NO158547B - Particulate, bleaching and softening coarse detergent for washing TOEY. - Google Patents

Description

The invention relates to detergents and in particular particulate coarse detergents for washing clothes and textile softening detergents which are intended for use both

when washing clothes by machine and by hand. It also relates to a method for producing a component in such detergents (essentially grain-free, agglomerated bentonite).

Detergents that can be used for machine washing

of textiles, are everyday household products that are widely used throughout the world for home washing of clothes.

In British patent specification 461 221 it is described

that laundry detergents that contain bentonite, synthetic anionic surfactants and building salt, "ensure that clothes washed with these get fullness and a soft grip". Bentonite has long been used in soap and detergent products as a filler and bulking agent, and it has also been recognized that cloth is softened due to the deposition of bentonite on it from aqueous baths, see US patent 3,594,212. Various such uses of bentonite and other suitable camps are as well

have been described in more recent patents. For example, various applications of softening are described in British Patents 1 40'0 898, 1 401 726, 1 455 873 and

1,572,815, in US Patents 3,936,537 and 4,141,841 and in

British patent application 2 063 289. However, certain bentonites do not contain significant proportions of exchangeable monovalent metal ions and are therefore not good softeners,

and some contain undesirable proportions of granular material which, however, become unacceptable for laundry detergents. With the help of the present invention, however

less such bentonites with progress are used for the production of softening detergent components, and detergents with excellent usage properties can be produced.

According to the invention, a bleaching and fabric-softening, particulate detergent for washing clothes in water is provided, containing 3-10% by weight of a sodium salt of a synthetic, organic, anionic detergent consisting of sulfonates or sulfates or mixtures thereof, 1-8% by weight

of a non-ionic detergent, 0-10% by weight of a water-soluble alkali metal soap, 20-75% by weight of a builder for the synthetic, organic detergent, 5-35% of a bleaching agent that

releases oxygen in aqueous solution at elevated temperature,

and 5-25% by weight agglomerated bentonite particles which have been produced by size reduction of naturally occurring bentonite with low swelling capacity and which contain exchangeable calcium and/or magnesium and contain grain material, and the particulate detergent is characterized by the fact that the bentonite particles have been reacted with sodium and/or or potassium carbonate to replace at least part of the bentonite's calcium and/or magnesium with sodium and/or potassium, and then dried and size-reduced, with subsequent separation of the bentonite from the granular material and agglomeration of the bentonite into particle sizes in the range of 149 µm to 2 etc.

It is preferred according to the invention that the anionic detergent is a sodium linear-higher alkylbenzene sulphonate, the non-ionic detergent is made up of a condensation product of a higher fatty alcohol and polyethylene oxide, a hydrogenated tallow fatty acid soap is present, the building salt is mainly made up of pentasodium tripolyphosphate or NTA or a mixture thereof (with a small proportion of sodium silicate also present), the bentonite is a swelling bentonite with a moisture content of at least 3%, and the bleaching agent is sodium perborate.

They used synthetic, organic detergents,

hereinafter called surfactants, will be non-ionic and anionic surfactants. in combination, but suitable amphoteric or ampholytic surfactants, such as those sold 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. those sold under the trademark Arosurf<®>,

may also serve as supplementary fabric softeners in these products, but they will not normally be used and, if present, will not be spray-dried with any anionic surfactant due to an undesirable interaction that may occur. These groups of materials are well known and have been repeatedly described in the surfactant literature. Due to the fact that they are not preferred components in the present detergents, it is not believed to be justified here to present any further description of them.

Various synthetic anionic organic surfactants, such as those designated as sulfonates or sulfates, usually in the form of alkali metal or sodium salts, may be used, but those considered preferred are the linear higher alkyl benzene sulfonates, higher alkyl or fatty alcohol sulfates or higher fatty alcohol polyethoxy or polyethoxylate sulfates. In the higher alkyl benzenesulfonates, the higher alkyl group is preferably linear and has 10-14 carbon atoms, more preferably 11-13 carbon atoms, 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 carbon atoms, more preferably 12 - 14 carbon atoms, e.g. 12 carbon atoms, and it is also used

in the form of the sodium salt. The higher fatty alcohol polyethoxy sulfates will similarly have 10-18 carbon atoms, more preferably 12-16 carbon atoms, e.g. 12 carbon atoms,

in the higher fatty alcohol, the ethoxy content will preferably be 3-30 ethoxy groups per molecule, 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 sulfo-

the nates and sulfates are preferably linear or higher fatty alkyl groups with 10-18 carbon atoms and that the cation is preferably sodium, and when a polyethoxy chain is

present, the sulfate group is located at the end of this. Other useful anionic surfactants include the higher olefin sulphonates and paraffin sulphonates, e.g. the sodium salts of these, where 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. In addition to the aforementioned preferred anionic surfactants, other surfactants within this well-known group may also be present, especially only in smaller proportions compared to that which has been described above. Moreover, mixtures of these can be used, and in some cases such mixtures can be superior to single surfactants. The various anionic surfactants have become known in the art and are extensively described on pages 25-138 of the book Surface Active Agents'and Detergents, II, by Schwartz, Perry

and Berch, published in 1958 by Interscience Publishers, Inc.

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 hydroxyl-containing aromatic or ali-

phatic bases, such as nonylphenol or alcohols of the oxo type,

it is strongly preferred that the nonionic surfactant

res of a higher fatty alkoxy-poly-lower alkoxy-lower alka-

nol which can also be described as a condensation product of ethylene oxide (and/or propylene oxide) and higher fatty alcohol.

In such products, the higher fatty alkoxy group or alcohol group has 10-16, preferably 12-15, carbon atoms, and the non-ionic surfactant contains 3-20, preferably 5-15, lower alkoxy groups and more preferably 9-13, e.g. 11, ethylene oxide groups per molecule.

The builder for the synthetic, organic surfactant, which helps to improve the surfactant's washing effect, consists of either a water-soluble or a water-insoluble builder or a mixture of these. Of course, mixtures of water-soluble builders can also be used, e.g. polyphosphate and NTA (nitrile triacetic acid salt, normal sodium salt), but

among the water-insoluble builders, as a rule, only the zeolites will be present, although mixtures of such zeolites may also prove to be advantageous. Although zeolites are useful components in the present detergents, in general the use of a water-soluble builder or builders will be preferred and often be the only builder or 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 or mixtures thereof. Among the inorganic builders, the various phosphates, preferably polyphosphates, e.g. tripolyphosphates or pyrophosphates, such as pentasodium tripolyphosphate or tetrasodium pyrophosphate. Trisodium nitrile triacetate (NTA), which is preferably used in the form of the monohydrate, or other nitrile triacetates, such as disodium nitrile triacetate, are preferred organic builders. The designation NTA, which is normally used 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 a hydrated state, which is often preferred, but anhydrous states can also be used. Of course, carbonates, such as sodium carbonate, are useful builders and can be used, if desired, alone or together with bicarbonates, such as sodium bicarbonate. When the polyphosphates are used, it may be preferable for sodium pyrophosphate to be present together with sodium tripolyphosphate in a ratio of 1:10 - 10:1, preferably 1:5 - 5:1, the total proportion of both builders being approximately the same as that which has been mentioned here for the sodium tripolyphosphate. Other water-soluble builders considered effective include various other inorganic and organic phosphates, borates, e.g. borax, citrates, gluconates, EDTA or iminodiacetates.

The various builders will preferably be present in form

of their alkali metal salts, either as the sodium or potassium salts, or as a mixture thereof, but the sodium salts are normally more preferred. In some cases, such as when neutral or slightly acidic detergents are produced, it may be preferred to use acidic forms of the builders, especially of the organic builders, but normally the salts will be neutral or basic. The silicates, preferably sodium silicate with a ratio Na2O:SiO2 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 building salts, but only relatively small proportions of these will be present. If it is desired that larger proportions of silicate should be present in the detergent, it may be preferable to subsequently add hydrated sodium silicate particles to spray drying particles that contain another builder or builders.

The water-insoluble builders in the sense in which this term is used here are such builders that help to improve the washing power of synthetic, organic surfactants, especially the washing power of synthetic, anionic, organic surfactants, and in such cases the mechanism for the increasing washing power seems to be in relation to the builder's water softening effect, such as calcium and/or magnesium ion removal from the washing water, usually by an ion exchange mechanism. Although, according to the invention, the aim is to use other water-insoluble builders than the zeolites, at present, for practical reasons, the zeolites are the main such insoluble builders used.

The zeolites used comprise crystalline, amorphous or mixed crystalline-amorphous zeolites of both natural and synthetic origin. Such materials are preferably able to react sufficiently quickly with calcium ions, so that alone or together with other water-softening compounds in the detergent, they will soften the washing water before adverse reactions between such ions and other components of the synthetic, organic detergent occur. The zeolites used can be described as having a high exchange capacity for calcium ions, and it is normally 200 -

400 or more milligram equivalents of calcium carbonate hardness per grams of the aluminum silicate, preferably 250 - 350 mg. eq./g.

Although other ion exchange zeolites can also be used, the finely divided, synthetic zeolite building particles used according to the invention will normally have the formula

(Na2O)x-(<l>2<0>3)y-(SiO2)z-W H2O,

wherein x is 1, y from 0.8 to 1.2, preferably approx. 1, z from 1.5 - 3.5, preferably 2 or 3 or approx. 2, and w from 0 to 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 which according to the invention can be used as good ion exchangers include, at least in part, zeolites with the following crystal structure groups: A, X, Y, L, mordenite or erionite, of which A, X and Y are preferred. Mixtures of such zeolites of the molecular sieve type can also be used, especially if zeolite of type A is present. These crystalline types of zeolites are known in the art and are described in more detail in the book Zeolite Molecular Sieves, by Donald W. Breck, published in 1974 by John Wiley & Sons.

Typical commercially available zeolites of the above structural types are listed in Table 9.6 on pages 74 7 - 74 9

in the above mentioned book. Moreover, suitable zeolites have been described in a large number of patents in recent years for use as builders in detergents.

Crystalline zeolites with ion exchange and water softening properties which are preferred are those which exist in hydrated form or in connection with water and contain bound water in an amount of 4 - 36% of the zeolite's total weight, depending on the zeolite used, and they are preferably hydrated to 15-70% of their capacity. The water content is normally within 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 individual particles with a diameter of up to 30 µm, e.g. 0.005 or 0.01 - 20 ym, more preferably 0.01 - 15 ym, e.g. 3-12 ym, 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 ym, e.g. 0.01 - 0.05 ym, if they are amorphous. Although the individual particle sizes are far smaller, the zeolite particles will generally have a size within the range from sieve no. 100 to sieve no. 400, preferably from sieve no. 140 to sieve no. 325. However, they can occasionally be agglomerated alone or together with spray-dried detergent particles to sizes similar to the size 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 because of their filling properties, and sodium sulfate is particularly useful as a treatment aid. Besides increasing the product's volume and weight so that the dosage of the detergent is easier, they also improve the stability and the physical properties of the detergent beads in which they are incorporated. Due to the fact that the available detergents are satisfactory without fillers being present, nevertheless such fillers are often avoided in their entirety or a possibly present proportion of these may be small.

The softening clay, which is an important component in the present detergents, is of the type known as "bentonite". Bentonites are colloidal clays (aluminium silicates) containing montmorillonite. They have varying compositions and can be obtained from natural deposits in a wide range of countries, including Italy, Spain, Russia, Canada and the USA (mainly in Wyoming, Mississippi and Texas). The bentonites which can be used according to the invention are such bentonites which have "lubricating" and dispersing properties, and these properties seem to be connected with the bentonite's ability to swell in water. Although some bentonites, mainly such bentonites as are referred to as calcium (or magnesium) bentonites, have low or negligible swelling properties, they can be transformed or "activated" so that the swelling properties are increased. Such a conversion can be carried out by suitable treatment with sodium and/or potassium carbonate, preferably with an aqueous sodium carbonate solution, in a manner known in the art, to introduce sodium (or potassium) into the clay structure instead of the divalent alkaline earth metal or magnesium. Besides improving the swelling ability of the bentonite, which promotes its fabric softening and dispersing properties, the alkali metal carbonate solution treatment of the non-swelling clay or poorly flowing clay will replace

e.g. 5 - 100, 10 - 90, or 15-50, % of the exchangeable calcium and/or magnesium with sodium (or potassium) and thereby improve the clay's exchangeability against ions that make water hard, such as ions of calcium or magnesium. The obtained by-products, which are made up of calcium carbonate or magnesium carbonate, remain in the bentonite and seem to contribute with desirable adjuvant properties in the final products. A possible excess of sodium carbonate can act as a build-up in the finished detergent.

Although the ion exchange capabilities of bentonites have been discussed

in the patent literature as being of importance for the softening ability, it is a distinctive feature of the present invention that good softening of textiles can be achieved with sodium bentonites with relatively low ion exchange capabilities. Treated Italian bentonites have proven particularly useful for the European market. An analysis of a typical Italian bentonite (after alkali treatment) shows that it contains 66.2% SiO2, 17.9% Al^, 2.80% MgO, 2.43% Na2O, 1.26% Fe2O3, 1.15% CaO, 0.14% TiO2 and 0.13% K2O. It is assumed that if the Na20 content in the clay is at least approx. 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 be satisfactorily swelling for the purposes of the invention,

with satisfactory softening and dispersing properties in an aqueous suspension (swelling of the bentonite facilitates the breakdown of the bentonite agglomerate). Although it is to be expected that proportions of the various components in the swelling bentonites treated according to the invention will lead to usable components for the present detergents, it is also considered that the typical analyzes for the treated bentonites can be extended by - 10%, as bentonite- tene within these areas will still be applicable. In addition, other swelling bentonites can be used, at least in part. The usable bentonites will generally have a swelling capacity of at least 1 or 2 ml/g, more preferably at least 5 or 10 ml/g. Of course, bentonites with a higher swelling capacity will also be applicable. Normally, the swelling capacity range will be 5-30 ml/g, and it will often be 5-20 ml/g.

The sodium bentonite or swelling bentonite will be agglomerated before being mixed with spray-dried, built-up detergent beads and any other auxiliaries to be subsequently added. Such agglomeration will be carried out in a known manner, such as by using a shower of water or aqueous binder against agitated bentonite powder, by extrusion, pressing, agglomeration in a pan or other methods. However, it is highly desirable that the bentonite is present as a finely divided powder before agglomeration, so that when the agglomerate breaks down in the wash water, the bentonite particles will be sufficiently small that they will act as effective lubricants, which are deposited on the laundry. It would therefore normally be desirable that essentially the entire quantity of the bentonite powder before agglomeration will pass through a sieve no. 100 (US sieve series), with at least 99% passing through such a sieve, and with over a substantial proportion of the bentonite powder passing through a sieve no. 200, preferably so that less than approx. 30% by weight

of the particles will not pass through such a sieve, and more preferably so that no more than 20% will remain on such a sieve. Of course, the final particle sizes are smaller.

In order to promote an easy breakdown of bentonite agglomerates and dispersion of these in the wash water so that the small particles of these can adhere to the textile fibers to soften them, the bentonite's moisture content is also important. 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% will not normally be used, it is even more important to ensure that the bentonite contains sufficient free moisture, a large proportion of which is assumed to be present between neighboring plates in the bentonite , so that a rapid breakdown of the bentonite will be facilitated and of any adjacent materials in the particles when such particles or detergents that contain

holds these, is brought into contact with water, such as washing water.

It has been found that at least 2%, preferably at least 3%, and more preferably approx. 4% or more, of water should be present in the bentonite (so-called "internal" moisture) and that the bentonite should not be dried so that a smaller amount of water than such a percentage is even transiently present in the bentonite. In other words, overdrying to the stage where the bentonite loses its internal moisture can greatly reduce the usefulness of the available 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 names Laviosa and Winkelmann, e.g. Laviosa AGB and Winkelmann G 13, and both of these are treated Italian bentonites, and under the designation Mineral Collid no. 101 (and other similar designations) corresponding to Thixo-Gels no. 1, 2, 3 and 4. As described below for the treated bentonites will also preferably be essentially grain-free and have preferably been further processed by grinding down to a finely divided powder before agglomeration. The commercial 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 approx. 8%,

a specific weight of approx. 2.6 and a viscosity at a concentration of 10% in water of 5 - 30 cp, preferably 10 - 30 cp.

The water-soluble soap which is a desirable component in the present detergents and which exerts a useful foam-limiting effect in the washing water which is particularly advantageous for washing machines with side-loading or horizontal cylinders, normally consists of a higher fatty acid soap of alkali metal, sodium or potassium, as sodium soaps are strongly preferred. Such soaps are well known and need not be described in detail here. It should be sufficient to mention that they may be prepared from natural fats or oils, such as those prepared from normal fats or shortenings or from vegetable oils or seed oils, e.g. tallow, hydrogenated tallow, coconut oil or palm kernel oil, or equivalent "natural" or synthetic fatty acids, and that they normally contain 10 - 24, preferably 14 - 18, carbon atoms. Such soaps are preferably made from hydrogenated tallow or hydrogenated tallow fatty acids, e.g. stearic acid. The water-soluble soap that can be incorporated into the present detergents will preferably be chosen so that a desired balance is achieved between good washing properties, an effective foam-reducing effect and other good physical properties. Among these other physical properties, a desired hardness, good binding effect and little or no tendency to form sticky gels under conditions of use (such as in the washing machine filling compartment) can be mentioned in particular.

Bleaching agents are incorporated into all washing

agents according to the invention which are based for use in automatic washing machines of "European design" in which very hot water (close to the boiling point) is used, because under such conditions an effective and safe bleaching takes place which leads to the desired whiter washed laundry. When the washing water temperature in the automatic washing machine is sufficiently high, sodium perborate is the detergent of choice because the elevated temperature, especially when it is above 80° C., e.g. 90 or 95° C, can cause decomposition of the perborate and release bleaching oxygen from it. Under such conditions, sodium perborate, which is often referred to as sodium perborate tetrahydrate or sodium borate perhydrate and will usually have an active oxygen content of approx. 10%, thus releasing such oxygen without it being necessary to use an activator or a cleavage catalyst. When washing clothes at: a lower temperature or if it is intended that the product can be used outside the washing machine, in cold water or in hot water, e.g. at a temperature of 20 - 60° C, sodium perborate will generally not be decomposed sufficiently for washed textiles to be sufficiently bleached, and in such circumstances an activator will be used or another suitable bleaching agent will be used, also usually together with an activator. A large number of such systems have been described in the literature, and most of these belong 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. the sodium or magnesium salts. Different activators for such materials are known which promote a regulated release of oxygen from them in systems with hot and cold water. Among such activators can be mentioned heavy metal salts, such as copper salt, or various inorganic or organic compounds which have been described within the relevant state of the art. Among the bleaches for use at lower temperature and which are preferred,

mention may be made of magnesium dimonoperoxyphthalate. Of course, various other oxygen-releasing bleaching materials, such as the hydroperoxides, can be used, and under the right circumstances, chlorine-releasing bleaching materials can be incorporated into the present detergents. Although in some cases it may be considered unnecessary to incorporate a bleaching agent into the detergent, such will normally be used. In the present detergents which comprise agglomerated bentonite particles, the perborate in particular can exert a whitening effect on bentonite which occasionally has an unwanted color and which can otherwise give a very noticeable unwanted color due to its large agglomerated particle size. Even if the agglomerated bentonite is intentionally coloured, the percompound can help to "cleanse" the color by removing the discolouration of the base.

Various auxiliary additives can be present in the slurry from which primers or detergents can be spray-dried, or such auxiliary additives can be added afterwards, as the decision regarding the addition method is often determined by the auxiliary's physical properties, its heat resistance, its resistance to breakdown in the aqueous medium in the slurry. ninqen oq its volatility. Among the auxiliaries that are often used, mention can be made of enzyme powders or pellets that are subsequently added to the base beads because they are heat-sensitive. These can be made up of a wide range of commercially available products, and among these can be mentioned Alacalase or Maxatase®, both of which are alkaline proteases (subtilisin). Among special enzyme preparations that can be used, mention can be made

(-§) (5)

Novo Alacalase"-^ 2M (2 Anson units per g) and Maxatasew P

4,40,000. Although the alkaline proteases are most frequently used, amylolytic enzymes, such as ct-amylase, can also be 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 calculated for the enzyme preparations and not the active part of these.

Among the fluorescent whiteners, the most commonly used are the stilbene whiteners, e.g. Tinopal^ 5 BM, especially in extra concentrated form. Among the stilbene compounds can be mentioned cotton whiteners, such as those which are sometimes referred to as CC/DAS whiteners, obtained from the reaction product of cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid, extensive variations thereof as regards the substituents on the triazine ring and the aromatic calls. This group of whitening agents is known within detergent technology and will most often be used when bleaching components are not available. present in the final product. If it is desired that the detergent should contain a bleaching agent, such as sodium perborate or other oxidizing bleaching agent, bleach-stable whitening agents can be incorporated into the slurry. Among these, benzidinesulfondisulfonic acids, naphthotriazolylstilbenesulfonic acids or benzimidazolyl derivatives can be mentioned. 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 in the form of their soluble salts, e.g. sodium salts, but they can be added in the form of the corresponding acids. The cotton bleaching agents will as a rule make up the main proportion of the bleaching agents used.

If it is desired for the product to be 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 leaf, are used, these exert the dual effect of coloring some or all of the detergent particles or particles of components in the detergent and help to give the washed laundry a desired bluish tint. It may be particularly desirable to color agglomerated bentonite particles with suitable dyes or pigments because natural bentonite can occasionally be discolored, so that the agglomerates can be changed from particles that look dirty to particles that have an appealing color and appearance.

The perfumes used are usually heat-sensitive and may contain moist ingredients, including a solvent, such as alcohol or a suitable glycol or polyol or hydrocarbon, are normally made up of synthetic perfume materials which are occasionally mixed with natural components, and they will in generally include alcohols, aldehydes, terpenes, fixing agents and/or other normal perfume ingredients which are known in the relevant art.

In addition to the aforementioned auxiliary additives can

also fluidity-promoting agents, anti-settling materials to prevent premature gel formation in the slurry,

dispersing aids, anti-deposition agents and

in some cases additional softeners, e.g. cationic softeners, such as the quaternary ammonium halides, e.g. dimethyldioctadecylammonium chloride, is used. As indicated above, however, the cationic softeners will not normally be used, and if they are used, they will be added afterwards.

Water is of course present in slurry

the composition from which the spray-dried component of the present detergent is produced, and the water there serves as a medium to dissolve or disperse the various components of the spray-dried beads. Some water is therefore present in the product both in a free state and in a hydrated state. In a similar way, water can be used to agglomerate the bentonite and the perborate powders. Although it may be preferable to use deionized water so that the content of hardness-promoting ions in this can be very low and so that metallic ions that can promote the decomposition of any organic materials that may be present,

will be kept to a minimum, tap water can be used instead, and this will occasionally be used exclusively due to economic or supply reasons. The hardness content in such water will not normally be greater than approx. 300 ppm, calculated as calcium carbonate.

The proportions of the various components in the final product according to the invention will be such that the final product will consist of a free flowing, effective cleaning, whitening, textile softening detergent. The proportion of the anionic surfactant will be 3-10, preferably 3 -

7, and more preferably 4-6, e.g. 5.% of the final product. The content of the non-ionic surfactant will be 1 -

8, preferably 2-5, e.g. 3 or 4, %. The builder content will lie within the range 20 - 75, preferably 30 - 50 (and this is often preferably exclusively a 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. If they are used in a mixture, the mixture will preferably contain 10 - 90% of one of these, the rest being made up of the other mentioned builder, and within such ranges preferred ranges are 20 - 80% and 40 - 60% and complementary percentages. Similar percentage ranges are applicable when the builder consists of a mixture of water-soluble builder's salt and water-insoluble builder, such as a zeolite.

The bentonite content of the textile softening detergent

and which is in the form of an agglomerate of more finely divided bentonite powder particles, will constitute a satisfactory softening proportion of this and will lie within the range 5 - 25, preferably 10 - 20, more preferably 14 - 18, e.g. about. 16.%. The proportion of bleach will lie within the range 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 that they will change if other oxidizing agents are used, so that approximately the same bleaching effect is obtained (or active oxygen content). When a fatty acid soap is present, the proportion of this will usually not be

over 10%. A preferred range for the soap content is 2-6, more preferably 2-4.%. The moisture content of the product, which does not include hydrate moisture that cannot be removed under standard heating at 105°C for 2 hours, will generally lie within the range 3 - 20%, the higher percentages within this range being permissible when a significant proportion, at least 1 /4 and preferably at least 1/2, of the moisture is in hydrate form. A preferred moisture content is 5 - 17%, and a more preferred moisture content is 10 - 15, e.g. 10%. Any moisture which cannot be removed by the standard test mentioned 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 exceed 20%, and is preferably limited to 15, and more preferably to 10,%. Because water-soluble sodium silicate has building properties, especially as regards its action against magnesium ions in hard water, the proportion of this is included in the overall building content. Because it also acts as a binding agent, however, the present proportion of this will be mentioned here together with other auxiliary additives for the present detergents. As a rule, it will make up no more than 8% of the product, and the normal range is 1 - 5, preferably 2-4, e.g. 3.%. In order to improve flowability, especially if the silicate content exceeds 3 or 4%, the remainder will occasionally be added in the form of a hydrated silicate. The content of filler salt, such as sodium sulphate if 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 or 1.5% of the product. The percentage of the proteolytic enzyme used will normally be 0.1 - 2, preferably 0.2 -

1, e.g. 0.3, %, and the percentage of optical whitening dye will be 0.1 - 2, preferably 0.1 - 0.5, e.g. approx. 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 of

and 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 diethyltriaminepentaacetic acid magnesium salt, but other diethylenetriamine acetates can be used instead. Magnesium silicate is a preferred flowability agent which can also serve as a carrier for the sequestering agent. A mixture of such products is commercially available and comprises 15% of magnesium DTA and 85% of MgSiO^, and when such is used, the proportion of this will preferably be 0.1 - 1, more preferably 0.1 - 0, 5, e.g. 0.2%. The proportion of the sequestering agent (or stabilizing agent) can be 0.01 - 1.2, preferably 0.02 - 0.1%, and for MgSiO^ the concentrations are in the range 0.1 - 0.9, preferably 0.2 - 0.5%. Quantities of other auxiliary additives will be such that the purposes for which the auxiliary additive is incorporated into the detergent are achieved. Normally, such shares will not be greater than 1 or 2%, and they will often lie within the range of 0.05 - 1%.

The bentonite used in the present detergents is essentially free of grains ("grit"), which means that it contains less than 1% grainy (sandy) particles. The substantially grain-free bentonite used will normally contain less than 0.4% of palpable, hard, grainy particles which are water insoluble and which are difficult to crush when placed on a hard surface and struck with a normal hammer blow. It is more preferred that less than 0.1% of such grains will be present, and such a bentonite can be described as grain-free. In the coarse bentonite in the form in which it is mined, the grain content can be as follows

as high as 15% in some cases, although as a rule it will be below 5%. Treatment of the bentonite to remove the grains from it will be carried out in connection with treatment of the bentonite to increase its exchangeable content of monovalent cations, and this content will preferably be increased to at least 2% (calculated as Na20) by such treatment. The treatment method and its benefits will be described in detail later

For the production of the products according to the invention, known spray drying, agglomeration and mixing methods (preferably all three) can be used. As these are not considered to constitute the essential distinctive features of the present invention, they will only be briefly discussed here. During spray drying, a slurry containing

where various components which are desired must be present in the spray-dried beads and are sufficiently stable to withstand the kneading and the spray-drying, such as surfactant, builder and suitable auxiliary additives, spray-dried from an aqueous slurry which will normally contain 40 - 70 or 75, preferably 50-65% solids, the rest being water. slurry-

the composition may contain the anionic surfactant and some or all of the nonionic surfactant, although as a rule no more than 5% of the nonionic surfactant (on a final product basis) will be present in the kneader mixture (the remainder, if some, will be added later). The entire quantity of building materials or of the mixture of building materials will normally be added to the kneading apparatus, even if this is not necessary. The bentonite powder is separately agglomerated and subsequently added to the spray-dried product, often in the form of a colored (preferably blue) pearl. Aqueous silicate solution, stable fluorescent whitening dye, soap and filler salt are usually added to the auxiliary device together with any stable pigment or other coloring materials that can be used. Instead of adding a neutralized surfactant can

the kneading device is used as a neutralization container in which anionic, organic surfactant acid is neutralized with aqueous alkali hydroxide. Such an acid can be e.g. of dodecylbenzenesulfonic acid containing 45 - 50% active ingredient and which can be neutralized with an aqueous solution of sodium hydroxide, as a solution containing 38% Na2O. If the surfactant acid is produced by sulphonating the alkyl benzene with sulfur trioxide, the content of active ingredient in the acid can be as high as 99%. A higher fatty acid mixture can also be neutralized in the kneading apparatus together with the surfactant acid to obtain a desired mixture of higher fatty acid soap surfactant.

The slurry can be spray-dried in a

normal spray tower in cocurrent or countercurrent. The mixture will normally have a temperature of 20 - 80, preferably 40 -

70, °C and will be spray-dried in 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 from sieve no. 10 to sieve no. 100 (US sieve series). Any particles that fall outside the desired area can be removed by sieving and processed again. The produced beads have a bulk density of 0.3 - 0.6 g/ml, e.g.

0.5 g/ml. They have a moisture content within a range that can be as little as 3 - 20%, but normally it will be 10 - 15%.

After the spray-dried part of the detergent has been prepared, other components for this can be mixed with the beads or sprayed on them (and on other components of the product if this is desired). It will generally be preferable that the bentonite, the enzyme, the bleaching agent and any other particulate products, such as those in powder, agglomerate or pellet form and which are intended for subsequent addition to the spray-dried beads, are mixed with these, after which any liquids which must be added afterwards, sprayed on the mixture. However, the order of subsequent addition of components can be varied, and occasionally a portion of particulate materials can be subsequently added after one or more of the liquids. Two or more of the particulate materials can be premixed 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 supplied in the form of liquids, and in some cases emulsions can be used. In some cases, it may be desirable to dilute the perfume with a suitable solvent, such as a relatively odorless alkylate (hydrocarbon). When a nonionic surfactant is subsequently added (and it will sometimes be preferred that the entire amount of the nonionic surfactant be added to the slurry), it may be sprayed or otherwise satisfactorily applied to the surfaces of the spray-dried beads. before mixing with the other particulate ingredients. As mentioned above, the non-ionic surfactant in liquid form can also be mixed with the perfume to be sprayed on the product, and in this case it can act as an emulsifier.

The apparatus for carrying out the various mixtures and sprayings is known in the relevant art and will therefore not be described in detail here. The spraying can be done through ordinary nozzles, usually with a construction to give a wide shower pattern, but other types of spraying equipment can also be used. The mixing devices can be of different construction, but they will preferably comprise rotating, sloping tubes or drums in which the spraying can be carried out. However, V-shaped mixers, especially those designed for continuous feeding, or other commercially available powder mixers may also be satisfactory.

The various mixing and spraying operations will normally take place approximately at room temperature, but it is preferred to carry out these at a temperature of 10 - 40, preferably 20 - 30, °C. The particle sizes for the materials that are mixed will, as a rule, be equal to the particle sizes for the final product, within the range from 2.0 mm to 149 pm or 74 pm (the ranges for the perborate and

the zyme can extend to 74 pm). The agglomerated bentonite particles will be those obtained by agglomeration or

pressing of more finely divided particles, such as particles of which more than 50% pass through a 74 µm sieve. Such particles will consist of essentially grain-free sodium bentonites. They can be sprayed together with a suitable dye or pigment, such as Acilan Brilliant Blue FFR, or various other suitable coloring agents can be added. Occasionally the bentonite agglomerates can be larger than the other particles in the product, e.g. have a 10 - 50% larger diameter, to emphasize their difference. The bentonite agglomerates consist of bentonite treated with potassium or sodium carbonate (such treatment improves the color of discolored clay) and will often contain magnesium carbonate and/or calcium carbonate resulting from such treatment.

The sodium carbonate treatment of the raw bentonite will be because the content of exchangeable sodium in the bentonite is lower than desired to achieve a satisfactory softening and agglomerate-dispersing effect of the bentonite when the agglomerated beads of this are added to the wash water. For bentonite containing exchangeable calcium and/or magnesium and insufficient exchangeable sodium, e.g. less than 0.5%, calculated as sodium oxide, the raw clay, which in a number of cases contained grains, is ground or otherwise broken down and treated with a suitable alkali, such as aqueous sodium carbonate which can have a concentration of 5 - 20%. After contact with the camp for a suitable time which can last from

0.5 to 24 hours, the mixture, which still contains some free excess of sodium carbonate (normally an excess of 10 - 50% will be used to replace the exchangeable calcium and magnesium), is dried. As a rule, such dried material, often in the form of large cakes, with a moisture content of 2 - 15% is broken down and then ground into particles with a diameter in the range of 0.8-8 mm. In such a state, the bentonite can be sold for such applications where the grain content is of no importance. If, however, the bentonite contains unwanted amounts of grains, it is then first reduced in size to particles of one size

below 149 um and with at least 50% of the particles with a

size below 74 pm. These particles were then centrifugally separated or separated by other methods which depend on the density, e.g. sedimentation under the influence of gravity, but preferably a cyclone separator is used. The grains are removed, and the concentration of these in the product is lowered to below 2%, e.g. to below 0.4%. Next, the bentonite, which is now substantially grain-free and contains sufficient exchangeable sodium for it to form a useful component in the softening detergent products according to the invention, is agglomerated into particles within the desired size range by means of a suitable method, such as a method which is been described above.

The products according to the invention offer a number of advantages, several of which have already been mentioned. The detergents obtained are excellent whitening laundry detergents and capable of effectively softening washed clothes, which has been determined by comparison tests with similar detergents that do not contain bentonite.

The products are satisfactorily free-flowing and dust-free and have the desired spatial density and an appealing appearance. The bentonite tends to give the washed clothes a

softer grip, but it does not cause the washed materials to acquire unwanted hydrophobic properties. It has been shown that bentonite can sometimes even increase the moisture absorption rates of textile materials, and it acts as a builder for surfactants and can help to provide dirt suspending properties.

It appears, for example, that 9 parts bentonite is equivalent to

about. one part sodium tripolyphosphate which builds for organic surfactants. Apparently due to its plate-like structure, the individual bentonite particles that are held onto the fibers in the cloth will act as a lubricant for such fibers and thereby make them feel soft. Because the particles have such a small size and apparently desirable optical properties, they will not undesirably brighten or discolor the fabric to which they adhere, and deposits of the particles will not accumulate on the fabric to an undesirable degree despite

for repeated washings with detergents containing bentonite.

The bentonite agglomerates decompose easily in the wash water, especially in very hot wash water, and this decomposition can be supported by the release of oxygen from the bleaching agent, such as sodium perborate. The agglomerates can be water absorbent as far as the per compound is concerned without being cemented to other particles in the detergent, at least when only relatively small amounts of external moisture are present. In this regard, the bentonite agglomerates can help to stabilize the bead compound and to prevent caking of such materials and the spray-dried beads in which most of the other components of the product are present.

Although it may occasionally be desirable for the perborates and the enzyme to be coated with other materials to stabilize them and prevent them from reacting with other ingredients in the detergent, this has not been shown to be necessary for the present detergents. Furthermore, when the bentonite is present in the agglomerated particles which do not contain the other product ingredients, it is more readily available for absorption of moisture and apparently exerts a stronger anti-caking effect than would have been the case if it had been spray-dried together with the other detergent ingredients. Furthermore, when bentonite is spray-dried together with other ingredients for the detergent, it may lose some of its softening power, and this often makes the present invention preferable. In some cases, it may nevertheless be desirable to use part of the bentonite, e.g. up to half of this, in the slurry, and in this case it will be present in the spray-dried beads and can facilitate a rapid breakdown of these in the wash water. However, it has been found that such spray-dried beads which do not contain bentonite degrade sufficiently quickly when they have the particle sizes mentioned above, so that no "internal" bentonite is necessary. The perborate, surfactant and builder component can apparently work with the bentonite to provide sites on the fabric to receive the softening particles. These places are thereby cleaned physically and chemically, and this can improve their ability to hold onto the bentonite. It thus appears that the various components in the present detergents can combine

work to improve the detergent's softening, cleaning and whitening effect.

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 an amount of 100 parts is prepared by reacting 11.38 parts of dodecyl benzenesulfonic acid (Dobane<®> JNQ [48.8% active ingredient]) and 5.22 parts of hydrogenated fatty acids (16 - 18 carbon atoms per molecule acetic acid) with 1.47 parts sodium hydroxide solution (38% Na 2 O) in an aqueous medium containing a suitable proportion (to maintain the reaction) of 2 9.75 parts tap water (300 ppm hardness, calculated as CaCO 2 ). The rest of this water is used to cool the reaction mixture as needed and to dilute other ingredients for the slurry. Next, 7.56 parts of aqueous sodium silicate solution are added to the kneader (Na20:SiO2 = 1:2.4) in a concentration of 44.1% solids, 0.23 parts of fluorescent whitening agent of

(R)

stilbene type, 0.22 parts Sydex^ 808 (85% MgSi03 and 15% magnesium DTPA), 39.14 parts hydrated sodium tripolyphosphate (TPP "H"), 1.69 parts anhydrous sodium sulfate (99.5% pure)

and 33.34 parts of a non-ionic surfactant which can be regarded as the condensation product of 11 molecules of ethylene oxide with 1 molecule of a higher fatty alcohol with 12 - 15 carbon atoms per molecule.

The slurry is heated for approx. 1 hour while stirring so that its temperature increases to approx. 55° C, after which it is pumped into a spray-dried tower where it is sprayed at elevated pressure through multiple shower nozzles into drying air at a temperature of approx. 300° C. Particles with a moisture content of approx. 12% are obtained, and most of these have a size in the range from 2.00 mm to

149 µm. Particles outside this size range are sieved away.

6 3.1 parts of the spray-dried powder

(space density approx. 0.4 g/ml) is then mixed with 0.3 part of pelletized proteolytic enzyme (Alcalase^with 2 Anson-

(s)

units per g although Maxatase^P 440,000 can be used instead), 20 parts granular sodium perborate and 16 parts agglomerated bentonite. All these powders have particle sizes within the particle size range of the spray-dried detergent component, but smaller particles of the enzyme and the perborate can also be used down to 7 4 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 agglomerating more finely divided bentonite particles (Laviosa AGB) with the diluted sodium silicate solution (in the water), after which they are colored. The bentonite used is a bentonite which has been treated with sodium carbonate to replace the calcium and magnesium in it with sodium and from which a natural content of granular material has been removed, after treatment, by centrifugal separation. Such treatment methods for the bentonite will be described later in this example. The moisture content of suitable agglomerated bentonite can be varied and can be as low as 3% when mixed with other ingredients of the present softening detergent.

0.5 part of the nonionic surfactant and 0.25 part of the detergent perfumes are sprayed onto the mixture of spray-dried beads, enzyme, perborate and colored bentonite particles in a pouring drum mixer. The spraying is regulated so that the sprayed liquid evenly covers the particles in the mixing device or in the stirring drum, forming approx. 100 parts of a uniform product.

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

0.5 g/ml and a moisture content of approx. 12% (although this can be reduced to 8 - 10% in case of delay). The particulate fabric softener obtained is dust-free and lint-free and has a pleasing appearance with somewhat larger (on average 20 - 200% larger diameter) blue, agglomerate

red bentonite particles that form a contrast to the other white particles. Although the spray-dried beads and bentonite agglomerates appear clearly separated from each other, the perborate and the enzyme, especially when the particles thereof have sizes within the lower end of the mentioned range, may appear to be mixed with the other beads, whereby the appearance of the enzyme is improved . However, they are not agglomerated, and if they are not present separately, they can be easily separated from the other such particles and from each other.

When the described product is subjected to testing

with washing clothes in practice, it turns out to be an excellent detergent with desirable fabric softening properties.

As modifications of the above method can

the anionic surfactant is replaced with a corresponding weight of sodium lauryl sulfate, sodium hydrogenated tallow alcohol sulfate or sodium tallow alcohol polyethoxy (3EtO) sulfate. Alternatively, mixtures of such materials, e.g. equal parts of sodium dodecylbenzene sulphonate and sodium hydrogenated tallow alcohol sulphate are used together. In all such cases, the finished detergent obtained is a detergent which is an excellent textile softening laundry detergent. Similar results can also be obtained when, instead of varying the anionic surfactant, the nonionic surfactant is changed, replacing it with a block copolymer of propylene oxide and ethylene oxide such as Pluronic<®> L-44 or L-62, nonylphenol polyethylene (12EtO )-glycol or-a condensation product of a C-^-xs fatty alcohol with 3 or 7 molecules of ethylene oxide per molecule, or with a mixture of two or more such surfactants, e.g. in equal parts. When half or all of the sodium tripolyphosphate is replaced with NTA, the end product is also a satisfactory detergent with softening properties.

When the soap is omitted from the recipe, the result is reduced foam control, but the product is otherwise acceptable and similar to those described above. When the sodium perborate is replaced with other bleaching agents, such as sodium persulphate, sodium perisophthalate or magnesium dimonoperoxyphthalate, good bleaching and cleaning can still be achieved with the product. When the bleach is omitted, the resulting detergent will not whiten clothes or remove stains as well. When known activators for oxidizing agents are present, bleaching can be achieved by using the detergent at lower temperatures than temperatures near the boiling point (which are normally used in the process according to this example to achieve maximum bleaching effect). If it is desired to incorporate more silicate into the product, the quantity of silicate is doubled by subsequently adding hydrated sodium silicate particles of a similar size together with the other particulate solids added afterwards. In a process variant, only the perfume is sprayed onto the mixture, the entire quantity of the non-ionic surfactant being incorporated into the kneading device mixture.

The bentonite tag agglomerates used according to this example are essentially regular balls which essentially consist of bentonite with a small proportion of silicate binder and with a blue dye on the surface. To produce these, an Italian clay with a low content of exchangeable sodium is treated to increase the sodium content, swelling capacity and softening effect. First, such a clay containing a smaller proportion, e.g. about. 3%, weeded hard, black, grain-like material, crushed and size-reduced so that the particles thereof pass through a 4.76 mm sieve, after which it is treated with an excess, e.g. an excess of 50%, of the sodium carbonate solution, as a solution with a concentration of approx. 10%. The mixture is allowed to stand, with intermediate mixing periods, for a suitable time for reaction, which is approx. 4 hours, and at this time a sufficient ion exchange has taken place between the exchangeable calcium and magnesium in the clay, so that a typical analysis of this is that indicated above for Italian bentonite (after alkaline treatment). With the help of such treatment, the clay's Na20 content has been significantly increased (approx. 2%), and the content of MgO and CaO has been correspondingly reduced. The clay is then dried, e.g. to a moisture content of approx. 5%, after which it is size-reduced to particles desirably smaller than 149 pm, although larger particle sizes may occasionally be present), and subjected to centrifugal air separation in a cyclone separator (although size sepa -ration methods can also be used) to remove the grains.

The grain-free bentonite, which contains less than 0.1% grain, has a swelling capacity of approx. 5 ml/g and a viscosity of approx. 15 cp at a concentration in water of 6%, and a moisture content of approx. 7%, was then agglomerated by the method described above, the dilute sodium silicate solution being sprayed onto the surfaces of the particles which are kept in motion but which are tumbled in a pouring drum. The tumbling is continued until the particles have reached the desired size range and have become satisfactorily round. At the end of the agitation period, which can last up to 1 hour on average, a diluted dye solution is sprayed onto the beads to color them, and they are ready to be mixed with the other ingredients to make a finished detergent product.

Example 2

An effective softening detergent similar to that according to the first recipe in 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 parts of the sodium hydroxide solution, 26.54 parts of water, 37 .2 parts of pentasodium tripolyphosphate (hydrated), 6.8 parts of the sodium silicate solution, 0.21 parts of fluorescent bleach, 1.46 parts of sodium sulfate, and 3.0 parts of the nonionic surfactant, added in order. This is spray-dried using the method described in Example 1, producing 6 2.5 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 of Sydex^SOS, and a mixture of 0.3 part of the detergent perfume and 0 .4 part of a C10-13 linear alkylate is sprayed onto the stirred powder mixture. When the dye Acilan Blue which was used for

to color the bentonite agglomerates, is replaced with ultramarine blue, good coloring and bluing effects are also obtained.

Example 3

When the proportions of the various components according to the above examples are changed by -10%, -20% and -30% while maintaining these within the ranges indicated above 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 is kept within the range 1:3 - 1:8 and the ratio between sodium bentonite and total amount of surfactant is kept within the range 1:1 - 2:1, obtained

products with similar properties to those described in Example 1. This is also the case when the water-soluble building salt or water-soluble building salts according to Example 1 are replaced by zeolite A (20% hydrated) and when any of a wide variety of different synthetic, Anionic and non-ionic surfactants are used in a mixture with each other, possibly together with an amphoteric surfactant, such as a surfactant of the Miranol R■ -" type. Furthermore, the bentonite tacclomerate detergent and its components can have different densities (0.2-0.9 g /ml) and sizes (from 2.0 mm to 420 µm).

Claims (2)

1. Bleaching and textile softening, particulate detergent for washing clothes in water, containing 3-10% by weight of a sodium salt of a synthetic, organic, anionic detergent consisting of sulfonates or sulfates or mixtures thereof, 1-8% by weight of a non- ionic detergent, 0-10% by weight of a water-soluble alkali metal soap, 20-75% by weight of a builder for the synthetic, organic detergent, 5-35% by weight of a bleaching agent which releases oxygen in aqueous solution at elevated temperature, and 5 -25% by weight of agglomerated bentonite particles which have been produced by size reduction of naturally occurring bentonite which has a low swelling capacity and contains exchangeable calcium and/or magnesium and granular material, characterized in that the bentonite particles have been reacted with sodium and/or potassium carbonate to replace at least part of the bentonite's calcium and/or magnesium with sodium and/or potassium, and then dried and reduced in size, with subsequent separation of the bentonite from the granular material and agglomerating the bentonite to particle sizes in the range of 149 µm to 2 mm. 2. Detergent according to claim 1, characterized in that the obtained bentonite has a moisture content of at least 3% and swells in water with a swelling capacity of at least 5 ml/g.