NO154758B - Particulate, textile softening, powerful detergent, usable for washing TOEY in an automatic washing machine. - Google Patents

Description

The invention relates to detergents and more particularly particulate, softening, powerful detergents for washing clothes and laundry and intended for use in machine washing

of cloth.

Bentonite is beneficial as a softening agent in detergents. Bentonite's softening properties and its desirable adhesion to substrates are important advantages, but its "gelling" properties can cause the detergent to become undesirably rubbery, and this will occasionally tend to adhere detergent beads and/or bentonite beads or agglomerates to surfaces and thereby inhibit free flow. Under highly humid conditions or in the presence of free moisture, bentonite can thus "gel" and become sticky or have reduced flowability, and it can even be held in place in channels or on chamber walls even if force is applied to the particles to remove them ( such as the force exerted by flowing water when it is filled in an automatic washing machine). Such adhesion could be significantly disadvantageous for a commercially available particulate detergent product with the desired free flowability and could lead to the product being less accepted by the consumer. Even if the flowability through production lines during the manufacturing and packaging processes and the flowability from the discharge box when the product is used by the final consumer is satisfactory, the presence of bentonite can cause detergent particles to be stuck on equipment walls, especially in the filling chamber, for washing machines equipped with a device to automatically fill detergent into the wash water in the machine cylinder or drum, even if such particles and the bentonite present have been moistened. Under such circumstances the bentonite may be inclined

to swell so that moist, adherent surfaces are obtained which can cause the particles to resist being removed from surfaces to which they adhere. In washing machines and other equipment that are equipped with automatic dosing devices or filling chambers, it may happen, e.g. that the detergent particles will not fall completely from the dosing

the device or be washed out of the dosing device, especially if the walls of the dosing chamber have been moistened before the detergent is added. If part of the desired amount is not added to the washing machine, the effective detergent and softener concentrations in the wash water will decrease and may lead to inaccurate detergent and softener concentrations being used. There may also be an unappealing build-up which the costumer may object to. In any case, the result is undesirable and should be avoided if possible.

The invention relates to a particulate, textile softening, heavy-duty detergent usable for washing clothes in an automatic washing machine and with improved dosing properties when dosed from a feed chamber in such a machine due to the action of water passed through the chamber, comprising 3-15% by weight of an anionic surfactant or 1-15% by weight of a non-ionic surfactant or a mixture of 3-10% by weight of an anionic surfactant and 1-5% by weight of a non-ionic surfactant, 20-75% by weight of a water-soluble and /or water-insoluble builder, and a softening proportion of bentonite and possibly common components for detergents, and the detergent is characterized by the fact that it contains 5-25% by weight of bentonite which is present in the form of particles coated with 0.05-5% by weight of a dosage improving salt of a lower alkyl silicic acid and/or a polymerization product or

-products thereof formed during storage.

The invention also relates to agglomerated bentonite particles which can be used for incorporation into a particulate powerful detergent for use in automatic washing machines, and which are distinctive in that they have particle sizes in the range from 2.00 mm to 149 µm and are agglomerates of substantially grain-free particles of sodium bentonite that pass through a sieve with a sieve opening of 149 µm and of which more than 50% pass through a sieve with a sieve opening of 74 µm, and in that they have been formed after sodium carbonate treatment of bentonite containing magnesium and/ or calcium, with the formed magnesium carbonate and/or calcium carbonate together with these, and the particles being fully or partially coated with 0.15-5%, preferably 0.15-1.5%, potassium methylsiliconate which has been sprayed onto the agglomerated particles' surfaces to at least partially coat them.

According to preferred embodiments of the invention, the synthetic, organic surfactant comprises both an anionic surfactant which is preferably a sodium linear higher alkyl benzene sulphonate, and a non-ionic surfactant which is preferably a condensation product of a higher fatty alcohol and polyethylene oxide, a higher fatty acid soap is present, the builder salt is primarily pentasodium tripolyphosphate or NTA or a mixture thereof with a small proportion of sodium silicate, the bentonite is a swelling bentonite with a moisture content of at least 3%, the siliconate is an alkali metal lower alkyl siliconate, more preferably potassium methylsiliconate , and 5 - 35% of a bleaching agent which emits oxygen in aqueous solutions at elevated temperature, such as sodium perborate, is present.

The synthetic, organic surfactant or surfactants used will normally be non-ionogenic or anion-active and will strongly preferably constitute a combination of these, although suitable amphoteric or ampholytic surfactants, such as those sold

(Sp

under the trademark Miranol^, can also be used in conjunction with non-ionic and anionic surfactants in the present detergents. Cation-active surfactants, such as the quaternary ammonium halides, e.g. such as those sold under the Arosurf brand, can also be used as supplementary fabric softeners

in these products, but normally they will not be used.

Various synthetic anionic organic surfactants, such as those designated sulfonates and sulfates, usually in the form of alkali metal or sodium salts, may be used, but those most preferred are linear higher alkyl benzene sulfonates, higher alkyl or fatty alcohol sulfates, and higher fatty alcohol polyethoxy or polyethoxylate sulfates.

In the higher alkylbenzene sulfates, the higher alkyl group is preferably linear and has 10 - 14, more preferably 11 - 13, e.g. 12, carbon atoms, and the sulfonate is a sodium salt. The alkyl sulfate is preferably a higher fatty alkyl or alcohol sulfate with 10 - 16, more preferably 12 - 14, e.g.

12, carbon atoms and is also used as the sodium salt. The higher fatty alcohol polyethoxysulphates will preferably have 10 - 18, more preferably 12 - 16, e.g. 12, carbon atoms in the higher fatty alcohol, the ethoxy content will preferably be 3-30, more preferably 3 or 5-20, ethoxy groups per molecule, and the surfactant will be a sodium salt. It thus appears that the alkyl groups in the sulphonates and sulphates are preferably linear or higher fatty alkyl groups with 10 - 18 carbon atoms, that the cation is preferably sodium, and that when a polyethoxy chain is present, the sulphate is at the end of this. Other useful anionic surfactants include the higher olefin sulphonates and paraffin sulphonates, e.g. the sodium salts in which the olefin or paraffin groups have 10 - 18 carbon atoms. Specific examples of the preferred surfactants are sodium dodecylbenzene sulfonate, sodium tallow alcohol polyethoxy (3 EtO) sulfate or sodium hydrogenated tallow alcohol sulfate. Besides the aforementioned preferred anionic actives

surfactants, other surfactants within this well-known group may also be present, especially only in smaller proportions compared to those described above. Moreover, mixtures of these can be used, and in some cases such mixtures can prove 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 or aliphatic bases, such as nonylphenol or alcohols of the oxo type, it is strongly preferred that the nonionic surfactant is made up of a higher fatty alkoxypoly-lower alkoxy-lower alkanol which can also be described as a condensation product of ethylene oxide (and/or propylene oxide) and a higher fatty alcohol. In such products, the higher fatty alkoxy group or alcohol has 10 - 16, preferably 12 - 15, carbon atoms, and the nonionic surfactant contains 3 - 20 lower alkoxy groups, preferably 5 - 15, and more preferably 10 - 13, e.g. 11, ethylene oxide groups per molecule.

The builder for the synthetic organic surfactant which helps to improve the surfactant's washing performance is a water-soluble or a water-insoluble builder or a mixture thereof. Of course, mixtures of water-soluble builders can also be used, e.g. polyphosphate and NTA (nitrile triacetic acid salt, normally the sodium salt), but among the water-insoluble builders, as a rule, only the zeolites will be present, although mixtures of such zeolites can also prove to be advantageous. Although zeolites are useful ingredients in the present detergents, it will be preferable to use water-soluble builders, and these will often be the only builders present.

The water-soluble builder or mixtures thereof used can be made up of one or more of the usual materials that have been used as builders or proposed for such a purpose. These include inorganic and organic builders and mixtures thereof. Among the inorganic builders, the various phosphates, preferably polyphosphates, e.g. tripolyphosphates or pyrophosphates, such as pentasodium tripolyphosphate or tetrasodium pyrophosphate. Tri-sodium nitrile triacetate (NTA), preferably in the form of the monohydrate, or other nitrile triacetates, such as disodium nitrile triacetate, are preferred organic builders. The term NTA, which normally stands for nitrile triacetic acid, is used here to also denote the various salts thereof, preferably the alkali metal salts, and preferably the trisodium salt. Sodium tripolyphosphate, sodium pyrophosphate or NTA can be used in hydrated form, which is often preferred, but anhydrous forms can also be used. Of course, carbonates, such as sodium carbonate, are useful builders and can be used alone or together with bicarbonates, such as sodium bicarbonate, if desired. When the polyphosphates are used, it may be preferable to have sodium pyrophosphate present together with sodium tripolyphosphate in a ratio of 1:10 - 10:1, preferably 1:5 - 5:1, relative to this, the total proportion of both builders being approximately the same as that mentioned here for the sodium tri-polyphosphate. Other water-soluble builders considered effective include the various other inorganic and organic phosphates, borates, e.g. borax, citrates, gluconates, EDTA or iminodiacetates. The various builders will preferably be present in the form of their alkali metal salts, either as the sodium salts or the potassium salts or a mixture thereof, but the sodium salts are normally more preferred. In some cases, such as when neutral or weakly acidic detergents are produced, the acid form of the builders, especially of the organic builders, may be preferred, but the salts will normally be neutral or basic in nature. The silicates, preferably sodium silicate with a ratio Na2O:SiC>2 within the range 1:1.6 - 1:3.0, preferably 1:2 - 1:2.8, e.g. 1:2.35 or 1:2.4, also serve as builder's salts, but because of their strong binding properties and because they will be able to promote an unwanted adhesion of detergent particles to the walls of the dosing device, they are considered special cases by builders, and relatively small proportions of these will be present (such shares will be described separately from the other builders). If it is desired that larger proportions of silicate should be present in the detergents, it may be preferable to subsequently add hydrated sodium silicate particles to spray-dried particles containing another builder or builders.

The water-soluble builders, in the sense that this term is used here, are those that help to

improve the detergency of synthetic, organic surfactants, especially the detergency of synthetic, anionic, organic surfactants, and in such cases the mechanism for increasing the detergency appeared to be associated with the builder's water-eliminating property, soir removal of calcium and/or magnesium ions from the wash water, usually via an ion exchange mechanism. Although, according to the invention, the aim is to use water-insoluble builders other than the zeolites, for practical reasons the zeolites will currently constitute the main of such insoluble builders that are used.

The zeolites used comprise crystalline, amorphous or mixed crystalline-amorphous zeolites of both natural and synthetic origin. Such materials should preferably be able to react sufficiently quickly with calcium ions that alone or together with other water-softening compounds in the detergent will soften the water before adverse reactions between such ions and other components in the synthetic, organic detergent take place.

The zeolites used can be characterized by having a high exchange capacity for calcium ions, and this is normally 200 - 400 milligram equivalents of calcium carbonate per gram of the aluminum silicate, preferably 250 - 350 mg.equiv./g.

Although other ion-exchange zeolites may also be used, normally the finely divided, synthetic zeolite builder particles used in the practice of the present invention will have the formula

in which x is 1, y is 0.8 - 1.2, preferably approx. 1, z is 1.5 - 3.5, preferably 2-3 or approx. 2, and w is 0 - 9, preferably 2.5 - 6. The zeolite should be a monovalent cation exchange zeolite, i.e. it should be an aluminum silicate of a monovalent cation, such as sodium or potassium.

Crystalline types of zeolites that can be used as good ion exchangers in the detergents according to the invention include at least partially zeolites of the following crystal structure groups: A, X, Y, L, mordenite or erionite, of which types A, X and Y are preferred. Mixtures of such zeolites of the molecular sieve type may also be useful, especially if a zeolite of type A is present. These crystalline types of zeolites are well known in the art and have been described in a number of patents in recent years for use as builders for detergents.

Crystalline zeolites with ion-exchange and water-softening properties which are preferred are those which exist in the hydrated or aqueous state and contain bound water in an amount of from 4% up to 36% of the total weight of the zeolite, depending on the type of zeolite used, and they are preferably hydrated to 15-70% of their capacity. Normally the water content is in the range 5-30, preferably 10 or 15 - 25, such as 17 - 22, e.g. 20, %.

The zeolite should preferably be present in a finely divided state with a diameter for individual particles of up to 20, e.g. 0.005 or 0.01 - 20, more preferably 0.01 - 15, e.g. 3 - 12, and particularly preferred 0.01 - 8, ym as average particle size, e.g. 3 - 7 ym if they are crystalline, and 0.01 - 0.1, e.g. 0.01 - 0.05, ym if they are amorphous. Although the size of the individual particles is far smaller, the zeolite particles will generally have a size within the range from 149 µm to 25 µm, preferably from 105 µm to 44 µm. However, they may occasionally be agglomerated, separately or together with spray-dried detergent particles, to sizes similar to those of the particles, e.g. -10 or 25%.

Although sodium sulfate and sodium chloride and other filler salts do not exhibit building properties, they are occasionally used in detergents for filling purposes, and sodium sulfate is particularly useful as a manufacturing aid. Besides increasing the volume and weight of the product so that dosing becomes easier, they also occasionally improve the stability and physical properties of the detergent beads in which they are incorporated. However, since the available detergents are satisfactory without any filler being present, it is often preferred to avoid these altogether or any proportion of these present can be kept to a minimum.

The softening clay which is an important component in the present detergents is of the type known as "bentonite". Bentonites are colloidal clays (alumino-silicates) containing montmorillonite. They have varying compositions and can be obtained from natural deposits in a number of countries, including Italy, Spain, Soviet Russia,

Canada and the USA (mainly from Wyoming, Mississippi and Texas). The bentonites used according to the invention are those which have "lubricating" and dispersing properties which are associated with swelling ability in water. Although some bentonites, mainly what can be termed calcium (or magnesium) bentonites, have low or negligible swelling properties, they can be transformed or "activated" so that the swelling properties increase. Such a conversion can be carried out by suitable treatment with an alkaline material, preferably with an aqueous sodium carbonate solution, in a manner known per se to introduce sodium (or potassium) into the structure of the clay. Besides improving the swelling ability of the bentonite, which favors fabric softening and dosing ability, the sodium carbonate solution treatment of the non-swelling clay or poorly flowing clay will replace e.g. 5 - 100, 10 - 90 or 15 - 50% of its divalent metal content with sodium and thereby improve the clay's exchange capacity for ions that make water hard, such as calcium and magnesium ions. The obtained by-products, which consist of calcium carbonate and magnesium carbonate, are left behind together with the bentonite and appear to have desirable additive properties in the final products.

Although the ion exchange capacity of bentonites has been mentioned

in the patent literature to be of importance for the softening ability,

it is a distinctive feature of the present invention that good softening of textile goods can be achieved by using sodium bentonites with relatively low ion exchange capabilities. Regardless of whether the swelling bentonite (also referred to here as sodium bentonite) is a naturally occurring clay or is obtained by alkali-

treatment of a non-swelling or poorly swelling bentonite, it can be used in the available fabric softening detergents. Treated bentonites from Italy have been shown to

be particularly applicable and are considered the most suitable for products intended for the European market. For the US market, Wyoming bentonite is often preferred, and this does not need to be treated because it already contains sodium ions in the bentonite structure and has swelling properties.

An analysis of a typical Italian bentonite (after alkali treatment) shows that it may contain 66.2% SiO2, 17.9% A<1>203, 2.80% MgO, 2.43% Na2O, 1.26% Fe203, 1.-15% CaO,

0.14% TiO2 and 0.13% K2O. A typical Wyoming or "western" bentonite (untreated) may contain 64.8 - 73.0% SiO2,

14 - 18% Al2O3, 1.6 - 2.7% MgO, 0.8 - 2.8% Na2O, 2.3 -

3.4% Fe2O3, 1.3 - 3.1% CaO and 0.4 - 7.0% K20. It thus appears that the compositions of the bentonites are very different, even though both types have swelling properties. It is assumed that if the Na20 content in the clay is at least 0.5, preferably at least 1, and more preferably at least 2.% (the equivalent proportion of K20 can also be taken into account), the clay will swell satisfactorily for the purposes of the invention and exhibit satisfactory softening and dispersing properties in aqueous suspension. Although it is expected that proportions of the various constituents of the swelling bentonites (which may be referred to herein as sodium bentonites regardless of whether they are natural or "activated") within the ranges of the typical analyzes given above, will result in useful constituents in the present detergents, it is also believed that the percentages of the constituents of the natural swelling bentonite can be increased or decreased by approx. 10% and that a typical analysis of the treated bentonite can be extended by -10% and that the bentonites within these ranges will still be usable. In addition, other bentonites can be used instead, at least partially. The usable bentonites will generally have a swelling capacity of at least 1 or 2, more preferably at least 5 or 10, ml/g. Of course, bentonites with a higher swelling capacity will also be applicable. Normally, the range for swelling ability will be 5 - 30, and often 5-20, ml/g.

The sodium bentonite or swelling bentonite will normally be agglomerated before it is mixed with spray-dried, built-up detergent beads and any other auxiliary additives to be added afterwards. This agglomeration will be carried out in a known manner, e.g. by showering moisture onto the bentonite powder which is kept in a tumbling motion, by extrusion, pressing, agglomeration in a pan or another method. However, it is strongly desired that the bentonite is in the form of a finely divided powder before the agglomeration, so that when the agglomerates break down in the washing water, the bentonite particles will be sufficiently small that they will effectively act as a lubricant when deposited on the laundry.

It would therefore normally be desirable that essentially the entire amount of the bentonite powder before agglomeration passes through a sieve with a 149 µm mesh opening and that at least 99% passes through such a sieve and that more than a substantial proportion of it passes through a sieve with 7 4 ^um mesh opening, preferably so that less than 30% by weight of the particles do not pass through such a sieve, and more preferably so that no more than 20% is retained on such a sieve.

The bentonite's moisture content is also important to promote a rapid breakdown of bentonite agglomerates and rapid dispersion in the wash water, so that the very small particles of the bentonite will adhere to the textile fibers and soften them. Although it is desirable to limit the content of free moisture in the bentonite used to approx. 10% or thereabouts, as a moisture content above 15% cannot normally be used, it is even more important to ensure that the bentonite contains sufficient free moisture, most of which is assumed to be present between neighboring plates in the bentonite, to facilitate rapid decomposition of the bentonite and any adjacent materials in the particles when such particles or detergents containing these are brought into contact with water, such as washing water. It has been shown that at least

2, preferably at least 3, and more preferably approx. 4.% or more water should be present in the bentonite (so-called "internal" moisture) and that the bentonite should not be dried so that a smaller percentage of water than this is present in the bentonite even

transient. In other words, overdrying to the stage where the bentonite loses its internal moisture could greatly reduce the applicability of the present detergents. When the bentonite moisture content is too low, the bentonite will not help achieve a satisfactory swelling and breakdown of the agglomerated beads in the wash water. .Preferred swelling bentonites of the types described above are sold under the trade names Laviosa and Winkelmann, e.g. Laviosa AGB and Winkelmann G 13, both of which are treated Italian bentonites and under the trade name Mineral Colloid Nr. 101 (and other similar designations) corresponding to Thixo-Gels with the quality designations 1, 2, 3 and 4. As described later, the treated bentonites will preferably also be free of grains, and they will preferably be further processed by grinding down to a finely divided powder before agglomeration. The commercially available bentonite used will usually have a pH in water (at a concentration of 6 within the range 8 - 9.4, a maximum free moisture content of about 8%, a specific gravity of about 2.6 and a viscosity in a concentration of 10% in water of 5 - 30, preferably 10 - 30, centipoise.

The siliconate which is used together with the bentonite to coat it and which can also be used for

to coat the detergent particles and which acts so that it

prevents the bentonite and the detergent from sticking to the walls of the dosing chamber in an automatic washing machine (or to the walls of other "containers" for the product), is a siliconate that can be easily applied to the bentonite and which can at least partially coat the bentonite particles and cause them to sticks to the walls off

a chamber in which they can be temporarily stored, even if such walls are damp or wet. The siliconate is a salt of silicic acid, preferably an alkali metal salt thereof, and the silicic acid is a lower alkyl silicic acid.

Although it is desirable that the salt-forming metal or another cation is one that will give a water-soluble siliconeate so that this can be applied to the bentonite in aqueous solution, this need not be necessary, and it is intended to also use water-dispersible siliconeates . The invention further aims to use lipophilic silicones which can be added dissolved in an organic solvent or in an aqueous solution in an organic solvent or in corresponding emulsions or dispersions. The alkali metal of the siliconate is preferably sodium or potassium, but other salt-forming cations may be used provided that the siliconate is suitable for the present purposes. The lower alkyl silicones in which the lower alkyl group has 1-3 or 4 carbon atoms, e.g. potassium methylsiliconate or sodium propylsiliconate are considered preferred. Instead of using the siliconate, a corresponding charge of the corresponding silicon acid and a corresponding base can be used.

In order to achieve the most effective results, it is strongly preferred to use the previously described lower alkyl silicones, but it is recognized that such compounds can polymerize, at least in part, to silicone compounds or other film-forming and antifoam compounds or polymers and that therefore also according to the invention, the aim is to use such "derivative" materials directly, at least partially, as a component in the present detergents. When such a derivative of the siliconate is used, this will be a derivative that helps to improve the dosing of the bentonite beads or detergent beads from a dosing chamber in an automatic washing machine, such as a chamber in which the particulate contents are washed out due to the flow of water into the washing cylinder of the machine .

Although it is not intended here that the present invention be limited to the mechanism described below, it may very well be that the water-soluble alkali metal-lower alkylsiliconates (which can also be described as alkali metal-lower alkylsilanolates) can be converted into polymethylsiloxanes, e.g. by the impact of atmospheric carbon dioxide or another acid-acting material, which could also result in the formation of alkali metal carbonate, such as sodium carbonate, which is a useful building salt. The polymethyl siloxanes 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 terms of obtaining improved dosing properties from the dosing chamber in an automatic washing machine. The preparation of siloxanes by means of the described reaction has been mentioned in the textbook Chemistry and Technology of Silicones, by Walter Noll, published by Academic Press in 1968. Although, however, silicones have previously been used in detergents, often because of their antifoam properties, is no description of a use of water-soluble silicones to coat bentonite and detergent particles to facilitate release from moist surfaces in dosing chambers, as according to the present invention, known, and such a process and the resulting mixtures are considered not imminent in relation to the state of the art.

The water-soluble soap which is a desirable component in the present detergents and which exerts a limited anti-foaming effect in the wash water, which is particularly advantageous for side loading or horizontal drum washing machines, is normally a higher fatty acid soap of an alkali metal, such as sodium or potassium, sodium soaps being strongly preferred. Such soaps can be made from natural fats and oils, such as soaps from animal fats and oils and from vegetable oils and seed oils, e.g. tallow, hydrogenated tallow, coconut oil, palm kernel oil or similar "natural" and synthetic fatty acids, and they normally have 10 - 24, preferably 14 - 18, carbon atoms. Such soaps are preferably made of hydrogenated tallow or hydrogenated tallow fatty acids, e.g. stearic acid. The water-soluble soap is preferably chosen so that it has a desired balance between good washing properties, effective foam-reducing action and other good physical properties. More specifically, a desirable hardness, good binding effect and limited tendency to form adhesive gels under conditions of use will be among these other physical properties. It has been shown that sodium hydrogenated tallow soaps best satisfy these conditions, but even mixtures containing these are also preferably treated with siliconate to further inhibit adhesion to moist chamber walls. For detergents where foaming is desirable, the soap content will of course be reduced as the soap is looped or a lower fatty acid soap, e.g. sodium laurate, is used instead.

Bleaching agents do not have to be incorporated into all detergents according to the invention, but in order to achieve the best cleaning and whitening effect for the laundry, it is often preferable that a bleaching agent is used. When the temperature of the wash water in the automatic washing machine is sufficiently high, sodium perborate is used as the preferred bleaching agent because the elevated temperature, especially when this is above 80°C (and it can be almost up to the boiling point, e.g.

90 or 95° C), can cause the perborate to split and bleaching oxygen to be released from it. Under such conditions, the sodium perborate, often referred to as sodium perborate tetrahydrate or sodium borate perhydrate and generally having an oxygen content of at least 10%, will release such oxygen without the need to use an activating agent or a cleavage catalyst. When washing is carried out at a lower temperature

in cold water or in warm water, e.g. at a temperature of 20 - 60° C, the sodium perborate will usually be broken down insufficiently for textiles to be washed to be satisfactorily bleached, and under such circumstances an activator will be used or another suitable bleaching agent will be used, also usually together with an activator. A number of such systems have been described in the literature, and most of these relate to the group of peroxygen compounds, such as persulphuric acid, peracetic acid, permauric acid, perphthalic or perbenzoic acid or salts thereof, such as the alkali metal or alkaline earth metal salts, e.g. sodium or magnesium salts. Various activators are known for such mixtures and promote a regulated release of oxygen from them in the system of hot and cold water, and among these activators can be mentioned heavy metal salts, such as copper salts, or various inorganic or organic compounds that have previously been described within this technical area. Among the preferred bleaching agents for use at lower temperatures can be mentioned magnesiurndi-

monoperoxyphthalate. Of course, various other oxygen-releasing bleaches, such as hydroperoxides, can be used,

and under the right conditions, chlorine-releasing bleaches can be incorporated into the present detergents.

Various auxiliary additives may be present in the slurry from which base pearls or detergents can be spray-dried, or such auxiliary additives may be subsequently added, the decision regarding the addition method often being determined by the auxiliary additive's physical properties, its resistance to heat,

its resistance to degradation in the aqueous medium of the kneader and its volatility. Among the auxiliary additives that are often used, mention can be made of enzyme powder, which is normally added afterwards to the base pearls because it is sensitive to heat. These enzymes can be made up of a number of different commercially available products, such as Alcalase® or Maxatase® which are both alkaline proteases (subtilisin). Among the specific enzyme preparations used are Novo Alcalase® 2M (2 Anson units per gram) and Maxatase® P 440,000. Although the alkaline proteases are most frequently used, amylolytic enzymes, such as α-amylase, can

also used. The mentioned materials usually contain active enzymes in combination with an inert, powdered carrier, such as sodium or calcium sulfate, and the proportion of active enzyme can vary greatly and usually amounts to 2 - 80% of the commercially available preparation. The proportions given here are based on the enzyme preparations and not the active part of these.

Among the fluorescent whitefish, they are the most

(S)

the commonly used stilbene whiteners, e.g. Tinopar^ 5 BM, especially in extra concentrated form. Among the stilbene compounds are cotton whiteners, such as those sometimes referred to as CC/DAS whiteners, which are derived from the reaction product of cyanuric chloride and the disodium salt of diaminostilbenesulphonic acid, with extensive variations thereof in terms of substituents on the triazine ring and the aromatic rings.

This group of bleaching agents is known in detergent technology and will most often be used when bleaching components are not present in the final product. When it is desired that detergents should contain a bleaching agent, such as sodium perborate or another oxidizing bleaching agent, bleaching agents that are stable against bleaching can be incorporated into the kneader mixture. Among these can be mentioned the benzidine sulphonic disulphonic acids, the naphthotriazolyl stilbenesulphonic acids and the benzimidazolyl derivatives. Polyamide whiteners which may also be present include aminocoumarin or diphenylpyrazoline derivatives, and polyester whiteners which may also be used include naphthotriazolyl stilbenes. Such whitening agents are normally used as their soluble salts, e.g. sodium salts, but they can be added in the form of the corresponding acids. As a rule, the cotton bleaching agents will make up major proportions of the used bleaching agent cylinders.

If it is desired that the product is to be produced so that it is fully or partially coloured, various suitable dyes or dispersible pigments can be used. When blue dyes, such as Acilan blue, or pigments, such as ultramarine blue, are used, these can have the dual effect of serving to color part or all of the detergent particles or of the detergent component particles and helping the washed laundry acquires the desired blue tint. It may be particularly desirable to color agglomerated bentonite particles with suitable dyes or pigments because natural bentonite can occasionally have a discolouration, so that the agglomerates can be converted from particles that look dirty to particles that have an appealing color and appearance.

Used perfumes which are generally heat-sensitive and may contain volatile ingredients, include a solvent such as alcohol or a suitable glycol, polyol or hydrocarbon, are normally synthetic perfume materials which are occasionally mixed with natural ingredients, and will generally include alcohols , aldehydes, terpenes, fixing agents and/or other normal perfume ingredients known in the art.

In addition to the auxiliaries mentioned, flowability-promoting agents, anti-settling materials to prevent premature gel formation in the kneading apparatus mixture, dispersing aids, anti-settling agents and in some cases further softening agents, e.g. cationic softeners, such as the quaternary ammonium halides, - e.g. dimethyldioctadecylammonium chloride, also be present. As stated above, however, the cationic softeners will not normally be used, and if they are used, they will be added afterwards.

Of course, water is present in the slurry from which the spray-dried component of the present detergents is prepared, and in the kneader the water serves as a means of dissolving or dispersing the various components of the spray-dried beads. For this reason, some water is found in the product both in free form and in hydrated form. Water can be used in a similar way to agglomerate the bentonite and the perborate powder and to dissolve the siliconate.

Although it may be preferable to use deionized water so that its content of hardness-promoting ions can be very low and so that metallic ions that can accelerate the decomposition of any organic materials that may be present will be kept to a minimum, tap water can be used instead and will occasionally be used exclusively for economic or supply reasons. The hardness content in such water will not normally be higher than approx.

300 parts per million, calculated as calcium carbonate.

The relative proportions of the various components in the final product according to the invention will be such that they will effectively contribute to the final product being a good fabric-softening detergent that is free-flowing and exhibits improved dosing from a dosing department in an automatic washing machine under the influence of the washing water flowing in through the department. The proportion of anionic surfactant will normally be 3-10, preferably 3-7, and more preferably 4-6, e.g. 5.% of the final product. The content of non-ionic surfactant will usually be 1-5, preferably 2-4, e.g.

3 or 4, %. In cases where non-ionic surfactant is not used, the proportion of anionic surfactant can be increased by as much as 5%, and in cases where the anionic surfactant is omitted, the content of non-ionic surfactant can be increased by up to 10%, provided that the detergent remains satisfactorily doseable. Although it is possible to produce effective detergents without anionic surfactant or without non-ionic surfactant, such products will not be as good as the preferred detergents according to the invention. The builder content will generally lie within the range 20 - 75, preferably 30 - 50 (and this is often preferably a completely water-soluble builder's salt), and more preferably 30 - 40, e.g. about. 35.%. As indicated above, sodium tripolyphosphate and NTA are preferred water-soluble builders that may be the only builders used. When they are used in admixture with each other, the mixture will preferably contain 10-90% of one of these, the rest being made up of the other builder, and within such ranges preferred proportions are 20-80% and 40-60% with complementary percentages. Similar percentage ranges apply when the builder consists of a mixture of a water-soluble builder's salt and a water-insoluble builder, such as a zeolite.

The bentonite content in the textile softening detergent, preferably in the form of a siliconate-coated agglomerate of more finely divided bentonite powder particles, will constitute a satisfactory softening proportion of this which will generally lie within the range 5-25, preferably 10-20, more preferably 14-18, e.g. e.g. about. 16.%.

The siliconate will be used in a proportion which is sufficient to exert the desired dosing aid effect, and this proportion will normally be 0.05 - 1, preferably 0.15 - 1.%, although up to 3% can be used. A preferred range for proportions 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 only to cover agglomerated bentonite, the siliconate content based on the coated bentonite agglomerates will usually be at least 0.15, often 0.15 - 5, preferably 0.15 - 1, and more preferably 0.15 - 0.5, e.g. 0.4%.

When a fatty acid soap is present, the proportion of this will not normally be greater than 10%. A preferred range for the soap content is 2-6, more preferably 2-4, e.g. 3.%. When a bleaching agent is present, the proportion of this will as a rule be 5-35, preferably 15-25, e.g. 20, %. However, it should be remembered that such proportions are based on the use of sodium perborate and will be changed when other oxidizing agents are used so that approximately the same bleaching effect (or content of active oxygen) is achieved. The product's moisture content, which does not include hydrate moisture that cannot be removed by standard heating at 105° C for 2 hours, will generally lie within the range 3 - 20%, with the higher percentages within this range being permissible when a significant proportion of at least 1/4 and preferably at least 1/2 of the moisture is in hydrate form. A preferred moisture content is 5 - 17, and more preferably 10 - 15.%. Any moisture that cannot be removed by the standard test method described above is considered to form part of the compound in which it is present as a hydrate, e.g. a zeolite.

The total proportion of various auxiliary additives which may also be present in the detergent will not normally amount to more than 20% and is preferably limited to 15%, and more preferably to 10%. Although water-soluble sodium silicate has building properties, particularly as regards its action against magnesium ions in hard water, because it also acts as a binder, the proportion of it present will not be limited by the builder content proportions stated above, and it will be considered here in the same way as other auxiliary additives for the available detergents. As a rule, it will make up no more than 8% of the product, and a normal range is 1 - 5, preferably 2-4, e.g.

3.%. The content of filler salt, sodium sulphate, if such is present, will also normally be limited to no more than 10%, and it will normally amount to 0.5 - 5, preferably 0.5 - 2, e.g. 1 - 1.5% of the product. The percentage of proteolytic enzyme will normally be 0.1 - 2, preferably 0.2 - 1, e.g. 0.3%, and the percentage of optical brightener dye will be 0.1 - 2, preferably 0.1 - 0.5, e.g. about. 0.2%. The perfume content will normally be 0.05 - 2, preferably

0.1 - 1, and more preferably 0.2 - 0.5, e.g. about. 0.3%. Among other auxiliary agents, it can occasionally be

it is desirable that small proportions of special sequestering agents and fluidity promoting agents are present. Among such materials, a preferred sequestering agent is the magnesium salt of diethylenetriaminepentaacetic acid (magnesium-DTPA), but other diethylenetriamine acetates can be used instead. Magnesium silicate is a preferred fluidity-promoting agent which can also serve as a carrier for the salt-releasing agent. A mixture of such products is commercially available comprising 15% magnesium DTPA and 85% MgSiO^, and when such a mixture is used, the proportion thereof will preferably amount to 0.1 to 1, more preferably 0.1 to 0.5 , e.g. 0.2%. The proportions of the sequestering. agent (or stabilizer) can be 0.01 - 0.2, preferably 0.02 - 0.1, %, and for MgSiO-j the concentrations are within the range 0.1 - 0.9, preferably 0.2 - 0.5%. Quantities of other auxiliary additives used will be such that the purpose for which the auxiliary additive is present in the detergent is achieved, but such proportions will not normally exceed 1 or 2%, and it will generally be within the range of 0.05 - 1%.

In addition to the detergent containing synthetic, organic surfactant, builder, bentonite and siliconate, as soap, bleach and auxiliary additives are often also present, siliconate-treated bentonite agglomerates are also included

of the present invention. For the siliconate-treated bentonite, the siliconate content will be 0.2-10, preferably 0.5-5, and more preferably 1-3.%. For the corresponding detergent without bentonite and for the enzyme and perborate, the proportions of siliconate will be the same as for the finished detergent, but such proportions can be increased from 10 to 100% depending on the conditions and the proportions of the different auxiliary additives in the detergent.

To produce the products according to the invention, known spray drying, agglomeration and mixing methods (preferably all three) can be used. Due to the fact that they are not considered essential features of the invention, they will only be briefly discussed here. In spray drying, a slurry is made in a kneading apparatus and which contains various components which are desired to be present in the spray dried beads and which are sufficiently stable to be able to withstand the conditions of the kneading and spray drying, such as surfactants, builders and suitable auxiliary additives, spray dried, and the aqueous slurry will normally contain 40-70 or 75, preferably 50-65, % solids, the rest being water. The slurry from the kneader

may contain the anionic surfactant and part or all of the non-ionic surfactant although as a rule not more than 5% non-ionic surfactant (on the basis of the final product)

will be present in the kneading machine (as any residue is added afterwards). The entire quantity of builders or the mixture of builders will normally be added to the kneader, even if this is not necessary. The bentonite is preferably separately agglomerated and subsequently added to the spray-dried product, but it can occasionally be incorporated into the kneader slurry. An aqueous silicate solution, a stable fluorescent bleach dye, soap and filler salt are usually added to the kneader along with any stable pigment and other coloring materials that may be used. Instead of adding a neutralized surfactant, the kneading apparatus can be used as a neutralization container in which an anionic, organic surfactant acid is neutralized with aqueous alkali hydroxide. Such an acid can e.g. be dodecylbenzenesulfonic acid containing 40 - 50% active ingredient, and can be neutralized with an aqueous sodium hydroxide solution, such as a solution containing 38% Na2O. If the alkylbenzene is sulphonated with sulfur trioxide, the content of active ingredient in the acid can be as high as 99%. A mixture of higher fatty acids can also be neutralized in the kneading apparatus together with the surfactant acid to produce a desired mixture of higher fatty acid soap surfactant.

The kneader slurry can be spray-dried in a conventional spray tower in co-flow or counter-flow. The slurry will normally have a temperature of 20 - 80, preferably 40 - 70, °C and will be spray-dried into a tower in which the drying air has a temperature of 200 - 400° C, for the production of spray-dried beads with a particle size within the range of 2fi0 mm

to 149^, um. Any particles that

lies outside the desired size range, can be removed by sieving and can be processed again. The produced beads have a room density within the range 0.3 - 0.6, e.g. 0.5, g/ml. They have a moisture content within a range that can be as wide as 3 - 20%, but normally the moisture content will be 10 - 15%.

After the spray-dried part of the detergents has been produced, other components for these can be mixed with the beads or sprayed on them (and on other components of the product if this is desired). It is generally preferred that the bentonite, the enzyme, the bleaching agent and any other particulate products, such as such products in the form of powders, agglomerates or pellets (apart from the siliconate) which are intended to be subsequently added to the spray-dried beads, are mixed with these, after which any liquids (including siliconate in solution) to be subsequently added, can be sprayed onto the mixture. The order of the subsequent addition of the components can, however, be varied, and occasionally a part of the particulate material can be added after one or more of the liquids. Two or more of the particulate materials can be pre-mixed before subsequent addition, and in a similar way mixtures of liquids can also be prepared.

Solvents can be used for various components that are to be used in the form of liquids, and in some cases emulsions can be used. Although the siliconate is preferably used in a dissolved state in water, it can thus be added 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 an aqueous emulsion together with perfume and/or non-ionic surfactant. However, it is far preferable to first coat the unperfumed detergent with an aqueous siliconate solution shower and then spray perfume onto the "siliconized" product. In some cases, it may be desirable to dilute the perfume with a suitable solvent, such as a relatively odorless alkylate (hydrocarbon). Instead of spraying the siliconate on the mixture of spray-dried (or otherwise produced products with similar properties) detergent beads, bentonite agglomerate, enzyme pellets or agglomerates and perborate particles in a mixture, the siliconate can be applied separately to each of these components or in different combinations -tions with each other. This can be carried out by using separate silicone showers, in which case the proportion of silicone deposited on the various components can be easily regulated, or a single silicone shower can be directed to different feed streams of such components as they enter a suitable mixing apparatus. When non-ionic surfactant is subsequently added (and it will sometimes be preferable that the entire quantity of the non-ionic surfactant is added to the kneading apparatus so that the silicone will exhibit the strongest dosage-assisting effect), this can be sprayed on or otherwise satisfactorily is applied to the surfaces of the spray-dried beads before these are mixed with the other particulate components for the final product and before the silicone shower is applied thereon. As indicated above, the non-ionic surfactant in liquid form can also be mixed with the siliconate and/or the perfume to be sprayed on the product, and in this case it can act in a similar way as an emulsifier.

The apparatus for performing the various mixtures

and spraying are known and will therefore not be described in detail here. The spraying can be carried out with ordinary nozzles, usually of the construction which gives a wide spraying pattern, but other types of spraying equipment can also be used. The mixers may be of various designs, but preferably comprise rotating, inclined tubes or drums within which the spraying can be carried out. However, V-shaped mixers, especially those designed for continuous feeding, and other commercial powder mixers may also be satisfactory to apply.

The amount of siliconate that will be sprayed onto the surfaces of the various particulate components in the detergent will be such that the final product will contain a portion of the siliconate (or a derivative thereof) that helps in dosing. As it is assumed that the bentonite agglomerates can to a certain extent adversely affect a satisfactory dosage of the particulate detergent from the feed chamber in an automatic washing machine (of the European type), it may be preferable to apply a larger proportion of silicone to such bentonite agglomerate particles, e.g. up to 5% if this is practically possible. In some cases, only the bentonite particles will be treated with the siliconate, and in these cases the proportion of siliconate in the final detergent can often be reduced, e.g. by as much as 50%. The supply of the siliconate includes the addition of moisture to the mixture being treated, when the siliconate is in an aqueous solution or in the form of an emulsion (but not if it is in a non-aqueous solution). This may or may not be desirable depending on the moisture content and the properties of the detergent and the treatment device. The concentration of silicone in the spray shower can therefore be regulated. Of course, the larger the shower volume and the stronger the dilution of the siliconate, the more evenly a shower can be distributed on the particulate material. If, on the other hand, the product has a moisture limit concentration or a moisture concentration that is too high, a diluted silicone shower can worsen this condition. In general, the concentration of siliconate in the liquid will be at least 5%, and it will preferably be at least 10%. Because the siliconate is completely miscible with water, higher concentrations can be used, generally in the range of 5 or 10 to 25 or 50%.

The various mixing and spraying operations will normally take place at approximately room temperature, but operations within the temperature range of 10 - 40, preferably 20 - 30, °C are preferred. The particle sizes of the materials that are coated with silicone will generally be similar to the particle sizes of the final product within the range from 2.00 mm to 149 µm or 74 µm (perborate and enzyme

the particles can have particles down to 7 4^ur$, ^e agglo-

aggregated bentonite particles will be those particles obtained by agglomeration or compaction of more finely divided particles, such as those particles of which more than 50% pass through a 74 µm sieve.

Such particles will be substantially free of sharp grains ("grit") and will normally contain 0.05 or 0.15 - 3 or 5, preferably 0.1 or 0.15 - 0.5 or 1.% siliconate, such as potassium methyl siliconate or sodium propyl siliconate, sprayed onto the surfaces of the particles until the siliconate at least partially covers the surfaces. They can be colored with a suitable dye or pigment, such as AcilanBrilliant Blue FFR, or such or another suitable colorant can be applied together

with the siliconate. The silicone does not mask the colour. Off and on

to, the bentonite agglomerates can be larger than the other particles in the product, e.g. a 10 - 50% larger diameter, to emphasize the difference between them. In a number of cases, the bentonite agglomerates will preferably consist of bentonite treated with sodium carbonate (such a treatment improves the color of the discolored clay) and contain magnesium carbonate and/or calcium carbonate resulting from such treatment. When the particles are only partially coated with siliconate, it is desirable that at least 10% of the surface area (up to

the equivalent spheres) are covered by the siliconate, and it is even more preferred that a greater percentage is covered, e.g. 50%, to facilitate dosing. Similar considerations and conditions apply if the enzyme, bleaching agent and surfactant particles are treated, except that in such cases a smaller proportion of siliconate can be used than the proportion used to coat bentonite agglomerates.

In the various cases mentioned above, the coating of the solid siliconate will normally be on

the outer 1% of the particles' thickness. For example, for a particle that has a thickness of 1 mm, such a silicone coating will have a thickness of approx. 5 ] im. The coating will preferably be on the outer 0.5% of the particle bead diameter, and more preferably on the outer 0.2% of this. If only a partial coating is applied and a larger percentage of silicone is used, as when only the bentonite agglomerates are coated, the thickness of the silicone will of course be greater, but it will preferably be less than 2%. Normally, this thickness will be at least 0.05% of the particle thickness.

"The products according to the present invention

offers a number of advantages, several of which have already been mentioned. The application of siliconate on particle surfaces improves the particle's dosing properties without adverse side effects, even if the entire particle is not covered with siliconate. Detergents of the types described here and the aforementioned particulate components in such detergents are thus easier to dose from a feed chamber for an automatic washing machine of the European type than control products that have not been treated with siliconate. This difference is most accentuated with regard to the agglomerated bentonite particles. The tests to compare these results are practical use tests using a number of different types of such European washing machines, and the person judging the results notes the number of particles remaining in the feed chamber after a normal feed and dosing operation or after such repeated operations . To highlight the differences and to <q>make the test more difficult, the walls of the feed chamber are first moistened to promote attachment of the bentonite (and other materials) to them. To simulate such a test, equal amounts of test product and control product by weight can be sprinkled on a wet, horizontal surface and allowed to stand for 1 or 2 minutes, then a weak water shower directed at the particles for a measured time, e.g. 30 seconds, after which the number of particles can be compared. In such tests, the products according to the invention show a marked improvement compared to the control products. It can normally be expected that less than half the number of particles will still stick to the pre-moistened surfaces when the "trial" product is used, compared to the control product. Often, no particles will adhere to the prewetted surface when at least 0.15% silicone is used, and more particles will adhere to the surfaces when at least 0.05%, but less than 0.15%, silicone is used, and a substantial number of particles will stick to the pre-moistened surface when no siliconate is present.

Although most of the detergent will be fed in

in the washing cylinder in terms of normal use of the automatic washing machine so that the retention of some particles in the feed chamber to begin with need not be more than psychologically undesirable, a larger number of particles can be retained during repeated washings, whereby the composition of the fabric softening detergent will be changed and the charging weight perhaps also significantly affected. In addition, the appearance of the feed chamber when particles are retained in it is unsatisfactory and may cause consumers to reject the product. Because of the different washing techniques used in America, it may not be as important to coat bentonite detergent particles with siliconate, but it is believed that the presence of the siliconate on the particle will help make the detergent more stable and more free-flowing, especially under humid conditions. conditions, and that it will help counteract any gelation of the bentonite under such conditions.

In addition to making dosing easier, the siliconate also has the beneficial effect of preventing excessive foam formation with the detergent in aqueous solution. The bentonite also helps to limit foaming, and this combination is "superior to the action of the individual ingredients. The siliconate also appears to exert a stabilizing effect on enzymes and bleaches coated with it, helping to prevent an unfortunate mutual influence between perfume ingredients and other detergent ingredients, whereby it helps to stabilize the perfume.

It can also exert such an effect on dyes. Nevertheless

these various advantages are achieved without the disadvantages that the product is too strongly hydrophobic (because it is initially soluble in water. It does not adversely affect the desired rapid dissolution and dispersion of the detergent components, and it does not seem to cause an undesirable accumulation of hydrophobic deposits on washed and softened clothes. It does not adversely affect the special softening effect of the hydrophilic bentonite, and it does not adversely affect the detergent's good washing power.

The detergents obtained are excellent detergents for washing clothes and for effectively softening washed clothes, which has been established by means of comparison tests with similar detergents that contain neither bentonite nor siliconate. The products are satisfactorily free-flowing and have the desired spatial density and appearance. They are also dust free, and this can be attributed at least in part to the siliconate.

Processes where siliconeate solutions or emulsions are sprayed onto surfactant, bentonite and other detergent component particles can be easily carried out and do not require special equipment. Because of the siliconeate's water solubility, it can be applied in an aqueous solvent without adding other components to the detergent recipe. However, it can also be emulsified or otherwise distributed together with other detergent components. The procedures can be changed so that different concentrations of siliconate can occur on different detergent components. The coating materials do not gel or thicken undesirably, they do not block spray nozzles, and they do not form rubber-like deposits in the spray and mixing equipment. The siliconate can be applied at room temperature because it does not require heating, unlike some other protective coating materials. The siliconate can mainly be kept on the surfaces of the particles so that less siliconate can be used while simultaneously achieving the desired dosing aid effect. Moreover, apparently due to the nature of the siliconeate or siliconeate derivative when it is on surfactant particles or a detergent particle, it is effective even when the particle is not completely covered therewith.

In the examples below, all parts are based

by weight and all temperatures in °c if nothing else is stated.

Example 1

A slurry in a total quantity of

3199^5 kg of material is prepared by reacting 364 kg of dodecylbenzenesulfonic acid (Dobane JNQ [48.8% active ingredient]) and 16 7 kg of hydrogenated fatty acids (16 - 18 carbon atoms per mole of fatty acid) with 47 kg of sodium hydroxide (38% Na2O) in an aqueous medium containing a suitable proportion (to maintain the reaction) of 952 kg of tap water (hardness 300 ppm calculated as

CaCO^). The rest of the water is used to cool the reaction mixture as needed and to dilute other components in the kneader mixture. Then, 242 kg of aqueous sodium silicate solution (Na20:SiO2 = 1:2.4) with a solids concentration of 44.1%, 7.5 kg of fluorescent whitener of the stilbene type, 7 kg of Sydex 808 are added to the kneader

(85% MgSiO3 and 15% magnesium DTPA), 1252 kg of hydrated sodium tripolyphosphate (TPP "H"), 54 kg of anhydrous sodium sulfate (99.5% pure) and 107 kg of a non-ionic surfactant which can be considered the condensation product of 11 molecules of ethylene oxide with 1 molecule of higher fatty alcohol with 12 - 15 carbon atoms per molecule.

The slurry is heated for approx. 1 hour while stirring so that its temperature rises to approx. 55° C, after which it is pumped into an atomization drying tower where it is sprayed at elevated pressure through multi-shower nozzles into drying air with a temperature of approx. 300° C. The spray drying produces particles with a moisture content of approx. 12%, and most of the articles range in size from 2.00 mm to 149 µm. Particles with a size outside this range are sieved away.

63.1 parts of the spray-dried powder (bulk density approx. 0.4 g/ml) was then mixed with 0.3 part of pelletized proteolytic enzyme (Alcalase<w>with 2 Anson units per gram although Maxatase^P 440,000 can also be used),

20 parts granular sodium perborate and 16 parts agglomerated bentonite. All these powders have particle sizes within the particle size range for the spray-dried detergent component, but smaller particles for the enzyme and perborate can also be used down to 74 µm. The bentonite particles consist of 82.3 parts anhydrous bentonite, 16.1 parts water, 1.5 parts sodium silicate (described above) and 0.06 part Acilan Brilliant Blue dye, the dye being applied to the surface of the particles. The bentonite particles are produced by agglomeration of more finely divided bentonite particles (Laviosa AGB) together with the diluted sodium silicate solution (in the water), after which they are colored. The bentonite used is a bentonite that has been treated with sodium carbonate to replace the calcium and magnesium in the bentonite with sodium (see the preceding description of this material), and from the bentonite is a natural content of granular material (hard enough that it is difficult to crush with a hammer) has been removed after the treatment by centrifugal separation. The moisture content of a suitable agglomerated bentonite can vary and can be as low as 3% when the bentonite is mixed with other components of the present softening detergent.

A mixture of 0.5 part of the non-ionic surfactant, 0.25 part of Rhodorsil Siliconate 51 T (50% solution of potassium methyl siliconate) and 0.25 part of detergent perfume is sprayed onto the mixture of spray-dried beads, enzyme, perborate and colored bentonite particles in an inclined drum mixing apparatus. The spraying is regulated so that the liquid that is sprayed evenly coats the particles in the mixing or stirring drum while producing approx. 10 0 parts of a uniform product.

The final product has particle sizes in the range from 2.00 mm to 250 µm', a space density of approx. 0.5

g/ml and a moisture content of approx. 12% (although this can drop to around 9% in the event of a grace period). The particle-shaped, fabric-softening detergent obtained is free-flowing and has an appealing appearance, as the somewhat larger (on average 20 - 200% larger diameter) blue, agglomerated bentonite particles form a contrast with the other white particles, and the detergent is dust-free.

The manufactured product is subjected to practical laundry tests and proves to be an excellent detergent with desired fabric softening properties. When judged, it appears easier to dose and leaves fewer particles in the feed chamber of an automatic washing machine of the European type than a control product with no siliconate coating present. This is of particular importance when the bentonite particles are larger because these may tend to adhere more to the wet chamber walls during dosing.

When the above experiment is repeated, but with 100 kg of dodecylbenzenesulfonic acid, 1324 kg of TPP"H" and 0.6 part of Rhodorsil

Siliconate 51 T used instead of the quantities previously used, the product obtained has satisfactory physical properties and functions, but in addition it is even easier to automatically dose and leaves no particles in the feed chamber of an automatic washing machine of the European type.

In modifications of the above example, the anionic surfactant is replaced with equal weights of sodium lauryl sulfate, sodium hydrogenated tallow alcohol sulfate and sodium tallow alcohol polyethoxy (3EtO) sulfate. Alternatively, mixtures of such materials are used, e.g. equal parts sodium dodecyl benzene sulfonate and sodium hydrogenated tallow alcohol sulfate, together. In all these cases, the finished detergent obtained is a detergent which is an excellent textile softening laundry detergent. All such products also have improved dosing properties when tested using the methods described above. Similar results can be obtained when the nonionic surfactant is changed instead of changing the anionic surfactant, replacing the nonionic surfactant with a block copolymer of propylene oxide and ethylene oxide, such as Pluroni c®L-44 or L-62, nonylphenol poly- oxyethylene (12 EtO)-glycol or a condensation product of C^2_25 fatty alcohol with 3 or 7 molecules of ethylene oxide per molecule or with a mixture of two or more such surfactants, e.g. used in equal parts.

When half or all of the amount of sodium tripolyphosphate is replaced with NTA, the end product is also a satisfactory detergent with softening properties and has improved dosing properties compared to a control detergent with the same recipe but without the siliconate.

When the soap is omitted from the recipe, control of the foaming is reduced, but the product is otherwise acceptable and similar to the previously described products. When sodium perborate is replaced with other bleaching agents, such as sodium persulfate or magnesium dimonoperoxyphthalate, the product still provides good bleaching and cleaning. When known activators for oxidizing agents are present, the bleaching can be carried out by using the detergent at lower temperatures than temperatures close to the boiling point (which are normally used in the method according to this example to achieve maximum bleaching effect). If it is desired to incorporate more silicate into the product, the amount of silicate is doubled by subsequently adding hydrated sodium silicate particles of a similar size together with the other particulate solid materials added afterwards.

When sodium propyl siliconate is used instead of the potassium methyl siliconate, comparable products can be obtained, and this is also the case when silicones with less water solubility are used as a substitute for a part, e.g. 25%, of the other silicones.

Example 2

The procedures according to Example 1 are varied by applying the siliconate in aqueous solution (20% solids) in the form of a finely divided shower (preferably with the small shower drops of "pm" size, e.g. a diameter of 1-50 or 1-10 ym) or in some other way as small liquid drops of a satisfactory small size, on each of the particulate components (spray-dried beads, bentonite, enzyme and perborate) which can be separately mixed together, before this mixing is carried out. The various coated particles all have bulk densities within the prescribed range (0.3 - 0.6, eg 0.5, g/ml). Then the perfume is similarly sprayed onto the mixture. The non-ionic surfactant is not subsequently sprayed on, but is instead incorporated into the slurry.

The product obtained is a product which also has improved dosing properties. The siliconate-coated agglomerated bentonite, the spray-dried detergent beads (without bentonite), the enzyme and the perborate can all be prepared and stored separately and later used for the production of fabric-softening detergents with different compositions and different desired properties, e.g. coated bentonite plus uncoated spray dried beads.

Example 3

A softening detergent similar to the detergent with the first recipe according to Example 1 is prepared from a slurry of 10.24 parts of the dodecylbenzenesulfonic acid, 2.81 parts of the hydrogenated fatty acid, 0.81 part of the sodium hydroxide, 26.54 parts of water, 37, 2 parts pentasodium tripoly-

phosphate (hydrated), 6.8 parts sodium silicate solution,

0.21 part fluorescent bleach, 1.46 parts sodium sulfate, and 3.0 parts of the nonionic surfactant, added in order. This is spray-dried using the method described in Example 1, obtaining 62.5 parts of a product with similar bulk density and particle size. The spray-dried particles are then mixed with

0.3 part proteolytic enzyme, 20.0 parts of the sodium perborate granules, 16.0 parts of the agglomerated bentonite and 0.2 part Sydex 808, and on the powder mixture kept in a tumbling motion, a mixture of 0.3 part of the detergent perfume and 0.4 part ^ iq^ ij linear alkylate, and 0.15 part potassium methyl siliconate are sprayed onto the product in a suitable liquid state, preferably dissolved in water (50% concentration). The manufactured product has better dosing properties for dosing from the feed chamber in an automatic washing machine during normal use. It exhibits a somewhat stronger tendency to foam than the similar products according to Example 1.

When 0.3 part of the siliconate is used, the dosing properties of the detergent are further improved.

When, instead of using, as in Example 1, an agglomerated, sodium carbonate-treated, Italian bentonite from which grain ("grit") has been removed, a competitive product (Winkelmann agglomerate) or a Wyoming-type bentonite, such as that sold under the trade name Mineral Colloid No. 101 (formerly Thixogel No. 1), is used, similar end products are obtained which are good softening detergents and can easily be dosed. Also when other lower alkyl siliconates, such as sodium propyl siliconate, are used, comparable results can be obtained. When the dye Acilan Blue, which was used to color the bentonite agglomerates, is replaced with ultramarine blue, a good coloring and bluing effect is also obtained. When in a similar way the siliconate is applied only to the agglomerated bentonite, the overall proportion of siliconate in the product being the same or 50% less in some cases, the properties of the detergent obtained are similar to those previously described, and the dosage is also improved in comparison with a control product.

Example 4

When the proportions of the various components according to the above examples are changed by -10%, -20% and -30% while maintaining them within the previously given ranges, and when the ratios between anionic surfactant and non-ionic surfactant are kept within the range 1:1 - 3:1, the ratio between total surfactant content and builder content within the range 1:3 - 1:8 and the ratio between sodium bentonite and total surfactant amount within the range 1:1 - 2:1, products with properties similar to those described in Example 1 are obtained. This is also the case when the water-soluble building salt or the water-soluble building salts according to Example 1 are replaced with zeolite A (20% hydrated) and when any of a number of synthetic anionic and non-ionic surfactants are used in admixture with each other, possibly together with a amphoteric surfactant, such as an amphoteric surfactant of the Mi ranor(^r*) type.

The present invention can also be utilized by improving the dosing properties of various other bentonites and particulate detergents of widely varying composition, densities (0.2 - 0.9 g/ml) and sizes (preferably 2.00 mm - 420 µm).

Claims (2)

1. Particulate, fabric softening, heavy-duty detergent usable for washing clothes in an automatic washing machine and having improved dosing properties when dosed from a feed chamber in such a machine due to the action of water passed through the chamber, comprising 3-15% by weight of a anionic surfactant or 1-15% by weight of a non-ionic surfactant or a mixture of 3-10% by weight of an anionic surfactant and 1-5% by weight of a non-ionic surfactant, 20-75% by weight of a water-soluble and/ or water-insoluble builder, and a softening proportion of bentonite and possibly common components for detergents, characterized in that it contains 5-25% by weight of bentonite which is present in the form of particles coated with 0.05-5% by weight of a dosage-improving salt of a lower alkyl silicic acid and/or a polymerization product or products thereof formed during storage. 2. Agglomerated bentonite particles which can be used for incorporation into a particulate powerful detergent for use in automatic washing machines, characterized in that they have particle sizes within the range from 2.00 mm to 149 µm and are agglomerates of essentially grain-free particles of sodium bentonite which pass through a sieve with a sieve opening of 149 µm and of which over 50% pass through a sieve with a sieve opening of 74 µm, and in that they have been formed after sodium carbonate treatment of bentonite containing magnesium and/or calcium, with the formed magnesium carbonate and/or calcium carbonate together with these, and the particles being fully or partially coated with 0.15-5%, preferably 0.15-1.5%, potassium methylsiliconate which has been sprayed onto the surfaces of the agglomerated particles to at least partially to coat these.