give to fabrics washed therewith a full feel and a soft handle". Bentonites have a longer history of use in soap and detergent products such as fillers and adhesives, and it has also been recognized that fabrics are softened by the deposition of bentonite thereon from aqueous baths? see U.S. Patent 3,594,212. Several such uses for bentonite and other suitable clays have also been described in more recent patents. For example, various softeners are described in British Patents 1,404,898? 1,401,726? 1,455,873? 1,460,616? 1,572,815? U.S. Patents 3,936,537? 4,141,847? and British patent application 2,063,289. However, some bentonites do not contain significant amounts of exchangeable monovalent metal ions and are therefore not good softeners, and some contain harmful amounts of grit making them unacceptable as washing detergents. However, using the present invention, such bentonites can be successfully used to prepare softening detergent components and detergent mixtures with excellent operating characteristics can be prepared.

According to the invention, a bleaching and fabric softening heavy duty particulate detergent composition for washing with water in the laundry comprises 3-10% of a sodium salt of a synthetic organic anionic detergent selected from the group consisting of 8301250 F ϊ -2-sulfonates and sulfates, 1-8% of a nonionic detergent, 0-10% of a water-soluble alkali metal soap, 20-75% of a builder for the synthetic organic detergent, 5-35% of a bleach that is raised in aqueous solution at temperature releases oxygen and 5-25% of an agglomerated bentonite with particle sizes ranging from Nos 10 to 100. In preferred embodiments of the invention, the anionic detergent is a sodium linear higher alkyl benzene sulfonate, it is nonionic detergent a condensation product of a higher fatty alcohol and polyethylene oxide, a hydrogenated tallow fatty acid soap is present, the builder salt is mainly pentana trium tripolyphosphate or NTA or a mixture thereof (with a small amount of sodium silicate also present) the bentonite is a swelling bentonite with a moisture content of at least 3% and the bleach is sodium perborate. Also included within the invention are methods of preparing substantially grit-free swelling bentonite agglomerates and detergent mixtures containing such bentonite.

The synthetic organic detergent (s) used will be nonionic or anionic detergents in combination, but suitable amphoteric or ampholytic detergents, such as those sold under the tradename Miranol, can also be used in combination with nonionic and anionic in the present mixtures . Cationic detergents, such as the quaternary ammonium halides, for example those sold under the trademark Arosurf, can also serve as an additional fabric softener in these products but will not normally be used and if present they will not be spray dried with any anionic detergent such as due to an unwanted reaction that may occur. These classes of materials are well known and have been repeatedly described in the detergent field. Since they are not preferred components of the invention, no further description thereof will be given.

Various synthetic anionic organic detergents such as those characterized as sulfonates and sulfates, usually as alkali metal or sodium salts, can be used, but those which are preferred are the linear higher alkyl benzene sulfonates, 8301250-4-3-higher alkyl or fatty alcohol sulfates and higher fatty alcohol polyethoxy or polyethoxylate sulfates. Preferably, in the higher alkylbenzene sulfonates, the higher alkyl is linear and contains 10-14 carbon atoms, more preferably 11-13, e.g. 12, and the sulfonate is a sodium salt.

The alkyl sulfate is preferably a higher fatty alkyl or alcohol sulfate having 10-16 carbon atoms, more preferably 12-14 carbon atoms, eg 12, and is also used as the sodium salt. The higher fatty alcohol polyethoxysulfates will likewise have 10-18 carbon atoms, more preferably 12-16, for example 12, in the higher fatty alcohol, the ethoxy content will preferably be 3-30 ethoxy groups per mole, preferably 3 or 5-20 and the detergent will be a sodium salt. Thus, it is seen that the alkyl groups of the sulfonates and sulfates are preferably linear or fatty higher alkyls of 10-18 carbon atoms, the cation is preferably sodium, and when a polyethoxy chain is present, the sulfate is at the end thereof. Other suitable anionic detergents include the higher olefin sulfonates and paraffin sulfonates, for example the sodium salts in which the olefin or paraffin groups have 10-18 carbon atoms. Specific examples of the preferred detergents are sodium R-20 dodecylbenzene sulfonate, sodium tallow alcohol polyethoxy (3 Eto) sulfate and sodium hydrogenated tallow alcohol sulfate. In addition to the stated preferred anionic detergents, others from this group may also be present, especially in only minor amounts with respect to the aforementioned. Mixtures thereof can also be used and in some cases such mixtures may be better than the individual detergents. The various anionic detergents are well known in the art and are described in detail on pages 25 to 138 of the article Surface Active Agents and Detergents,

Full. II, Schwartz, Perry and Berch, (1958), Interscience Publishers, Inc).

Although various non-ionic detergents with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxy-containing aromatic and aliphatic bases, such as nonyl phenol, and oxo-type alcohols, it deserves highly preferred that the nonionic detergent be a higher fatty alkoxy poly-lower alkoxy lower alkanol which can also be described as a condensation product 8301250

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-4- of ethylene oxide (and / or propylene oxide) and a higher fatty alcohol.

In such products, the higher fatty alkoxy or alcohol contains 10-16 carbon atoms, preferably 12-15 carbon atoms, and the nonionic detergent contains about 3-20 lower alkoxy groups, preferably 5-15, and more preferably 9-13 ethylene oxide groups per mole , for example 11.

The synthetic organic detergent builder which will enhance the detergent wash performance is either a water-soluble or water-insoluble builder or a mixture thereof. Of course, mixtures of water-soluble builders can also be used, for example polyphosphate and NTA (nitrilotriacetic acid salt, normally the sodium salt), but of the water-insoluble builders usually only the zeolites are used, although mixtures of such zeolites have also been found to be advantageous. Although zeolites are common components of the present blends, it will generally be preferred to use a water-soluble builder or water-soluble builders and often these will be the only builder present or the only builders present.

The water-soluble builder or mixture thereof may be one or more of the usual materials used as builders or proposed for such purpose. They include inorganic and organic builders and mixtures thereof. Among the inorganic builders are preferred the various phosphates, preferably polyphosphates, for example tripolyphosphates, pyrophosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate. Trisodium 25 nitrilotriacetate (NTA), preferably used as the monohydrate and other nitrilotriacetates, such as disodium nitrilotriacetate, are also preferred organic builders. The designation NTA, which normally stands for nitrilotriacetic acid, is also used in this application to refer to its various salts, in particular the alkali metal salts and most preferably the trisodium salt.

Sodium tripolyphosphate, sodium pyrophosphate and NTA can be used in hydrated forms, which are often preferred, but anhydrous forms can also be used. Of course, carbonates, such as sodium carbonate, are suitable builders and may be used individually or together with bicarbonates, such as sodium bicarbonate, as desired. When using the polyphosphates, it is preferable to have sodium pyrophosphate present with sodium tripolyphosphate in the ratio 1:10 to 10: 1, preferably 1: 5 to 5: 1 relative to each other in a total amount. of both builders approximately equal to those reported herein for the sodium 5 tripolyphosphate. Other water soluble builders contemplated to be effective include the various other inorganic and organic phosphates, borates, for example, borax, citrates, gluconates, EDTA and iminodiacetates. Preferably, the different builders will be in the form of their alkali metal salts, either the sodium or potassium salt, or a mixture thereof, but sodium salts are normally preferred. For example, in certain cases when neutral or mildly acidic detergent mixtures are prepared, acidic forms of the builders, especially the organic builders, may be used preferably, but normally the salts will be either neutral or basic in nature. The silicates, preferably sodium silicate with Na 2 O: SiO 2 ratio in the range from 1: 1.6 to 1: 3.0, preferably 1: 2 to 1: 2.8, e.g. 1: 2.35 or 1: 2 , 4, also serve as builder / salts but only minor amounts of them will be present.

If large amounts of silicate are desired in the detergent mixture, it may be advantageous for hydrated sodium silicate particles to be added subsequently to spray-dried particles containing other builders.

The water-insoluble builders as this term is used in the present specification are those that help improve the detergent performance of synthetic organic detergents, in particular that of synthetic anionic organic detergents, and in such cases the mechanism of the enhanced detergent appears to be related to the water softening effect of the builder, such as calcium and / or magnesium ion removal from the wash water, usually by an ion exchange mechanism. Although it is within the scope of the invention to use water-soluble builders other than the zeolites, practically the zeolites are currently used as the most important of such insoluble builders.

The zeolites used include crystalline, amorphous and mixed crystalline amorphous zeolites of both natural and synthetic origin. Preferably, such materials are capable of reacting with calcium ions sufficiently quickly that alone or combined with other water softening compounds in the detergent, they soften side wash water before undesired reactions of such ions with other components of the synthetic organic detergent mixture 5 take place. . The zeolites used may be characterized as having a high exchange capacity for calcium ion, which is normally from about 200-400 or more milligrams equivalent of calcium carbonate hardness per gram of the aluminosilicate, preferably 250-350 mg eq./g.

Although other ion exchange zeolites can also be used, normally the finely divided synthetic zeolite builder particles used in the present invention will have the formula: <Na20> x. <ai203> y. (SiO2) z.wH2O in which formula x is 1, y is 0.8-1.2, preferably about 1.2, z is 1.5-3.5, preferably 2-3 or about 2, and w is 0-9, preferably 2.5-6. The zeolite should be a monovalent cation-exchanging zeolite, i.e. it should be an aluminosilicate of a monovalent cation such as sodium or potassium.

Crystalline types of zeolites useful as good ion exchangers in 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 suitable, especially when type A zeolite is present. These crystalline types of zeolites are well known in the art and are further described in Zeolite Molecular Sieves,

Donald W. Breek, 1974; John Wiley & Sons. Typical commercially available zeolites of the above structural types are listed in Table 9.6 on pages 747-749 of the reported work, which table is considered incorporated herein. Also suitable zeolites have been described in many patents in recent years for use as detergent mixture builders.

8301250 -7- - «

Crystalline zeolites with ion-exchange and water-softening properties that are preferred are those that are in hydrated or water-laden form, containing bound water in an amount of about 4% to about 36% of the total weight of the zeolite, depending on the type of zeolite used, and are preferably hydrated to about 15-70% of their capacity. Normally, water contents are in the range of about 5-30%, preferably about 10 to 15-25%, such as 17-22%, e.g. 20%.

Preferably, the zeolite should be in a finely divided state with an ultimate particle size of up to 20 µm, for example 0.005 or 0.01 to 20 µm, more preferably 0.01-15 µm, for example 3-12 µm, and most preferably 0 0.01-8 µm mean particle size, for example 2 µm, if crystalline and 0.01-0.1 µm, for example 0.01-0.05 µm if amorphous. Although the extreme particle sizes are much lower, 15. zeolite particles usually have dimensions in the range of the screen nos. 100-400, preferably 140-325. However, they can sometimes be agglomerated individually or with spray-dried detergent mixtures to sizes such as those of the particles, for example, 10% or 25%.

Although sodium sulfate and sodium chloride and other filler salts do not have builder properties, they are sometimes used in detergent mixtures because of their filler properties and sodium sulfate is particularly suitable as a processing aid. In addition to increasing the volume and weight of the product to aid metering, they also sometimes improve the grain stabilities and physical properties of the detergent blend granules in which they are incorporated. However, since the present mixtures are satisfactory without any filler present, they are often completely avoided or the amounts contained therein are only minor.

The emollient clay, which is an important component of the detergent compositions herein, is of the type characterized as "bentonite". Bentonites are colloidal clays (aluminum silicates) that contain montmorillonite. They are of varying composition and are produced from natural deposits in many countries, including Italy, Spain, Russia, Canada, 35 and the United States (in particular

Wyoming, Mississippi and Texas) won. The bentonites suitable according to the present invention 8301250-8 are those which have lubricity and dispersion properties which are found to be associated with water swelling ability. Although some bentonites, primarily those that can be characterized as calcium (or magnesium) bentonites, have low or negligible swelling capabilities, they * can be converted or activated to improve this swelling ability. Such conversion can be effected by suitable treatment with an alkaline material, preferably an aqueous sodium carbonate solution, in a known manner for introducing a monovalent metal, such as an alkali metal, for example sodium (or potassium) in the clay structure instead of the divalent alkaline earth metal or magnesium. In addition to the swelling ability of the bentonite, thereby promoting fabric softening and dispersancy thereof, the alkali or alkali metal carbonate solution treatment of the non-swelling clay or poorly flowing clay replaces, for example, 5-100%, 10-90% or 15-50 % of the exchangeable calcium and / or magnesium by sodium (or potassium), thereby improving the exchanging ability of the clay for water hardness ions, such as that of calcium and magnesium.

The resulting by-products, calcium carbonate and magnesium carbonate, are left in the bentonite and are found to have desirable additive properties in the final products. Any excess sodium carbonate can act as a builder in the finished detergent mixture.

Although ion exchange capabilities of bentonites have been reported in the patent literature as relevant to emollient, it is a feature of the present invention that good fabric softening is achieved with sodium bentonites containing. relatively low ion exchange capabilities. Whether the swelling bentonite (also referred to herein as sodium bentonite which will in most cases be the exchanging metal sodium) is a naturally occurring clay or is obtained by an alkali treatment of a non-swelling or poorly swelling bentonite it may be used in the present textile softening detergent mixtures. Treated Italian bentonites have proven to be particularly suitable for European markets. For US markets, Wyoming bentonite often deserves recommendation, and this need not be treated because it already contains sodium ion in its structure and has swelling properties.

8301250 ί —9—

Analysis of a typical Italian bentonite (after alkali-treatment) shows that it contains 66.2% SiC ^, 17.9% Al ^ O ^ / 2.80% MgO, 2.43% Na2O, 1.26% Fe ^ ^, 1.15% CaO, 0.14% TiO2 and 0.13% K20. A typical Wyoming or Westembentonite (untreated) contains 64.8 to 73.0% SiO2, 14 to 18% 5 a12 ° 3 'lr & up to 2.7% MgO, 0.8 to 2.8% Na20, 2.3 up to 3.4% Fe 2, 1.3 to 3.1% CaO and 0.4 to 7.0% K 2 O. Thus it is noted that the compositions of the bentonites are completely different, although both types have swelling properties. It is contemplated that if the Na 2 O content of the clay is at least about 0.5%, preferably at least 10 1%, and more preferably at least 2% (an equivalent amount of K 2 O may also be taken), the clay will be satisfactorily swelling for the objects of the present invention having satisfactory softening and dispersing properties in aqueous suspension (swelling of the bentonite promotes breaking of the bentonite agglomerate).

Although amounts of the various components of the swelling bentonites (which may be referred to hereinafter as sodium bentonites, whether natural or activated) are expected to result in suitable components of the present mixtures within the ranges between the typical analyzes given, it is also contemplated that the percentages of the components of the natural swelling bentonite can be increased or decreased by about 10% and typical analyzes of the treated bentonites can be extended by ± 10%, while the bentonites are still suitable within these ranges. Furthermore, other swelling bentonites can be at least partially substituted. Generally, the suitable bentonites will have swelling capabilities of at least 1 or 2 ml / g, more preferably at least 5 or 10 ml / g. Bentonites with higher swelling capacity are of course also suitable. Normally, the swelling range will be 5-30 ml / g and will usually be in the range 5-20 ml / g.

The sodium bentonite or swelling bentonite will be agglomerated before it is mixed with spray dried molded detergent granules and any additives subsequently added.

Such an agglomeration will be carried out in a known manner such as using water or spraying with an aqueous binder on tumbling bentonite powders, extrusion, compacting, pan agglomeration or other techniques. However, it is highly desirable that the bentonite be a particulate powder prior to agglomeration so that when the agglomerates in the wash water are broken, the bentonite particles will be small enough to be effective lubricants as deposited on the laundry. Therefore, it would normally be desirable for substantially all of the bentonite powder to give a No. 100 sieve passes (US sieve ranges) with at least 99% passing such a sieve and more than a larger amount of it passing a sieve No. 200 passes with less than about 30% by weight of the 10 particles that do not pass through such a screen, and more preferably with more than 20% remaining on such screen. Of course, the extreme particle sizes are smaller.

Also of interest in promoting breakage of bentonite agglomerates and dispersion in the wash water so that their very small particles can be adhered to the textile fibers to soften them is the moisture content of the bentonite. While it is desirable to limit the free moisture content of the bentonite used to about 10% or so, with moisture contents above 15% not normally used, it is even more important to ensure that the bentonite contains sufficient free moisture, much of which is believed to be present between adjacent plates of the bentonite to promote rapid disintegration of the bentonite and all adjacent materials in the particles when such particles of detergent mixtures containing them are contacted with water, such as wash water. It has been found that at least about 2%, preferably at least 3%, and more preferably about 4% or more, water should be present in the bentonite (so-called "internal" moisture) and the bentonite should not be dried so that less than such percentages of water are even temporarily present in it. In other words, over-drying to an extent where the bentonite loses its internal moisture can significantly reduce the utility of the present blends. If the bentonite moisture content is too low, the bentonite does not promote satisfactory swelling and disintegration of the agglomerated granules in the wash water.

Preferred swelling bentonites of the types described above are sold under the trade names Laviosa and Winkelmann, 8301250 * -11- e.g. Laviosa AGB and Winkelmann G 13, both of which are treated Italian bentonites and Mineral Colloid No. 101 (and other similar designations) corresponding to Thixo-Gelen No's 1, 2, 3, and 4 (marketed by Benton Clay Company, a sister-5 organization of Georgia Kaolin Co.). As will be described later, the treated bentonites will also preferably be free of grit, preferably in that they have been further treated by grinding to a fine agglomeration powder. Usually, the commercial bentonite used will have a pH in water (at a 6% concentration) in the range of 8 to 9.4, a maximum free moisture content of about 8%, a specific gravity of about 2.6 and a viscosity at 10% concentration in water in the range of 5 to 30 cps, preferably 10 to 30 CBs.

The water-soluble soap, which is a desirable component of the present detergent compositions and which has a useful scum-limiting effect in the wash water which is particularly suitable for side loading or horizontal tub washing machines, is normally a higher fatty acid soap of an alkali metal, such as sodium or potassium with sodium soaps being very preferred. Such soaps are known and need not be described in detail. It is sufficient if they are stated that they can be prepared from natural fats and oils such as those from animal fats and lubricants and from vegetable and seed oils, for example, talc, hydrogenated talc, coconut oil, palm kernel oil and corresponding "natural" and synthetic fatty acids and that they normally have 10-24 carbon atoms, preferably 14-18 carbon atoms. These soaps are preferably hydrogenated talc or hydrogenated talc fatty acids, for example stearic acid. The water-soluble soap that can be incorporated into the present blends will preferably be selected such that there is a desired balance of good detergent properties, an effective foam-reducing effect and other good physical properties. In particular, among these other physical properties are desirable hardness, good binding ability, and little or no tendency to form adhesive gels under conditions of use (such as in the loading compartment of the washing machine).

8301250 -12-

Bleaching agents are usually added to all detergent mixtures according to the invention intended for use in European construction automatic washing machines, which use very hot water (at the boiling point), which under such conditions produces effective and safe bleaching which leads to desirable whiter washed goods. leads. If the temperature of the washing water in the automatic washing machine is high enough, sodium perborate will be chosen as the bleaching agent because the elevated temperature, especially if it is above 80 ° C, for example 90 or 95 ° C, can decompose the perborate and bleach releases oxygen from it. Therefore, the sodium perborate, often referred to as sodium perborate tetrahydrate or sodium borate perhydrate, which will usually have an active oxygen content of at least about 10%, will release such oxygen without the need for the use of an activator or decomposition catalyst. If automatic washing is done at a lower temperature or if the product is intended for use outside the washing machine either in cold or in hot water, for example at temperatures of 20-60 ° C, the sodium perborate will usually not decompose sufficiently to satisfactorily wash the textile material being washed. bleaching and under such conditions an activator or suitable bleach will be used also usually with an activator. Many such systems have been described in the literature, many of which belong to the class of peroxygen compounds, such as persulfuric acid, peracetic acid, permicic acid, perphthalic acid and perbenzoic acid and salts thereof such as the alkali metal and alkaline earth metal salts, for example sodium and magnesium salts. Various activators for such mixtures are known to promote controlled oxygen delivery from hot and cold water systems. Such activators include heavy metal salts such as copper salts and various inorganic and organic compounds described in the art. Among the lower temperature bleaching treatments, magnesium dimonoperoxy phthalate is preferred. Of course, various other oxygen-emitting bleaches, such as the hydroperoxides, may be used, and under the appropriate conditions, chlorine-emitting bleaches may be included in the detergent compositions herein. While it is 8301250

V

• In some cases it may be considered that it is unnecessary * to include a bleach in a detergent mixture, this will normally be used. Particularly in the present mixtures, which contain agglomerated bentonite particles, the perborate will exert a whitening effect on sometimes mis-colored bentonite, which may otherwise be very noticeably mis-colored, due to its highly agglomerated particle size. Even when the agglomerated bentonite is intentionally stained, the per-compound can promote "purification" of the color by removing the mis-color from the base.

Different additives may be present in the "soap" mixture from which base granules or detergent mixtures may be spray dried or such additives may be added afterwards, the manner of addition often being determined by the physical properties of the additive, its heat resistance , its resistance to degradation in the aqueous "soap" medium and its volatility. Among the commonly used additives are enzyme powders or prills, which are subsequently added to the base grains because they are heat sensitive. It can be any of a variety of commercially available products including Alcalase, Novo 20 Industri, A / S, and Maxatase, both of which are alkaline proteases (subtilisin). Among specific enzyme preparations that can be used are Novo Alcalase 2M (2 Anson units per gram) and Maxatase P 440,000. Although the alkaline proteases are most frequently used, amylolytic enzymes, such as alfa-25 amylase, can also be used. The listed mixtures usually contain active enzymes in combination with an inert powdery carrier, such as sodium or calcium sulfate, and the amount of the active enzyme can be very wide, usually ranging from 2-80% of the commercial formulation. In the present disclosure, the amounts indicated are those of the enzyme preparations, not of the active part thereof.

Among the fluorescent brighteners, the most commonly used are the stilbene brighteners, for example Tinopal 5 BM, especially in extra concentrated form. Amongst the stilbene compounds are cotton clarifiers, such as those sometimes referred to as CC30 / DAS clarifiers, derived from the reaction product of cyanuric chloride and the disodium salt of diamino stilbene disulfonic acid, including variations thereof with respect to substituents on the trazine and aromatic rings. This class of 5 brighteners is known in the detergent field and will most often be used when missing components are not present in the final product. If it is desired that the detergent mixture contains a bleaching agent, such as sodium perborate or another oxidizing bleaching agent, bleach stable brighteners should be included in the "soap" mixture. Among these may be mentioned the benzidine sulfone disulfonic acids,. Naphthotriazolylstilbene sulfonic acids and benzimidazolyl derivatives. Polyamide clarifiers, which may also be present, include aminocoumarin or diphenylpyrazoline derivatives, and polyester brighteners, which may also be used, include naphthriazolyl stilbenes. Such brighteners are normally used in the form of their soluble salts, for example sodium salts, but they can be used as the corresponding acids. The cotton brighteners will usually contain greater amounts of the brightness systems used.

If it is desired that the prepared product be fully or partially colored, various suitable dyes and dispersible pigments can be used. When blue dyes, such as Acilan blue or pigments, such as ultramarine blue, are used, they have the dual effect of coloring some or all of the detergent mixture particles, or particles of components of the detergent mixture, and imparting a desired blue tint to the washed laundry. . Coloring agglomerated bentonite particles with suitable dyes or pigments may be particularly desirable because natural bentonite often has a mis-color, so that the agglomerates can be converted from particles that appear dirty to those that have attractive color and appearance.

Fragrances used which are usually heat sensitive and may contain volatile materials including a solvent such as alcohol or a suitable glycol or polyol or hydrocarbon are normally 35 liter synthetic fragrances sometimes mixed with natural components and will generally fix alcohols, aldehydes, terpenes, 8301250-15 agents and / or other normal fragrance components known in the art.

In addition to the listed additives, the flow promoters, anti-hardening materials to prevent premature gelling of the soap soap mixture, dispersing aids, anti-redeposition agents and in some cases additional emollients, for example, cationic softeners such as the quater, may also be present. -nary ammonium halides, for example dimethyldioctadecylammonium chloride However, as previously indicated, the cationic emollients will normally not be used and if used they will be added afterwards.

Of course, water is present in the soap mixer from which the spray-dried component of the present mixture is prepared when it serves as a medium for dissolving or dispersing the various components of the spray-dried granules. Therefore, some water in both free and hydrate form is contained in the product. Likewise, water can be used to agglomerate the bentonite and perborate powders. Although it is recommended that de-ionized water is used so that its hardness ion contents can be very low and so that metal ions that can promote decomposition of any organic materials present will be minimized, tap water will instead become exclusive and sometimes for economic or supply reasons used. Normally, the hardness content of such water will not exceed about 300 ppm as calcium carbonate.

The amounts of the various components in the final product of the invention will be such that a free-flowing, effective cleaning, whitening, fabric-softening detergent is obtained. The amount of the anionic detergent will normally range from 3-10% of the final product, preferably 3-7% and more preferably 4-6%, for example 5%. Usually the nonionic detergent content will range from 1-8%, preferably from 2-5%, for example 3 or 4%. The builder content will generally be in the range of 20-75%, preferably 30-50% (and that is usually preferably completely water-soluble builder salt), and more preferably 30-40%, for example about 35%.

8301250 -1 · 6-

As mentioned previously, sodium tripolyphosphate and NTA are preferred water-soluble builders, which may be the only builders used. When mixed they are used, the mixture will preferably contain 10-90% of one with the remainder consisting of the other such builder 5 and within such ranges preferred amounts may be 20-80% and 40-60% and additional percentages. Similar percentage ranges apply when the builder is a mixture of water-soluble builder salt and water-soluble builder salt such as a zeolite.

The bentonite content of the fabric softening detergent in the form of an agglomerate of finely divided bentonite powder particles will be a satisfactory softening content thereof, which is usually in the range of 5-25%, eg 10-20%, more preferably 14-18%, eg about 16%. The amount of bleach will be in the range of 5-35%, preferably 15-25%, for example 20%.

However, it should be considered that such amounts are based on the use of sodium perborate and will be modified when other oxidizing agents are used to obtain approximately the same bleaching effect (or active oxygen content).

When a fatty acid soap is used, its amount will usually not exceed 10%. A preferred range of soap levels is 2-6%, more preferably 2-4%. The moisture content of the product which does not include the hydrate moisture that cannot be removed during standard heating at 105 ° C for 2 hours will usually be in the range of 3-20%, the higher contents being permissible as a major proportion, at least 1/4 and preferably at least 1/2 of the moisture is in hydrate form. A preferred moisture content is 5-17% and more preferably such a content is 10-15%, for example 10%. Any moisture that is not removed by the above standard test is considered to be part of the compound in which it is present as a hydrate, for example a zeolite.

The total content of various additives which may also be present in the detergent mixture will usually not exceed 20%, preferably be limited to 15% and even more preferably to 10%.

Since water-soluble sodium silicate has builder properties, particularly with regard to its action against magnesium ions in hard water, the amount is included within the total builder content. However, since it also acts as a binder, its amount present will be reported here with other additives for the present blends. Usually it will not be more than 8% of the product 5 with a normal range of 1-5%, preferably 2-4%, for example 3%. Sometimes, to improve the flowability, especially if the silicate content is greater than 3 or 4%, the remainder will be added afterwards as an aqueous silicate. The filler salt content, such as sodium sulfate if present, will also normally be limited to no more than 10% and will normally be 0.5-5%, preferably 0.5-2%, e.g. 1 or 1.5% of the product. The proteolytic enzyme content will normally be 0.1-2%, preferably 0.2-1%, e.g. 0.3%, and the optical clarity dye content will be 0.1-2%, preferably 0.1-0 .5%, for example, about 2%. The fragrance content will normally be 0.05-2%, preferably 0.1-1% and even more preferably 0.2-0.5%, for example about 0.3%. Among other additives, it may sometimes be desirable to have small amounts of special sequestrants and flow promoters present. Among such materials, a preferred sequestrant is diethylene triamine pentaacetic acid, the magnesium salt, but other diethylene triamine acetates can also replace it. Magnesium Silicate is a preferred flow promoter, which can also serve as a carrier for the sequestrant. There is commercially available a mixture of such products comprising 15% of the magnesium DTPA and 85% MgSiO 2 and, if used, its content is preferably 0.1-1%, more preferably 0.1-0.5% , for example 0.2%. Amounts of the sequestrant (or stabilizer) can be from 0.01-0.2%, preferably 0.02-0.1%, and for MgSiO 2, the concentrations are in the range 0.1-0.9%, preferably 0.2-0.5%.

Amounts of other additives used will be such as to achieve the purpose for which they are added, but normally such amounts will not exceed 1 or 2% and will usually be in the range of 0.05-1%.

In addition to the detergent mixture, which includes synthetic organic detergent, builder, bentonite, and bleach, and soaps and additives, the invention also includes detergent mixtures whose bentonite is a disadvantageous debris bentonite and is also preferably one that has been converted to an alkali metal bentonite, such as sodium bentonite, by treatment of a bentonite containing a replaceable magnesium and / or calcium content with an alkali such as sodium carbonate solution. The bentonite used is characterized as essentially grit-free, which means that it contains less than 1% grit particles. The substantially grit-free bentonite will normally contain less than 0.4% tactile hard grit particles, which are water-insoluble and difficult to crush when applied to a hard surface and hammered with a normal hammer. More preferably, less than 0.1% of such grit will be present and such bentonite can be termed grit-free.

In the raw bentonite as mined, the grit content can be up to 15% in some cases, although it is usually less than 5%. Treatment of the bentonite to remove the grit therefrom will be in conjunction with a treatment for increasing the exchangeable monovalent cation content, which will preferably be increased to at least 2% (as Na 2 O) by such treatment. The method of treatment and its advantages will be further explained in detail when method aspects of the present invention are discussed.

For preparing the products of the invention in the spray drying operation, a "soap" mixture containing various components which are desired in the spray dried granule and which are sufficiently stable to withstand the treatment in the soap mixer and the spray drying operation resistant such as detergent, builder and suitable additives spray-dried from an aqueous soap mixture, normally containing from about 40 to about 70 or 75% solids, preferably 50-65% thereof with the balance water. The soap mixture may contain the anionic detergent and some or all of the nonionic detergent, although usually no more than 5% nonionic detergent (based on the final product) will be present in the soap mixer (the remainder is added afterwards). Any builder or mixture of builders will be added nor-35 maliter into the soap mixer, although this is not necessary. The bentonite powder is agglomerated separately and subsequently added to the spray dried product as a colored (tide blue) grain. Silicate aqueous solution, stable fluorescent brightening dye, soap and filler salt are usually added in the soap mixer along with any stable pigment and other dyes that can be used. Instead of using a neutralized detergent, the soap mixer can be used as a neutralizing vessel in which anionic organic detergent acid is neutralized with aqueous caustic. Such an acid can be, for example, dodecylbenzenesulfonic acid containing about 45-50% of the active ingredient which can be neutralized with an aqueous sodium hydroxide solution, such as one containing 38% Na2O. When the detergent acid is prepared by sulfonating the alkylbenzene with sulfur trioxide, the active ingredient content of the acid can be up to 99%. A higher fatty acid mixture can also be neutralized in the soap mixer wherein the detergent acid forms a desired higher fatty acid soap detergent mixture.

The soap mixer mixture can be spray dried in a conventional spray tower, with counter or direct current. Normally the mixture will be at a temperature of 20-80 ° C, preferably 40-70 ° C and will be spray dried in a tower in which the drying air is at a temperature of 200-400 ° C to obtain spray-dried granules with particle sizes in the range of No. 10 to 100 (US sieve ranges) sieves. Any particles that are outside the desired range can be removed by sieving and can be retreated. The prepared granules have a bulk density of 0.3-0.6 g / ml, for example 0.5 g / ml. They have a moisture content in a range that can be 3-20% but will normally be about 10-15%. After the preparation of the spray dried part of the. mixtures, other components thereof can be mixed or sprayed with the granules (and on other components of the product if desired). Generally, this will be preferred for the bentonite, enzyme, bleach and any other particulate products, such as those in powder, agglomerate or prill form, which are intended to be subsequently added to the spray-dried granules for mixing thereafter any liquids to be added later on the 1 8301250 -20 mixture can be sprayed. However, sequences of addition of components afterwards can be varied, and sometimes a portion of a particulate material can be added afterwards after one or more of the liquids. Two or more of the particulate material faucets are pre-mixed before being added afterwards and likewise mixtures of. liquids are prepared. Solvents can be used for various components which are applied as liquids and in some cases emulsions can be used. In some cases it may be desirable to dilute the fragrance with a suitable solvent such as relatively odorless alkylate (hydrocarbon). If nonionic detergent is subsequently added (and it will sometimes be preferred that all nonionic detergent be added in the soap mixer) it can be sprayed on the surfaces of the spray-dried granules or otherwise applied satisfactorily before mixing with the other particulate components.

Also, as previously indicated, the nonionic detergent can be mixed in liquid form with the fragrance to be sprayed on the product, in which case it can act as an emulsifier.

The apparatus for carrying out the various mixing and spraying operations is known and therefore does not need to be described in detail. Spraying can be done through conventional nozzles, usually of a wide spraying pattern, but other types of spraying equipment can also be used. The mixers 25 can be of different construction but preferably comprise rotating inclined tubes or drums within which the spraying is performed. However, V-shaped mixers, especially those with continuous feed and other commercial powder mixers, are satisfactory.

The various mixing and spraying or spraying operations will normally take place at about room temperature, but operations in the range of 10-40 ° C, preferably 20-30 ° C are preferred. The particle sizes of the materials to be mixed will usually be those of the final product within the numbers 10 to 100 or 200 sieve range (the perborate and enzyme ranges can extend to No. 200). The agglomerated bentonite particles 8301250 -21- will result from agglomerations or compaction of finer-distributed particles such as those, of which more than 50% a No. 200 sieve passes. Such particles will be essentially grit-free sodium bentonites. They can be sprayed with a suitable dye or pigment such as Acilan Brilliant Blue FFR and various other suitable dyes can be applied. Sometimes the bentonite agglomerates can be larger than the other particles in the product, for example 10-50% larger in diameter to accentuate their difference. Although Western or Wyoming bentonites can be used to prepare the agglomerates, in many cases the bentonite agglomerates will preferably be bentonite treated with sodium carbonate (such treatment improves the color of mis-color clay) and magnesium carbonate and / or calcium carbonate therein as a result of such treatment.

The sodium carbonate treatment of the crude bentonite will be carried out if the exchangeable sodium content in the bentonite is less than desired for a satisfactory softening and agglomerate dispersing action of the bentonite when its agglomerated granules are added to the wash water. For bentonite containing exchangeable calcium and / or magnesium and insufficiently exchangeable sodium, for example less than 0.5% as sodium oxide, the raw clay containing in many cases grit is ground or otherwise broken and treated with suitable alkali, such as aqueous sodium carbonate, which may be at a concentration in the range of 5-20%. After contacting the clay for an appropriate time which can be from half an hour to 24 hours, the mixture still containing some free excess sodium carbonate (normally 10-50% excess will be used to replace the exchangeable calcium and magnesium) dried. Usually such dried material is often broken into large cakes with a moisture content in the range of 2-15% and then ground into particles with the particles having diameters in the range of 0.8-8 mm. In such a state, the bentonite can be sold commercially for those applications where grit content is not important. However, when the bentonite contains disadvantageous amounts of grit, it is then more narrowed to particles smaller than sieve No. 100 and with at least 8301250 i * -22- at least 50% smaller than 200 sieve. These are then subjected to centrifugal separation or other density-responder separation techniques, e.g. gravity settling, but preferably a cyclone separator is used. The grit is removed and its concentration in the product is driven to below 2%, for example below 0.4%. Then, the bentonite which is now substantially grit-free and contains a sufficient amount of exchangeable sodium to be a suitable component in the softening detergent products of the invention is agglomerated to 10 particles in the desired particle size range by a suitable method as previously described herein.

The products and methods of the invention have many advantages, several of which have already been mentioned. With regard to products, the resulting detergent mixtures are excellent whitening laundry detergents and effectively soften washed goods, as determined by comparative tests compared to similar mixtures, which do not contain bentonite. The products are satisfactorily free-flowing, not dusty and of a desired bulk density and attractive appearance. The bentonite tends to give the washed goods a softer grip but does not cause adverse hydrophobic properties in the washed materials. Bentonite has also been shown to sometimes even increase the moisture absorption rates of tissues, and it acts as a detergent builder and can provide dirt-suspending properties. For example, 9 parts of bentonite is found to be equivalent to about 1 part of sodium tripolyphosphate as a builder for organic detergents. Apparently due to its plate-like structure, the final bentonite particles held by the fiber of the laundry act as a lubricant for such fibers and therefore make them feel soft. Because the particles are so small in size and apparently have desirable optical properties, they do not adversely lighten or discolor the fabrics to which they are attached and deposits them on the fabrics to an objectionable degree regardless of repeated washings with bentonite. -containing detergent mixtures.

The bentonite agglomerates readily disintegrate in the wash water, especially in very hot wash water, and these dissociation are aided by delivery of oxygen from the bleach such as sodium perborate. The agglomerates can be water absorbent with respect to the per-compound without being adhered to other particles in the detergent mixture, at least when relatively small amounts of external moisture are present. In this regard, the bentonite agglomerates can promote the stabilization of the per-compound and help prevent caking of such materials in the spray-dried granules in which most of the other components of the product are present. Although it may sometimes be desirable for the perborates and the enzyme to be coated with other materials to stabilize them and prevent reaction with other detergent blend components, it has not been found necessary in the present blends. Furthermore, with the bentonite in the agglomerated particles not containing the other product components, it is more available for moisture absorption and apparently has a greater anti-caking effect than it would if it were combined with the other detergent components by spray was dried. Also, when spray dried bentonite with other detergent blend components, it may lose some of its softening power and this often makes the present invention preferred. However, in some instances it may be desirable to use part of the bentonite, for example, up to half of it in the soap mixer mixture, in which case it will be present in the spray dried granules and may help promote its rapid disintegration in the wash water. However, it has been found that such spray-dried grains not containing bentonite decompose sufficiently quickly when they are of the particle sizes disclosed herein, so that "internal" bentonite is not required. The perborate detergent and builder components apparently can interact with the bentonite to create sites on the washed fabric for the softener particles. Such sites are thereby physically and chemically cleaned which can improve their endurance for the bentonite. Thus, it is seen that the various components of the present blends can interact with each other to enhance its softening, cleansing and whitening effects.

8301250 -24-

The invention is further illustrated by the examples below. All parts listed therein are parts by weight and all temperatures reported are in ° C unless otherwise indicated. EXAMPLE I

5 A "soap" mixture of a total of 100 parts is prepared by reacting 11.38 parts of dodecylbenzenesulfonic acid (Dobane JNQ) and 5.22 parts of hydrogenated fatty acids (16-18 carbon atoms per mole of fatty acid) with 1.47 parts of sodium hydroxide solution ( 38% Na 2 O) in an aqueous medium containing an appropriate amount (to maintain the reaction) of 29.75 parts of city water (300 ppm hardness as CaCO 2). The rest of that water is used to cool the reaction mixture as desired and dilute other components of the "soap" mixture. Then, 7.56 parts of aqueous sodium silicate solution (Na 2 O 3 SiO 2 = 1: 2.4) with a 44.1% solids concentration, 0.23 parts of fluorescent stilbene clarifier, 0.22 are added to the soap mixer. parts Sydex 808 (85% MgSiC> 3 and 15% magnesium DTPA), 39.14 parts hydrated sodium tripolyphosphate (TPP "H"), 1.69 parts anhydrous sodium sulfate (99.5% pure) and 33.34 parts of a non-ionic detergent, which can be considered as the condensation product of 11 moles of ethylene oxide with one mole of higher fatty alcohol with 12-15 carbon atoms per mole.

The "soap" mixture is heated with stirring for about 1 hour so that its temperature rises to about 55 ° C after which it is pumped after a spray drying tower, where it is sprayed under elevated pressure through a number of spray nozzles in dry air at a temperature of about 300 ° C. Particles with a moisture content of about 12% are the result, most of which are within the numbers 10 to 100 sieve range. Particles outside this area are screened.

63.1 parts of the spray dried powder (bulk density about 0.4 g / cin) are then mixed with 0.3 parts of prilled proteolytic enzyme (Alcalase, from 2 Anson units per gram, although Maxatase P 440,000), 20 parts of granular sodium perborate and 16 parts of agglomerated bentonite. All such powders are of particle sizes within the particle size range for the spray dried detergent mixture component, but smaller particles of the enzyme and perborate can also be used down to about. 200. The bentonite particles consist of 8301250 * - · -25- 82.3 din anhydrous bentonite, 16.1 din water, 1.5 din sodium silicate (as previously described) and 0.06 din Acilan Brilliant Blue dye, with the dye is applied to the surface of the particles. The bentonite particles were prepared by agglomerating finer divided bentonite particles (Laviosa AGB) with the dilute sodium silicate solution (in water) and then painting them. The bentonite used is one which has been treated with sodium carbonate to replace calcium or magnesium therein with sodium and from which a natural content of grit material has been removed after treatment by centrifugal separation. Such treatment methods for the bentonite will be described in this example below. The moisture content of suitably agglomerated bentonite can be varied and can be up to 3% when mixed with other components of the present softening detergent.

0.5 parts of the nonionic detergent and 0.25 parts of detergent fragrance are sprayed on the mixture of the spray-dried granules, enzyme, perborate and colored bentonite particles in a slanting drum mixer. The spraying is adjusted so that the sprayed liquid uniformly coats the particles in the mixer or tumbler drum to produce about 100 parts of uniform product.

The final product has particle sizes within the range of Nos. 10 to 60 sieve, a bulk density of about 0.5 g / cm 2 and a moisture content of about 12% (although this can be reduced to about 8-10% on standing). The resulting particulate fabric softening detergent is non-dusty, free flowing and pleasant in appearance with slightly larger (20-200% larger in diameter on average) blue agglomerated bentonite particles contrasting with the other white particles. While the spray-dried granules 30 and the bentonite agglomerates are apparent, the perborate and enzyme, especially when particles thereof are sized in the lower end of the stated range, may appear to be mixed with the other granules, thereby improving the enzyme appearance. However, they are not agglomerated and if not separate, they can be easily separated from the other such particles and from each other.

8301250 -26-

When the product described is subjected to a practical washing test, it appears to be an excellent detergent with desirable fabric softening properties.

In modifications of the above method, the anionic detergent is replaced with equal weights of sodium lauryl sulfate, sodium hydrogenated tallow alcohol sulfate and sodium tallow alcohol polyethoxy (3 EtO) sulfate, respectively. Alternatively, mixtures of such materials, for example equal parts of sodium dodecylbenzene sulfonate and sodium hydrogenated tallow alcohol sulfate, are used together. In all such cases, the resulting final detergent mixture is one which is an excellent fabric softening solid detergent. Similar results are also obtained when, instead of varying the anionic detergent, the nonionic detergent is changed by replacement with a block copolymer of propylene oxide and ethylene oxide, such as Pluronic L-44 or L-62, nonylphenol polyoxyethylene (12 EtO glycol or a condensation product of fatty alcohol with 3 or 7 moles of ethylene oxide per mole, or with a mixture of two or more such detergents, for example in equal parts. When half or all of the sodium tripoly-20 phosphate is replaced by NTA, the end product is also a satisfactory detergent with softening properties.

If the soap is omitted from the recipe, a reduced foam control results, but, on the other hand, the product is acceptable and as previously described. When the sodium perborate is replaced by other bleaching agents such as sodium persulfate, sodium perisophthalate or magnesium dimonoperoxyphthalate, good bleaching and cleaning by the product is still available. If the bleach is omitted, the resulting laundry detergent mixture will not whiten or remove stains. When known oxidizing agent activators are present, bleaching can be accomplished using the mixture at temperatures lower than those at the boiling point (which are normally used in the methods of this example to obtain maximum bleaching activity). If it is desired to include more silicate in the product, the amount of silicate is doubled by adding similarly large aqueous sodium silicate particles with the other subsequently added particulate solids 8301250-27 afterwards. According to a change in treatment, only the fragrance is sprayed onto the mixture while the nonionic detergent is completely introduced into the soap mixer.

The bentonite agglomerates used in this example are substantially regular spheres consisting essentially of bentonite with a small amount of silicate binder and with a bluing dye on its surface. To prepare them, an Italian clay, low in exchangeable sodium, is treated to increase the sodium content, swelling ability and softening effects.

First, such a clay containing a minor amount, for example about 3%, of hard, black grit material is crushed and reduced in size so that its particles have a No. Pass through 4 sieve after which they are treated with an excess, for example 50% excess, of sodium carbonate solution, such as one at a concentration of about 10%. The mixture is allowed to stand with intermediate mixing periods for a suitable reaction time such as about 4 hours at which point sufficient ion exchange has taken place between the exchangeable calcium and magnesium of the clay to give a typical analysis thereof for Italian bentonite 20 (after alkaline treatment) earlier in this description. As a result of this treatment, the Na 2 O content of the clay has increased significantly (about 2%) and the MgO and CaO contents have been correspondingly lowered.

The clay is then dried, for example to a moisture content of about 5%, after which it is reduced in size to particles desirably smaller than a No. 100 sieve (although sometimes larger sized particles may be present) and subjected to centrifugal air separation in a cyclone separator (although size separation techniques may also be used) to remove the grit. The grit-free bentonite, which contains less than 0.1% grit, and has a swelling capacity of about 5 ml / g and a viscosity of about 15 cPs at 6% concentration in water and with a moisture content of about 7% is then agglomerated according to the previously described method in which the dilute sodium ilicate solution is sprayed onto the surfaces of the moving particles while they are tumbled in an inclined drum. Tumbling is continued until the particles are of the desired dimensions and are satisfactorily rounded. At the end of the drum period, which can last up to one hour on average, a dilute dye solution is sprayed onto the grains to color them and they are then ready to be mixed with the other components to prepare a final detergent product.

EXAMPLE II

An effective softening detergent such as that of Example I is prepared from a "keep" mixture of 10.24 parts of the dodecylbenzenesulfonic acid, 2.81 parts of the hydrogenated fatty acid, 0.81 parts of the lye, 26.54 parts of water, 37.2 parts of pentasodium tripolyphosphate (hydrated), 6.8 parts of sodium silicate solution, 0.21 parts of fluorescent brightener, 1.46 parts of sodium sulfate, and 3.0 parts of the non-ionic detergent added successively. spray dried according to the method described in Example 11 to obtain 62.5 parts of a product of similar bulk density and particle size The spray dried particles are then mixed with 0.3 parts of proteolytic enzyme, 20.0 parts of sodium perborate granules, 16.0 parts of the agglomerated bentonite and 0.2 parts of Sydex 808, and a mixture of 0.3 parts of the detergent fragrance and 0.4 parts of linear alkylate is sprayed on the tumbling powder mixture.

In place of an agglomerated sodium carbonate treated Italian bentonite, from which grit has been removed as in Example I, a competitive grit-free swelling clay product (Winkelmann-25 agglomerate) or a Wyoming-type bentonite, such as that sold under the trade name Mineral Colloid No. 101 (formerly Thixogel No. 1) is used, similar end products are obtained which are good emollient detergents. When the Acilan Blue dye used to color the bentonite agglomerates is replaced with ultramarine blue, good coloring and bluing effects are also obtained.

EXAMPLE III

When the proportions of the various components in the preceding examples are modified ± 10%, ± 20% and ± 30%, keeping them within the ranges previously indicated and with the ratios of anionic detergent to nonionic 8301250 V - -29- detergent is kept in the range of about 1: 1 to 3: 1 / the ratio of total detergent content to builder content in the range of about 1: 3 to 1: 8 and the ratio of sodium bentonite to total detergent in the range of about 1: 1 to 2: 1.5 products with properties similar to those described in Example 1 are obtained. This is also the case when the water-soluble builder salts of Example I are replaced with zeolite A (20% hydrated) and when using any of a variety of synthetic anionic and nfetionic detergents, as well. 10 with an amphoteric detergent, such as one of the Miranol type.

Also, the bentonite agglomerate detergent mixture and its components 3 may have different densities (0.2 to 0.9 g / cm) and sizes (No. 10-40 sieve).

8301250

Claims (13)

Detergent mixture according to claim 1, characterized in that the sodium salt of the anionic detergent is selected from the group consisting of sodium linear higher alkyl benzene sulfonates in which the higher alkyl contains 10-14 carbon atoms, sodium higher in fatty alcohol sulfates in which the higher fatty alcohol is 10-16 contains carbon atoms and sodium higher fatty alcohol polyethoxy sulfates in which the higher fatty alcohol contains 10-18 carbon atoms and which contain 3-20 ethoxy groups per mole and mixtures thereof, the nonionic detergent is a higher fatty alkoxy poly-lower alkoxy in which the higher fatty alkoxy is 10-16 carbon atoms and the lower alkoxy and lower alkanol have 2-3 carbon atoms and which contains 3-20 lower alkoxy groups per mole, the soap is a soap of higher fatty acids, with 10-24 carbon atoms per mole, the builder is selected from the group consisting of water-soluble and water-insoluble builders and mixtures thereof, the bleaching agent is sodium perborate and the bentonite has a moisture content of at least 3% and swells in water with a swelling capacity thereof of at least 1 ml / g. The detergent mixture of claim 2, comprising 3-7% sodium linear higher alkyl benzene sulfonate in which the higher alkyl has 11-13 30 carbon atoms, 2-5% of a higher fatty alkoxy polyalkoxy lower alkanol in which the higher fatty alkoxy has 12-15 carbon atoms, the lower alkoxy and lower alkanol has 2 carbon atoms and the molar ratio of higher fatty alkoxy to lower alkoxy is 1: 5 to 1:15, 2-6% sodium soap of higher fatty acids with 14-18 carbon atoms per mole, 30-50% in water soluble builder salt, 15-25% sodium perborate and 10-20% sodium bentonite. 8301250 -31- The detergent mixture of claim 3 wherein the particles have dimensions in the range of No. 1 to No. 100 O.S. sieve series, the sodium higher alkyl benzene sulfateate, soap and builder salt together are substantially homogeneous particles which have been spray dried from the same soap mixture, the sodium perborate is in separate or separable particles and the bentonite is in separated particles. Detergent mixture according to claim 4, wherein the higher alkyl of the sodium-1 inearic higher alkyl benzene sulfonate is dodecyl, the nonionic detergent condensation is a product of a higher fat alcohol having 12-15 carbon atoms and 9-13 moles ethylene oxide per mole higher fatty alcohol, the soap is a sodium soap of hydrogenated tallow fatty acids, the builder salt is mainly pentasodium tripolyphosphate and the bentonite particles are obtained in the form of agglomerates after sodium carbonate treatment of bentonite, which contains magnesium and / or calcium to produce sodium bentonite , with resulting magnesium carbonate and / or calcium carbonate therewith. The detergent mixture according to claim 5, comprising 1-5% sodium sulfate, 0.1-2% optic brightness dye and 0.1-1% proteolytic enzyme, wherein the agglomerated bentonite particles have mean particle sizes greater than the mean particle sizes of the sputtering dried particles and the perborate particles and are colored differently so that they are easily identifiable in the detergent mixture. The detergent mixture according to claim 6, wherein the sodium bentonite has a swelling capacity in the range of 5-30 ml / g and has a viscosity as a 10% dispersion in water of 5-30 cPs and from an agglomerate of smaller particles. of crushed sodium bentonite from which accompanying grit has been removed after grinding and before agglomerating. The detergent mixture of claim 7, oravattad about 5% sodium linear dodecylbenzene sulfonate, about 3% higher fatty alkoxy poly-lower alkoxy lower alkanol anionic detergent, wherein the higher fatty alkoxy has 12-15 carbon atoms, the lower alkoxy and lower alkanol has 2 carbon atoms, and the molar ratio of higher fatty alkoxy to lower alkoxy is about 1:11, about 5% sodium 8301250 ► Λ * -32 soap of hydrogenated tallow fatty acids, about 20% sodium perborate, about 16% sodium bentonite, about 35% hydrated pentasodium tripolyphosphate, about 3% sodium silicate, about 0.3% proteolytic enzyme, about 0.6% fragrance, about 0.2% optical clarity, and about 9% moisture. Detergent mixture according to claim 1, wherein the bentonite particles are in the form of agglomerated particles obtained after sodium carbonate treatment of bentonite containing magnesium and / or calcium to replace such magnesium and / or calcium with sodium, with resulting magnesium carbonate and / or calcium carbonate. The detergent mixture of claim 9, wherein the sodium bento non-agglomerate has a swelling ability in the range of 5-30 ml / g and has a viscosity as 6% dispersion in water of 5-30 cPs and r from an agglomerate of smaller particles of ground sodium bentonite 15 with accompanying grit removed after grinding and before agglomeration. 11. A method of preparing a heavy duty bleaching and fabric softening particulate detergent mixture for water washing of goods containing 3-10% sodium salt of a synthetic organic anionic detergent or mixture selected from the group consisting of sulfonates and sulfates, 1- 8% of a non-ionic detergent, 0-10% of a water-soluble alkali metal soap, 20-75% of a builder for the synthetic organic anionic detergent, 5-35% of a bleach that releases oxygen in an aqueous solution when -25 high temperature, 5-25% agglomerated bentonite, characterized in that a bentonite clay containing magnesium and / or calcium and grit with sodium carbonate are treated to convert at least some of the calcium and / or magnesium contained therein is present to sodium, thereby obtaining magnesium carbonate and / or calcium carbonate in which the sodium bentonite produced accompanies, comminuting the particles of the resulting p product, removing grit therefrom, agglomerating the grit-free product and spray drying a "soap" mixture containing the sodium salt of the synthetic organic anionic detergent, soap and, if present, builder 35 and blending the bleach in particulate form and the agglomerated bentonite with the spray dried particles to obtain the described product. 8301250 a -_ - Λ -33- 12. A method according to claim 11, characterized in that the agglomerated bentonite particles are larger than the spray-dried detergent mixture particles and the agglomerated bentonite particles are colored blue so that they can be distinguished from the detergent and bleach particles and they have a bluing effect on the goods have been washed with the detergent mixture. 13. A method of preparing a heavy duty textile softening particulate detergent mixture for washing in water containing goods containing a detersive amount of a synthetic organic detergent selected from the group consisting of anionic and nonionic detergents, an amount of a builder for synthetic synthetic anionic detergent and a fabric-softening amount of agglomerated bentonite, characterized in that the particle size of bentonite with accompanying grit is reduced, the reduced bentonite is separated from the grit according to a size or density-dependent separation process, the separated grit-free bentonite agglomerates to particle sizes in the range of Nos. 10 to 100 (US Standard sieve ranges) and mixes the bentonite particles with spray-dried particles comprising the synthetic detergent and builder and having sizes approximately in the range of that of the agglomerated benton not. 14. Process for the preparation of agglomerated bentonite particles -suitable for mixing with spray-dried particles containing a synthetic organic detergent selected from the group consisting of anionic and non-ionic detergents and an anionic detergent builder for preparing fabric softening Tender detergent mixtures, characterized in that naturally occurring bentonite containing an interchangeable bivalent metal selected from the group consisting of calcium and magnesium and mixtures thereof is reacted with an alkali to replace at least some of said divalent metal by a monovalent metal selected from the group consisting of sodium and potassium, the bentonite obtained dries, the particle size is reduced with the grit material therein, then the bentonite separates from the grit material and the bentonite agglomerates to a particle size in the area of No. 10 to 100 (U.S. Standard sieve ranges). 8301250