NL8301249A - FABRICATING DETERGENT. - Google Patents

Description

S.

-1- W. -w V0 4709

Fabric softening detergent.

The invention relates to a detergent mixture and more particularly to particulate heavy duty laundry and fabric softening detergent mixtures intended for use in the washing machine.

It also relates to the method of preparing such mixtures.

Bentonite has advantages as an emollient in detergents.

The softening properties of bentonite and its desired adhesion to substrates are important advantages, but its gelling properties can cause detrimental gum formation in the detergent, whereby detergent granules and / or bentonite granules or agglomerates sometimes tend to adhere to surfaces, causing the free flow is inhibited. This is possible. under conditions of high moisture or in the presence of free moisture bentonite to gel, become tacky or have reduced fluidity, and even become bound to 15 channels or chamber walls despite the application of forces on the particles to remove them (such as the force of running water, which is put in an automatic washing machine). Such adhesion could become very detrimental to a desired free-flowing particulate detergent commercial product and lead to a reduced acceptability of the product by the consumer. Even when flowability through production lines during preparation and packaging. operations and fluidity from the dispensing packages when the product is used by the final consumer are satisfactory, the presence of bentonite can cause the particles of the detergent mixture to adhere to appliance walls, inside the loading compartment walls of washing machines, equipped with means for automatically loading detergent mixture into the wash water in the machine tub or drum when such particles and the bentonite present are wetted. Under such conditions, the bentonite may tend to swell to yield moist adhesive surfaces, so that the particles can resist removal of surfaces on which they rest. For example, in washing machines and other appliances equipped with automatic dispensers or loading compartments, the detergent particles may not completely fall off the dispenser or be washed out of the organ, especially if the walls of the dispenser are moist for the addition of the detergent. Failure to deliver a portion of the desired batch to the washing machine reduces the effective detergent and softens the wash water concentrations and can lead to an inaccurate detergent and softener concentration being used. It can also cause unsightly build-up, which can be a problem for the user. The result is always undesirable and should be avoided if possible.

According to the present invention, a "heavy duty" wax and fabric softening particulate detergent mixture suitable for automatic machine washing or water washing and dispensable from a loading or dispensing compartment of such a machine by the action of water, which is added to such compartment is fed a synthetic organic detergent, which is an anionic or non-ionic detergent or a mixture thereof, an amount of a builder for the synthetic organic detergent, which is water-soluble or water-insoluble or a mixture thereof, and a softening amount of bentonite, wherein the bentonite is in particles, which incorporates a release promoting amount, preferably of at least 0.15% of a silicate and / or a release promoting derivative thereof.

In the preferred embodiments of the invention, the synthetic organic detergent includes both an anionic detergent, which is preferably a sodium linear high alkyl benzene sulfonate, and a nonionic detergent, which is preferably a condensation product of a higher fatty alcohol and polyethylene oxide, is a higher fatty acid soap present, the house salt is mainly pentasodium tripolyphosphate or NTA or a mixture thereof, with a small amount of sodium silicate, the bentonite is a swelling bentonite with a moisture content of at least 3%, the siliconate is an alkali metal low alkyl silicate, and more preferably potassium methyl silicate, and 5- 35% of a bleach, which releases oxygen in aqueous solution at elevated temperature, as sodium perborate are present. The invention also relates to methods of preparing the improved products as described above.

The synthetic organic detergents used will normally be either nonionic or anionic, and preferably a combination of both, but suitably amphoteric or ampholytic detergents such as those sold 8301249

Tl ^ "h ·" -3- under the trademark Miranol can also be used in conjunction with nonionic and anionic in the present mixtures. Cationic detergents, such as the quaternary ammonium halides, eg those sold under the trademark Arosurf, can also serve as additional fabric softeners in these products, but will not normally be used.

Various synthetic anionic organic detergents, such as those characterized as sulfonates and sulfates, usually can be used as alkali metal or sodium salts, but those most preferred are linear higher alkyl benzene sulfonates, 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 to 14 carbon atoms, more preferably 11 to 13, e.g. 12, and the sulfonate is a sodium salt. The alkyl sulfate is preferably a higher fatty alkyl or alcohol sulfate of 10-16 carbon atoms, more preferably 12-14 carbon atoms, eg 12, and is also used as the sodium salt. The higher fatty alcohol polyethoxy sulfates will preferably have 10 to 18 carbon atoms, more preferably 12 to 16, e.g. 12 in the higher fatty alcohol, the ethoxy content will preferably be 3 to 30 ethoxy groups per mole, more preferably 3 to 5 to 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 alkyl groups of 10 to 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, e.g. the sodium salts, wherein the olefin or paraffin group contains from 10 to 18 carbon atoms. Specific examples of the preferred detergents are sodium dodecylbenzene sulfonate, sodium tallow alcohol polyethoxy (3 EtOX sulfate and sodium hydrogenated tallow alcohol sulfate.

In addition to the preferred disclosed anionic detergents, other from this well-known group may also be present, especially in only minor amounts, based on the aforementioned. Mixtures thereof can also be used and in some cases such mixtures are better than the individual detergents.

Although various nonionic detergents with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxy-containing aromatics and aliphatic bases, such as nonylphenol and oxotype alcohols, it is highly desirable much recommendation that the nonionic detergent be a higher fatty acid poly-lower alkoxy lower alkanol, which can also be described as a condensation product of ethylene oxide (and / or propylene oxide) and a higher fatty alcohol. In such products, the higher fatty oxygen or alcohol contains 10 to 16 carbon atoms, preferably 12 to 15 carbon atoms, and the nonionic detergent contains about 3 to 20 lower alkoxy groups, preferably 5 to 15 and more preferably 10 to 13 ethylene oxide groups per mole, eg 11.

The synthetic organic detergent builder, which promotes the detergent wash performance, is either a water-soluble or a water-insoluble builder or a mixture thereof. Of course, mixtures of water-soluble builders can also be used, eg polyphosphate and NTA (nitrilotriacetic acid salt, normally sodium salt), but of the water-soluble builders usually only the zeolites will be present, although mixtures of such zeolites are also advantageous may turn out. Although zeolites are suitable components of the present blends, it will be recommended to use water-soluble builders and often these will be the only builders present.

The water-soluble builder or mixture thereof can be one or more of the usual materials used as builders or proposed for that purpose. These include inorganic and organic builders and mixtures thereof. Among the inorganic builders are preferred the various phosphates, preferably polyphosphates, e.g., tripolyphosphates and pyrophosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate. Trisodium nitrilotriacetate (NTA), preferably used as the monohydrate and other nitrilotriacetates, such as disodium nitrilotriacetate, are preferred organic builders.

The designation NTA, which normally stands for nitrilotriacetic acid in this specification, is used to also refer to its various salts, preferably the alkali metal salts and more 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 such as sodium carbonate are suitable builders and may be desirably alone or combined with bicarbonates such as sodium bicarbonate. When using the polyphosphates, it may be preferable that the sodium pyrophosphate is present with sodium tripolyphosphate in the ratio 1:10 to 10: 1, preferably 1: 5 to 5: 1 with respect to the total amount of both builders are about the same as those listed here for the sodium tripolyphosphate. Other water-soluble builders contemplated to be effective include the various other inorganic and organic phosphates, borates, eg, 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 more preferred. In some cases, such as when preparing neutral or mildly acidic detergent mixtures, acidic forms of the builders, especially of the organic builders, may be recommended, 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 because of their strong binding properties and since they may promote undesirable adhesion of detergent particles to release walls, they are considered special cases of builders and will present relatively small amounts thereof (such amounts will are described separately from the other builders). If it is desired that larger amounts of silicate be present in the detergent mixture, it may be recommended that hydrated sodium silicate particles be subsequently added to spray-dried particles containing other builders.

The water-insoluble builders, as this term is used in the present specification, are those which help promote the detergency of synthetic organic detergents, especially those of synthetic anionic organic detergents, and in such cases the mechanism for enhancing the detergent being related to the water softening effects 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-insoluble builders other than the zeolites in 8301249, the zeolites are currently the major insoluble builders used for practical reasons.

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

Although other ion exchange zeolites may also be used, normally the finely divided synthetic zeolite builder particles used in the invention will have the formula: (Na2O) x. (Al2O3) y. (SiO2) zw H2O in which formula x is 1, y is 0.8-1.2, preferably about 1.2, z is 1.5 to 3.5, preferably 2 to 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 or 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 having 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 type zeolites may also be suitable, especially when a type A zeolite is present. These crystalline types of zeolites are known and have recently been described in many patents for use as detergent mixture builders.

Crystalline zeolites with ion-exchange and water-softening properties, which are preferred are those which are in hydrated or water-laden form and contain bound water in an amount of from 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 to 70% of their capabilities. Normally, water contents are in the range of about 5 to 30%, preferably about 10 or 15 to 25%, such as 17 to 22%, e.g. 20%.

Preferably, the zeolite should be in finely divided form with an ultimate particle diameter of up to 20 µm, eg 0.005 or 0.01 to 20 µm, more preferably 0.01 to IS µm, eg 3-12 µm , and in particular 0.01 to 8 µm average particle diameter, e.g., 3 to 7 µm, if crystalline, and 0.01 to 0.1 µm, e.g., 0.01 to 0.05 µm, if amorphous. Although the extreme particle sizes are much smaller, the zeolite particles will usually have sizes in the range from 100 to 400 sieves, preferably 140 to 325. However, they can sometimes be agglomerated, individually or with spray-dried detergent mixture particles to sizes such as those. of the particles, e.g. + 10 or 25%.

Although sodium sulfate and sodium chloride and other filler salts do not have builder properties, they are sometimes used in detergent blends for filling properties, and sodium sulfate is particularly suitable as a processing aid. In addition to increasing the volume and weight of the metering aid product, they sometimes also 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 fillers being present, they are preferably often completely avoided or any amount present is minimized.

The softening clay, which is an important component of the present detergent mixture, is of the type characterized as "bentonite". Bentonites are colloidal clays (aluminum silicates) that contain mont-morillonite. They are of varying composition and are obtained from natural deposits in many countries, including Italy, Spain, Russia, Canada and the United States (especially Wyoming, Mississippi and Texas). The bentonites which are suitable according to the present invention are those which have "lubricating" and dispersing properties, which are associated with an aqueous swelling ability. Although some bentonites, especially those, may be characterized as calcium (or magnesium) bentonites, which have low or negligible swelling capacities, can be converted or "activated", 8301249

0 V.

-8- so that this swelling capacity increases. Such conversion can be effected by appropriate treatment with an alkaline material, preferably an aqueous sodium carbonate solution in a known manner for introducing sodium (or potassium) into the clay structure. In addition to improving the swelling ability of the bentonite, thereby promoting its fabric softening and release capabilities, the sodium carbonate solution treatment replaces the non-swelling clay or poorly flowing clay, eg 5-100%, 10 up to 90% or 15 to 50% of its divalent metal content, by sodium, thereby improving the clay's exchange ability for water hardness ions, such as those of calcium and magnesium. The by-products obtained, calcium carbonate and magnesium carbonate are left in the bentonite and are found to have desirable additive properties in the final products.

Although ion exchange capabilities of bentonites in the patent literature have been reported as relevant to emollient, a feature of the present invention is that good fabric softening is achieved with sodium bentonites of relatively low ion exchange capabilities. Whether the swelling bentonite (also referred to as sodium bentonite herein) is a naturally occurring clay obtained by an alkali treatment of non-swelling or poorly swelling bentonite, it can be used in the present fabric softening detergent compositions. Treated Italian bentonites have proven to be particularly suitable and are considered the most suitable for products intended for the European market. For US markets, Wyoming bentonite is often preferred and does not need to be treated because it already has sodium ion in the bentonite structure and has swelling properties. Analysis of a typical Italian bentonite (after alkali treatment) shows that it may contain 66.2% SiC> 2.17.9% Al 2, 2.80% MgO, 2.43% Na 2 O, 1.26% Fe 2 O 3, 30 1.15% CaO, 0.14% TiO2 and 0.13% K20. A typical Wyoming or western bentonite (untreated) can be 64.8 to 73.0% SiC> 2.14 to 18% A ^ O ^, 1/6 to 2.7% MgO, 0.8 to 2.8% Na2O 2.3 to 3.4% Fe 2, 1.3 to 3.1% CaO and 0.4 to 7.0% K 2 O. Thus, it is seen that the compositions of the bentonites are very different, although both types have swelling properties. It is contemplated that if the Na20 content of the clay is at least about 0.5%, preferably at least 1%, and more preferably at least 2%, (the equivalent amount of K20 may also be taken into account) the clay will be satisfactory swelling for the purposes of the present invention having satisfactory softening and dispersing properties in aqueous suspension. Although it is expected that amounts of the various constituents of the swelling bentonites (which may be referred to herein as sodium bentonites, either natural or "activated") within the ranges between the typical given analyzes will result in suitable components of the In the present mixtures, it is also contemplated that the amounts of the components of the natural swelling bentonites may be increased or decreased by about 10% and that the typical analysis of the treated bentonite may be increased by + 10%, the bentonites within these areas are still usable. Furthermore, other swelling bentonites can completely or at least partially replace the present. Generally, the useful bentonites will have swelling powers of at least 1 or 2 milliliters per gram, more preferably at least 5 or 10 ml / g. Bentonites with high swelling will of course. may also be suitable. Normally, the swelling range will range from 5 to 30 ml / g, and will often be in the range from 5 to 20 ml / g.

The sodium bentonite or swelling bentonite will normally be agglomerated before being mixed with spray-dried detergent granules and any other additives which are added afterwards. Such agglomeration will be carried out in a known manner, such as by applying moisture spraying to tumbling bentonite powder, extrusion, contacting, pan agglomeration or other techniques. However, it is highly desirable that the bentonite be in a finely divided powder form for the agglomeration, so that when the agglomerate crumbles in the wash water, the bentonite particles will be small enough to effectively spread when deposited on the laundry. Therefore, it will normally be desirable for substantially all of the bentonite powder to pass through a number 100 screen (US standard series) prior to agglomeration, with at least 99% passing through such a screen and a greater amount thereof passing through a screen 200, preferably while less than about 30% by weight of the 35 particles does not pass through such a screen, and more preferably not more than 20% remains on such a screen.

8301249 * * -10-

Also of interest in promoting easy crumbling of the bentonite agglomerates and dispersion in the wash water so that their very small particles are adhered to the textile fibers to soften them is the moisture content of the bentonite.

Although it is desirable to limit the free moisture content of the bentonite used to about 10%, with moisture contents above 15% not normally used, it is even more important to ensure that the bentonite contains sufficient free moisture, most of which is believed appears to be present between adjacent plates of the bentonite 10 to promote rapid depletion of bentonite and all adjacent materials in the particles when such particles or 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 that the bentonite is not dried, so that less than such percentages of water are even temporarily present in it. In other words, drying to the point where the bentonite loses its internal moisture can significantly reduce the utility of the instant blends. When the moisture content of the bentonite is too low, the bentonite does not promote satisfactory swelling and decomposition of the agglomerated granules in the wash water.

Preferred swelling bentonites of the types described above are sold under the trademarks Laviosa and Winkelmann, 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 organization of Georgia Kaolin Co.). Also, as will be described later, the treated ben-tonites will preferably be free of grit and will preferably have been further treated by grinding to a fine powder before agglomeration. Usually, the commercial bentonite used will have a pH in water (at a 6% concentration) in the range of 8-9.4, a maximum free moisture content of about 8%, a typical weight of = 35 about 2.6, and a viscosity at 10% concentration in water in the range of 5 to 30 cps, preferably 10 to 30 cps.

8301249 'Ί -11-

The silicate, which is used together with the bentonite, preferably to coat it, and also can be used to coat the detergent mixture particles, and which has the function of adhering the bentonite and the detergent to loading compartment walls of the automatic washing machine. (and to walls of other containers for the product) is one which can be easily applied to the bentonite and which can at least partially coat its particles and reduce their adhesion to walls of a compartment in which they are temporarily stored even when such walls are damp or wet. The siliconate is a salt of silicone acid, preferably an alkali metal salt thereof, and the silicone acid is preferably a lower alkyl silicone acid. Although it is desired that the salt-forming metal or other cation be one that will provide a water-soluble siliconate so that it can be applied to the bentonite in aqueous solution, this need not be necessary and is contemplated in water dispersible silicates can also be used. Furthermore, it is within the invention to use lipophilic silicates which can be applied in a solution of an organic solvent or in a solution of an aqueous organic solvent or in corresponding emulsions or dispersions. The alkali metal of the siliconate is preferably either natrus or potassium, but other salt-forming cations can also be used provided the siliconate is suitable for the present purposes. It is contemplated that alkali metal salts of silicic acids other than the lower alkyl silicates may be used, including both aliphatic and aromatic silicates, but the lower alkyl silicates, wherein the lower alkyl has 1-3 or 4 carbon atoms, eg, potassium methyl silicate and sodium propyl silicate are preferred. Instead of using the siliconate, an equivalent batch of the corresponding silicone acid and a corresponding base can be used.

For the best results, it is highly recommended to use the lower alkyl silicones described previously, but it is recognized that such compounds can polymerize and at least partially to form silicone or other film-forming and foam retardant compounds or polymers, and therefore fall within the broader 8301249 - Limits of the invention to use such "derivative" materials directly, at least in part as a component of the detergent compositions herein. If such a derivative of the silicate is used, it will be one that the release of the bentonite granules or promotes detergent mixture particles from an automatic washing machine loading compartment, such as a compartment, in which the particulate contents are washed out by a stream of water in the washing tub of the machine.

Although the operation of the present invention should not be considered to be limited by the mechanism to be described, it may be that the water-soluble alkali metal lower alkyl silicates (which may also be described as alkali metal lower alkyl siloxide) can be converted in polymethylsiloxanes, such as by the action of atmospheric carbon dioxide or other acid-working material, which may also result in the formation of alkali metal carbonate, such as sodium carbonate, a suitable builder salt.

The polymethylsiloxanes are known to be hydrophobic and their presence may be responsible for the improved properties of the coated bentonite (or other detergent particles) in terms of the improved release and loading compartment properties of the an automatic washing machine. The preparation of siloxanes by the reaction described is reported in Chemistry and Technology of Silicones, Walter Noll, (Academie Press; 1968). Although 25 have been silicone constituents of detergent mixtures in the past, often because of their anti-foaming properties, there is no disclosure of the use of water-soluble silicates for coating bentonite and detergent particles to promote free release of moist surfaces or loading compartments, such as at 30 known in the present invention and it is believed that such methods and the mixtures obtained are not obvious from the prior art.

The water-soluble soap, which is a desirable component of the detergent compositions herein and which has a useful foam-inhibiting action in the wash water, which is particularly advantageous for side-loading or horizontal tub washers, is normally a higher fatty acid soap of 8301249-13. an alkali metal, such as sodium or potassium, with sodium soaps being highly preferred. Such soaps can be prepared from natural fats and oils, such as those from animal fats and lubricants, and from vegetable and seed oils, eg talc, hydrogenated talc, coconut oil, palm kernel oil, and corresponding "natural" synthetic fatty acids and they normally contain 10 up to 24 carbon atoms, e.g., 14 to 18. Preferably, such soaps are of hydrogenated talc or hydrogenated tallow fatty acids, e.g. stearic acid. The water-soluble soap will preferably be selected such that there is a desired balance of good detergent properties, effective foam reduction and other good physical properties. Notably, among these other physical properties, may be mentioned, as desired, hardness, good binding ability, and limited tendency to form adhesive gels under conditions of use. It has been found that the sodium hydrogenated talc soaps best meet these conditions, but even mixtures containing them are desirably also treated with siliconate to further reduce adhesion to moist compartment walls. Of course, in mixtures where foaming is desired, the soap content is reduced, the soap is omitted or a lower fatty acid soap, e.g.

20 sodium laurate used instead.

Bleaching agents do not need to be included in all detergent compositions of the invention, but for the best cleaning and whitening of laundry it is often preferred that a bleaching agent be used. If the washing water temperature in the automatic washing machine 25 is high enough, sodium perborate is the bleach of choice, because the elevated temperature, especially when it is above 80 ° C (and it can go almost to the boiling point, e.g. 90 or 95 ° C) can cause deboration of the perborate and release bleaching oxygen. Thus, under such conditions, the sodium borate, which is often referred to as sodium perfborate tetrahydrate or sodium borate perhydrate, and which will usually have an active oxygen content of at least about 10%, liberates such oxygen without the use of an activator or decomposition catalyst. When washing at a low temperature is performed either in cold water or hot water, e.g.

At temperatures of 20 to 60 ° C, the sodium perborate will not usually decompose sufficiently to bleach the textile materials to be washed satisfactorily and in such conditions an activator will be used or some other suitable bleaching agent will be employed, also usually with an activator. Many such systems have been described in the literature, most of which belong to the class 5 of peroxygen compounds, such as per sulfuric acid, peracetic acid, performic acid, perphthalic acid and perbenzoic acid and salts thereof, such as the alkali and alkaline earth metal salts, e.g. sodium and magnesium salts. Various activators for such mixtures are known which promote controlled release of oxygen therefrom in hot and cold water systems, among which activators are heavy metal salts, such as copper salt, and various inorganic and organic compounds described in the art. Among the preferred lower temperature bleaches is magnesium dimonoperoxyphthalate. Of course, various other oxygen-releasing bleaching materials such as the hydroperoxides may be used, and under the appropriate conditions, chlorine-releasing bleaches may be incorporated into the present detergent compositions.

Various 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 subsequently, 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 mixture medium and its volatility. Among the additives commonly used are enzyme powders, which are normally added afterwards to the base granules because they are heat sensitive. They can be of a wide variety of commercially available products, including Alcalase (Novo Industri, A / S) and Maxatase, both of which are alkaline proteases (subtilisin). Among the specific enzyme preparations which can be used are Novo Alcalase 2M (2 Anson units per g) and Maxatase P 440,000. Although the alkaline proteases are most commonly used, amylolytic enzymes such as alpha amylase can also be used. The listed mixtures usually contain active enzymes in combination with an inert powdery carrier, such as sodium 35 or calcium sulfate, and the amount of the active enzyme can vary widely, usually from 2 to 80% of the commercial formulation. In the 8301249 # -15- .....

The present description refers to the amounts of the enzyme preparations, not the active part thereof.

Among the fluorescent brighteners, the most common are the stylized brighteners, eg Tinopal 5 5 BM, especially in extra concentrated form. Among the stilbene compounds are cotton clarifiers, such as those sometimes referred to as CC / DAS brighteners, from the reaction of cyanuric chloride and disodium salt of diamino stilbene disulphonic acid, including variations thereof with respect to substituents on the triazine and aromatic rings. This class of the brighteners is known in the detergent field and will be most commonly used if bleaching constituents are not present in the final product. If it is desired that the detergent mixture contain bleach, such as sodium perborate or other oxidizing bleach, bleach stable brighteners may be included in the soap mixture. Listed below are the benzidine sulfone disulfonic acids, naphtho-triazolylstilbene sulfonic acids and benzimidazolyl derivatives. Polyamide clarifiers, which may also be present, include aminocoumarin, or diphenylpyrazoline derivatives, and polyester clarifiers, which can also be used, including naphthotriazolyl stilbenes. Such brighteners are normally used as their soluble salts, e.g., sodium salts, but they can be introduced as the corresponding acids. Cotton brighteners will usually contain greater amounts of the brightness systems used.

When it is desired that the 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 can have the dual effect of coloring some or all of the detergent mixture particles or particles of components of the detergent mixture and a desired bluish tint to the laundry. to give. Coloring agglomerated bentonite particles by suitable dyes or pigments may be particularly desirable because natural bentonite sometimes exhibits mis-coloration, so that the agglomerates can be converted from particles that see soil to those of attractive color and appearance.

8301249 Ύ -16-

Fragrances used, which are usually heat sensitive and may contain volatile materials, including a solvent such as an alcohol or a suitable glycol, polyol or hydrocarbon, are normally synthetic fragrances, sometimes mixed with natural components and will generally include alcohols, aldehydes, terpenes, fixatives and / or other normal odor components known in the art.

In addition to the listed additives, there may also be present liquid promoters, anti-hardening materials used to prevent premature gelling of the soap mixture, dispersing aids, anti-redispersing agents and in some cases additional emollients, eg cationic softeners, such as the quaternary ammonium halides e.g. dimethyldioctadecylammonium chloride.

However, as previously indicated, normally the cationic softeners will not be used and if used will be added afterwards.

Of course, water is present in the soap mixture, from which the spray-dried component of the present mixture is prepared, in which 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 in the product. Likewise, water can be used to agglomerate the bentonite and perborate powders and dissolve the siliconate.

Although it may be preferred to use deionized water, so that the hardness ion contents thereof may be very low and so that metal ions which promote decomposition of any organic materials that may be present may be city or tap water instead sometimes applied and will sometimes be used exclusively for economic and supply reasons. Normally, the hardness content of such water will not exceed about 300 ppm as calcium carbonate.

The proportions of the various components in the final product of the invention will be such that they are effective as a fabric softening detergent, free flowing and of improved delivery from a loading compartment of an automatic washing machine by the action of washing water which such a compartment passes 8301249-17. The amount of the anionic detergent will normally be 3 to 10% of the final product / preferably 3 to 7% and more preferably 4 to 6%, e.g. 5%. Usually the nonionic detergent content will be 1 to 5%, preferably 2-4%, e.g. 3 or 4%. In those cases where no nonionic detergent is used, the amount of anionic detergent can be increased by 5% and in cases where the anionic detergent is omitted, the nonionic detergent content can be increased to 10% provided the detergent mixture is satisfactorily dispensable remains. Although it is possible for effective detergent mixtures to be prepared either without the anionic or nonionic detergent, such products will not be suitable as preferred mixtures of the invention. The builder content will generally be in the range of 20 to 75%, preferably 30 to 50% (which is often preferably completely water-soluble builder salt), and more preferably 30 to 40%, e.g., about 35%. As indicated previously, sodium tripolyphosphate and NTA are preferred water-soluble builders, which may be the only builders used. When used mixed, the mixture will preferably contain 10 to 90% of one, the remainder being the other builder, and within these ranges are preferred amounts of 20 to 80% and 40 to 60% and additional percentages. Similar percentage ranges apply when the builder consists of a mixture of a water-soluble builder salt and a water-insoluble builder, such as a zeolite.

The bentonite content of the fabric softening detergent, preferably in the form of a siliconate-coated agglomerate of finely divided bentonite powder particles, will be a satisfactory softening amount thereof, which is usually close to 5 to 25%, preferably 10 to 20% , preferably 14 to 18%, e.g. about 16%.

The siliconeate used will be used in a sufficient amount to promote the desired release, and such amount will normally be 0.05 to 1%, preferably 0.15 to 1%, although up to 3% can be used. A preferred amount of the siliconate is 0.1 to 0.15 to 0.3 or 0.4%, e.g. 0.15% or 0.3%.

When the siliconate is used to coat the agglomerated bentonite alone, on a coated bentonite agglomerate base t 8301249 -18- the siliconate content will usually be at least 0.15%, often 0.15 to 5%, preferably 0.15 to 1% and more preferably 0.15 to 0.5%, e.g. 0.4%.

When a fatty acid soap is present, the amount thereof will usually not exceed 10%. A preferred range of soap contents is 2 to 6%, more preferably 2 to 4%, e.g. 3%. When a bleaching agent is present, the amount thereof will usually be in the range of 5 to 35%, preferably 15 to 25%, e.g. 20%. However, it should be remembered that such amounts are based on the use of sodium perborate and should be modified when using other oxidizing agents to have approximately the same bleaching effect (or active oxygen content). The moisture content of the product, which does not contain hydrate moisture, which cannot be removed during standard heating at 105 ° C for 2 hours will usually be in the range of 3-20%, the higher percentages thereof being allowable as a significant amount, 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 a more preferred content is 10-15%. Any moisture that cannot be removed by the above standard test is considered to be part of the compound 20 in which it is present as a hydrate, e.g., a zeolite.

The total amount of the various additives which may also be present in the detergent mixture will usually not be more than 20% and preferably limited to 15% and more preferably to 10%. Although water-soluble sodium silicate possesses builder properties, particularly with regard to its action against magnesium ions in hard water, as it also acts as a binder, the amount thereof will not be limited by the aforementioned builder amounts and will are contemplated therein with other additives for the present blends. Usually it will not exceed 8% of the product with a normal range of 1-5%, preferably 2-4%, eg 3%. 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 to 5%, preferably 0.5 to 2%, e.g. 1 or 1.5 % of the product. The percentage of proteolytic enzyme will normally be 0.1 to 2%, preferably 0.2 to 1%, e.g. 0.3% and the percentage of optical clarity dye will be 0.1 to 2%, preferably 0.1 to 2% 0.5% 8301249 -r -19- e.g. about 0.2%. The fragrance content will normally be 0.05 to 2%, preferably 0.1 to 1%, more preferably 0.2 to 0.5%, e.g. about 0.3%. Among other additives, it may sometimes be desirable for small amounts of particulate sequestrants and flow promoters to be present. Among such materials, a preferred sequestrant is diethylene triamine pentaacetic acid, magnesium salt (magnesium DTPA), but other diethylene triamine acetates can replace it. Magnesium Silicate is a preferred flow promoter, which can also serve as a carrier for the sequestrant. A mixture of such products is available commercially, comprising 15% of the magnesium DTPA and 85% MgSiO 4, and when used the amount thereof is preferably 0.1 to 1%, more preferably 0.1 to 0.5 % e.g. 0.2%. Amounts of the sequestrant (or stabilizer) can range from 0.01 to 0.2%, preferably 0.02 to 0.1%, and for the MgSiO, concentrations ranging from 0.1 to 0.9%, preferably 0.2 to 0.5%. The amounts of other additives used will be such that they meet the purpose for which they are added to the detergent mixture, but normally such amounts will not exceed 1 or 2 and will generally range from 0.05 to 1%. "

In addition to the detergent compositions containing synthetic organic detergent, builder, bentonite, and silicate, often containing soap, bleach, and additives, silicate-treated bentonite, siliconate-treated perborate, and siliconate-treated enzymes are also included in the invention. For the siliconate-treated bentonite, the siliconate content will be 0.2 to 10%, preferably 0.5 to 5%, more preferably 1-3%. For the corresponding detergent mixture without bentonite and for the enzyme and perborate, the amounts of siliconate will be the same as those for the final detergent mixture, but such amounts can be increased from 10 to 100% depending on the conditions and the amounts of the different additives in the detergent mixture.

Known spray drying, agglomeration and mixing techniques (preferably all three) can be used to prepare the products according to the invention. Since these are not considered to be important features of the invention, it is only briefly referred to here 8301249 -20-. When spray-drying a soap mixture containing various components which are desired in the spray-dried granule and are sufficiently stable to withstand the mixing and spray drying operations such as detergent, builder 5 and suitable spray dried additives from an aqueous soap mixture, which will usually contain about 40 to about 70 or 75% solids, preferably 50 to 65% thereof, with the remainder of water. The soap mixture may contain the anionic detergent and some or all of the nonionic detergent, although usually no more than 10% nonionic detergent (based on the final product) will be present in the soap mixture (with any residual added afterwards). Any builder or mixture of builders will normally be added to the soap mixer, although this is not necessary.

The bentonite is preferably agglomerated separately and is added to the spray dried product, but sometimes it can be added in the soap mixer mixture. Aqueous silicate solution, stable fluorescent brightness dye, soap and filler salt are usually added in the soap mixer along with some stable pigment and other dyes that can be used. Instead of loading a neutralized detergent, the soap mixture can be used as a neutralization vessel in which the anionic organic detergent acid is neutralized with aqueous caustic. Such an acid can be, for example, dodecylbenzene sulfonic acid, which contains about 45 to 50% active ingredient, which may be neutralized with an aqueous sodium hydroxide solution, such as one containing 38% NajO. When the alkylbenzene is sulfonated with sulfur trioxide, the active ingredient content of the acid can be 99%. A high fatty acid mixture can also be neutralized in the soap mixer with the detergent acid to produce a desired high fatty acid soap detergent mixture.

The soap mixer mixture can be spray dried in a conventional spray tower using DC or counter current. Normally, the mixture will be at a temperature of 20 to 80 ° C, preferably 40 to 70 ° C and will be spray dried in a tower, wherein the drying air is at a temperature of 200 to 400 ° C, before producing spray-dried granules with particle sizes ranging from no's 10 to 100 (US sieve ranges). Particles that are outside the desired range can be removed by sieving and can be retreated. The granules can have a bulk density in the range of 0.3 to 0.6 g / ml, e.g.

0.5 g / ml. to have. They have a moisture content in a range that can be from about 3 to 20%, but will normally be from about 10 to about 15 * 5.

After preparing the spray dried portion of the mixtures, other components thereof can be mixed or sprayed onto the granules (and onto other components of the product, if desired). In general, it is recommended that the bentonite, enzyme, bleach, and any other particulate products, such as those in powder, agglomerate or prill form (excluding the silicate), be used for subsequent spray drying of the granules are added, mixed therewith, after which optionally liquids (including siliconate in solution), which are added afterwards, can be atomized on the mixture. However, sequences of post-addition of components can be varied, and sometimes some of the particulate material can be added after one or more of the liquids. Two or more of the particulate materials can be pre-mixed before being added afterwards and likewise mixtures of liquids can be prepared.

Solvents can be used for various components, which are applied as liquids and in some cases emulsions can be used. Thus, while the siliconate is preferably used in dissolved form in water, if a less soluble siliconate is used, it can be applied as an aqueous emulsion. In certain cases, it may be desirable to use the siliconate in an aqueous emulsion with fragrance and / or nonionic detergent. However, it is highly recommended to coat the unperfumed detergent mixture by spraying with an aqueous silicate solution and then spraying fragrance onto the silicated product. In certain cases it may be desirable to dilute the fragrance with a suitable solvent, such as a relatively odorless alkylate (hydrocarbon). Instead of spraying the siliconate onto the mixture of the spray dried (or otherwise manufactured to similar product characteristics) detergent granules, bentonite agglomerate, enzyme prills or agglomerates and perborate particles in the mixture, the silicate can be applied to such separate components, separately or in different combinations. This can be done with separate sprays of siliconate, in which case the amount thereof deposited on the different components can be easily controlled or a single siliconate sputter can be directed to different feed streams of such components as they enter a suitable mixer. When nonionic detergent is added afterwards (and it will sometimes be preferred that all nonionic detergent is added in the soap mixer so that the greatest release siliconate will be promoting effect) it can be sprayed on or otherwise satisfactorily applied on the surfaces of the spray-dried granules, before mixing with the other particulate components of the final product and before applying the siliconate spray thereon. Also, as mentioned earlier, the nonionic detergent in liquid form can be mixed with the siliconate and / or fragrance to be sprayed onto 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 will therefore not be described in detail here. The spraying can be done by conventional nozzles, usually with a wide spraying pattern, but other types of spraying equipment can also are used. The mixers can be of different construction, but preferably include rotating inclined tubes or drums within which to atomize. However, V-shaped mixers, especially those of continuous feed construction and other technical powder mixtures, can also be satisfactory.

The amount of siliconate that will be sprayed on the surfaces of the various particle components of the detergent mixture will be such that the final product comprises a release promoting amount of the siliconate (or a derivative thereof). Because it is believed that the bentonite agglomerates have some degree of satisfactory release of the particulate detergent mixture from the feed chamber of an automatic washing machine (of the "European type"), 8301249. However, it may be recommended that a larger amount of siliconate or such bentonite agglomerate particles be applied, eg up to 50% if this can be done. In some cases, only the bentonite particles will be treated with siliconate, in which cases the amount of siliconate in the final detergent mixture can often be reduced, eg by 50%. Application of the siliconate involves addition of moisture to the mixture to be treated when the siliconate is in aqueous solution or emulsion (but not if in non-aqueous solution). This may or may not be desirable, depending on the moisture content and the properties of the detergent mixture and treatment equipment. As a result, the concentration of siliconate in the atomizing liquid can be adjusted. Of course, the greater the atomization volume and the greater the dilution of the silicate, the more uniform atomization will be distributed on the particulate material. On the other hand, however, if the product is a limiting case or has too high a moisture concentration, a dilute siliconate spray can sharpen this condition. Generally, the concentration of siliconate in the liquid will be at least 5%, and preferably at least 10%. Since the silicate is completely miscible with water, higher concentrations can be used, which are usually in the ranges of 5 or 10-25 or 50%.

The various mixing and sputtering operations will normally take place at about room temperature, but operations in the range of 10 to 40 ° C, preferably 20 to 30 ° C are preferred. The particle sizes of the materials coated with siliconate will usually be those of the final product in the numbers 10 to 100 or 200 sieve region (the perborate and enzyme regions can extend to no.200). The agglomerated bentonite particles will be those that result from agglomeration or compaction of fine divided particles, such as that of more than 50% passing through a number 200 screen. Such particles will be substantially grit-free and will normally contain 0.05 or 0.15 to 3 or 5%, preferably 0.1 or 0.15 to 0.5 or 1%, of siliconate, such as potassium methyl silicone or sodium propyl silicone, sprayed on the surfaces thereof, so that such surfaces are at least partially coated. They can be colored with a suitable dye or pigment, such as Acilan 8301249 -24-

Brilliant Blue FFR, or any such or other suitable colorant, can be applied with the silicate. The silicate does not obscure the color. Sometimes the bentonite agglomerates can be larger than the other particles in the product, e.g. 10 to 50% larger in diameter 5 to accentuate their difference. In many cases, the bentonite agglomerates will preferably be from sodium carbonate-treated bentonite (such treatment improves the color of mis-colored clay) and will contain magnesium carbonate and / or calcium carbonate from such treatment. When the particles are only partially coated with siliconate, it is desirable that at least 10% of the surface area (of the equivalent spheres) is coated with the siliconate and even more preferably a larger amount is coated, e.g. 50% to promote release . Similar considerations and conditions apply when the enzyme, bleach and detergent particles are treated except that in such cases a smaller amount of siliconate can be used than that used to coat bentonite agglomerates.

In the above various cases, the coating of the solid siliconate would normally be on the outer 1% of the thicknesses of the particles. For example, for a particle that is one millimeter thick, such a siliconate coating will again have a thickness of 5 µm. Preferably, the coating will be on the outer 0.5% of the particle grain diameter, more preferably the outer 0.2% thereof. Of course, when only partial coatings are applied and when larger amounts of siliconate are used, such as when only the bentonite agglomerates are coated, the silicone thicknesses will be greater, but preferably less than 2%. Normally such thicknesses will be at least 0.05% of the particle thickness.

The products and methods of the present invention have many advantages, some of which have already been mentioned. With regard to the products, the application of siliconate to the particle surfaces, even when the entire particle is not covered with the siliconate, improves the release properties of such a particle without any adverse effect occurring. Thus, detergent blends of the types described herein and the particulate components of such disclosed blends are easier to dispense from 8301249-25. , Ί loading compartment of an automatic washing machine of the European type than control products, which are not treated with siliconate.

This difference is most pronounced with respect to the agglomerated bentonite particles. The tests for comparing such results are practical use tests using a variety of different manufacturers of such European washing machines where the evaluator notes the number of particles remaining in the loading compartment after normal loading and dispensing operation or after repeated such operations. To accentuate the differences and make the tests more difficult, the walls of the loading compartment are first moist to promote adhesion to the bentonite (and other materials). To simulate such a test, one can test equal weights and sprinkle control product on a damp horizontal surface, leave it to itself for one or two minutes and then direct a mild spray of water on the particles for a predetermined time, eg 30 seconds , after which the numbers of particles are compared. In such tests, the products according to the invention show a marked improvement over the control products; normally it would be expected that less than half of the number of particles still adhering to the pre-wetted surfaces when the "experimental" product is used, compared to the control, will be obtained. Often no particles will adhere to the pre-wetted surface Adhesive, if at least 0.15% siliconate is used, different particles will stick if at least 0.05% but less than 0.15% siliconate is used and a significant number of particles will adhere if no siliconate is present.

While most of the detergent will be put into the washing tub during normal use of the automatic washing machine, so that the leaving of a single particle in the loading chamber is initially no more than psychologically objectionable, with repeated washings larger numbers will be withheld. the composition of the fabric softening detergent is changed and possibly even the loading weight is significantly affected. Also, the appearance of the loading compartment with particles remaining therein is unsatisfactory and may cause the consumer to discard the product. Because of the various washing techniques used in America, coating bentonite detergent particles with siliconate there may not be so important, but it is contemplated that the presence of the siliconate on the particle will help the detergent to be more stable and more free flowing, in the especially under humid conditions and will prevent any gelation of the bentonite under such conditions.

In addition to promoting release, the silicate also has the desired effect of preventing excessive foaming of the detergent mixture in aqueous solution. The bentonite also helps to limit foaming and the combination is better than the individual components. The siliconate has also been found to have a stabilizing effect on enzymes and bleaches coated therewith, and helps to prevent interaction between fragrance components and other detergent ingredients, thereby promoting stabilization of the fragrance. It can also have such an effect on colorants. However, these various advantages are obtained without the disadvantages that the product is very hydrophobic, that it is initially water-soluble. It does not interfere with the desired rapid dissolution and dispersion of the detergent components and does not appear to cause a troublesome accumulation of hydrophobic deposits on washed and softened laundry. It does not interfere with the special softening effect of the hydrophilic bentonite and does not interfere with the good washing effect of the mixture. The resulting detergent mixtures are excellent laundry detergents and they soften washed goods efficiently as determined from comparative tests against similar mixtures containing neither bentonite nor silicate. The products are satisfactorily free flowing and have a desired bulk density and appearance. They are also not dusty, which can be partly attributed to the silicate.

Methods in which siliconate solutions or emulsions are sprayed onto detergent, bentonite and other detergent component particles are easily performed and do not require special equipment. Due to the water solubility of the siliconate, it can be applied in aqueous solvent without addition of components other than. the detergent composition. However, it can also be emulsified or otherwise distributed with other detergent components.

8301249

Dj -27-

The methods can be modified to apply different concentrations of siliconate to different detergent components. The coating materials are not subject to objectionable gelling or thickening, do not clog atomization nozzles, and do not form gummy deposits in the atomization and mixing equipment.

The silicate can be applied at room temperature because it does not require heating like some other protective coating materials. The silicate can remain essentially on the surfaces of the particles, whereby less is used, while still obtaining the desired release-promoting effect. Also, apparently due to the nature of the siliconate or its derivative on the detergent or component particle, it is effective even when the particle is not completely coated by it.

The invention is further elucidated by means of the examples below. Unless otherwise stated, all parts are by weight and all temperatures are expressed in ° C.

Example I

A "soap mixture" with a total weight of 3,199.5 kg is prepared by reacting 364 kg of dodecylbenzenesulfonic acid (Dobane JNQ [48.8% active ingredient]) and 167 kg of hydrogenated fatty acids (16 to 18 carbon atoms per mole of fatty acid) with 47 kg of sodium hydroxide (38% Na2O) in an aqueous medium containing an appropriate amount (to maintain the reaction) of 952 kg of city water (300 ppm hardness as CaCO2). The rest of such water is used to cool the reaction mixture as desired and to dilute other components of the soap mixture. Then, to the "soap mixture" are added 242 kg of aqueous sodium silicate solution (Na2O: SiO2 = 1: 2.4) at a 44.1% solids concentration, 7.5 kg of fluorescent stilbene clarifier, 7 kg of Sydex 808 (85% MgSiO ^). and 15% magnesium DTPA), 1.252 kg of hydrated sodium tripolyphosphate (TPP "H"), 54 kg of anhydrous sodium sulfate (99.5% pure) and 107 kg of a nonionic detergent, which can be considered as the condensation product of 11 moles ethylene oxide with 1 mole higher fatty alcohol with 12 to 15 carbon atoms per mole.

The soap "mixture" is heated for one hour with stirring, so that its temperature rises to about 55 ° C, after which the 8301249 -28- is pumped to sputter drying speeds, where it is sputtered under elevated pressure through a number of sputtering nozzles in dry air at a temperature of about 300 ° C. As a result of the spray drying, particles with a moisture content of about 5 12% are obtained, most of which are in the range of 10 to 100 sieves, particles outside this range are sieved out.

63.1 parts of the spray dried powder (bulk density about 0.4 q / cn?) Is then mixed with 0.3 parts of prilled proteolytic enzyme (Alcalase, with 2 Anson units per 10 grams, although Maxatase P 440,000 may be substituted ), 20 parts of granular sodium perborate and 16 parts of agglomerated bentonite.

All such powders have 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 No. 200. The bentonite particles consist of 82.3 parts of anhydrous bentonite, 16.1 parts of water, 1.5 parts of sodium silicate (previously described) and 0.06 parts of Acilan Brilliant Blue dye, the blue dye being applied to the surface of the particles. The bentonite particles are obtained by agglomerating finer divided particles of bentonite (Laviosa AGB) with the dilute sodium silicate solution (in the water), after which they are colored.

The bentonite used is a bentonite, which has been treated with sodium carbonate, for the replacement of calcium and magnesium therein with sodium (see above for the description of the material) 25 and from which a natural content of grit material (hard enough to be difficult to hammer to be crushed) has been removed, after treatment by centrifugal separation. The moisture content of suitably agglomerated bentonite can be varied and can be 3% when mixed with other components of the present emollient detergent.

30 A mixture of 0.5 parts of the non-ionic detergent, 0.25 parts Hhodorsil silicate 51 T (50% solution) is sprayed in a slanting drum mixer on the mixture of spray-dried granules, enzyme, perborate and colored bentonite particles. of potassium methylsiliconate) and 0.25 part detergent fragrance. The atomization 35 is controlled so that the atomized liquid evenly coat the particles in the mixer or tumbler drum to obtain about 100 parts of uniform product.

8301249 -29-

The final product has particle sizes in the range of from 10 to 60 screen, a density of 0.5 g / mL and a moisture content of about 12% (although this can be reduced to about 9% on standing). The resulting particulate fabric softening detergent 5 is free flowing and has a pleasant appearance, the slightly larger (20 to 200% larger in diameter) blue agglomerated bentonite particles contrasting with the other white particles and is not dusty.

The product prepared is subjected to practical washing tests and proves to be an excellent detergent with desirable fabric softening properties. When evaluated, it is noted that it is more easily dispersible, leaving fewer particles in the loading compartment of an automatic washing machine of the European type, than in control, where the siliconate coating 15 is not present. This is especially important if the bentonite particles are larger because they have a stronger tendency to adhere to wet chamber walls during delivery.

• When the above test is repeated, but with 100 kg dodecylbenzenesulfonic acid, 1.324 kg TPP "H" and 0.6 part Ehodorsil 20 siliconate 51 T instead of the amounts used previously, the product obtained has equally satisfactory physical properties and works equally well but it can be delivered even better automatically, with no particles remaining in the loading compartment of an automatic washing machine of the European type.

When the above-described example is modified, the anionic detergent is replaced by equal weights resp. of sodium lauryl sulfate, sodium hydrogenated tallow alcohol sulfate and sodium tallow alcohol polyethoxy (3EtO) sulfate. Alternatively, mixtures of such materials, eg equal amounts of sodium dodecylbenzene sulfonate and sodium hydrogenated tallow alcohol sulfate, are used together. In all such cases, a final detergent mixture is obtained, which is an excellent softening laundry detergent. All of these products also have improved release properties when tested by the previously described methods. Similar results are also obtained when instead of an anionic detergent change, the nonionic detergent is changed and replaced with a block copolymer of propylene oxide 8301249-30 and ethylene oxide, such as Pluronic L-44 or L-62, nonylphenol polyoxyethylene (12 EtO) glycol or a condensation product of 2-15 fatty alcohol with 3 or 7 moles ethylene oxide per mole or with a mixture of two or more such detergents, e.g. in equal amounts.

When half or all of the sodium tripolyphosphate is replaced by NTA, the final product is also a satisfactory detergent with emollient and improved release properties compared to a control of the same composition without the silicate.

10 When the soap is omitted from the composition, is

reduced foam control results, but otherwise the product is acceptable and equal to those previously described. When the sodium perborate is replaced by other bleaching agents, such as sodium persulfate and magnesium dimonoperoxyphthalate, good bleaching and cleaning by the product is still obtained. When known oxidizing activators are present, bleaching can be performed using the mixture at low temperatures than those close to the boiling point (which are normally used in the methods of this example to obtain maximum bleaching activity. it is desirable to include more silicate in the product, the amount of silicate is doubled by adding water-containing sodium silicate particles of similar size together with the other subsequently added solid particles.When replacing potassium methyl silicate with sodium propyl silicone 25, similar products are obtained, and this is also the case when silicates with lower degrees of water solubility are used to replace something, eg 25% of the other silicates Example II

The methods of Example I are modified by applying the siliconate in aqueous solution (20% solids) as a finely divided mist (where the atomized droplets are preferably "micron sized", eg 1 to 50 or 1 up to 10 µm in diameter), or otherwise as satisfactorily small liquid droplets on each of the particulate components to be mixed together separately for such mixing. The differently coated particles all have bulk densities in the prescribed range (0.3 to 0.6 8301249 -ffl -31- g / cm 2, e.g. 0.5 g / cm 2). Then the fragrance is likewise sprayed onto the mixture. The non-ionic detergent is not sprayed afterwards, but is instead introduced into the "soap" mixture.

The product obtained has improved release properties. The siliconate-coated agglomerated bentonite, spray-dried detergent mixture granules (without bentonite), enzyme and perborate can all be produced and stored separately and are subsequently suitable for preparing fabric softening detergents of various compositions and desired properties, eg coated bentonite plus uncoated spray dried granules.

Example III

An emollient detergent, such as that of the first composition of Example I, is prepared from a "soap" mixture of 10.24 parts of dodecylbenzene sulfonic acid, 2.81 parts of hydrogenated fatty acid, 0.81 parts of sodium hydroxide, 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 nonionic detergent are added sequentially. The mixture is spray-dried according to the method described in Example 1 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 the sodium perborate granules, 16.0 parts of the agglomerated bentonite and 0.2 parts of Sydex 808 and sprayed onto the tumbling powder mixture. mixture of 0.3 part of the detergent fragrance and 0.4 part of C 1 -C 13 linear alkylate and 0.15 part of potassium methylsiliconate is sprayed onto the product in a suitable liquid state, preferably dissolved in water (50% concentration).

The prepared product has better delivery properties for delivery from the loading compartment of an automatic washing machine in normal use. It exhibits a slightly greater foaming tendency than the similar products of Example 1. When 0.3 parts of the siliconate is used, the release properties of the detergent mixture are further improved.

When, instead of an agglomerated sodium carbonate-treated Italian bentonite, it has been removed from grit, as in Example 8301249 * -32- a competing product (Winkelmann agglomerate) or a Wyoming type bentonite, such as that sold under the trade name Mineral Colloid No. 101 (formerly Thixogel No.1), similar end products are obtained, which are good emollient detergents, which are easily dispensed. Similar results are also obtained when using other lower alkyl silicates, such as sodium propyl silicate. When the Acilan Blue dye used to color the bentonite agglomerates is replaced with ultramarine blue, good coloring and bluing effects are also obtained. Likewise, when only the siliconate is applied to the agglomerated bentonite, the total siliconate content in the product being the same, or in some cases less than 50%, the properties of the obtained detergent are similar to those previously described and the release 15 is also improved, compared to a control.

Example IV

When the amounts of the various components in the previous examples are modified by + 10%, 20%, and + 30%, they are kept within the limits stated herein and the ratios of anionic detergent to non-ionic detergent in the range from about 1: 1 to 3: 1 the ratio of total detergent content to builder content in the range from about 1: 3 to 1: 8 in the ratio of sodium bentonite to total detergent in the range from about 1: 1 to 2 : 1, products 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 by zeolite A (20% hydrated) and when each of a choice of synthetic anionic and non-ionic detergents is used, optionally mixed with an amphoteric detergent such as one of the Miranol 30 type. The invention can also be used to improve the release properties of various other bentonites and particulate detergent mixtures of widely different compositions, densities (0.2 to 0.9 q / cm) and sizes (preferably Nos. 10-40 sieve).

35 8301249

Claims (27)

The detergent mixture of claim 1, comprising from 15 to 10% of a sodium salt of a synthetic anionic organic detergent, which is a sulfonate or a sulfate or a mixture thereof, from 1 to 5% of a nonionic detergent, from 0 to 10% of a water-soluble alkali metal soap, 20 to 75% builder, 5 to 35% of a bleach, which releases oxygen in aqueous solution at elevated temperature, 5 to 25% bentonite, and 0.05 to 3% of an alkali metal lower alkyl silicone and / or a release-enhancing derivative thereof. Detergent mixture according to claim 2, characterized in that the sodium salt of the anionic detergent is a sodium linear higher alkyl benzene sulfonate, in which the higher alkyl contains 10 to 14 carbon atoms, a sodium higher fatty alcohol sulfate, in which the higher fatty alcohol contains 10 to 16 carbon atoms contains or a sodium higher fatty alcohol polyethoxysulfate, wherein the higher fatty alcohol has 10 to 18 carbon atoms and which has 3 to 30 ethoxy groups per mole or a mixture thereof, the nonionic detergent is a higher fatty alkoxy-30 poly-lower alkoxy lower alkanol, wherein the higher fatty alkoxy has 10 to 16 carbon atoms and the lower alkoxy and lower alkanol have 2 to 3 carbon atoms and which has 3 to 20 lower alkoxy groups per mole, the soap is a sodium soap of higher fatty acids with 10 to 24 carbon atoms per mole, the builder is a water-soluble salt or a water-insoluble zeolite or a mixture thereof, a bleaching agent is sodium perborate, the bentoni it has a moisture content of at least 3% 8301249 v -34- and swells in water, the swelling capacity of which is at least 3 1 cm / g and the alkali metal lower alkyl silicone is soluble in water, its alkali metal is potassium or sodium and the lower alkyl thereof contains 1-3 carbon atoms. The detergent mixture of claim 3, comprising 3-7% sodium linear higher alkylbenzene sulfonate, wherein the higher alkyl contains 11-13 carbon atoms, 2-4% higher fatty alkoxy poly-lower alkoxy lower alkanol, wherein the higher fatty alkoxy contains 12-15 carbon atoms and the 10 mol 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 mol, 30-50% water-soluble builder salt, 15-25% sodium perborate , 10-20% sodium bentonite and 0.15-0.3% potassium methylsiliconate. Detergent mixture according to claim 4, characterized in that the particle sizes are in the range from 10 to 100, the sodium higher alkyl benzene sulfonate, the soap and builder salt together are substantially homogeneous particles, spray dried from the same " soap "mixer mixture, the sodium perborate is in discrete or isolated particles and the bentonite is in discrete particles. Detergent mixture according to claim 5, characterized in that the higher alkyl of the sodium is linear higher alkylbenzenesulfonate dodecyl, the nonionic detergent is a condensation product of a higher fatty alcohol with 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, a builder salt is mainly pentasodium tripolyphosphate, the bentonite particles are obtained in the form of agglomerates after treatment with sodium carbonate of bentonite, which contains magnesium and / or calcium to produce sodium bentonite, with resulting Magnesium carbonate and / or calcium carbonate and the particles thereof are wholly or partly coated with potassium methyl silicone. The detergent mixture according to claim 6, comprising 1-5% sodium sulfate, 0.1-2% optical brightening dye and 0.1-1% proteolytic enzyme, wherein the agglomerated bentonite particles have average particle sizes greater than the average particle sizes of the spray dried particles and the perborate particles and 8301249 -35- are colored differently so that they can be easily identified in the detergent mixture. Detergent mixture according to claim 7, characterized in that the sodium bentonite has a swelling capacity in the range of 5-30 cm / g and as a 10% dispersion in water has a viscosity of 5-30 cps and agglomerate of smaller particles of sodium bentonite. The detergent mixture of claim 8, comprising about 5% sodium linear dodecylbenzene sulfonate, about 3% higher fatty alkoxy-poly-lower alkoxy lower alkanol nonionic detergent, wherein the higher fatty alkoxy contains 12-15 carbon atoms, the lower alkoxy and lower alkanol 2 carbon atoms and the molar ratio of higher fatty alkoxy to lower alkoxy is about 1:11, about 5% sodium soap of hydrogenated tallow fatty acids, about 20% sodium perborate, about 15 16% sodium bentonite, about 35% hydrated pentasodium tripolyphosphate, about 3% sodium silicate, about 0, 1% potassium methylsilonate, about 0.3% proteolytic enzymes, about 0.3% fragrance, about 2% optical brightener and about 12% moisture. Detergent mixture according to claim 1, characterized in that the bentonite particles are in the form of agglomerated particles obtained after treatment with sodium carbonate of bentonite, which contains magnesium and / or calcium, to replace at least some of such magnesium and / or calcium by sodium, with resulting magnesium carbonate and / or calcium carbonate. Detergent mixture according to claim 10, characterized in that the sodium bentonite agglomerate has a swelling capacity of 5-30 cm / g and as a 10% dispersion in water has a viscosity of 5-30 cps and consists of an agglomerate of smaller particles. bentonite exists. 12. Agglomerated bentonite particles suitable for inclusion in a particulate heavy duty detergent mixture for use in automatic washing machines comprising bentonite which incorporates a release promoting amount of the silicate and / or a release promoting derivative thereof. Agglomerated bentonite particles according to claim 12, 35 containing 0.05 to 3% alkali metal lower alkyl silicone and / or a release promoting derivative thereof on the surfaces of the particles. 8301249 ί -36- 14. Agglomerated bentonite particles according to claim 13, having dimensions in the range of from 10 to 100 US sieve ranges formed after treatment with sodium carbonate of bentonite containing magnesium and / or calcium to produce sodium bentonite with a. accompanying deformation of magnesium carbonate and / or calcium carbonate and which are coated in whole or in part by 0.05 to 1% potassium methylsiliconate. 15. Particulate synthetic organic detergent mixture comprising a synthetic organic detergent, which is an anionic or a nonionic detergent or a mixture thereof, an amount of a builder for the synthetic organic detergent, which is a water-soluble or a water-insoluble builder or a mixture thereof, and a release promoting amount of a silicate and / or a release promoting derivative thereof. The detergent mixture of claim 15, which is in a spray-dried granular form of particles having sizes ranging from 0.10 to 100, comprising about 3-7 parts of sodium linear higher alkylbenzene sulfonate, wherein the higher alkyl contains 11-13 carbon atoms, 2-4 parts higher fatty alkoxy poly-lower alkoxy lower 20 alkanol, wherein the higher fatty alkoxy contains 12-15 carbon atoms and the molar ratio higher fatty alkoxy to lower alkoxy is 1: 5 to 1:15, 2-6 parts sodium soap of higher fatty acids with 14- 18 carbon atoms per mole, 30 to 50 parts of pentasodium tripolyphosphate and 0-15 parts of additives, the total being 100%, the particles of which are at least partly coated by 0.05 to 1% potassium methyl silicone. 17. Particles of sodium perborate of sizes ranging from Nos. 10 to 200, which are at least partially coated with a siliconate and / or derivative thereof. 18. Sodium perborate particles according to claim 17, which are coated with 0.05 to 1% potassium methylsiliconate. 19. Particles of enzyme having sizes ranging from Nos. 10 to 200, which are at least partially coated with a siliconate and / or derivative thereof. Enzyme particles according to claim 19, which are coated with 0.05 to 1% potassium methylsiliconate. 21. A process for preparing a heavy duty wax-and-fabric softening particulate detergent mixture, suitable for automatic machine washing of goods in water and dispensable from a loading compartment of such a machine by the action of water that through such a compartment is supplied, comprising a synthetic organic detergent, which is an anionic or nonionic detergent or mixture thereof, an amount of a builder for the synthetic organic detergent, which is a water-soluble or a water-insoluble builder or a mixture thereof, and a softening amount of bentonite, wherein the bentonite 10 is present in particles, which includes a release promoting amount of the siliconate and / or a release promoting derivative thereof, comprising agglomerating particles of bentonite of a finely divided form, passing through a No.100 sieve and with more than 50% going through a No.200 z sieve to agglomerates of particle sizes in the range of Nos. 10 to 100 sieves, spray drying an aqueous "soap" mixture of the synthetic organic detergent and builder to detergent mixture particles of sizes in Nos. 10 to 100 series, mixing of the agglomerated bentonite particles and spray-dried detergent mixture particles and the application on the surfaces of such particles of a release promoting amount of a silicate and / or a release promoting derivative thereof. A method according to claim 21, characterized in that 0.05 to 1% of potassium methylsiliconate is sprayed onto the surfaces of the particles so that they are at least partially coated. A method of preparing a "heavy duty" detergent / detergent mixture, suitable for automatic machine washing of laundry in water and dispensable from a loading compartment of such a machine by the action of water supplied through said compartment, comprising a synthetic organic detergent, which is an anionic or a nonionic detergent or a mixture thereof and an amount of a builder for the synthetic organic detergent, which is a water-soluble or water-insoluble builder or mixture thereof, comprising drying an aqueous "soap" mixer mixture of the synthetic organic detergent and builder to particles of sizes in Nos. 10 to 100 sieve series and applying such particles to the surface of a dispensing agent 8301249 • -38- amount of a silicate and / or a release promoting derivative thereof. 24. A method according to claim 23, characterized in that the detergent comprises sodium dodecylbenzene sulfonate, the builder is pentasodium tripolyphosphate or NTA or a mixture thereof and 0.05 to 1% potassium methylsiliconate is sprayed on the surfaces of the spray dried particles, so that they are at least partially coated. 25. A process for preparing agglomerated ben-10 tonite particles, suitable for inclusion in a particulate heavy duty detergent mixture, which is dispensed from the loading compartment of an automatic washing machine by the action of water supplied through said compartment, with characterized in that a release-promoting amount of a siliconate and / or a release-promoting derivative thereof is applied to the surfaces of agglomerated bentonite particles. A method according to claim 25, characterized in that the agglomerated bentonite particles have particle sizes in the range of nos. 10 to 100 sieve and agglomerates of substantially 20 grit-free particles of sodium bentonite, which pass through a no. 100 sieve and of which more than 50 % passes a No. 200 screen and in which 0.05 to 1% of potassium methylsiliconate is sprayed onto surfaces of the agglomerated particles so that they are at least partially coated. A heavy-duty wax and fabric softening particulate detergent composition according to claim 1, wherein the release promoting amount of the silicate and / or the release promoting derivative thereof is at least 0.15%. Agglomerated bentonite particles according to claim 12, wherein the release promoting amount of the siliconate and / or the release promoting derivative thereof is at least 0.15%. 8301249