SE459658B - PARTICULAR HIGH-EFFICIENT TEXTILE SOFT DETERGENT COMPOSITION INTENDED FOR MACHINE WETS, AGGLOMERATED BENTONITE PARTICLES, POSSIBLE TO INTRODUCE IN A PARTICULAR BIO-EFFECTIVE DETERGENT DETERGENT DETERGENTS - Google Patents

Description

459 658 10 15 20 25 30 35 35 can resist being removed from the surfaces on which they are adhered. For example, in washing machines and other appliances equipped with automatic dosing or filling compartments, not all detergent particles may flow or be flushed out of the dosing compartment, especially when the compartment walls were wet before the introduction of the detergent. Incomplete dispensing of the desired amount to the washing machine reduces the concentrations of the effective cleaning and emollient components in the washing water and can lead to incorrect concentrations of detergent and emollients being used.

It can also lead to an unpleasant accumulation that the consumer may find disturbing. The results are in both cases undesirable and should be avoided if possible.

The present invention provides a high performance washing and fabric softening particulate detergent composition which is useful in automatic machine washing of laundry in water and which can be dispensed from a metering compartment of the machine by the aid of water fed through this compartment, which composition contains 3 to 10 % sodium salt of a synthetic anionic organic surfactant which is a sulfonate or a sulphate or a mixture thereof, 1 to 5% of a nonionic surfactant, 0 to 10% of a water-soluble alkali metal soap, 20 to 75% of a detergent , 5 to 35% of a bleaching agent which releases oxygen in aqueous solution at elevated temperature and an emollient quantity of bentonite, and the composition contains 5 to 25% by weight of bentonite present in the form of coated particles (LOS - 3% by weight of an aliquot). ring facilitating lower alkali metal alkyl silicone and / or dispensing facilitating derivatives thereof.

Preferably, the siliconate ratio is in the range of 0.15 - 1% in preferred embodiments of the invention. The synthetic organic surfactant includes both an anionic surfactant which preferably consists of a linearly higher sodium alkyl benzene sulfonate, and a nonionic surfactant which preferably consists of a condensation product of a higher fatty alcohol and polyethylene oxide, 459658 and a higher fatty acid soap are present, the detergent salt being primarily pentasodium tripolyphosphate or NTA or a mixture thereof, with a small amount of sodium silicate, the bentonite is a swelling bentonite having a water content of at least 3% and the siliconate is a lower alkali metal alkyl silicone, or more preferably potassium methyl silicone, and 5 to 35% of bleaching agent which releases oxygen in aqueous solution at elevated temperature, such as sodium perborate, is present. The invention also relates to agglomerating bentonite particles according to claim 12 and a method according to claim 16 for producing the particles. Embodiments of the various aspects of the invention are set forth in the appended dependent claims.

The organic surfactant (s) used should usually be either nonionic or anionic and a combination of both is very advantageous, but suitable amphoteric or ampholytic surfactants, such as those sold under the brand name Miranol, can also be used together with nonionic and anionic substances. in the present compositions fi a. Cationic surfactants, such as the quaternary ammonium halides, such as those sold under the trademark Arosurf, may also serve as complementary fabric softeners in these products, but are generally not used.

Various synthetic anionic organic surfactants, such as the designated form of alkali metal or sodium salts, may be used, such as sulfonates and sulfates, usually in but most preferred are the linear higher alkyl benzene sulfonates, the higher alkyl or fatty alcohol sulfates and the higher fatty alcohol polyethoxy or -polyethoxylate sulfates. Preferably the higher alkyl group in the higher alkylbenzene sulfonates is linear with 10 to 14 carbon atoms and more preferably 11 to 13 carbon atoms, eg 12, and the sulfonate is a sodium salt. The alkyl sulphate is preferably a higher fatty alkyl or alcohol sulphate having 10 to 16 carbon atoms and more preferably 12 to 14 carbon atoms, for example 12, and this too is used in the form of the sodium salt. The higher fatty alcohol polyethoxy sulfates should preferably have 10 to 18 carbon atoms and more preferably 12 to 16 carbon atoms, eg 12, in the higher fatty alcohol moiety, the ethoxy content should preferably be between 3 and 30 ethoxy groups per mole, more preferably 3 or 5 to 29, and the surfactant should be a sodium salt. Thus, it appears that the alkyl groups of the sulfonates and sulfates are preferably linear or higher fatty alkyl groups having 10 to 18 carbon atoms, that the cation is preferably sodium and that when a polyethoxy chain is present the sulfate group is present at the end thereof.

Other useful anionic surfactants are the higher olefin sulfonates and the paraffin sulfonates, for example the sodium salts in which the olefin or paraffin groups have 10 to 18 carbon atoms. Particular examples of preferred surfactants are sodium dodecylbenzenesulfonate, sodium tallow alcohol polyethoxy (3 EtO) sulfate and sodium hydrated tallow alcohol sulfate. In addition to the mentioned preferred anionic surfactants, other ones from this well known group may also be present, in particular in only smaller quantities relative to the previously mentioned. Mixtures thereof can also be used and in some cases the mixtures may be superior to the individual surfactants. Although various nonionic surfactants with satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxy-containing aromatic and aliphatic bases, such as nonylphenol and the oxotype of alcohols, it is preferable that the nonionic surfactant be a higher -fatalko- xipoly-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 these products, the higher fatty alkoxy or alcohol moiety has 10 to 16 carbon atoms, preferably 12 to 15 carbon atoms, and the nonionic surfactant contains between about 3 and 20 lower alkoxy groups, preferably 5 to 15 and more preferably 9 to 13 ethylene oxide groups per mole, eg II.

The detergent of the synthetic organic surfactant, which helps to improve the detergent action of the surfactant, is either a water-soluble or water-insoluble builder or a mixture thereof. Of course, mixtures of water-soluble builders can also be used, such as polyphosphate and NTA (nitrilotriacetic acid salt, usually the sodium salt), but of the water-insoluble builders, only the zeolites should generally be present, although mixtures of the zeolites may also be advantageous. . Although zeolites are useful components in the compositions, it is generally more advantageous to use one or more water-soluble detergent salts, and often this or these are the only detergent present.

The water-soluble detergent composition used or the mixture thereof may consist of one or more of the materials conventionally used or suggested as suitable for this purpose. They include inorganic and organic detergent salts and mixtures thereof. Among the preferred inorganic detergent salts may be mentioned various phosphates, preferably polyphosphates, for example tripolyphosphates and pyrophosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate. Trisodium nitrilotriacetate (NTA), preferably in the form of the monohydrate, and other nitrilotriacetates, such as disodium nitrilotriacetate, are preferred organic detergent salts. The term NTA, which normally stands for nitrilotriacetic acid, is also used in this specification to denote various salts thereof, preferably the alkali metal salts and in particular the triitride sodium salt. Sodium tripolyphosphate, and NTA can be used in hydrated sodium pyrophosphate forms, which are often preferred, but anhydrous forms can also be used. Of course, carbonates, such as sodium carbonate, are useful detergent salts, which can be used if desired alone or in combination with bicarbonates, such as sodium bicarbonate. When the polyphosphates are used, it may be advantageous for sodium pyrophosphate to be present together with sodium tripolyphosphate in a ratio of 1: 10 to 10: 1, preferably 1: 5 to 5: 1 with respect to this, the total content of these two Detergent salts are about the same as those indicated here for the sodium tripolyphosphate.

Other water-soluble detergent salts which may be effective include the various other inorganic and organic phosphates, the borates such as borax, the terna, the gluconates, the EDTA and the iminodiacetates.

Preferably the various detergent salts should be in the form of the alkali metal salts, either the sodium or potassium salts, or a mixture thereof, the citramene sodium salts being usually the more preferred ones. In some cases, such as when preparing neutral or slightly acidic detergent compositions, acidic forms of the detergents, especially the organic detergents, may be preferred, but usually the salts should be either neutral or alkaline. The silicates, and preferably sodium silicate having a Na 2 O: SiO 2 ratio in the range 1: 1.6 to 1: 3.0, preferably 1: 2 to 1: 2.8, eg 1: 2.35 or 1: 2.4 , can also serve as detergent salts, but because of their strong binding properties and because they can promote undesired adhesion of the detergent particles to the walls of the dosing compartment, they are considered to be a special kind of detergent, and relatively small levels of which must be present (which levels will be indicated independently of the other detergent salts). When it is desired to have higher levels of silicate present in the detergent composition, it may be advantageous to subsequently add particles of hydrated sodium silicate to spray-dried particles containing one or more other detergent salts.

The water-insoluble detergent salts used in this specification are those which help to improve the cleaning ability of the synthetic organic surfactants, in particular that of the synthetic anionic organic surfactants, and in this case the mechanism which increases the cleaning action the ability to be associated with the water softening effects of the detergent salt, such as the removal of calcium and / or magnesium ions from the wash water, usually by an ion exchange mechanism. Although it is within the scope of the invention to use other water-insoluble detergent salts, for practical reasons the zeolites are currently the major insoluble detergent salts used.

The zeolites used include crystalline, amorphous and mixed crystalline-amorphous zeolites, both of natural and synthetic origin. Preferably, the materials can react rapidly enough with calcium ions so that they, alone or in combination with other water softening compounds in the detergent, soften the water before adverse reactions occur between these ions and other components of the synthetic organic detergent composition.

The zeolites used can be characterized as having a high exchange capacity for calcium ions, which is generally between about 200 and 400 or more milligram equivalents of calcium carbonate hardness per gram of aluminum silicate, preferably 250 to 350 mg / eq / g. Although other ion exchange zeolites may also be used, the finely divided synthetic detergent zeolite particles used in carrying out the process of the invention should generally have the formula (Na 2 O) x. (Al 2 O 3) y. (SiO 2) y H 2 O in which x is 1, y is between 0.8 and 1, 2, preferably about 1, z is between 1, 5 and 3.5, preferably 2 to 3 or about 2, and w is between 0 and 9, preferably 2.5 to 6. the zeolite shall be a monovalent cation-exchanging zeolite, i.e. it shall be an aluminosilicate with a monovalent cation, such as sodium or potassium.

Crystalline types of zeolites which according to the invention are useful as good ion exchangers, at least in part, are zeolites from the following crystal structure groups: A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of this type of molecular sieve zeolites may also be suitable, especially when type Aeolite type A is present. These crystalline types of zeolites are well known in the art and have been described in many patents in recent years as being useful as detergents in detergent compositions.

The preferred crystalline zeolites with ion exchange and water softening properties are those present in hydrated or aqueous form and contain bound water in an amount of between about 4% and up to about 36% of the total weight of the zeolite, depending on the type of zeolite used, and they are preferably hydrated to about 15-70% of their capacity. Generally, the water content is in the range of about 5 to 30%, preferably about 10 or 15 to 25%, such as 17 to 22%, eg 20%. Preferably the zeolite should be in finely divided form, the outermost particle diameters being up to 20 microns, for example 0.005 or 0.01 to 20 microns, more preferably between 0.01 and 15 microns, for example 3 to 12 microns, and most preferably between 0.01 and 8 microns average particle size, for example 3 to 7 microns, if it is xrystalline, and 0.01 in 0.1 microns, so as: 0.01 to 0, 05 microns, if amorphous. Although the outermost particle sizes are much smaller, the zeolite particles should generally have particle sizes within the field of view No. 100 to 400, preferably 140 to 325. However, they may sometimes be agglomerated, separately or together with spray-dried particles of detergent composition, to sizes similar to those of the particles, for example 1 10 or 25%. Although sodium sulphate and sodium chloride and other salts added as fillers have no detergent properties, they can sometimes be included in detergent compositions due to their excipient properties, and sodium sulphate is particularly useful as a process aid. In addition to increasing the volume and weight of the product and thereby facilitating dosing, they can also sometimes improve the stability and physical properties of the detergent composition granules in which they are incorporated. Since the compositions in question are satisfactory without any fillers being present, they are often preferably omitted altogether, or any quantity thereof may be very small.

The emollient clay which is an important component in the detergent compositions of the invention is of the type referred to as "bentonite". The bentonites are carbon clay clays (aluminum silicates) containing montmorillonite. Their compositions vary, and they can be obtained from natural deposits in many countries, including Italy, Spain, 459 658 10 15 20 25 30 35 10 U.S.S.R., Canada and the United States (mainly Wyoming, Mississippi and Texas). The bentonites useful in the present invention are those having "lubricating" and dispersing properties which are associated with the swelling ability of water. Although some bentonites, mainly those characterized as calcium (or magnesium) bentonites, have low or negligible swelling capacity, these can be converted or "activated" so that the swelling increases. This conversion can be accomplished by appropriate treatment with alkaline material, preferably an aqueous solution of sodium carbonate, in a manner known in the art, to introduce sodium (or potassium) into the structure of the clay. In addition to improving the swelling of the bentonite, which promotes the softening of the fabric and the dispersibility of the bentonite, in the treatment of the non-swelling clay or the poorly flowing clay with the sodium carbonate solution, for example, 5 to 100%, 10 to 90% or 15 to 50% of the divalent metal content therein to sodium, thereby improving the exchange capacity of the clay with respect to hard water ions, such as calcium and magnesium ions. The resulting by-products, calcium carbonate and magnesium carbonate, are left in the bentonite and appear to have desirable adjuvant properties in the final products. Although the exchange capacity of bentonites in the patent literature has been stated to be relevant for the softening ability, it is a feature of the present invention that good softening of textiles can be achieved with sodium bentonites which have a comparatively low ion exchange capacity. Whether the swelling bentonite (also referred to as sodium bentonite) is a naturally occurring clay, or it is obtained by alkali treatment of a non-swelling or poorly swelling bentonite, it is useful in the fabric softening detergent compositions according to 10 15 20 25 30 The invention. Treated Italian bentonites have proven to be particularly useful, and they are considered to be the most suitable in products intended for the European market. The US market often prefers Wyoming bentonite, and this does not need to be treated, as it already contains sodium ions in the bentonite structure and has swelling properties. Analysis of a typical Italian bentonite (after alkali treatment) shows that it may contain 66.2% S10 2, 17.9% Al2O3, 2.80% MgO, 2.43% Na2O, 1.26% Fe2O3, 1.15% CaO, 0.14% TiO2 and 0.13% K2O. A typical Wyoming or western bentonite (untreated) may contain between 64.8 and 73.0% SiO 2, 14 to 18% Al 2 O 3, 1.6 to 2.7% MgO, 0.8 to 2.8% Na 2 O, 2, 3 to 3.4% Fe 2 O 3, 1.3 to 3.1% CaO and 0.4 to 7.0% K 2 O. It thus appears that the composition of the bentonites is completely different, even though both types have good swelling ability. It is believed that if the Na 2 O content of the clay is at least about 0.5%, preferably at least 1% and more preferably at least 2% (the equivalent K 2 content may also be included), then the clay is sufficiently swellable for the purpose of the present invention and has satisfactory emollient and dispersing properties in water suspension. Although it can be expected that levels of the various constituents of the swelling bentonites (hereinafter referred to as sodium bentonites whether they are natural or "activated") within the ranges between the given typical assays, result in components which are useful in the compositions in question, it is also conceivable that the percentages of the components of the natural swelling bentonite may be increased or decreased by about 10%, and that the typical analyzes of the treated bentonite may be modified by: '10% while the bentonites in these areas are still useful. In addition, other swelling bentonites can be used instead, at least in part. In general, the useful bentonites should have a swelling of at least 1 or 2 milliliters per gram, more preferably at least S or 10 ml / g. Of course, bentonites with greater swelling are also useful. Normally the swelling should be between 5 and 30 ml / g and often it is in the range 5 to 20 ml / g.

The sodium bentonite or the swelling bentonite should generally be agglomerated before being mixed with spray-dried detergent granules and any other adjuvants to be added afterwards. The agglomeration is carried out in a known manner, such as by applying water spray to tumbling bentonite powder, extrusion, compaction, agglomeration in a container or some other technique. However, it is highly desirable that the bentonite be in the form of a finely divided powder prior to agglomeration so that, when the agglomerate decomposes in the wash water, the bentonite particles are small enough to be effective as lubricants when deposited on the laundry. Thus, it is generally desirable that all bentonite powder, prior to agglomeration, pass through a No. 100 sieve (American sieve series), with at least 99% passing through this sieve and more than most of it passing through a No. 200 sieves, and preferably less than about 30% by weight of the particles do not pass through this sieve and more preferably no more than 20% remain on the sieve.

An important factor which promotes the rapid decomposition of the bentonite agglomerates and the dispersion in the washing water, so that the fine particles thereof can adhere to the textile fibers and soften them, is the water content of the bentonite. Although it is desirable to limit the free water content of the bentonite used to about 10% or so, with water contents higher than 15% generally not being used, it is even more important to make sure that the bentonite 20 25 30 35 459 658 13 nitene includes a sufficient amount of free water, most of which is considered to be present between adjacent plates of bentonite, to facilitate rapid decomposition of the bentonite and any other adjacent materials in the particles when the particles or detergent compositions containing them are brought into contact with water, such as washing water. It has been found that at least about 2%, preferably at least 3% and more preferably about 4% water or more should be present in the bentonite (so-called "internal" water), and that the bentonite should not be dried so that less than these percentages of water, not even temporary, are present therein. In other words, excessive drying to the point where the bentonite loses its internal water can significantly reduce the usefulness of the present compositions. When the water content of the bentonite is too low, the bentonite does not contribute to satisfactory swelling and decomposition of the agglomerated grains in the washing water.

Preferred swelling bentonites of the types described above are sold under the brands Laviosa and Winkelmann, eg Laviosa AGB and Winkelmann G 13, both of which are treated Italian bentonites, and Mineral Colloid No. l0l (and other similar designations) corresponding to Thixo-Gel No. 1, 2, 3 and 4 (sold by Benton Clay Company, a subsidiary of Georgia Kaolin Co.). As will be described later, the treated bentonites should preferably also be free of sand and preferably be previously treated by grinding to a fine powder before agglomeration. In general, the commercial bentonite used should have a pH in water (at 6% concentration) in the range of 8 to 9.4, a maximum free water content of about 8%, a specific gravity of about 2.6 and a viscosity at 10% concentration in water in the range 5 to 10 centipois, preferably 10 to 30 cP. The siliconate, which is used in combination with the bentonite, preferably as a coating thereon, and can also be used as a coating on the particles of detergent composition, and which helps to prevent the bentonite and the detergent adheres to the walls of the dosing compartment of an automatic washing machine (and to the walls of other "containers" for the product), is one which can be easily applied to the bentonite and which can at least partially cover these particles and prevent their adhesion to walls in a space in which they can be temporarily stored, even if the walls are damp or wet. The siliconate is a salt of silicic acid, preferably an alkali metal salt thereof, and the silicic acid is preferably a lower alkylsilicic acid. Although it is desirable that the salt-forming metal or other cation be such as to give a water-soluble siliconate so that it can be applied to the bentonite in aqueous solution, this is not necessary, but it may also be possible to use water-dispersible siliconates. It is further within the scope of the invention to use lipophilic siliconates, which can be applied dissolved in an organic solvent or in an aqueous organic solvent, or in corresponding emulsions or dispersions.

The alkali metal in the siliconate is preferably either sodium or potassium, but other salt-forming cations may also be used, provided that the siliconate is suitable for the intended purpose. It is also conceivable that alkali metal salts of silicic acids other than the lower alkyl siliconates may be used, including both aliphatic and aromatic siliconates, but the lower alkyl silicones in which the lower alkyl group has 1 to 3 or 4 carbon atoms, for example potassium methyl silicone and sodium propyl silicone. considered to be preferable. Instead of using the siliconate, an equivalent amount of the corresponding silicic acid and a corresponding base can be used. To achieve the most effective results, it is very convenient to use the lower alkyl siliconates described above, but it is also conceivable that these compounds may polymerize, at least in part, into silicone-containing or other film-forming and antifoam compounds. or polymers, and consequently it is within the broader limits of the present invention to directly incorporate these "derivative" materials, at least in part, as a component of the detergent compositions in question. When a silicone derivative is used, it should be one which helps to improve the dispensing of the bentonite grains or particles of detergent composition from a dosing compartment of an automatic washing machine, such as a compartment from which the particulate contents are rinsed out of the water stream into the washing drum of the machine. Although the process of the present invention should not be construed as limited by the process to be described, it may be that the water-soluble lower alkali metal alkyl silicones (which may also be described as lower alkali metal alkyl silanolates) may be converted to polymethylsiloxanes, such as by atmospheric carbon dioxide or any other acidic material, which may also result in the formation of alkali metal carbonate, such as sodium carbonate, a useful detergent salt. The polymethylsiloxanes are known to be hydrophobic and it is possible that their presence is the reason for the improved properties of the coated bentonite (or other detergent particles) in the improved dispensing from the dosing compartment of an automatic washing machine. The formation of siloxanes by the described reaction has been mentioned in - the publication "Chemistry and Technology of Silicones", by Walter Noll, published by Academic Press, 1968. Although silicones have previously been included in detergent compositions, 459 658 10 15 20 25 30 35 16 due to their antifoam properties, however, there is no known description of the use of water-soluble siliconates as a coating on bentonite and detergent particles to facilitate unhindered release from moist surfaces in the dosing compartment, as in the present invention, and this process and the resulting compositions can not be considered clear from previous technology.

The water-soluble soap which is a desirable component in the present detergent compositions and which has a useful antifoam action in the washing water, which is particularly advantageous in side feed or in horizontal drum washing machines, generally consists of a higher fatty acid soap of alkali metal, such as sodium or potassium, with sodium soaps being highly preferred. The soaps can be made from natural fats and oils, such as those from animal fats and tallow and from vegetable oils and seed oils, such as tallow, hydrogenated tallow, coconut oil, palm kernel oil and the corresponding "natural" and synthetic fatty acids, and they generally have 10 to 24 carbon atoms , preferably 14 to 18 carbon atoms.

Preferably the soaps are made from hydrogenated tallow or hydrogenated tallow fatty acids, for example stearic acid. The water-soluble soap should preferably be chosen so that you get the desired balance between good cleansing properties, effective foam-reducing effect and other good physical properties. In particular, among these other physical properties, mention should be made of the desired hardness, good binding effect and limited tendency to produce adhesive gels under the conditions of use. It has been found that the hydrated sodium tallow soaps best meet these conditions, but compositions containing them should preferably also be treated with silicone to further counteract the adhesion to the dosing compartment walls. In compositions which are to give a desired foaming, the soap content is of course reduced, the soap is omitted or a lower fatty acid soap is replaced instead, for example sodium laurate. Bleach does not need to be incorporated into all detergent compositions of the present invention, but in order to achieve the best cleaning and whitening of the laundry, it is often advantageous to include a bleach. When the temperature of the washing water in the automatic washing machine is sufficiently high, the bleach selected is sodium perborate, as the high temperature is especially when it is higher than 80 ° C (and it can be almost up to the boiling point, eg 90 ° C or 95 ° C) can cause decomposition of the perborate and release bleaching oxygen therefrom. Under these conditions, the sodium perborate, which is often referred to as sodium perborate tetrahydrate or sodium borate perhydrate and which generally has an active oxygen content of at least about 10%, releases the oxygen without the need for any activating agent or decomposing catalyst. When washing takes place at a lower temperature, either in cold water or hot water, for example at temperatures between 20 and GOOC, the sodium perborate generally does not decompose sufficiently to satisfactorily bleach the washed fabrics, and under these conditions an activator should be added or another suitable bleach should be used, also usually together with an activator.

Many such systems have been described in the literature, most of which belong to the class of peroxy compounds, such as persulfuric acid, peracetic acid, permyric acid, perphthalic acid and perbenzoic acid, and salts thereof, such as alkali metal and alkaline earth metal salts, such as sodium and magnesium salts.

Various activators for the compositions are known which promote the controlled release of oxygen therefrom in hot and cold water systems, which activators include heavy metal salts, such as copper salts, as well as various organic and organic compounds, which have been described in the technical literature. Of the low temperature bleaches, magnesium dimonoperoxyphthalate is preferred. Of course, various other oxygen-releasing bleaches, such as the hydroperoxides, can be used, and under appropriate conditions, chlorine-releasing bleaches can be incorporated into the present detergent compositions. 459 658 10 15 20 25 30 35 18 Different adjuvants may be present in the base mixture which can be spray-dried into base granules or detergent compositions, or such adjuvants may be added afterwards, the decision regarding the method of addition often being determined by the adjuvant. physical properties, its heat resistance, resistance to degradation in the aqueous base mixture and volatility. Among the adjuvants that are often added are enzyme powders, which are usually added afterwards to the base grains because they are heat-sensitive. They may consist of some of a large number of commercially available products, which include Alcalase, manufactured by Novo Industri A / S, and Maxatase, both of which are alkaline proteases (subtilisin).

Specific enzyme preparations that can be used are Novo Alcalase ZM (2 Anson units per gram) and Maxatase P 440,000. Although the alkaline proteases are the most widely used, amylolytic enzymes, such as alpha-amylase, can also be used. . The compositions mentioned usually contain active enzymes in combination with an inert powdered medium, such as sodium or calcium sulphate, and the content of active enzyme can vary widely and is generally between 2 and 80% of the commercially available preparation. In this specification, the levels of enzyme preparations given do not refer to the active moiety therein; The fluorescent whitening agents most commonly used are stilbene whitening agents, eg Tinopal 5 BM, especially in extra concentrated form. Among the stilbene compounds may be mentioned cotton bleaches, such as those sometimes referred to as CCIDAS bleaches, derived from the reaction product of cyanuric acid chloride and the disodium salt of diaminostilbene disulfonic acid, including variations thereof with respect to substituents on triazine and aromatic. This class of bleach is known in the detergent art and should most often be used when bleaching components are not present in the final product. When it is desired that the detergent composition include bleaching agents, such as sodium perborate or some other oxidizing bleaching agent, bleach stable bleaches may be incorporated into the base composition. These include benzidine sulfonic disulfonic acids, naphthotriazolyl-stilbenzulfonic acids and benzimidazolyl derivatives. The polyamide whites, which may also be present, include aminocuramine or diphenylpyrazoline derivatives, and the polyester whites which may also be used include naphthotriazolyl style bones. These bleaches are generally used in the form of their soluble salts, for example sodium salts. but they can also be added in the form of the corresponding acids. Cotton bleaches should usually make up the majority of the bleach systems used. When it is desired that the product obtained be completely or partially colored, various suitable dyes and dispersible pigments may be used. When blue dyes, such as acylan blue, or pigments, such as ultramarine blue, are used, they can have a dual effect, as they color some or all of the detergent particles or particles of components in the detergent composition and additionally help to give washed laundry a desired effect. blue hue.

Dyeing of the agglomerated bentonite particles with suitable dyes or pigments may be particularly desirable as the natural bentonite may in some cases be discolored, so that the agglomerate may be converted from particles with a dirty appearance to particles having attractive color and attractive appearance.

The perfumes used, which are usually heat sensitive and may contain volatiles, including a solvent such as alcohol or a suitable glycol or polyol or hydrocarbon, generally consist of synthetic perfume materials, sometimes in admixture with natural components, and usually include alcohols. aldehydes, terpenes, fixatives and / or other normal perfume components known in the art. In addition to the adjuvants mentioned, there may also be included agents which improve the flow properties, anti-settling agents which are added to prevent premature gelation of the mixture in the mixer, dispersing aids, anti-redeposition agents and, in some cases, additional emollients, such as cationic plasticizers such as the quaternary ammonium halides, such as dimethyl dioctadecylammonium chloride. However, as mentioned earlier, the cationic plasticizers should not normally be used, and when used, they should be added afterwards.

Of course, water is present in the mixture from which the spray-dried component of the composition in question is prepared, where it serves as a medium for dissolving or dispersing the various components in the spray-dried granules. A certain amount of water, both in free form and hydrate form, is thus present in the product.

Water can also be used for the agglomeration of the bentonite and perborate powders and for dissolving the siliconate. Although it may be desirable to use deionized water so that the content of hard ions therein can be very low and so that the amount of the metal ions which can promote the decomposition of any organic materials which may be present is reduced to a minimum, or tap water is used instead, and for economic reasons or because of the supply, only such is sometimes used. In general, the hardness of the water should not be higher than about 300 ppm, such as potassium carbonate.

The levels of the various components of the final product according to the invention should be such that they contribute to the formation of an effective fabric softening detergent which is free-flowing and can be more easily dispensed from the dosing compartment of an automatic washing machine by means of washing water passing through this dosing compartment. . The content of anionic surfactant should usually be between 3 and 10% of the final product, preferably 3 to 7% and more preferably 4 to 6%, eg 5%. In general, the nonionic surfactant content should be between 1 and 5%, preferably 2 to 4%, eg 3 or 4%. In cases where nonionic surfactant is not used, the anionic surfactant content can be increased by as much as 5%, and in cases where the anionic surfactant content is excluded, the nonionic surfactant content can be increased by up to 10%, provided that the portioning of the detergent composition remains satisfactory. . Although it is possible to prepare effective detergent compositions without either the anionic or the nonionic surfactant, these products will not be as good as the preferred compositions of the present invention. The content of detergents should generally be in the range of 20 to 75%, preferably 30 to SO% (and this is often preferably a completely water soluble support salt) and more preferably 30 to 40%, eg tripolyphosphate and NTA preferred water soluble detergents below about 35% . As previously mentioned, sodium laxatives may be the only detergents used. When using a mixture thereof, it should preferably contain between 10 and 90% of one of them, the remainder being the other of these supporting agents, and in this range the preferred levels may be 20 to 80% and 40 to 60%. , with supplementary percentages. The same percentages ranges can be used when the detergent comprises a mixture of a water-soluble detergent salt and a water-insoluble detergent, such as a zeolite.

The bentonite content of the fabric softening detergent, preferably in the form of a silicone-coated agglomerate of finer particles of bentonite powder, should be a satisfactory softening amount, which is usually in the range of S to 25%, preferably 10 to 20% and more preferably 14 to 18%, eg about 16%. The silicone used should be used in an amount sufficient to achieve the desired effect on the dispensing, and this amount should normally be between 0.05 and 1%, preferably 0.15. up to 1%, although up to 3% can be deposited. A preferred range for the siliconate content is between 0.1 or 0, 15 and 0.3 or 0.4%, for example 0.15% or 0.3%. When the siliconate is used only as a coating on the bentonite agglomerate, the siliconate content, based on the coated bentonite agglomerate, should generally be at least 0.15%, often 0.15 to 5%, preferably 0.5 to 15% and more preferably 0. 15 to 0.5%, eg 0.4%.

When a fatty acid soap is present, its content should generally not be greater than 10 .mu.m. A preferred range for the soap content is between 2 and 6%, more preferably between 2 and 4%, eg 3%. When a bleach is present, its content should generally be in the range of 5 to 35%, preferably 15 to 25%, eg 20%. It should be noted, however, that these levels are based on the use of sodium perborate and should be modified when other oxidizing agents are used, so as to obtain approximately the same bleaching effect (or active oxygen content). The water content of the product, which does not include hydrate water which cannot be removed by standard heating at 105 ° C for 2 hours, should generally be in the range of 3 to 20%, the higher percentages being permissible when a substantial portion, 1/4 and preferably at least 1/4 2 of water, at least in hydrate form. A preferred water content is between 5 and 17% and an even more preferred such content is between 10 and 15%. All water which cannot be removed in the above-mentioned standard experiment is considered as part of the compound in which it is present as a hydrate, for example a zeolite. 10 15 20 25 30 35 459 658 23 The total content of the various adjuvants which may also be present in the detergent composition should generally not exceed 20%, and preferably be limited to 15% and more preferably to 10%. Although water-soluble sodium silicate has detergent properties, especially in view of its effect on magnesium ions in hard water, its content as it also acts as a binder should not be limited by the previously given levels of detergents, but also are mentioned here together with other adjuvants for the compositions in question. In general, it should not constitute more than 8% of the product, with a general range of 1 to 5%, preferably 2 to 4%, eg 3%.

The salt content in the form of fillers, such as sodium sulphate, when present, should generally be limited to not more than 10%, and is generally between 0.5 and 5%, preferably 0.5 to 2%, e.g. 1.5% of the product. The percentage of proteolytic enzyme used should normally be between 0.1 and 2%, preferably 0.2 to 1%, for example 0.3%, and the percentage of optical brightener dye should be between 0.1 and 2%. %, preferably 0.1 to 0.5%, eg about 0.2%. The perfume content should usually be between 0.05 and 2%, preferably 0.1 to 1% and more preferably 0.2 to 0.5%, eg about 0.3%. Like other adjuvants, it may sometimes be desirable to use small amounts of special sequestering agents and agents which promote the flow properties. A preferred sequestering agent among these materials is diethylenetriaminepentaacetic acid, the magnesium salt (magnesium-DTPA), but other diethylenetriamine acetates may be substituted. Magnesium silicate is a preferred agent that promotes flowability, and it can also serve as a carrier for the sequestering agent.

There is a commercially available mixture of these products which comprises 15% magnesium DTPA and 85% MgSiO 3, and when used the content thereof is preferably between 0.1 and 1% and more preferably 0.1 to 0.5%, t ex 0.2%. The content of sequestering agent (or stabilizer) may be between 0.01 and 0.2%, preferably 0.02 to 0.1%, and for MgSiO 3 the concentration is in the range 0.1 to 0, 9%, preferably 0.2 to 0.5%. The amounts of other adjuvants used should be such that the purpose of including æ fi uwæmæt in the detergent composition is achieved, but in general the amounts should not exceed 1 or 2%, and in general they should be in the range of 0.05 to 1%.

In addition to detergent composition containing synthetic organic surfactant, detergent, bentonite and siliconate, with soap, bleach and adjuvants often also present, the present invention also relates to silicone treated bentonite. In the case of the siliconate-treated baronite, the siliconate content should be between 0.2 and 10%, preferably 0.5 to 5% and more preferably 1 to 3%. For the corresponding detergent composition without bentonite, the siliconate content should be the same as for the final detergent composition, but these levels can be increased by 10 to 100%, depending on the conditions and levels of the different adjuvants in the detergent composition.

In the preparation of the products according to the invention, known spray-drying, agglomeration and mixing techniques (preferably all three) can be applied. Since these are not considered to be particular features of the invention, they are to be described here only briefly. In the spray-drying process, a base mixture is spray-dried which contains the various components which are desirable in the spray-dried grains and which are sufficiently stable to withstand the mixing and spray-drying treatments, such as surfactants, detergents and suitable adjuvants. juvans, in form, of an aqueous base mixture, which should generally contain between about 40 and about 70 or 75% solids, preferably 50 to 65% thereof, the remainder being water. The base mixture may contain the anionic surfactant and some or all of the nonionic surfactant, although no more than 5% nonionic surfactant (based on the final product) should generally be present in the base mixture (the remaining amount, if any, being added to gradually). All detergents or the whole mixture of detergents should generally be included in the base mixture, although this is not necessary.

The bentonite is preferably agglomerated separately and subsequently added to the spray-dried product, but in some cases it can be incorporated into the base mixture. The silicate aqueous solution, stable fluorescent bleach, soap and the salt in the form of fillers are usually added to the base mixture together with some stable pigment and other dyes that can be used. Instead of charging a neutralized surfactant, the mixer can be used as a neutralizing vessel in which anionic organic acid surfactant is neutralized with sodium hydroxide solution. The acid may be, for example, dodecylbenzenesulfonic acid containing about 45 to 50% of active ingredient, which acid may be neutralized with an aqueous solution of sodium hydroxide, such as that containing 38% of Na 2 O. If the alkylbenzene is sulfonated with sulfur trioxide, the active ingredient in the acid may be as high as 99%. A higher fatty acid mixture can also be neutralized in the mixer together with the surfactant to obtain a desired mixture of higher fatty acid soap and surfactant.

The base mixture can be spray dried in a conventional spray tower, using either a cocurrent or countercurrent flow. In general, the mixture should have a temperature in the range of 20 to 80 ° C, preferably 40 459 658 10 was 26 to 70 ° C, and it should be spray dried in a tower in which the drying air has a temperature of 200 to 400 ° C, to obtain spray-dried grains with particle sizes within the sieve range Nos. 100-100 (U.S. sieve series). Any particles that are outside the desired area can be removed by sieving to treat food.

The granules produced have a bulk volume in the range 0.3 to 0.6 g / ml, eg 0.5 g / ml. They have a water content in a range that can be as wide as about 3 to 20%, but this should usually be about 10 to 15%.

After preparation of the spray-dried part of the compositions, other components thereof can be mixed with the granules or sprayed on them (and on other components of the product, if desired). In general, it is preferred that the bentonite, enzymes, bleaches and any other particulate products, such as those in powder, agglomerated or spherical form (excluding the siliconate), which are subsequently added to the spray-dried granules, be mixed therewith. after which any liquids (including the siliconate in solution) to be added afterwards are sprayed onto the mixture. However, the order in which the components are subsequently added may vary, and in some cases some of the particulate material may be added after one or more of the liquids. Two or more of the particulate materials may be mixed together before they are added afterwards and mixtures of liquids may also be present.

Solvents can be used for various components to be applied in the form of liquids and in some cases emulsions can be used. Although the siliconate is preferably applied in dissolved form, in water, this can thus be applied in the form of an aqueous emulsion if a less soluble siliconate is used. In some cases it may be desirable to use the siliconate in the form of an aqueous emulsion together with perfume and / or nonionic surfactant.

However, it is much better to first cover the unscented detergent composition with a spray of silicone aqueous solution and then spray perfume on the "siliconed" product. It may sometimes be desirable to dilute the perfume with a suitable solvent, such as a comparatively odorless alkylate (hydrocarbon). Instead of spraying the siliconate on the mixture of spray-dried detergent grains (or otherwise manufactured products with similar properties), bentonite agglomerates, enzyme beads or agglomerates and perborate particles, the siliconate can be applied separately to one of these different components or to different combinations of these. This can be accomplished with separate spray liquids of the siliconate, in which case the amount of this deposited on the various components can be easily controlled, or a single filter fluid can be sprayed on different fed streams of these components when fed into a suitable mixer. When nonionic surfactant is added afterwards (and it may sometimes be preferable to introduce the entire amount of nonionic surfactant into the mixer so that the beneficial effect of the siliconate during the dispensing is the best possible) it can be sprayed or otherwise satisfactorily applied to the spray dried grain surface. before mixing with the other particulate components of the final product and before applying the silicone spray liquid thereon. As previously mentioned, the nonionic surfactant in liquid form is also mixed with the silicone and / or the perfume to be sprayed on the product, in which case it may serve as an emulsifier. Devices for performing the various mixing and spraying processes are known in the art, so no detailed description is given here. The spraying can take place via conventional nozzles, usually with a broadly designed spraying pattern, but other types of spraying devices can also be used. The mixers may be designed in different ways, but preferably the rotating inclined tubes or drums, within which the spraying can take place, include V-shaped mixers, in particular those intended for continuous feeding, and other commercial powder mixers may also be acceptable.

The amount of siliconate to be sprayed on the surface of the various particulate components of the detergent composition should be such that the final product contains a quantity of siliconate (or a derivative thereof) involved in the dispensing. Since it is likely that the bentonite agglomerate may to some extent counteract a satisfactory discharge of the particulate detergent composition from the dosing compartment of an automatic washing machine (of the "European type"), it may be advantageous for a larger proportion of the siliconate to be applied to the agglomerated bentonite particles, eg up to S%, whenever possible. In some cases only the bentonite particles should be treated with the siliconate, in which case the siliconate content of the final detergent composition can often be reduced, for example by as much as 50%. The application of the siliconate involves the addition of water to the composition to be treated, when the siliconate is in the form of an aqueous solution or water emulsion (but not if it is in the form of a non-aqueous solution). This can be both desirable and undesirable, depending on the water content and properties of the detergent composition and the manufacturing apparatus. The concentration of dewlikonate in the spray liquid can thus be adjusted. The larger the volume of the spray liquid and the larger the dilution of the siliconate, the more evenly, of course, a spray liquid can be distributed on the particulate material. On the other hand, if the product is at the boundary line or has an excessively high water content, a dilute silicone spray liquid may aggravate this condition. In general, the concentration of siliconate in the liquid should be at least 5% and preferably at least 10%.

Since the siliconate is completely miscible with water, higher concentrations can be used, which are usually in the range of 5 or 10 to 25 or 50%.

The various mixing and spraying procedures are generally to be carried out at about room temperature, but operating temperatures in the range of 10 to 40 ° C, preferably 20 to 30 ° C are preferred. The particle sizes of the materials to be coated with siliconate shall generally be the same as those of the final product, within the areas of vision Nr. The range of 10 to 100 or 200 of the perborate and enzyme may extend to No. 200) ~ The agglomerated bentonite particles shall be those resulting from the agglomeration or pressing of finer particles, such as those of which more than SO% passes through a No. 200 sieve. The particles should be substantially sand-free and usually between 0.05 or 0.15 and 3 or 5%, preferably 0, 1 or 0.15 to 0.5 or 1% siliconate, such as potassium methylsilicone or sodium propylsilicone, be sprayed. on the surface of the particles so that it is at least partially coated therewith. They may be colored with a suitable dye or pigment, such as Acilan Brillianzßlue FFR, or this or any other suitable color may be applied together with the silicone. The silicone does not weaken the color. The bentonite agglomerate can sometimes be larger than the other particles in the product, eg 10 to 50% larger in diameter, to accentuate the difference. In many cases, the bentonite agglomerate should preferably consist of sodium carbonate-treated bentonite (which treatment improves the color of discolored clay) and contain magnesium carbonate and / or calcium carbonate resulting from this treatment. When the particles are only partially coated with silicone, it is desirable that at least 10% of the surface (in equivalent spheres) is covered by the silicone, and more preferably a larger portion thereof should be covered, e.g. eg 50%, to facilitate dispensing.

Similar assessments and conditions apply when treating enzyme, bleach and detergent particles, except that in this case a smaller amount of silicone can be used than is the case when coating bentonite agglomerates.

In the various cases mentioned above, the coating of solid siliconate should usually be present on the outside and constitute 1% of the thickness of the particles. For a particle with a thickness of 1 millimeter, for example, the siliconate coating should have a thickness of about 5 microns. Preferably, the coating should be present at 0.5% of the outer part of the particle diameter, of the outer part thereof. and even more preferably at 0.2%. When only partial coating is applied and when larger percentages of the siliconate are used, such as when only the bentonite agglomerate is coated, of course the siliconate thickness becomes larger, but preferably less than 2%. Usually the thickness should be at least 0.05% of the particle thickness.

The products and methods of the invention have many advantages, several of which have already been mentioned. With regard to the products, the application of siliconate to the surface of the particles, even when the whole particle is not coated with the siliconate, improves the dispensing properties of the particles without causing any adverse effects. Detergent compositions of the types described herein, and the particulate components of the compositions mentioned, are easier to dispense from the dosing compartment of a European-type automatic washing machine than control products not treated with siliconate. This difference is most noticeable when it comes to the agglomerated bentonite particles. The experiments performed to compare the results were practical experiments, using a number of different 10 15 20 25 30 35 40 31 - 459 658 makes of European washing machines and the evaluation was done by noting the number of particles remaining in the dosing compartment after normal refilling and "dispensing or after repeated execution thereof.

To emphasize the differences and make the experiment more difficult, the walls of the dosing compartment were first soaked to facilitate the adhesion of the bentonite (and the other materials) thereto.

To mimic this experiment, one can sprinkle the same amount of weight of test product and control product on a wet horizontal surface, leave it for one or two minutes and then direct a weak jet of water towards the particles for a measured period of time, eg 30 seconds, after which the number particles can be compared. In these experiments the products of the invention showed a marked improvement over the control products: in general it can be expected that less than half the number of particles still adhere to the pre-moistened surfaces when the "experiment" product is used, compared to the control product. . Often no particles adhere to the pre-moistened surface when at least 0.15% silicone is used, several particles adhere when at least 0.05% but less than 0.15% silicone is used, and a significant number of particles adhere when no silicone are present. Although most of the detergent is introduced into the washing drum during normal use of the automatic washing machine, so that the retention of some particles in the dosing compartment can initially be only psychologically disturbing, in repeated washing procedures a larger number of particles can be retained, whereby the fabric softener the composition of the detergent changes and possibly also significantly affects the amount of weight invested. The appearance of the dosing compartment with particles retained therein is also unsatisfactory and can lead to the consumer refusing to use the product. Due to the different washing techniques used in the USA, the coating of the detergent's bentonite particles with siliconate may not be as significant there, but it should be noted that the presence of siliconate on the particles helps to make the detergent more stable and free flowing, in particular. under humid conditions, and helps counteract gelation of the bentonite under these conditions.

In addition to facilitating the dispensing, the siliconate also has the desirable effect of preventing excessive foaming of the detergent composition in aqueous solution. The bentonite also helps to limit the foaming and the combination of the two is superior to the individual components. The siliconate also appears to have a stabilizing effect on enzymes and bleaches coated therewith, and it helps to prevent reactions between perfume components and other constituents of the detergent, thereby helping to stabilize the perfume. It can also have such an effect on dyes. However, these various advantages are obtained without the disadvantage that the product becomes excessively hydrophobic, since it is initially water-soluble. The silicone does not interfere with the desired rapid dissolution and dispersion of the detergent components and does not appear to cause any undesired accumulation of hydrophobic deposits on washed and softened laundry. It does not counteract the special emollient effect of the hydrophilic bentonite and it does not impair the good cleaning ability of the composition. The resulting detergent compositions are excellent detergents which effectively soften washed laundry, as determined by comparative experiments with similar compositions which did not contain either bentonite or siliconate. The products are satisfactorily free-flowing and have the desired bulk volume and appealing appearance. In addition, they are non-dusting, which can be attributed at least in part to the siliconate.

Processes in which silicone solutions or emulsions are sprayed on surfactants, bentonite and other particulate detergent components can be easily performed and do not require any special equipment. Due to the water solubility of the silicone, it can be applied in an aqueous solvent without the addition of other components to the detergent.

However, it can also be emulsified or otherwise distributed among the other detergent components. The methods can be modified to allow different concentrations of siliconate on different detergent components. The coating materials do not gel or thicken improperly, they do not clog spray nozzles and they do not form rubbery deposits on the spraying and mixing devices.

The siliconate can be applied at room temperature because it does not require any heating, as is the case with some other protective coating materials. The siliconate can mainly be held on the surface of the particles, which means that a smaller amount can be used while at the same time obtaining the desired contributing effect when dispensing. In addition, probably due to the properties of the siliconate or derivative thereof present on the detergent or component particles, this is also effective even when the particles are not completely coated therewith.

The following examples illustrate the present invention without limiting it. Unless otherwise indicated, all parts are by weight, and all temperatures are in ° C.

Example 1 A base mixture consisting of a total of 3,199.5 kg of material was prepared by adding 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). was reacted with 47 kg of caustic soda (38% Na 2 O) in an aqueous medium containing a suitable proportion (to maintain the reaction) of 952 kg of tap water (300 ppm hardness, as CaCO 3) .The remainder of the water was used to cool the reaction mixture, as desired. , and to dilute the other components in the basic mixture, then 242 kg of aqueous sodium silicate solution (Na 2 O: SiO 2 = 1: 2.4) were introduced into the mixer with a concentration of 44.1 % solids, 7.5 kg stilbene type fluorescent bleach, 7 kg Sydex 808 (85% MgSiO 3 and 15% magnesium DTPA), 1252 kg hydrated sodium tripolyphosphate (TPP "H"), 54 kg anhydrous sodium sulphate (99 , 5% purity) and 107 kg of nonionic active surfactant, which was considered a cow condensation product of 11 moles of ethylene oxide and 1 mole of higher fatty alcohol with 12 to 15 carbon atoms per mole.

The base mixture was heated for about 1 hour with stirring so that its temperature rose to about 55 ° C, and then it was pumped to a spray drying tower where at elevated pressure it was sprayed through a plurality of spray nozzles into drying air at a temperature of about 300 ° C. during the spray-drying, particles with a water content of about 12% were obtained, most of which were within the field of view No. 10 to 100. Particles outside this range were screened away. 63.1 parts of the spray-dried powder (bulk volume about 0.4 g / ml) were then mixed with 0.3 parts of proteolytic enzyme in spherical form (Alcalase, 2 Anson units per gram, although Maxatase P 440,000 can be used instead) , 20 parts granulated sodium perborate and 16 parts agglomerated bentonite. All of these powders had particle sizes within the size range of the spray dried component of the detergent composition, but smaller particles of enzyme and perborate may also be used, down to about no. 200. The bentonite particles consisted 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 were prepared by agglomerating more finely divided bentonite particles (Laviosa AGB) together with dilute sodium silicate solution (in water), after which they were dried. The bentonite used was one treated with sodium carbonate for the exchange of calcium and magnesium therein for sodium (see above detailed description of this material) and from which a natural content of sandy material (hard enough to be difficult to crush with a hammer) after treatment had been removed by centrifugal separation.

The water content of suitable agglomerated bentonite can vary and it can be as low as 3% when mixed with the other components of the emollient detergent in question.

To the mixture of spray-dried grains, enzyme, perborate and colored bentonite particles in an inclined drum mixer was sprayed a mixture of 0.5 parts of nonionic active tensia, 0.25 parts of Rhodorsil siliconate 51 T (50% solution of potassium methyl silicone) and 0 , 25 parts detergent perfume. The spraying was adjusted so that the sprayed liquid evenly covered the particles in the mixer or the tumbling drum, whereby about 100 parts of uniform product were obtained.

The final product had a particle size within the field of view No. 10 to 60, a bulk volume of about 0.5 g / ml, and a water content of about 12% (although this could be reduced to about 9% when the product was allowed to stand). The resulting particulate fabric softening detergent was free-flowing and had an attractive appearance, with a slightly larger average of 20 to 200% larger diameter) blue agglomerated bentonite particles contrasting with the other white particles, and it was non-dusty. 459 658 10 15 20 25 30 35 36 The product produced was subjected to practical washing tests and it proved to be an excellent detergent with the desired fabric softening properties. The assessment noted that it was easier to portion out and left a smaller number of particles in the dosing compartment of a European-type automatic washing machine than a control product without a silicone coating. This is especially important when the bentonite particles are larger, as these may have a greater tendency to adhere to the wet walls of the compartment when dispensing.

When the above experiments were repeated but with 100 kg of dodecylbenzenesulfonic acid, 1324 kg of TPP "H" and 0.6 parts of Rhodorsil Siliconate 51 T instead of the previously stated amounts, the resulting product had the same appealing physical properties and functions but was in addition, it is even more easily automatically dispensable, and it leaves no particles in the dosing compartment of a European-type automatic washing machine.

In modifications of the above examples, the anionic surfactant was exchanged for the same amounts by weight of sodium lauryl sulphate, hydrogenated sodium tallow alcohol sulphate and sodium tallow alcohol polyethoxy (3EtO) sulphate, respectively. Alternatively, mixtures of these materials were used, for example equal parts of sodium dodecylbenzenesulfonate and hydrogenated sodium tallow alcohol sulphate were used together. In all these cases, the final detergent composition was an excellent fabric softening detergent. All products also had improved dispensing properties when tested by the methods described above. Similar results could also be obtained when, instead of changing the anionic surfactant, the nonionic surfactant was changed, which was exchanged for a block polymer of propylene oxide and ethylene oxide, such as Pluronic L-44 or L-62, nonylphenol polyoxyethylene ( EtO) glycol or a condensation product of C12-25 fatty alcohol with 3 or 7 moles of ethylene oxide per mole, or against a mixture of two or more of these surfactants, for example in equal parts.

When half or the whole amount of sodium tripolyphosphate was exchanged for NTA, the final product was also a satisfactory detergent with emollient properties, and it had improved dispensing properties compared with a control sample of the same composition but without silicone. ' When soap was excluded from the composition, a reduced foam control was obtained, but otherwise the product was acceptable and similar to those described above. When the sodium perborate was exchanged for other bleaching agents, such as sodium persulfate and magnesium dimonoperoxyphthalate, good bleaching and cleaning products were still obtained. When known activators of the oxidizing agents were present, the bleaching could be carried out using the composition at lower temperatures than the near boiling point (which are generally used in the performance of this example to achieve maximum bleaching effect). When it is desired to include more silicate in the product, the amount of silicate is doubled by the subsequent addition of aqueous silicate particles of the same size together with the other subsequently added particulate solids. When sodium propyl silicone was used instead of potassium methyl silicone, comparable products could be obtained, and this was also the case when silicones with a lower solubility in water were used instead of a part, eg 25%, of the other silicones. 459 658 10 15 20 25 30 35 38 Example 2 The procedures of Example 1 were varied by applying the siliconate, in aqueous solution (20% solids) in the form of a finely divided spray liquid (preferably with the sprayed droplets in "micron size", eg 1 to 50 or 1 to 10 microns in diameter), or otherwise in the form of satisfactorily small droplets of liquid, on each of the particulate components to be mixed, separately before this mixing. The various coated particles all had a bulk volume within the prescribed range (0.3 to 0.6 g / ml, eg 0.5 g / ml), then the perfume was sprayed in the same way on the mixture, the nonionic surfactant was not sprayed afterwards but was instead incorporated into the base mixture. The resulting product also had improved dispensing properties.

The siliconate-coated bentonite agglomerate, the spray-dried grains of detergent composition (without bentonite), enzymes and perborates can all be prepared separately and stored, and are later suitable for use in the preparation of fabric softening detergents of different compositions and with different desired properties, e.g. ex coated bentonite plus uncoated spray dried grains.

Example 3 An emollient detergent, similar to the first composition of Example 1, was prepared from a base mixture of 10.24 parts of the dodecylbenzene sulfonic acid, 2.81 parts of the hydrogenated fatty acid, 0.81 parts of the caustic soda, 26, 54 parts of water, 37.2 parts of pentasodium tripolyphosphate (hydrated), 6.8 parts of sodium silicate solution, 0.21 parts of fluorescent bleach, 1.46 parts of sodium sulphate and 3.0 parts of the nonionic surfactant, which were added sequentially. The mixture was spray dried in the manner described in Example 1 to give 62.5 parts of a product having a similar bulk volume and particle size. The spray-dried particles were then mixed with 0.3 parts of proteolytic enzyme, Z0 parts of sodium perborate granules, 16.0 parts of the agglomerated bentonite and 0.2 parts of Sydex 808, and a mixture of 0 was sprayed onto the tumbling powder mixture. 3 parts of the detergent perfume and 0.4 parts of linear C10-10 alkylate, and 0.15 parts of potassium methyl silicone were sprayed on the product in a suitable liquid state, preferably dissolved in water (50% concentration). The product produced had better distributing properties when dispensing from the dosing faucet of an automatic washing machine in normal use. It showed a slightly greater foaming tendency than the similar product according to Example 1.

When 0.3 parts of the siliconate was used, the dispensing properties of the detergent composition were further improved.

When, instead of an agglomerated sodium carbonate-treated Italian bentonite which has been freed from sand, as in Example 1, a comparable product (Winkelmann agglomerate), or a Wyoming-type bentonite, such as that sold under the trademark Mineral Colloid No. l0l (formerly Thixogel No. 1), similar end products were obtained, which were good emollient detergents which could be easily portioned out.

When other lower alkyl silicones, such as sodium propyl silicone, were used, similar results could be obtained. When the Acilan Blue dye, which was used to dye the bentonite agglomerate, was replaced with ultramarine blue, a good coloring and blue tinting effect was also obtained. Similarly, when the siliconate was applied only to the agglomerated bentonite, with the same total amount of siliconate in the product, or in some cases by 50% less, the properties of the resulting detergent were the same as those previously mentioned and - the operation was also improved, compared with a control sample. Example 4 When the levels of the various components in the previous examples were modified by 3 10%, 1 20% and 1 30%, while maintaining them within the previously given limits and maintaining the ratio of anionic surfactant to nonionic surfactant within the ratio of about 1: 1 to 3: 1, the ratio of the total surfactant content to the detergent content in the range of about 1: 3 to 1: 8 and the ratio of the sodium bentonite to the total amount of surfactant in the range of about 1: 1 to 2: 1, products having properties similar to those described in Example 1 were obtained. This was also the case when the water-soluble detergent builder or salts of Example 1 were exchanged for zeolite A (20% ~ hydration) and when any of a number of synthetic anionic and nonionic surfactants were added to the mixture, optionally together with an amphoteric surfactant, such as one of the Miranol type. The present invention can also be applied to improve the dispensing properties of various other bentonites and particulate detergent compositions of widely differing compositions, densities (0.2 to 0.9 g / ml) and particle sizes (preferably No. 10- 40 field of view).

The present invention has been described with reference to various examples and embodiments thereof, but is not limited thereto, as one skilled in the art having the description in front of him may, of course, use substituents and equivalents without departing from the scope of the invention.

Claims (18)

10 15 20 25 30 459 658 41 P a t e n t k r a v High-performance washing and fabric softening particulate detergent composition useful in automatic machine washing of laundry in water and which can be dispensed from a dosing compartment of the machine by the aid of water fed through this compartment, which composition contains 3 to 10% sodium salt of a synthetic anionic organic surfactant which is a sulfonate or a sulphate or a mixture thereof, 1 to 5% of a nonionic surfactant, 0 to 10% of a water-soluble alkali metal soap, 20 to 75% of a detergent, 5 to 35% of a bleach which releases oxygen in aqueous solution at elevated temperature and an emollient quantity of bentonite, characterized in that it contains S - 25% by weight of bentonite which is present in the form of particles coated with 0.05 - 3% by weight of an aliquot facilitating lower alkali metal alkyl silicone and / or the aliquot facilitating derivatives thereof. Detergent composition according to claim 1, characterized in that the proportion of the lower alkali metal alkyl silicone coated with the bentonite particles is in the range 0.15 - 1%. Detergent composition according to claim 2, characterized in that the sodium salt of the anionic surfactant is a linearly higher sodium alkyl benzene sulfonate in which the higher alkyl group has 10 to 14 carbon atoms, a higher sodium fatty alcohol sulfate in which the higher fatty alcohol group has 10 to 16 carbon atoms, or a higher sodium fatty alcohol polyethoxy sulphate in which the higher fatty alcohol group has 10 to 18 carbon atoms and which contains between 3 and 30 ethoxy groups per mole, 459 or a mixture thereof, the nonionic surfactant is a high fat alkoxy-poly-lower alkoxy- lower alkanol in which the higher fatty alkoxy group has 10 to 16 carbon atoms and the Kåge alkoxy group and the lower alkanol group has 2 to 3 carbon atoms and which contains between 3 and 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 detergent is a water-soluble salt or a water-insoluble zeolite or a mixture thereof, the bleaching agent is sodium perborate, the bentonite has a water content of at least 3% and swells in water, its swelling being at least 1 ml / g, and the lower alkali metal alkyl silicone is water soluble, the alkali metal therein being potassium or sodium and the lower alkyl groups fi ki have 1 to 3 carbon atoms. Detergent composition according to claim 3, characterized in that it contains between 3 and 7% linearly higher sodium alkylbenzenesulfonate in which the higher alkyl group has 11 to 13 carbon atoms, 2 to 4% of a higher-fatty alkoxy-poly-lower-alkoxy lower alkanol in which the higher fatty alkoxy group has 12 to 15 carbon atoms and the molar ratio of higher fatty alkoxy to lower alkoxy is between 1: 5 and 1.5: 2 to 6% sodium soap of higher fatty acids having 14 to 18 carbon atoms per mol, 30 to 50% water-soluble detergent salt, 15 to 25% sodium perborate, 10 to 20% sodium bentonite and 0.15 to 0.3% potassium methyl silicone. Detergent composition according to claim 4, characterized in that the size of the particles is within the range of sight No. 10 to No. 100, the higher sodium alkylbenzenesulfonate, the soap and the detergent salt are present together in substantially homogeneous particles spray-dried from the same base mixture, the sodium perborate is in the form of separate or separable particles and the bentonite present in the form of separate particles. Detergent composition according to claim 5, characterized in that the lower alkyl group in the linear higher sodium alkyl benzene sulfonate is dodecyl, the nonionic surfactant is a condensation product of a higher fatty alcohol having 12 to 15 carbon atoms and 9 to 13 moles of ethylene oxide per mole of higher fatty alcohol, the soap is a sodium soap of hydrogenated tallow fatty acids, the detergent salt is primarily pentasodium tripolyphosphate and the bentonite particles are in the form of an agglomerate prepared after sodium carbonate treatment of bentonite containing magnesium and / or calcium to get sodium sodium benotite and / or calcium carbonate therein, which particles are coated with or partially coated with potassium methyl silicone. Detergent composition according to claim 6, characterized in that it contains between 1 and 5% sodium sulphate, 0.1 to 2% optical brightener dye and 0.1 to 1% proteolytic enzyme, the agglomerated bentonite particles having an average particle size that is larger than the average particle size of the spray-dried particles and perborate particles, and are differently colored so that they can be easily identified in the detergent composition. Detergent composition according to claim 7, characterized in that the sodium benotnite has a swelling in the range 5 to 30 ml / 9 and a viscosity, in 44% dispersion in water, of 5 to 30 centipois, and consists of an agglomerate of smaller particles of sodium bentonite. Detergent composition according to claim 8, characterized in that it contains about 5% linear sodium dodecylbenzenesulfonate, about 3% nonionic higher-fat alkoxy-poly-lower-alkoxy-lower-alkanol surfactant, wherein the higher fatty alkoxy group has 12 to 15 carbon atoms, the lower alkoxy group and the lower alkanol group have 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 16% sodium bentonite, about 35% hydrated pentasodium trifoliate 3% sodium silicate, about 0.1% potassium methyl silicone, about 0.3% proteolytic enzyme, about 0.3% perfume, about 0.2% optical brightener and of 12% water. k ä n n e - Detergent composition according to claim 1, characterized in that the bentonite particles are in the form of agglomerated particles, prepared after sodium carbonate treatment of bentonite containing magnesium and / or calcium to exchange at least a part of this magnesium and / or calcium for sodium, and with the resulting magnesium carbonate and / or calcium carbonate therein. Detergent composition according to claim 10, characterized in that the sodium bentonite agglomerate has a swelling in the range of 5 to 30 ml / g and a viscosity in 10% dispersion in water, of 5 to 30 centipoise and consists of an agglomerate of less particles of bentonite. Agglomerated bentonite particles, suitable for incorporation into a particulate high performance detergent composition for automatic washing machines containing such bentonite, characterized in that they include a portioning facilitating quantity of a siliconate and / or a the dispensing facilitating derivatives thereof. Agglomerated bentonite particles according to claim 12, characterized in that there is between 0.05 and 3% lower alkali metal alkyl silicone and / or a portioning facilitating derivative thereof on the surface of the particles. Agglomerated bentonite particles according to claim 13, characterized in that they have a size within the field of view No. 10 to 100 according to the American screen series, and prepared after sodium carbonate treatment of bentonite containing magnesium and / or calcium to obtain sodium bentonite, with the resulting magnesium carbonate and / or calcium carbonate therein, and which particles are coated with or partially coated with 0 .05 to 1% potassium ethyl silicone. Agglomerated bentonite particles according to claim 13, characterized in that the proportion of lower alkali metal alkyl silicones is in the range 0.15 to 1%. 16. A method of preparing agglomerated bentonite particles suitable for incorporation into a particulate high performance detergent composition which can be dispensed from the metering compartment of an automatic washing machine by the aid of water fed through this compartment, characterized in that on the surface of the agglomerated bentonite particles, a dispensing quantity of a silicone and / or a dispensing derivative thereof facilitates the dispensing quantity. 17. A method according to claim 16, characterized in that the agglomerated bentonite particles have particle sizes within the field of view No. 10 to 100, and consists of agglomerates of substantially sand-free particles of sodium bentonite which pass through a No. 100 sieve and of which more than 50% pass through a No. 200 sieve, whereby 0.05 to 1% of potassium methyl siliconate is sprayed on the agglomerated particles so that they are coated, at least partially. 18. A method according to claim 16, characterized in that the portioning facilitating portion of a siliconate and / or a portioning facilitating derivative thereof is in the range of 0.15 to 1%.