DK160102B - PARTICULATE, TEXTILE EMERGENCY POWERFUL WASHING AGENT FOR WASHING TOYS IN AUTOMATIC WASHING MACHINES AND AGGLOMERATED CONCRETE PARTICLES FOR WORKING IN SUCH A DETERGENT. - Google Patents

Description

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The present invention relates to a detergent of the kind specified in the preamble of claim 1, as well as agglomerated concrete in particles of the kind specified in the preamble of claim 6. The detergent and bentonite particles of the invention are characterized by the characterizing part of claim 1 and claim 6, respectively.

Bentonite is advantageous as an emollient in detergents. Bentonite's softening properties and its desirable adhesion to substrates are important advantages, but its "gelation" properties can cause an adverse adhesive to the detergent which will sometimes tend to retain detergent grains and / or bentonite grains or agglomerates to surfaces. and thereby tend to counteract free flow. Thus, under high humidity conditions or in the presence of free moisture, the bentonite may become "gels" and become sticky or have reduced flowability and even be retained to passageways or chamber walls despite the application of forces to the particles to remove them (such as the force of flowing water that is fed to an automatic washing machine).

Such an attachment could be significantly disadvantageous to a desirable free-flowing commercial particulate shaped detergent product and could lead to an inferior degree of consumer acceptance of the product. Even when the flowability through the production lines during manufacturing and packaging processes and the flowability from the dispensing box when the product is used by the final consumer is satisfactory, the presence of bentonite can cause the detergent particles to be retained on the walls of the appliance, especially the walls of the filling room. washing machines equipped with means for automatically supplying detergent to the washing water in the machine or drum when such particles and the bentonite present are moistened. In such circumstances, the bentonite may tend to swell to form moist, adherent surfaces, so that the particles can withstand removal from surfaces on which they rest. In washing machines and other appliances equipped with automatic dispensers or

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2, the detergent particles cannot completely fall out of the dispenser or be washed out of the dispenser, especially if the walls of the dispenser have become wet before adding the detergent. Failure to dispense the desired filling to the washer diminishes the effective concentration of detergent and plasticizer in the wash water and may lead to the use of inaccurate detergent and plasticizer concentrations. It can also cause an accidental build-up that can be unfortunate for the consumer. In each case, the result is undesirable and should be avoided if possible.

These shortcomings are remedied in accordance with the present invention, which relates to a high performance particulate and fabric softening detergent which can be used for automatic machine washing of water in water and dispensed from a filling room or dispensing space in such machine by the action of water passing through such a space. , a composite synthetic organic detergent which is an anionic or nonionic detergent or a mixture thereof, a builder-producing amount of a synthetic organic detergent builder which is water-soluble or water-insoluble builders or a mixture thereof, and a softening amount bentonite, the bentonite being present as particles in which an amount of dispensing effect is incorporated, preferably at least 0.15% siliconate and / or a dispensing effect derivative thereof. In preferred embodiments of the invention, the synthetic organic detergent includes both an anionic detergent which is preferably a sodium linear higher alkylbenzenesulfonate and a nonionic detergent which is preferably a condensation product of a higher fatty alcohol and polyethylene oxide. higher fatty acid soap is present, the builder salt is primarily pentane sodium tripolyphosphate or NTA or a mixture thereof together 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 lower alkylsilicate, more preferably potassium methyl siliconate, and 5 to 35% of a bleaching agent which releases oxygen in aqueous solution at elevated temperature such as sodium perborate is present.

The synthetic organic detergents used will usually be either nonionic or anionic and very preferably a combination of both, but suitable amphoteric or ampholytic detergents such as those sold under the trade mark "Miranol" may also be used. is used in conjunction with nonionic and anionic detergents in the disclosed 1Q agents. Cationic detergents such as the quaternary ammonium halides, e.g. those sold under the trademark "Arosurf" may also serve as supplemental fabric softeners in these products, but will not normally be used.

Various synthetic anionic and organic detergents, such as those characterized as sulfonates and sulfates, usually as alkali metal or sodium salts, may be used, but the most preferred are the straight chain higher alkyl benzene sulfonates, higher alkyl or fatty alcohol sulfates and higher fatty alcohol polyethoxyl or polyethoxyl or polyethoxyl . Preferably, the higher alkyl group in the higher alkylbenzenesulfonates is straight chain and has from 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 fatty alcohol sulfate having 10 to 16 carbon atoms, more preferably 12 to 14 carbon atoms, e.g. 12, and it is also used as the sodium salt. The higher fatty alcohol polyethoxy sulfates preferably have 10 to 18 carbon atoms, more preferably 12 to 16, e.g. 12, in the higher fatty alcohol, and the ethoxy content will preferably be from 3 to 30 ethoxy groups per minute. moles, more preferably 3 or 5 to 20, and the detergent will be a sodium salt. Thus, it will be seen that the alkyl groups of the sulfonates and sulfates are preferably straight or fatty higher alkyl groups of 10 to 18 carbon atoms, that the cation is preferably sodium and when a polyethoxy chain is present,

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4 at the end position. Other useful anionic detergents include the higher olefin sulfonates and paraffin sulfonates, e.g. the sodium salts in which the olefin or paraffin groups have 10 to 18 carbon atoms. Particular examples of preferred 5 detergents are sodium dodecylbenzenesulfonate, sodium talc alcohol polyethoxy (3 EtO) sulfate and hydrogenated sodium talc alcohol sulfate. In addition to the preferred anionic detergents mentioned, others belonging to this known group may also be present, especially in only minor amounts compared to the ones previously described. Mixtures thereof may also be used, and in some cases these mixtures may be superior to individual detergents.

Although various nonionic detergents with satisfactory physical characteristics can be used, including ethylene oxide and propylene oxide condensation products with each other and with hydroxy-containing aromatic and aliphatic bases such as nonylphenol and oxotype alcohols, it is highly preferred that the ionic detergent is a higher fat-alkoxy-poly-lower alkoxy-lower alkanol, which can also be described as a condensation product of ethylene oxide (and / or propylene oxide) and higher fatty alcohol. In such products, the higher fatty alkoxy group or fatty alcohol has from 10 to 16 carbon atoms, preferably 12 to 15 carbon atoms, and the nonionic detergent contains from ca. 3 to 20 lower alkoxy-25 groups, preferably 5 to 15 and more preferably 9 to 13 ethylene oxide groups per moles, e.g. 11th

The synthetic organic detergent builder which helps to improve the detergent washing effect is either a water soluble or a water insoluble builder or a mixture thereof. Mixtures of water-soluble builders can of course also be used, e.g. polyphosphate and NTA (nitrilotriacetic acid salt, usually the sodium salt), but of the water-insoluble builders, usually only zeolites will be present, although mixtures of such zeolites may also prove advantageous. Although zeolites are useful components

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5 of the present compositions, it will usually be preferable to use one or more water-soluble builders, and often such will be the only builder (s) present.

The water-soluble builder used or mixture thereof may be one or more of the conventional materials used as builders or proposed for such purposes. These include inorganic and organic builders and mixtures thereof. Among the inorganic builders, the preferred are the various phosphates, preferably polyphosphates, e.g. tripolyphosphates and pyrophosphates such as pentane sodium tripolyphosphate and tetrasodium pyrophosphate. Trisodium nitrilotriacetate (NTA), preferably used as the monohydrate, and other nitrilotriacetates, such as disodium nitrilotriacetate, are preferred organic builders. The term NTA, which usually stands for nitrilotriacetic acid, is also used in this specification to describe various salts thereof, preferably alkali metal salts and more preferably the trisodium salts. Sodium tripolyphosphate, sodium pyrophosphate and NTA can be used in hydrated forms which are often preferred, but anhydrous forms can also be used. Carbonates, such as sodium carbonate, are, of course, useful builders and, if desired, can be used alone or together with bicarbonates such as sodium bicarbonate. When the polyphosphates are used, it may be preferable that sodium pyrophosphate be present with the sodium tripolyphosphate in a ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1 with respect thereto, the total amount of both builders being about . the same as the one mentioned herein for sodium tripolyphosphate. Other water-soluble builders considered effective include the various other inorganic and organic phosphates, borates, e.g. borax, citrates, gluconates, EDTA and iminodiacetates. The various builders will preferably be in the form of their alkali metal salts, either the sodium or potassium salts or a mixture thereof, but sodium salts are usually more preferred. In some cases, such as when neutral or slightly acidic detergents are produced, can

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6 acidic forms of the builders, especially of the organic builders, are preferred, but usually the salts will be either neutral or basic in nature. The silicates, preferably sodium silicate, with a ratio of 0.5SiC 2 within the range of 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 bonding capabilities and because they could promote undue adhesion of detergent particles to dispenser walls, are considered special cases by builders, and relatively small amounts thereof will be present 10 (such quantities will be described separately in relation to the other builders). When greater amounts of silicate are desired in the detergent, it may be advantageous to add hydrated sodium silicate particles to spray-dried particles containing the other builder (s).

The water-insoluble builders used in this term in this specification are those which help to improve the purity of synthetic organic detergents, especially of the purity of synthetic anionic organic detergents, and in such cases, the purifying effect mechanism seems to may be associated with the builder's water softening effects, such as removal of calcium and / or magnesium ions from the wash water, usually by an ion exchange mechanism. While it is within the scope of the invention to use water-insoluble builders, other than the zeolites, in practice, zeolites 25 are currently the most important of such insoluble builders used.

The zeolites used include crystalline, amorphous and mixed crystalline-amorphous zeolites, both of natural and synthetic origin. Such materials are preferably capable of reacting rapidly enough with calcium ions so that they, alone or in conjunction with other water-softening compounds in the detergent, soften the wash water before adverse reactions between such ions and other components. 2 3 7 ter in the synthetic organic detergent takes place. The zeolites used can be characterized as having a high ion-exchange capacity for calcium ions, which are usually from ca. 200 to 400 or more milligram equivalents of the calcium carbonate hardness per grams of the aluminum silicate, preferably 250 to 550 mg eq / g.

Although other ion-exchanging zeolites may also be used, the finely divided synthetic zeolite builder particles used in the practice of the present invention will usually have the formula (Na 2 O) x. (Al 2 O 3) y. (SiO 2) zw H 2 O where x is 1, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2 to 3 or approx. 2, and w is from 0 to 9, preferably 2.5 to 6. The zeolite must be a monovalent cation exchange zeolite, i.e. it must be an aluminum silicate of a monovalent cation such as sodium or potassium.

Crystalline types of zeolites useful as good ion exchangers according to the invention, at least in part, include zeolites belonging to the following crystal structure groups: A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of such types of molecular sieve zeolites may also be useful, especially when type A zeolite is present. These crystalline zeolite types are known and have been described in many patents in recent years for use as 25 detergent builders.

Preferred crystalline zeolites with ion-exchange and water-softening properties are those present in hydrated or aqueous form and containing bound water in an amount of from about 30 to about 100. 4¾ up to approx. 36¾ of the total weight of the zeolite, depending on the type of zeolite used, and they are preferably hydrated to ca. 15 to 70¾ of their capabilities. Usually the water content is in the range of approx. 5 to 30¾, preferably 8

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ca. 10 or 15 to 25%, such as 17 to 22%, e.g. 20%.

The zeolite should preferably be in a finely divided state with maximum particle diameters up to 20 microns, e.g. 0.005 or 0.01 to 20 microns, more preferably 0.01 to 15 microns, e.g. 3 to 12 microns, and most preferably from 0.01 to 8 microns of average particle size, e.g. 3 to 7 microns, if crystalline, and 0.01 to 0.1 microns, e.g. 0.01 to 0.05 micron if amorphous. Although the final particle sizes are much lower, the zeolite particles will usually have sizes corresponding to the sieve range of from 100 to 400, preferably 140 to 325. However, they can sometimes be agglomerated separately or together with spray-dried detergent particles to sizes similar to that of the particles. .g. +10 or 25%.

Although sodium sulfate and sodium chloride and other filler salts have no builder properties, they are sometimes used in detergents due to their filler properties, and the sodium sulfate is particularly useful as a treatment aid. In addition to increasing the volume and weight of the product to facilitate measurement, they sometimes also improve the grain stability and physical properties of the detergent grains in which they are incorporated. However, because the agents in question are satisfactory without the presence of any fillers, such are often avoided, preferably completely, or even any amount present may be minimized.

The softening clay, which is an important component of the detergents in question, is of the type characterized as "bentonite". Bentonites are colloidal clays (aluminum silicates) containing montmorillonite. They are of varying compositions and can be obtained from natural deposits in many countries, including Italy, Spain, U.S.S.R., Canada and U.S.A. (especially Wyoming, Mississippi and Texas). The bentonites which can be used according to the present invention are those DK 16nin2 s 9 which have "lubricating" and dispersing properties which are associated with swelling ability in water. Although some bentonites, especially those which may be characterized as calcium (or magnesium) bone tonites, have low or negligible swelling abilities, these may be converted or "activated" to increase such swelling ability. Such conversion can be effected by appropriate treatment with alkaline material, preferably aqueous sodium carbonate solution, in a manner known per se for introducing sodium (or potassium) into the clay structure. In addition to improving the swelling ability of bentonite, which benefits its textile softening and dispersing properties, replacing treatment with the sodium carbonate solution of the non-swelling clay or poorly flowing clay, e.g. 5 to 100 µm, 10 to 90 µm, or 15 to 50 µm of its sodium divalent metal content, thereby improving the ion exchange capacity of clay 15 for water hardness ions such as calcium and magnesium ions. The resulting by-products, calcium carbonate and magnesium carbonate, are left with the bentonite and appear to have desirable adjuvant properties in the final products.

Although the ion exchange capacities of bentonites are mentioned in the patent literature as being relevant to softening capacity, it is a feature of the present invention that good text softening can be achieved with sodium bentonites with relatively low ion exchange capacities. Whether the swelling bentonite (also called sodium bentonite herein) is a naturally occurring clay or is obtained by the alkali treatment of a non-swelling or poorly swelling bentonite, it can be used in the fabric softening detergents. Treated Italian bentonites have proven to be particularly useful and considered most appropriate for products intended for the 30 European markets. For the US markets, Wyoming bentonite is often preferred and does not need to be treated as it already contains sodium ions in the bentonite structure and has swelling properties. Analyzes of a typical Italian bentonite (after alkali treatment) show that it

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10 may contain 66.2 µl SiO 2, 17.9% Al 2 O 3, 2.80% MgO, 2.43% Na 2 O, 1.26% Fe 2 O 3, 1.15% CaO, 0.14% TiO 2 and 0.13% K20. A typical Wyoming or western bentonite (untreated) may contain from 64.8 to 73.0% SiO 2, 14 to 18% Al 2 O 3, 1.6 to 2.7% MgO, 0.8 to 2.8% Na 2 , 3 to 3.4% Fe 2, 1.3 to 3.1% CaO, and 0.4 to 7.0% K 2 O. Thus, the composition of the bentonites is quite different, although both types have swelling properties. It is believed that if the Na2 content of the clay is at least approx. 0.5%, preferably at least 1% and more preferably at least 2% (the equivalent amount of K2O may also be included), the clay will swell satisfactorily for the purposes of the present invention with satisfactory softening and dispersing properties in aqueous suspension. While it is expected that amounts of the various constituents of the swelling bentonites 15 (which bentonites are referred to herein as sodium bentonites, either natural or "activated"), within intervals of the typical assays indicated, will result in useful components of the agents disclosed. considering that the percentages of the components of the naturally suffocating bentonite 20 can be raised or lowered by approx. 10% and the typical analysis of the bentonite treated can be changed + 10%, the bentonites within these limits still being useful. Further, other swelling bentonites can be used instead, at least in part. In general, useful bentonites will have swelling capacities of at least 1 or 2 ml / g, more preferably at least 5 or 10 ml / g. Of course, bentonites with greater swelling ability can also be used. Usually, the range for swelling will be from 5 to 30 ml / g and is often in the range of 5 to 20 ml / g.

The sodium bentonite or the swelling bentonite will usually be agglomerated before being mixed with spray-dried composite detergent grains and any other adjuvants to be added. Such agglomeration will be carried out in known manner, such as using moisture spray application to bentonite powder during tumbling, extrusion, compression, brow agglomeration or other techniques. It's 11

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however, it is highly desirable that the bentonite be in finely divided powder form prior to agglomeration so that when the agglomerate breaks up in the wash water, the bentonite particles will be sufficiently small to be effective lubricants when deposited on the laundry. Thus, it would normally be desirable that substantially all the bentonite powder prior to agglomeration pass through a No. 100 sieve (US sieve series), with at least 99% passing such a sieve, and more than most passing through a No. 200 sieve. screen, wherein 10 is preferably less than ca. 30% by weight of the particles cannot pass through such a sieve and more preferably at most 20% by weight remain on such a sieve.

The moisture content of the bentonite is also important in promoting slight breakage of bentonite agglomerates and dispersion in the wash water so that the fine particles thereof can be adhered to the textile fibers to soften them. Although it is desirable to limit the free moisture content of the bentonite used to approx. 10% or similar, with moisture content above 15% not normally used, it is even more important to ensure that the bentonite 20 contains sufficient free moisture, most of which is considered to exist between adjacent bentonite slabs, to facilitate rapid disintegration of the bentonite and which any adjacent materials in the particles when such particles or detergents containing them are contacted with water, such as wash water. It has been found that at least approx. 2%, preferably at least 3% and more preferably approx. 4% or more water should be found in the bentonite (so-called "internal" moisture) and the bentonite must not be dried so that less than such percentages of water are even temporarily present therein. In other words, over-drying to the point where the bentonite loses its internal moisture can significantly diminish the utility of the agents in question. When the moisture content of the bentonite is too low, the bentonite does not adequately assist in the swelling and degradation of agglomerated grains in the washing water.

Preferred swelling bentonites of the type described above are sold under the trademarks "Laviosa" and "Winkelmann", e.g. "Laviosa" AGB and "Winkelmann" G 13, both treated with 5 Italian bentonites, and "Mineral Colloid" No. 101 (and other similar names) corresponding to "Thixo-Geler" Nos. 1, 2, 3 and 4 ( marketed by Benton Clay Company, a subsidiary of Georgia Kaolin Co.). As will be described later, the treated bentonites will also preferably be free of hard grains jLO and will preferably be further treated by grinding to a fine powder prior to agglomeration. The commercial bentonite used will usually have a pH in water (at a concentration of 6? Ό) in the range of 8 to 9.4, a maximum free moisture content of approx. 8 in, a density of approx.

2.6 and a viscosity at a 10¾ concentration in water in the range of 5 to 30 centipoise, preferably 10 to 30 centipoise.

The silicon used in conjunction with the bentonite which functions to prevent the adhesion of the bentonite and the detergent to the walls of the filling compartment 20 in an automatic washing machine (and to the walls of other "containers" of the product) is one that can be easily applied to the bentonite and can at least partially coat the particles thereof and inhibit their adhesion to the walls of a room in which they may be temporarily stored, although such walls are moist or wet. The siliconate is a silicic acid salt, preferably an alkali metal salt thereof, and the silicic acid is a lower alkylsilicone acid. While it is desirable that the salt-forming metal or other cation be one which will form a water-soluble siliconate so that it can be applied to the bentonite in aqueous solution, such an option may not be necessary and water-dispersible silica is contemplated. -conater will also be used. Furthermore, it is within the scope of the invention to use lipophilic silicones which can be used in organic solvent solution or in aqueous organic solvent solution or in corresponding emulsions or dispersions. The silicon potassium metal is preferably either sodium or potassium, but other salt-forming cations can also be used provided the siliconate is suitable for the present purposes. It is believed that other alkali metal metals can be used, but the lower alkyl siliconates wherein 10 lower alkyls have from 1 to 3 or 4 carbon atoms, e.g.

potassium methyl siliconate and sodium propyl siliconate are considered preferred. Instead of using the siliconate, an equivalent amount of the corresponding silicone acid and base can be used.

To obtain the most effective results, the lower alkyl siliconates described herein are used, but it is known that such compounds can polymerize, at least in part, to silicones or other film-forming and foam-inhibiting compounds or polymers, and accordingly it is within the broader scope of the invention to utilize such "derived" materials directly, at least in part, as a component of the detergents. When such a derivative of the siliconate is used, it will help improve the dispensing of the bentonite grains or detergent particles from a filling compartment in an automatic washing machine, such as a space in which the particulate content is leached by the flow of water into the machine's washing drum. .

Although the practice of the present invention is not to be considered limited by the mechanism that will be described, it may well be understood that the water-soluble alkali metal lower alkyl siliconates (which may also be described as alkali metal lower alkyl silanolates) can be converted to polymethylsiloxanes, such as by the influence of atmospheric

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14 carbon dioxide or other acid-acting material, which could also result in the formation of alkali metal carbonate, such as sodium carbonate, which is a useful builder salt. The polymethylsiloxanes are known to be hydrophobic, and it is possible that their presence is the cause of the improved bentonite (or other detergent particles) properties with respect to delivery from an automatic washing machine filling space. The preparation of siloxanes by the reaction described is disclosed in the work of Chemistry and Technology of Silicon 10 by Walter Noll, published by Academic Press in 1968. Although silicones have previously been incorporated in detergents, often due to their anti-foaming properties , however, no mention is made of the use of water-soluble siliconates for coating bentonite and detergent particles to promote the release from the moist surfaces of the filling compartment as contemplated by the present invention, and such methods and the resulting agents are not considered to be approachable in the light of the prior art.

The water-soluble soap, which is a desirable component of the present detergents and which has a useful foam-limiting effect in the washing water, which is particularly advantageous for washing machines with side-loading or horizontal washing drum, is usually a higher fatty acid soap of alkali metal, such as sodium or potassium, with sodium soaps being highly preferred. Such soaps may be prepared from natural fats and oils, such as those derived from animal fats and fats and from vegetable oils and seed oils, e.g. tallow, hydrogenated tallow, coconut oil, palm kernel oil, and the corresponding "natural" and synthetic fatty acids, and they usually have 10 to 24 carbon atoms, preferably 14 to 18 carbon atoms. Preferably, such soaps are derived from hydrogenated tallow or hydrogenated tallow fatty acids, e.g. stearingsyre. The water-soluble soap will preferably be chosen such that it has a desirable balance between good cleaning properties, effective foam reducing effect and other good physical properties. Among such other physical properties, hardness, good bonding and limited tendency to form adhesive gels under conditions of use will be particularly desirable.

It has been found that the hydrogenated sodium tallow soaps best meet these conditions, but even agents containing them it is also desirable to treat with silicone to further inhibit the adhesion to moist container walls. For agents in which foaming is desirable, the soap content is obviously lowered or the soap omitted or a lower fatty acid soap, e.g. sodium laurate, may be used instead.

Bleaches do not need to be incorporated into all the detergents of the invention, but for the best purity and whiteness of laundry, it is often preferred that a bleaching agent be used. When the washing water temperature in the automatic washing machine is high enough, sodium perborate is the preferred bleach because higher temperature, especially when above 80 ° C (and it can be almost up to the boiling point, e.g. 90 or 95 ° C), may cause decomposition of the perborate and release bleaching oxygen therefrom. Under such conditions, the sodium perborate, often referred to as sodium perborate tetrahydrate or sodium borate perhydrate, and which will usually have an active oxygen content of at least approx. 10¾, such oxygen without the need for the use of an activating agent or a decomposition catalyst. When washing at a lower temperature, either in cold water or hot water, e.g. at temperatures of 20 ° C to 60 ° C, the sodium perborate will usually not sufficiently decompose to obtain satisfactory bleached fabrics which are washed, and in such circumstances an activator will be used, or another suitable bleach will also be used, also usually along with an activator. Many such systems have been described in the literature and most of them belong to the class of peroxygenic compounds such as persulfuric acid, peracetic acid, peracetic acid, perphthalic acid and perbenzoic acid.

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and salts thereof, such as the alkali metal and alkaline earth metal salts, e.g. sodium and magnesium salts. Various activators for such agents are known which promote the controlled release of oxygen therefrom in hot and cold water systems, such activators being heavy metal salts such as copper salts and various inorganic and organic compounds previously described. Among the low temperature bleaches, magnesium dimonoperoxyphthalate is preferred. Various other oxygen-releasing bleaches, such as the hydroperoxides, can, of course, be used and, under appropriate circumstances, chlorine-releasing bleaches can be incorporated into the detergents.

Various adjuvants may be present in the soap blend mixture from which base grains or detergents can be sprayed or alternatively such adjuvants may be added, the decision of the additive often depending on the physical properties of the adjuvant, its resistance to heat, its resistance to degradation. the aqueous soap mixer medium and its volatility. The frequently used auxiliaries include enzyme powders, which are usually added to the basic grains because they are heat sensitive. These may be any of a number of commercially available products, including "alkalase" manufactured by Novo Industri A / S and "Maxatase", both of which are alkaline proteases (subtilisin). For specific enzyme preparations that can be used, Novo "Alcalase" includes 2M (2 Anson units per gram) and "Maxatase" P 440,000. Although the alkaline proteases are the most frequently used, amylolytic enzymes such as alpha-amylase can also be used. Said agents usually contain active enzymes in combination with an inert powdered carrier or matrix such as sodium or calcium sulfate, and the amount of active enzyme can vary widely, the amount usually being from 2 to 80% of the commercial product. . In this specification, amounts listed are 35 amounts of the enzyme preparations and not amounts of the active

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17 part thereof.

Among the fluorescent detergents, the most commonly used silencing agents, e.g. "Tinopal" 5 BM, especially in extra concentrated form. Cotton compounds include cotton clearing agents such as those sometimes referred to as CC / DAS clearing agents derived from the reaction product of cyanuric acid chloride and the disodium salt of diamino-stilbene disulphonic acid, including variations thereof for triazine and aromatic substituents . This class of detergents is known in the field of detergent and will most often be used when bleaching components are not present in the final product. When it is desirable that the detergent contains a bleach such as sodium perborate or another oxidizing bleach, bleach stable clarifiers can be incorporated into the soap blend mixture. These include benzidine sulphon disulphonic acids, naphtho triazolylstilbenzulfonic acids and benzim. Polyamide clarifiers which may also be present include aminocoumarin or diphenylpyrazoline derivatives, and polyester clarifiers which may also be used include naphthotri azolylstilbenes. Such clarifiers are usually used as soluble salts thereof, e.g. sodium salts, but they can be added as the corresponding acids. The cotton clearing agents will usually comprise the majority of the clearing agent systems used.

When it is desirable that the manufactured product be fully or partially colored, various suitable dyes and dispersible pigments may be used. When blue dyes, such as acilane blue, or pigments, such as ultramarine blue, are used, they can have a dual effect by functioning to stain some or all of the detergent's particles or particles of the detergent's components, and to assist in giving the washed clothing a desirable bluish tone. Staining of agglomerated bentonite particles by appropriate dyes 18

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or pigments may be particularly desirable because natural ben- tonite can sometimes be colorless so that the agglomerates can be transformed from particles that look dirty to particles that have attractive color and appearance.

Perfumes used, which are usually heat sensitive and may contain volatiles including a solvent such as alcohol or a suitable glycol, polyol or hydrocarbon, usually consist of synthetic perfume materials, sometimes mixed with natural components, and generally will contain alcohols, aldehydes, terpenes, fixatives and / or other normal perfume components known in the art.

In addition to the adjuvants mentioned, flow promoting agents may also be included, anti-sedimenting materials used to prevent premature gelation of the soap mixer, dispersion aids, anti-repellents, and in some cases additional emollients, e.g. cationic plasticizers, such as the quaternary ammonium halides, e.g. Dimethyldioctadecylammonium. However, as previously stated, the cationic plasticizers will not normally be used and if used, they will be added.

Of course, water is present in the soap mixer from which the spray-dried component of the present invention is prepared, wherein the water serves as the medium for dissolving or dispersing the various components of the spray-dried grains. Therefore, some water, both in free form and in hydrate form, is found in the product. Similarly, water can be used to agglomerate the bentonite and perborate powder and to dissolve the siliconate. While it may be preferable to use deionized water, so that its hardness ion content may be very low, and so that metal ions which promote decomposition of any organic materials present will be minimized, urban or tap water may be used instead. and sometimes it will be used solely for economic or supply reasons. Normally the hardness content of such water will not be greater than about 300 parts per million, calculated as calcium carbonate.

The amount of the various components of the final product of the invention will be such as to result in it being effective as a textile softening detergent which is free flowing and has improved ability to discharge from a filling space into an automatic washing machine as a result of the effect 10 of wash water passing through such a room. The amount of anionic detergent will usually comprise from 3 to 10¾ of the final product, preferably 3 to 7¾ and most preferably 4 to 6? Ό, e.g. 5¾. The content of the nonionic detergent will usually be from 1 to 5%, preferably 2 to 4 µm, e.g.

3 or 4¾. In cases where nonionic detergent is not used, the amount of anionic detergent can be increased by as much as 5%, and in cases where the anionic detergent is omitted, the content of the nonionic detergent can be increased by up to 10¾, provided that the detergent remains capable of being discharged satisfactorily. While it is possible to prepare effective detergents without either the anionic or the nonionic detergent, such products will not be as useful as preferred agents of the invention. The builder content will generally be in the range of 20 to 75 °, 25 preferably 30 to 50 ° (and one is often preferably completely water-soluble builder salt) and most preferably 30 to 40 °, e.g. ca. 35¾. As previously stated, sodium tripolyphosphate and NTA are preferred water-soluble builders, which may be the only builders used. When used in admixture, the admixture will preferably contain from 10 to 90¾ of one of them, the remainder being the other builder, and within such ranges, preferred amounts may be 20 to 80¾ and 40 to 60¾ as well as complementary percentages. Similar ranges of percentages are applicable when the builder is a mixture of water-soluble builder salt

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20 and water-insoluble builder, such as a zeolite.

The bentonite content of the fabric softening detergent, preferably in the form of a silicone coated agglomerate of more finely divided bentonite powder particles, will be a satisfactory softening amount thereof, ranging from 5 to 25%, preferably 10 to 20%, and most preferably 14 to 18%, e.g. ca. 16%.

The used siliconate will be used in an amount sufficient to have the desired depletion effect, and such amount will usually be from 0.05 to 1%, preferably 0.15 to 1%, although until 5% can be used.

A preferred range of amounts of the siliconate is from 0.1 or 0.15 to 0.3 or 0.4%, e.g. 0.15% or 0.3%. When the siliconate is used to cover only agglomerated bentonite, the siliconate content, calculated on a coated bentonite agglomerate basis, will usually be at least 0.15% and often 0.15 to 5%, preferably 0.15 to 1% and most preferably 0.15 to 0.5%, e.g. 0.4%.

When a fatty acid soap is present, the amount thereof will usually not be greater than 10%. A preferred range of soap content is from 2 to 6%, most preferably from 2 to 4%, e.g. 3%. When a bleach is present, its amount will usually range from 5 to 35%, preferably 15 to 25%, e.g. 20%. However, it must be remembered that such quantities are based on the use of sodium perborate and will be modified when other oxidizing agents are used so as to obtain approximately the same bleaching effect (or active oxygen content). The moisture content of the product, which does not include hydrate moisture which cannot be removed during standard heating to 105 ° C for 2 hours, will usually range from 3 to 20%, the higher percentages thereof being permissible when a significant amount, at least 1/4, and preferably at least half of the moisture, is in a high form. A preferred moisture content is from 5 to \ T% and the more preferred moisture content is from 10 to 15¾. cannot be removed by the standard sample used above is considered to be part 5 of the compound in which it is present as a hydrate, for example a zeolite.

The total amount of various excipients which can also be found in detergent will usually not exceed 20% and preferably be limited to 15% and most preferably to 10¾. Although water-soluble sodium sieve in cat has builder properties, especially with respect to its action against magnesium ions in hard water, because it also acts as a binder, the amount thereof present will not be limited by the previously stated amounts of builder content, and it will here are considered together with other adjuvants in the said compositions. Usually, the water-soluble sodium silicate will not constitute more than 8% of the product, with a normal range being from 1 to 5¾, preferably 2 to U%, preferably 3¾. The content of filler salt, such as sodium sulfate, when present, will also normally be limited to a maximum of 10S, and will usually be from 0.5 to 5 µm, preferably 0.5 to 2%, e.g. . 1 or 1.5¾ of the product. The percentage of proteolytic enzyme used will normally be from 0.1 to 2%, preferably 0.2 to 1? Ό, e.g. And the percentage of optically clear dye will be from 0.1 to 2%, preferably 0.1 to 0.5 0, e.g. ca. 0,2¾. The perfume content will usually be from 0.05 to 2? 0, preferably 0.1 to 1¾, and most preferably 0.2 to 0.5¾, e.g. ca. 0,3¾. Among other auxiliaries, it may sometimes be desirable to incorporate small amounts of particulate sequestering agents and flow promoters. Among such materials, a preferred sequestering agent is diethylenetriamine pentaacetic acid, magnesium salt (magnesium DTPA), but other diethylenetriamine acetates may be used instead. Magnesium silicate is a preferred flow promoter which can also act as a carrier for sequestration.

DK 160102 B

22. Commercially, a mixture of such products is available comprising 15 µl of magnesium DTPA and 85 µ MgSiO 2, and when such a mixture is used, the amount thereof is preferably from 0.1 to 1%, more preferably 0.1 to 0.5%. eg.

0.2%. Amounts of the sequestering agent (or stabilizer) may be from 0.01 to 0.2%, preferably 0.02 to 0.1%, and the MgSiO 2 concentrations are in the range of 0.1 to 0.9%, preferably 0, 2 to 0.5%. Amounts of other excipients used will be such as to achieve the purpose for which the Xo excipient is incorporated into the detergent, but normally such amounts will not be greater than 1 or 2% and generally range from 0.05 to 1%.

In addition to the detergent containing synthetic organic detergent, builder, bentonite and siliconate, soaps, bleaches and auxiliaries are also often present, according to the present invention, agglomerated bentonite particles which are characterized by the characteristic of claim 6 are also disclosed. The siliconate content is in particular 0.5 to 5% and most preferably 1 to 3%.

20 For the preparation of the products according to the invention, known spray drying, agglomeration and mixing techniques (preferably all three) can be used. Because such are not considered as essential features of the invention, they will only be briefly discussed herein. In spray drying, a soap blend mixture containing various components desired to be present in the spray dried grains is spray dried and is sufficiently stable to withstand the mixing and spray drying operations such as detergent, builder and suitable excipients.

DK 1 0102B

23, wherein the spray drying is effected from an aqueous soap blend mixture which will normally contain from approx. 40 to approx. 70 or 75% solids, preferably 50 to 65% thereof, the remainder being water. The soap blend mixture may contain the anionic detergent and some or all of the nonionic detergent, although usually no more than 5% of the nonionic detergent (based on the final product) will be found in the mixer, adding any residue). All the builder or the whole mix of builders will usually be added in mixer-1 g of pure, although this is not necessary. Preferably, the bentonite is agglomerated separately and added to the spray-dried product, but sometimes it can be incorporated into the soap mixer mixture. Aqueous sieve solution, stable fluorescent, clear dye, soap and filler salt are usually added to the mixer as well as any stable pigment or other dyes that may be used. Instead of loading a neutralized detergent, the soap mixer can be used as a neutralizing container in which anionic detergent acid is neutralized with aqueous base. Such an acid, for example, may be dodecylbenzenesulfonic acid containing ca. 45 to 50% active ingredient which can be neutralized with an aqueous sodium hydroxide solution, such as a solution containing 39% Na 2 O.

If the alkylbenzene is sulfonated with sulfur trioxide, the acid content of the active ingredient can be as high as 99%. A mixture of higher fatty acids can also be neutralized in the mixer containing the detergent acid to produce a desirable mixture of higher fatty acid soap and detergent.

The soap blend mixture can be spray dried in a conventional spray tower using either down-flowing or counter-flowing flow. Typically, the mixture will have a temperature in the range of 20 to 80 ° C, preferably 40 to 70 ° C, and it will be spray dried in a tower wherein the drying air has a temperature of 200 to 400 ° C to produce spray dried grains of particle sizes in range from screen # 10 to screen # 100 (United States screen series).

24 ΓΊ \ f Ί ρ, Ί no η

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Any particles that are outside the desired range can be removed by screening and can be re-treated. The grains may have a weight in the range of 0.3 to 0.6 g / ml, e.g. 0.5 g / ml. They have a moisture content in an interval that can be as wide as about 3 to 20%, but the moisture content will usually be approx. 10 to 15%.

After preparing the spray-dried portion of the agents, other of the components therein may be mixed with the grains or sprayed thereon (and on other components of the product if desired). In general, it will be preferred for the bentonite, enzyme, bleach and any other particulate products such as the powder, agglomerate or prill form (with the exception of the siliconate) which it is intended to add for the spray-dried grains, to be mixed with these, after which any liquids (including siliconate in solution) to be added can be sprayed onto the mixture. However, the order of the components after addition can be varied, and sometimes a portion of the particulate material can be added after one or more of the liquids. Two or 20 more of the particulate materials may be premixed prior to addition, and similarly liquid mixtures may also be prepared.

Solvents can be used for various components to be used as liquids, and in some cases emulsions can be used. Thus, although the siliconate is preferably used in dissolved form in water, if a less soluble siliconate is used, it can be used as an aqueous emulsion.

In some cases, it may be desirable to use the siliconate in an aqueous emulsion together with perfume and / or nonionic detergent. However, it is very preferable first to coat the unpainted detergent with an aqueous siliconate solution spray and then to spray perfume on the "siliconized" product. In some cases, it may be desirable to stretch the perfume with a suitable solvent, such as a relatively odorless alkylate (hydrocarbon). Instead of spraying the siliconate onto the mixture of spray dried (or otherwise prepared for similar product characteristics) detergent grains, bentonite agglomerate, enzyme prills or agglomerates and perborate particles in admixture, the siliconate may be applied to such individual components separately or in various combinations, such application being made with separate sprays of siliconate, in which case the amount thereof applied to the various components, can be easily controlled, or a single silicon spray can be performed on different feed streams of such components as they enter a suitable mixer. When nonionic detergent is added (and it will sometimes be preferably, all the nonionic detergent is added in soap mixture-15 clean, so that the siliconate will have the greatest depletion-assisting effect), it can be sprayed or otherwise satisfactorily applied to the surfaces of the spray-dried grains before mixing with the other particulate components of the final product and before applying siliconate spray thereon. As previously stated, the liquid nonionic detergent can also be mixed with the siliconate and / or perfume to be sprayed onto the product, in which case it can act as an emulsifier.

Apparatus for carrying out the various mixtures and sprays is known and will therefore not be described in detail herein. Spraying can be done through conventional nozzles, usually with wide spray pattern design, but other types of spraying equipment can also be used. The mixers may be of different designs, but preferably include the rotating, sloping tubes or drums within which spraying may be performed. However, V-shaped mixers, especially those with continuous feed design, as well as other commercial powder mixers may also be satisfactory.

The amount of silicon that will be sprayed onto the surfaces of the various detergent-shaped components of the detergent will

DK 160102 B

26 may be such that the final product contains a depletion-contributing amount of the siliconate (or a derivative thereof). Because it is believed that the bentonite agglomerates can to some extent generate satisfactory discharge of the particulate detergent from the filling chamber into an automatic washing machine ("European type"), it may be preferable that a greater amount of the siliconate be applied to the such bentonite agglomerate particles, e.g. until 525, when such is favorable. Only in some cases, the bentonite particles will be treated with the siliconate, in which case the amount of silicon in the final detergent can often be reduced, e.g. by as much as 50¾. Application of the siliconate involves adding moisture to the treated product when the siliconate is in aqueous solution or emulsion (but not, if it is in non-aqueous solution). Such a humidity addition can be either desirable or undesirable, depending on the moisture content and properties of the detergent as well as the treatment apparatus. The concentration of siliconate in the spray liquid can be adjusted accordingly. Of course, the larger the spray volume and the greater the silicon thinning, the more uniformly a spray can be distributed on the particulate material. On the other hand, if the product is at or near too high a moisture concentration, a diluted silicone spray can aggravate this condition. Generally, the siliconate concentration in the liquid will be at least 5¾ and preferably at least 10¾. Because the siliconate is completely miscible with water, higher concentrations can be used which are usually in the ranges of 5 or 10 to 25 or 50¾.

The various mixing and spraying operations will usually take place at approx. room temperature, but such 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 similar to the particle sizes of the final product and are within the range of sieve readily from screen # 10 to 100 or 200 (the intervals for perborate and enzyme can go up to screen # 200). The agglomerated bentonite particles will be thus obtained by agglomerating or compressing finer particles, such as 5, of which more than 50% pass through a No. 200 sieve. Such particles will be substantially free of hard particles and will usually get from 0.05 or 0.15 to 3 or 5%, preferably 0.1 or 0.15 to 0.5 or 1% siliconate, such as potassium methyl siliconate or sodium propyl siliconate. 10 sprayed onto the surfaces thereof to at least partially coat such surfaces. They may be colored with a suitable dye or pigment, such as "Acilan" Brilliant Blue FFR, or another such or other dye may be applied together with the siliconate. The silicone does not make the color 15 dark. Sometimes the bentonite agglomerates may be larger than the other particles in the product, e.g. 10 to 50¾ larger in diameter, to accentuate their difference in size. In many cases, the bentonite agglomerates will preferably be sodium carbonate-treated bentonite (such treatment improves the color of colorless clay) and will contain magnesium carbonate and / or calcium carbonate therein resulting from such treatment. When the particles are only partially coated with siliconate, it is desirable that at least 10¾ of the surface area (of the corresponding spheres) be covered by the siliconate, and most preferably a greater percentage will be coated, e.g. 50¾, to facilitate dispensing. Similar considerations and conditions apply when treating the enzyme, bleach and detergent particles, except that in such cases a smaller amount of siliconate may be used than the amount used for coating bentonite agglomerates.

In the various cases mentioned above, the coating of the solid siliconate will normally occur on the outer 1¾ of the thickness of the particles. For a particle 1 mm in thickness, such a silicon coating, for example, would be approx. 5 microns thick. The coating will preferably occur on the outer 0.5¾ of the grain diameter of the particle, most preferably the outer 0.2¾ thereof.

When only partial coatings are applied and when larger percentages of silicon are used, such as when only the bentonite agglomerates are coated, the silicon thicknesses will of course be greater, but preferably less than 2¾. Usually, such thicknesses will be at least 0.05¾ of the particle thickness.

The products. The invention has many advantages, several of which have already been mentioned. With respect to the products, the application of siliconate to the particle surfaces, even when the entire particle is not covered by the siliconate, improves the dispensing properties of such particles without any adverse effects. Detergents of the types described herein as well as the particulate components thereof in such agents are easier to dispense from a filling compartment in an automatic European type washing machine than is the case for control products 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 experiments employing a variety of brands of such European washing machines, the assessor noticing the number of particles remaining in the filling compartment after a normal filling and dispensing operation or after 25 such repeated operations. In order to accentuate the differences and make the experiment more difficult, the walls of the filling compartment are first moistened to promote the attachment of the bentonite (and other materials) thereto. To simulate such an experiment, one can sprinkle equal weight amounts of the test product and the control product on a wet, horizontal surface and leave the products for 1 or 2 minutes, then direct a gentle spray of water onto the particles for a metered period, e.g. .

30 seconds, after which the number of particles can be compared. In such experiments, the products of the invention show a marked improvement over the control products. Normally, less than half the number of particles can still be expected to adhere to the pre-wetted surfaces when the "test product" is used, compared to the control product. Often, no particles will adhere to the pre-moistened surface when at least 0.15? 0 siliconate is used, while more particles will adhere when at least 0.05 but less than 0.15% siliconate is used, and a significant number particles by attach when no siliconate is present.

While most of the detergent will be discharged into the washroom ·· 10 during normal use of the automatic washing machine, so that retention of some particles in the filling chamber may initially be no more than psychologically regrettable, greater numbers may be retained by repeated washing, thereby altering the composition of the fabric softening detergent and possibly also significantly affecting the filling weight. Also, the appearance of the filling compartment with particles contained therein is unsatisfactory and may lead to consumer rejection of the product. Because of the different washing methods used in the United States, coating of bentonite-detergent particles with siliconate may not be so important there, but it is believed that the presence of the siliconate on the particles will help to make the detergent more stable and more free-flowing, especially under moist conditions and will help counteract any gelling of the bentonite under such conditions.

In addition to promoting dispensing, the silicone also has the desirable effect of preventing excessive foaming of the detergent in aqueous solution. The bentonite also helps to reduce foaming, and the combination is superior to the effect of the individual components. The siliconate is also found to have a stabilizing effect on the coated enzymes and bleaches thereby, and helps prevent reaction between perfume components and other detergent ingredients, thereby assisting in the stabilization of perfume. λ η ^ γ · ο π

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but. It can also have such an effect on dyes.

These various advantages are obtained even without the disadvantages of the product, which consists in the product becoming too hydrophobic, because it is initially water-soluble. It does not generate the desired rapid dissolution and dispersion of the detergent components, and does not appear to cause undue build-up of hydrophobic deposits on washed and softened laundry. It does not generate the particular softening effect of the hydrophilic bentonite, nor does it generate the good purity of the agent. The resulting detergents are excellent detergents and effectively soften washed laundry, which has been established by comparative tests with similar agents containing neither bentonite nor siliconate. The products are satisfactorily free-flowing and 15 have desirable room weight and appearance. Furthermore, they are non-dusty, which may be at least partly due to the siliconate.

Methods in which siliconate solutions or emulsions are sprayed on detergent, bentonite and other detergent component particles are readily performed and do not require special equipment. Due to the water solubility of the siliconate, this can be applied in aqueous solution without the addition of other components to the detergent composition. Nevertheless, it can also be emulsified or otherwise distributed with other detergent components. The methods are suitable for modification to allow different concentrations of siliconate on different detergent components. The coating materials do not gel or thicken inadvertently, do not block spray nozzles, and do not form rubbery deposits in the spray and mixing equipment. The silicon 30 can be applied at room temperature because it does not require heating, as some other protective coating materials do. In particular, the siliconate can be retained on the surfaces of the particles, making it possible to use less while still producing the desired dispensing effect. Apparently due to the nature of the siliconate or derivative thereof on the detergent particle or component particle, this is also effective even when the particle is not completely covered therein.

The following examples illustrate the invention. Unless otherwise stated, all parts are parts by weight and all temperatures are in ° C.

Example 1.

A soap blend mix of a total of 3,199.5 kg of material is prepared by reacting 364 kg of dodecylbenzenesulfonic acid ("Dobane" 10 JNQ 448.8¾ active ingredient)) and 167 kg of hydrogenated fatty acids (16 to 18 carbon atoms per mole of fatty acid) with 47 kg of caustic soda (38¾ Na₂O) in an aqueous medium containing an appropriate amount (to maintain the reaction) of 952 kg of urban water (300 ppm hardness, such as CaCO₂). The remainder of the water is used to cool the reaction mixture as needed and to dilute other components of the soap mixer mixture. To the soap mixer is then added 242 kg of aqueous sodium silicate solution (Na 2 O: SiO 2 = 1: 2.4) with a concentration of 44.1¾ solids, 7.5 kg of fluorescent brightening agent, 7 kg "Sydex" 808 ( 85 µg MgSiO 2 and 15¾ magnesium DTPA), 1,252kg of hydrated sodium tripolyphosphate (TPP "H"), 54kg of anhydrous sodium sulfate (99.5¾ pure) and 107kg of a nonionic detergent which can be considered as a condensing agent. the product of 11 moles of ethylene oxide with 1 mole of higher fatty alcohol 25 having 12 to 15 carbon atoms per moth.

The soap blend mixture is heated for approx. 1 hour with stirring so that its temperature rises to approx. At 50 ° C, it is pumped to a spray drying tower, where, at increased pressure, it is sprayed through several spray nozzles into the drying air at a temperature of approx. 300 ° C. Particles with a moisture content of approx. 12¾, most of which are in the range from screen # 10 to screen # 100. Particles outside this range are deposited.

32

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63.1 parts of the spray-dried powder (room weight of about 0.4 g / ml) is then mixed with 0.3 parts prill form enzyme in prill ("Alcalase" at 2 Anson units per gram, although "Maxa-tase" P 440,000 can be used instead), 20 parts of granular 5 sodium perborate and 16 parts of agglomerated bentonite. All such powders have particle sizes in the particle size range of the spray-dried detergent component, but smaller particles of the enzyme and perborate can also be used, down to approx. screen No. 200. The bentonite particles are composed 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 dye being applied to the surface of the particles. The bentonite particles are prepared by agglomerating more finely divided particles of bentonite ("Laviosa" AGB) with the dilute sodium silicate solution in the water) and then staining. The bentonite used is a bentonite that has been treated with sodium carbonate to replace calcium and magnesium therein with sodium (see the previous description for a description of this material), and from which a natural content of hard material grains (hard enough to being difficult to crush with a hammer) has been removed after treatment by centrifugal separation. The moisture content of suitably agglomerated bentonite can be varied and may be as low as 3¾ after mixing with other 25 components of the present softening detergent.

On the mixture of spray-dried grains, enzyme, perborate and colored bentonite particles in a sloping drum mixer is sprayed a mixture of 0.5 parts of the non-ionic detergent, 0.25 parts of "Rhodorsil" siliconate 51 T (50¾ solution of potassium methyl siliconate) and 0.25 parts detergent pair of fumes. The spraying is controlled so that the sprayed liquid uniformly coats the particles in the mixer or tumbling drum to produce approx. 100 parts uniform product.

The final product has particle sizes in the range from screen DK 16 :: -: 02 3 33 No. 10 to screen No. 60, a room weight of approx. 0.5 g / ml and a moisture content of approx. 12% (although this can be reduced to about 9% on standing). The resulting particulate fabric softening detergent is free flowing and has a pleasing appearance with the somewhat larger (average 20 to 200% larger in diameter) blue agglomerated bentonite particles in contrast to the other white particles and it is non-hesitant.

The manufactured product is subjected to practical washing experiments 10 and is found to be an excellent detergent with desirable textile softening properties. Without judgment, it is noted that it is easier to dispense, leaving fewer particles in the filling compartment of an European-type automatic washing machine than a control sample in which the silicone coating does not exist. This is especially important when the bentonite particles are larger, since they have a greater tendency to adhere to wet chamber walls during dispensing.

When the above experiment is repeated, but using 100 kg of dodecylbenzenesulfonic acid, 1,324 kg of TPP "H" and 0.6 parts of 20 "Rhodorsil" siliconate 51 T instead of the amounts previously used, the resulting product has satisfactory physical properties and effects, but it is even more easy to dispense automatically, leaving no particles left in the filling compartment of an European washing machine of European type.

In modifications of the above example, the anionic detergent is replaced with equal amounts of sodium lauryl sulfonate, hydrogenated sodium tallow sulfate and sodium tallow alcohol polyethoxy (3 EtO) sulfate, respectively. Alternatively, mixtures of such materials are used together, e.g. equal parts sodium dodecylbenzenesulfonate and hydrogenated sodium tallow alcohol sulfate. In all such cases, the resulting final detergent is a detergent which is an excellent 34

DK 160102B

fabric softener detergent. All such products also have improved dispensing properties when tested using the methods previously described. Similar results are also obtained when, instead of varying the anionic detergent, the nonionic detergent is changed by replacing it 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 ethyl alcohol of 3 or 7 moles of ethylene oxide per liter. moles, or with a mixture of two or more such detergents, e.g. in equal parts.

Also, when half or all of the sodium tripolyphosphate is replaced with NTA, the final product is a satisfactory detergent with emollient properties and it has improved dispensing properties compared to a control sample of the same composition without the siliconate.

When the soap is omitted from the composition, diminished foam control is obtained, but otherwise the product is acceptable and is just as described above. When sodium perborate is replaced by other bleaching agents such as sodium persulfate and magnesium dimonoperoxyphthalate, good bleaching and cleaning by the product can still be achieved. When known oxidizing activators are present, bleaching can be performed using the agent at temperatures lower than the boiling point (which temperatures are normally used in the procedures of this example to obtain maximum bleaching effect). When it is desirable to incorporate more silicate into the product, the amount of silicate is doubled by addition of aqueous sodium silicate particles of similar size together with the other post-added particulate solids.

When sodium propyl siliconate is used in place of potassium methyl siliconate, similar products are obtained, and this is also the case when siliconates with lesser degrees of water solubility are used instead of some, e.g. 25%, of the other si-35 liconates.

DK '-,: 1102 3

Example 2.

The procedures of Example 1 are varied by applying the siliconate in aqueous solution (20¾ solids), in the form of a finely divided spray (preferably with "micron size" spray droplets, for example from 1 to 50 or from 1 to 10 microns in diameter), or otherwise in the form of satisfactorily small size liquid droplets on each of the particulate components to be mixed separately before such mixing. The various coated particles all have room weights 10 in the prescribed range (0.3 to 0.6 g / ml, eg 0.5 g / ml). Then the perfume is sprayed in a similar manner on the mixture. The non-ionic detergent is not post-sprayed but is instead incorporated into the soap blend mixture. The resulting product is one which also has improved dispensing properties. The silicon-coated agglomerated bentonite, the spray-dried detergent grains (without bentonite), the enzyme and the perborate can all be separately produced and stored and are then suitable for composition of fabric softening detergents of different compositions and with different desirable properties, e.g. coated bentonite plus non-overwrapped spray-dried grains.

Example 3

An emollient detergent corresponding to the detergent of the first composition of Example 1 is prepared from 25 a soap blend mixture of 10.24 parts of the dodecylbenzenesulfonic acid, 2.81 parts of the hydrogenated fatty acid, 0.81 part of the caustic soda, 26.54 parts water, 37.2 parts pentane sodium tripolyphosphate (hydrated), 6.8 parts sodium silicate solution, 0.21 parts fluorescent brightener, 1.46 parts sodium sulfate and 3.0 parts of the nonionic detergent, added in order. This is spray dried by the method described in Example 1 to prepare 62.5 parts of a product of similar bulk weight and particle size. The spray-dried particles are then mixed with 0.3 parts proteolytically

DK 16 D1Π 2 B

36 enzyme, 20.0 parts of the sodium perborate granulate, 16.0 parts of the agglomerated bentonite and 0.2 parts of "Sydex" 808, and on the round swirled powder mixture is sprayed a mixture of 0.3 parts of detergent perfume and 0.4 parts linear 5 alkylate and 0.15 part potassium methyl siliconate are sprayed onto the product in suitable liquid state, preferably dissolved in water (50 S5 concentration). The manufactured product has better dispensing properties for dispensing from the filling compartment of an automatic washing machine under normal use.

It exhibits a slightly greater foaming tendency than the corresponding products of Example 1. When 0.3 parts of the siliconate is used, the dispensing properties of the detergent are further improved.

When, instead of using an agglomerated sodium carbonate-treated Italian bentonite from which hard particles have been removed, as in Example 1, a competing product (Winkelmann agglomerate) or a Wyoing-type bentonite such as that sold is used. under the trade name Mineral Colloid No. 101 (formerly "Thixogel" No. 1), 20 similar end products are obtained, which are good softening detergents and easily dispensed. Also, when other lower alkyl siliconates are used, such as sodium propyl siliconate, similar results are obtained. When the blue "Acilan" dye used to stain the bentonite agglomerates is replaced by ultramarine blue, good coloring and bluing effects are obtained. Similarly, when the siliconate is applied to the agglomerated bentonite, the total amount of siliconate in the product being the same or in some cases 50¾ smaller, the resulting detergent's properties are similar to those previously described and the dispensing is also improved compared to dispensing of a control sample.

Example 4

When the amounts of the various components of the previous examples are modified + 10%, + 20% and + 30%, being kept within the previously stated ranges and the ratios of anionic detergent to nonionic detergent are kept in the range from approx. 1: 1 to 3: 1, the ratio of total detergent-5 content to builder content is kept in the range of approx. 1: 3 to 1: 8, and the total ratio of sodium bentonite to detergent is kept in the range of approx. 1: 1 to 2: 1, products having properties similar to those described in Example 1 are obtained. This is also the case when the water-soluble builder salt (s) of Example 1 are replaced with zeolite A (20% hydrated). and when any of a variety of synthetic anionic and nonionic detergents is used in admixture, optionally with an amphoteric detergent such as a "Miranol" type detergent. The invention can also be used to improve the dispensing properties of various other bentonites and particulate detergents with widely different compositions, bulk density (0.2 to 0.9 g / ml) and sizes (preferably sieve 10-40).

Claims (7)

A high performance textile softening particulate detergent suitable for automatic machine washing of water in water and may be dispensed from a filling space in such machine by the action of water passing through such space comprising a composite synthetic organic detergent which is an anionic or a nonionic detergent or a mixture thereof, a builder's amount of synthetic organic detergent builder which is a water-soluble or a water-insoluble builder or a mixture thereof and a softening amount of bentonite, and optionally other usual detergent components, in that it contains 5-25% by weight of bentonite present in the form of particles coated with 0.05-5% by weight of dosage enhancing salt of a lower alkylsilonic acid and / or a polymerization product or products thereof formed during storage . Detergent according to claim 1, characterized in that it comprises 3-15% by weight anionic organic detergent or 1-15% by weight non-ionic organic detergent or a mixture of 3-10% by weight anionic detergent and 1-5% by weight not -ionic detergent and 20-75 wt.% water soluble and / or water insoluble builder 25 and 2-25 wt.% bentonite coated with 0.05 to 5 wt.% salt of a lower alkyl of 1 iconic acid and / or a polymerization product or products. thereof formed during storage. Detergent according to claim 1, characterized in that it comprises 3-10% of a sodium salt of a synthetic anionic organic detergent which is a sulfonate or a sulfate or a mixture thereof, 1-5% of a nonionic detergent, 0-10% of a water-soluble alkali metal soap, 20-75% of a builder, 5-35% of a bleaching agent which releases oxygen in aqueous solution at 35 elevated temperature, 5-25% of concrete and 0.05-3% of an alkali metal lower alkyl siliconate and / or a polymerization product or products thereof formed during storage. DK 16 ^ 02 B Detergent according to claim 3, characterized in that the sodium salt of the anionic detergent is a sodium linear higher alkylbenzenesulfonate, wherein the higher alkyl group contains 10 to 14 carbon atoms, a sodium higher fatty alcohol sulfate wherein the higher fatty alcohol contains 10 to 15 carbon atoms. , or a sodium-higher fatty carbon polyethoxysulfate, wherein the higher fatty alcohol contains 10 to 18 carbon atoms and contains from 3 to 30 ethoxy groups per minute. or a mixture thereof that the nonionic detergent is a 10 higher fat 1koxy-poly-lower alkoxy lower alkanol, wherein the higher fat 1koxy group contains 10 to 16 carbon atoms and the lower alkoxy group and lower alkanol contains 2 to 3 carbon atoms and containing from 3 to 20 lower alkoxy groups per mole, that the soap is a sodium soap of higher fatty acids with 10 to 24 carbon atoms per that the builder is a water-soluble salt or a water-insoluble zeolite or a mixture thereof, that the bleach is sodium perborate, that the bentonite has a moisture content of at least 3% and swells in water, its swelling capacity being at least 1 ml / g, that alkali metal -20 lower alkyl siliconate is water soluble, the alkali metal therein is potassium or sodium and its lower alkyl group has 1 to 3 carbon atoms. Detergent according to claim 1, characterized in that the bentonite particles are in the form of agglomerated pairs of particles formed after sodium carbonate treatment of bentonite containing magnesium and / or calcium in order to replace at least some of such magnesium and / or calcium with sodium, thereby obtaining magnesium carbonate and / or calcium carbonate. 6. Agglomerated bentonite particles which can be used for incorporation into a particulate heavy duty detergent containing anionic and / or nonionic detergents and water-insoluble and / or water-insoluble builders for use in automatic washing machines, characterized in that the bentonite particles are fully or partially coated with 0.15-5% salt DK 16 Π'ύ2Β of a lower alkylsilonic acid and / or a polymerization product or products thereof. Agglomerated bentonite particles according to claim 6, characterized in that they have particle sizes in the range of 149 microns to 2.00 mm and are agglomerates of substantially grain-free particles of sodium bentonite passing through a layer having a sieve opening of 149 µm, of which more than 50% pass through a sieve having a sieve opening of 74 µm, and 10 formed after sodium carbonate treatment of bentonite containing magnesium and / or calcium, with the magnesium carbonate and / or calcium carbonate formed therewith, and wherein the particles are fully or partially coated with 0.15-5%, preferably 0.15-1% potassium methylsiliconate, which has been sprayed onto the surfaces of the agglomerated particles to at least partially coat them. / 20 25 1 35