SE502089C2 - Detergent composition consisting of a bead material into which a nonionic detergent is absorbed - Google Patents

Abstract

Free-flowing base beads, into which nonionic detergent in liquid form may be absorbed to make a free- flowing particulate built synthetic nonionic organic detergent product of improved washing properties, include 15 to 30% of sodium carbonate, 10 to 22% of sodium bicarbonate, 10 to 50% of water softening aluminium silicate (zeolite), 0 to 18% of sodium silicate, 1 to 20% of bentonite and/or 0.05 to 2% of polyacrylate of molecular weight in the range of 1,000 to 5,000, and 1 to 15% of moisture, together with suitable adjuvants and processing aids in small proportions (normally totalling less than 10% and preferably less than 5%).

Description

20 25 30 35 sozëšs ¿g these are prepared by spray-drying a basic mixture of the components of the detergent composition. However, it is well known that zeolites often have a tendency to precipitate in the form of a visible residue on laundry washed in a washing liquid containing this substance, and various researchers have reported that the presence of a silicate in a medium containing zeolite increases the amount of deposits. .

Bentonite, which is a swellable clay with a comparatively small softening ion exchange capacity, has been proposed as suitable for use in various detergent products, such as in soaps and washing detergents, where it has often acted primarily as a filler. In some cases, however, it has been claimed to have other functions. For example, U.S. Pat. No. 4,107,039 discloses it as an aid in the production of homogeneous detergent slurries when they contain phosphate (s). In general, however, clays are mixed into detergent compositions, as these are insoluble and can be expected to deposit on the washed materials. The ability to remove clay contaminants is in fact one of the tests performed to assess the detergent's effectiveness. Although it can be expected that the addition of bentonite would only aggravate the deposition problems associated with washing clothes in an aqueous medium containing detergent compositions which include zeolite and silicate, it has surprisingly been found that the amount of deposits decreases. The degree of ion binding with respect to calcium has also increased.

Polyacrylates, often of comparatively high molecular weight, have been proposed as components in detergent compositions. They have been described as components of powdered and slurry detergents and have been proposed as substitutes for detergent activating phosphate in non-phosphate detergents. It is known that the polyacrylates have dispersing properties, and a manufacturer of these materials has claimed that they are suitable as dispersants, for example for maintaining a suspension of pigments in paints.

It is further known that in some aqueous media they tend to inhibit the deposition of insoluble calcium compounds and the reprecipitation of insoluble material on laundry. Although polyacrylates have been included in detergent compositions, the mixtures in question, the carrier material in the form of beads and the detergent compositions are new and surprising. The presence of a very small quantity of a particular type of polyacrylate in the specified compositions, in conjunction with the other components of these compositions, has been found to result in an improved product with better cleaning properties, which can be prepared using practical manufacturing methods.

The present invention relates to a free-flowing bead material in the form of beads, in which a nonionic detergent can be absorbed to produce particulate, activated, synthetic, nonionic organic detergent products, which have improved washing properties and which, after rinsing, leave smaller quantities of deposited substance with the products, which material is characterized by the fact that it contains / e $ '15 - 30% by weight of sodium carbonate. 10 - 22% by weight of sodium bicarbonate, 10 - 50% by weight of water-softening aluminosilicate, 0 - 18% by weight of sodium silicate and 1 - 20% by weight of bentonite and / or 0.05 - 2% by weight of polyacrylate with a molecular weight within range 1000 - 5000.

The products generally contain 1 to 15% by weight of water and they can be worked up into organic detergent compositions by adding liquid nonionic detergent thereto in such a way that the detergent is absorbed and the resulting product is still free flowing. The amount of detergent added is generally such that the final detergent composition contains / eg 8 - 30% by weight thereof. När- r \ 10 15 20 25 30 w-rgf. The presence of the polyacrylate contributes to increasing the ability of the bead material to absorb the liquid nonionic detergent. It often also improves spray-drying processes by adhering smaller amounts of material to the walls of the dryer, thereby increasing the capacity of the drying tower and reducing the number of cleanings required.

The various components of the bead material of the invention, with the exception of the water, are generally in solid form, although some when added to the mixer may be in the form of hydrate or be dissolved or dispersed in an aqueous medium, such as water. The sodium bicarbonate is anhydrous, and the sodium carbonate is generally used in the form of calcined soda. However, if desired, carbonate hydrates may be used, for example the monohydrate, and in some cases it may be possible to substitute other carbonates and bicarbonates, such as other alkali metal salts, eg potassium salts, instead of at least part of the sodium salt, although the sodium salts highly preferred.

The silicate, when included, is generally added to the mixer in the form of an aqueous solution, in which the solids content is normally 40-50%, eg 47.5%, and preferably this addition takes place near the end of the mixing process.

The silicate used should generally have a Na 2 O: SiO 2 ratio which is in the range 1: 1, 4 to 1: 3, preferably 1 = 1, e: in 1 = 2.4 or 1 = 2.6, one even lower 1: 2 to 1: 2.4. Although sodium silicate is the preferred silicate, some of the sodium silicate may be exchanged for potassium silicate or some other suitable soluble alkali metal silicate.

The zeolites used include crystalline and amorphous zeolites and mixtures thereof, both of natural and synthetic origin, which can counteract the hardness caused by calcium ions in the washing liquid sufficiently quickly and sufficiently effectively. Preferably these materials have us '' gu -_- | 'Fi w fi w' ~ ability to react quickly enough with the calcium ions so that they, alone or in conjunction with other water-softening compounds in the detergent, soften the washing liquid before adverse reactions between these ions and other components of the synthetic organic detergent composition occur.

The zeolites used can be said to have a large ion exchange capacity relative to calcium ions, which is generally between about 200 and 400 mg equivalents or more of the calcium (T carbonate hardness per gram of aluminosilicate, preferably 250 - 350 mg / eq / g). Preferably they also have a softening rate with respect to residual hardness of 0.02 - 0.05 (Û mg CaCO3 / liter within 1 minute, preferably 0.02 - 0.03 mg / l, 'and less than 0.01 mg / liter Although within 10 minutes, all based on anhydrous zeolite Although other ion exchange zeolites may also be used, in the practice of the present invention the synthetic zeolite is used, in the form of atomized detergent particles having the formula (Na 2 O) x (A12o3) y.1s1o2) zw no 20 in which x is 1, y is between 0.8 and 1.2, preferably about 1, z is between 1.5 and 3.5, preferably 2 - 3 or about 2 , and w is between 0 and 9, preferably 2.5 - 6. É The zeolite must be a monovalent cation-exchanging zeolite, ie it must consist of an aluminum silicate with a monovalent cation, such as sodium, potassium, lithium (whenever possible) or any other alkali metal, ammonium or hydrogen (in some cases).

Preferably the monovalent cation of the zeolite used is an alkali metal cation, in particular sodium or potassium and most preferably sodium. Crystalline types of zeolite which, at least in part, are useful as good ion exchangers according to the invention include zeolites from the following crystal structure groups: A, X, Y, L, mordenite and erionite, and of these types, A, X and Y are preferred. Mixtures of these molecular sieve zeolites may also be suitable, especially when the zeolite of the Artype is present. These crystalline types of zeolites are well known in the art, and are described in more detail in Zeolite Molecular Sieves by Donald W. Breck, published in 1974 by John Wiley & Sons. Typical commercially available zeolites of the mentioned structure types are listed in Table 9.6 on pages 747 - 749 of the said Breck. These zeolites are known in the art.

Some suitable zeolites have been described in many patents in recent years as useful as detergent activators in detergent compositions.

The zeolite used according to the invention is generally synthetic, and it is often characterized in that it has a network of substantially uniform pores in the range of about 3 to 10 Angstroms, often about 4 Å (normally), the size of which is determined solely by the uniform the structure of the zeolite crystal. Preferably, this is of type A or similar structure as described in particular on page 133 of the said publication. Good results have been obtained when using a molecular sieve zeolite of type 4A, the monovalent cation of the zeolite being sodium and the pore size of the zeolite being about 4A. These molecular sieve zeolites are described in U.S. Pat. No. 2,882,243, designated Zeolite A.

Molecular sieve zeolites can be prepared either in a dehydrated or calcined form, containing between about 0 or about 1.5% to about 3% moisture, or in a hydrated or aqueous form containing bound water in an amount of from about 4% up to to about 36% of the total weight of the zeolite, depending on the type of zeolite used. The aqueous hydrated form of the molecular sieve zeolite (preferably hydrated to about 15-70%) is preferred in the practice of the present invention when the crystalline product is used. The method of preparing the crystals is well known. preparation of zeolite A as above, the hydrated zeolite crystals formed in the crystallization medium (such as an aqueous amorphous naphthrium aluminum silixate gel without high temperature aehyarafization (calcination to water content or less) were used, which The crystalline zeolite, either in fully hydrated or in partially hydrated form, can be collected by filtering the crystals from the crystallization medium and air drying at ambient temperature to its water content therein is in the range of about 5 - 30% moisture, preferably about 10 - 25 %, eg 17 -_22%. However, the moisture content of the molecular sieve zeolite used can be much lower, as mentioned earlier, in which case the zeolite is usually hydrated during the mixing and other processing.

Preferably the zeolite should be in a finely divided form with a maximum particle diameter of up to 20 microns, for example 0.005 or 0.01 to 20 microns, preferably between 0.01 and 15 microns and most preferably have an average particle size of 0.01 to 8 microns, eg 3 to 7 or 12 microns, if crystalline, and 0.01 to 0.1 microns, eg 0.01 to 0.05 microns, if amorphous. Although the final particle size is much smaller, the zeolite particles should generally have a size in the range of 100 to 400 mesh, preferably 140 to 325 mesh. Zeolites of smaller sizes often emit unpleasant dust and those of larger sizes cannot adequately and satisfactorily cover the particle cores of carbonate-bicarbonate on which they can be deposited during the spray-drying of a mixture for the production of the bead material. 10 15 20 25 30 502 G89 n! The bentonite used is a colloidal clay (aluminum silicate) containing montmorillonite. Montmorillonite is a hydrated aluminum silicate in which about 1/6 of the aluminum atoms may be exchanged for magnesium atoms, and with which varying amounts of hydrogen, sodium , potassium, calcium, magnesium and other metals may be loosely combined.The type of bentonite clay specifically described herein for the preparation of the bead material of the invention is that designated sodium bentonite (or Wyoming or western bentonite) and which is normally a light to off-white soft powder, which in water forms a colloidal suspension with strong thixotropic properties.In water, the swelling capacity of the clay should generally be in the range 3 - 15 ml / gram, preferably 7 - 15 ml / g, and its viscosity at 6 % concentration in water should generally be in the range of 3 - 30 centipois, preferably 8 - 30 cP.

Preferred swellable bentonites of this type are those sold under the trademark THIXO-JEL, in the form of industrial bentonites, by Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials are selectively recovered and processed bentonites, and those considered most suitable are those designated THIXO-JEL Nos. 1, 2, 3 and 4. These materials have a pH value (6% concentration in water) in the range 8-9, {, a maximum free moisture content of about 8% and a specific gravity of about 2.6, and in the case of the powdered quality, about 85% passes through a 200 mesh screen according to the US screen series. The materials have a content of exchangeable calcium oxide which is in the range of about 1 - 1.8%, and for magnesium oxide this content is normally in the range of 0.04 - 0.41%. A typical chemical analysis of the materials is 64.8 - 73.0% SiO2, 1.4 - 1.3% Al2 O3, 1.6 - 2.7% Mg0, 1.3 - 3.1% CaO, 2.3 - 3.4% Fe 2 O 3, 0.8 - 2.8% Na 2 O and 0.4 - 7.0% K 2 O. Although these bentonites are preferred, they can be exchanged for equivalent materials from other sources. The polyacrylate present in the preferred bead material of the invention is a low molecular weight polyacrylate, generally in the range of about 1000 - S000, preferably 1000 - 3000 and in particular 1000 - 2000 or ca 2000.

The polyacrylate may be partially or completely neutralized, eg about 1/2 or 1/3 Na salt. Although modified polyacrylates may be substituted for the sodium polyacrylate described, including certain other alkali metal polyacrylates and hydroxylated polyacrylates, such yield should preferably be limited to a minor portion of the material, and most preferably the polyacrylate should be an unsubstituted sodium polyacrylate. Such materials are available from Alco Chemical Corporation under the trademark Alcosperse. The sodium polyacrylates are available in the form of clear amber liquids or powders, the solids content of the solutions being about 25-40%, eg 30%, and the pH of the solutions, or in a 30% aqueous solution of the powder, is in the range of about 7.5 - 9.5, eg about 9. The materials are completely soluble in water and have been used as dispersants. They have been shown to bind calcium ions and have been used to prevent the precipitation of insoluble calcium compounds from aqueous solutions.

The presence of polyacrylate, even in very small quantities, facilitates the mixing in the mixer of the various components which, in preferred compositions, include ultramarine blue which, if inadequately distributed, can stain the laundry washed with a detergent made from the bead material. The polyacrylate also makes it easier to evenly distribute any fluorescent bleach in the mixture and detergent composition, so that an even bleaching of the laundry is obtained. Furthermore, the polyacrylate contributes to the final product (apart from the nonionic detergent) becoming more homogeneous. Process aids which may be present to prevent gelation and hardening of the inorganic materials in the mixer during mixing and I. 10 15 20 25 30 _ .. 502 goose »» _ 10 when the mixture is allowed to stand, disperses more evenly in the mixture, which means that their effect increases. The polyacrylate helps the bead material, which is produced by spray drying, to better absorb the nonionic detergent in liquid form that is sprayed on the beads. In some cases, it increases the beads' ability to absorb the detergent, while remaining free-flowing. The spray-drying process is improved because a smaller quantity of the sprayed material adheres to the walls of the dryer, whereby the capacity of the tower increases and the number of cleaning required can be reduced.

The only additional material needed in the preparation of the bead material in question is water, and during the drying of the beads their moisture content can be reduced so that the product becomes virtually anhydrous. Although the use of deionized water is preferred, so that the content of hard ions in the water can be very low, and so that the amount of metal ions which can cause decomposition of any organic materials in the final bead material and the detergent is reduced to a minimum, ordinary city or tap water can be used instead. Normally the hardness of the water should be less than 150 ppm, such as CaCO 3, and preferably the hardness should be less than 100 ppm and most preferably lower than SO ppm.

Since relatively concentrated aqueous mixtures of silicate, carbonate, bicarbonate, zeolite and bentonite and / or polyacrylate can "solidify" in the mixer due to interaction between the components, if these are retained beyond the permitted time, process aids are preferably included in the mixture, and consequently in the finished bead material and in the detergent composition, when silicate is present, to prevent premature solidification or gelation of the mixture. Preferably these consist of citric acid and magnesium sulphate. Instead of citric acid, soluble citrates, such as sodium citrate, may be used, and although anhydrous magnesium sulfate is preferred, various hydrates thereof may be used, such as epsom salts. Magnesium citrate can also be used instead. In exchange for the preferred anti-gelling system, other adjuvants and suitable systems may be added to maintain the mixture in liquid form, such as sodium sesquicarbonate, which is added in place of a portion of the sodium carbonate and sodium bicarbonate.

Various adjuvants, such as perfumes, enzymes, dyes, bleaches and flow-promoting substances, can often be sprayed on or otherwise mixed with the bead material after its preparation, together with the nonionic detergent or separately, so as not to adversely affect the spray drying and also for that the presence of the same in the spray-dried bead material should not inhibit the absorption of nonionic detergent. However, in the case of stable and normally solid adjuvants, it is also possible to mix them into the slurry of inorganic salts in the mixer. It is thus possible that dyes and fluorescent brighteners are normally included in the mixture from which the bead material in question is prepared by spray drying. The preferred dye is ultramarine blue, but other stable pigments and dyes may also be used or substituted. Of the fluorescent whitening agents, Tinopal SBM is the most preferred.

However, various other cotton whitening agents may be used, such as those sometimes referred to as CC / DAS whitening agents, derived from the reaction product of cyanuric chloride and the disodium salt of diaminostilbene disulfonic acid, including variations thereof with respect to the substituents on the triazine and aromatic rings. This class of bleach is known in the art of detergent and is commonly used when bleaching components are not included in the final product. In such cases, bleach-stable bleaches can be used. Of these, mention may be made of the benzidine sulfonic disulfonic acids, the naphthotriazolyl stilbenzulfonic acids and benzimidazolyl derivatives. Polyamide whitening agents which may also be included include aminocoumarin or diphenylpyrazoline derivatives, and polyester whitening agents which may also be included include naphthotriazolyl stilbenes. All these bleaches are normally used in the form of the soluble salts, but they can also be used in the form of the corresponding acids. Cotton bleaches generally make up the majority of bleaching systems.

Of the materials that can be added to the spray-dried bead material, the most important is of course the nonionic detergent. Although various nonionic detergents with satisfactory physical properties may be used, including condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl-containing bases such as nonylphenol and the oxo type of alcohols, it is generally preferred that the nonionic detergent be a higher condensation product of ethylene oxide. fatty alcohol. In these products, the higher fatty alcohol has 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and the nonionic detergent contains from about 3 to 20 ethylene oxide groups per mole, preferably between 6 and 12. Such detergents are prepared by Shell Chemical Company and are available in trade under the Neodol brand 23-6.5 and 23-7.

The enzyme preparation that is normally added to the bead material afterwards can be any of the commercially available products, among which may be mentioned Alcalase, manufactured by Novo Industri, A / S, and Maxatas, both of which are alkaline proteases (subtilisin). . Although the alkaline proteases are preferred, amylolytic enzymes such as alpha-amylase as well as proteolytic enzymes can be used. The said compositions generally contain active enzymes in combination with an inert powdery form. v, | 13 vehicle, such as sodium or calcium sulphate, and the content of active enzyme can vary widely, generally being between 2 and 80% in the commercial product. The perfumes used, which are usually heat sensitive and may include some volatile solvents, such as alcohol, generally consist of synthetic perfume materials, sometimes mixed with natural components, and usually contain alcohols, aldehydes, terpenes, fixatives and spirits. - ra for perfumes normal components. Fluid-promoting agents, such as special clays, which are sometimes added to detergent products because they often improve the flowability of and reduce the adhesion of various compositions, are in this case unnecessary, possibly partly due to the presence of bentonite and / or polyacrylate. . However, they can be added, if desired, to further increase flowability.

The contents of the various components of the bead material must be such that it becomes free-flowing and can sufficiently absorb a nonionic detergent which is applied to it in liquid form, and so that the detergent composition prepared therefrom by incorporating the detergent also becomes sufficiently free-flowing. The detergent composition prepared from the bead material must, of course, be an effective detergent, the detergent agents present supporting the organic detergent in an aqueous solution of the composition, and it is important that the resulting product be such as not to cause undesired deposits. of zeolite particles (possibly together with other substances, such as normally water-soluble silicates) on washed material. It has been found that a completely satisfactory bead material which meets these requirements, when silicate is present, can contain 15 - 30% by weight of sodium carbonate, 10 - 22% by weight of sodium bicarbonate, 20 - 40% by weight of water-softening aluminum. silicate (zeolite), 3 or 4 to 12% by weight of sodium silicate 10 15 20 25 30 35 502 Él89 V fi ~ 14 and 1 - 15% by weight of bentonite, as active components, and 1 - 15% by weight of water. In these beads, the aluminum silicate preferably consists of a sodium zeolite containing 15-25% by weight of hydrate water, and most preferably the zeolite should be zeolite A. The preferred weight ratio between sodium carbonate and sodium bicarbonate in the product is in the range of approx. 1-3, the beads having a bulk volume in the range 0.6 - 0.9 g / cc, preferably 0.7 - 0.8 g / cc, and the particle size of the beads is in the range of 10 to 100 (through No. 10 and at No. 100) according to the US sight series, preferably Nos. 10 - 60 in this sight series. Other preferred contents of the components are 20 - 25% by weight of sodium carbonate, 13 - 19% by weight of sodium bicarbonate, 30 - 37% by weight of hydrated zeolite, 5-38 or 10% by weight of sodium silicate, S - 8% by weight bentonite and 4 - 10% by weight of water, excluding the hydrated water of zeolite. In these preferred products, the weight ratio of sodium carbonate: sodium bicarbonate is in the range of 1-2.

When a polyacrylate is present together with the zeolite in the composition of the bead material, its content is normally in the range 0.1 - 2% by weight, preferably 0.2 - 1.6% by weight and in particular 0.8 - 1.4% by weight. . The content of adjuvants and processing aids and fillers, if any, in the bead material is generally limited to 20% by weight thereof, preferably 1 to 10% by weight and in particular 3 to 7% by weight thereof. The levels of process aids when magnesium sulphate and citric acid are used are generally 1 to 3% by weight of magnesium sulphate and preferably 1.5 to 2.5% by weight thereof, and 0.2 to 1% by weight of sodium citrate and preferably 0%. 2 - 0.5% by weight thereof. In the case of pigments and fluorescent whitening agents, their contents are preferably 0.05 to 0.6% by weight of pigments, such as ultramarine blue and in particular 0.2 to 0.4% by weight, and 0.1 to 4% by weight. fluorescent brighteners and in particular 1 to 1.5 to 3% by weight thereof. These levels of process aids and adjuvants apply to the various types of bead materials of the invention, when such aids or adjuvants vantia was used.

The levels of the various components of the mixture and of the bead material, in the production of beads containing polyacrylate but without the presence of bentonite, must be such as to obtain a homogeneous or almost homogeneous mixture, and the beads must be free-flowing and sufficiently absorb a nonionic detergent which is applied to them in liquid form, so that even the detergent composition prepared thereby, by incorporating the detergent, becomes sufficiently free-flowing. It has been found that a satisfactory bead material which meets these requirements contains 15 - 30% by weight of sodium carbonate, 10 - 22% by weight of sodium bicarbonate, 20 - 40% by weight of water-softening aluminum silicate (zeolite), 3 or 4 more 18% by weight of sodium silicate and 0.1 - 2% by weight of polyacrylate, as active components, and 1 - 12 or 15% of water. The preferred weight ratio of sodium carbonate: sodium bicarbonate in the product is in the range of about 1 to 3, the beads produced having a bulk volume in the range of 0.5 to 0.8 g / cc, preferably 0.7 to 0.8 g / cc. and the particle size of the beads is in the range of No. 10 to 100 (through No. 10 and at No. 100) according to the US sight series, preferably No. 10 - 60 in this series. Other preferred contents of the components are 20 - 25% by weight of sodium carbonate, 13 - 19% by weight of sodium bicarbonate, 30 - 37% by weight of hydrated zeolite, 7 - 15% by weight of sodium silicate, 0.5 - 1.5% by weight of % sodium polyacrylate and 3 - 10% by weight of water, excluding the hydrated water of zeolite. In the more preferred products of this type, the weight ratio of sodium carbonate: sodium bicarbonate is in the range of 1-2.

When the beads to be prepared should contain only 10 15 20 25 30 35 502 agg '. vf »16 a small amount or no water-soluble silicate, previously mentioned with reference to other types of bead material according to the invention, the contents of the various components of the bead material should be such that the beads become free-flowing and can sufficiently absorb a nonionic detergent which in liquid form is applied to them, so that even the detergent composition produced thereby, by incorporating the detergent, becomes sufficiently free-flowing. It is also important that the resulting product is such that it does not cause unpleasant deposits of zeolite particles (possibly together with other substances) on washed material. It is also desirable that the bead material produced has a suitable bulk volume and color. It has been found that a satisfactory bead material which meets these requirements contains 15 to 30% by weight of sodium carbonate, 10 to 22% by weight of sodium bicarbonate, 10 to 50% by weight of water-softening aluminum silicate (zeolite), 3% by weight of sodium silicate and 3 - 20% by weight of bentonite, as active components, and 1 - 15% by weight of water. The stated percentage of water refers to free water and does not include the hydrated water of zeolite. Correspondingly, the percentage of zeolite includes the hydrate water. In some cases the product may be anhydrous with respect to free water, but these cases are rare, and it is generally desirable that a small quantity of water be present in the bead material to prevent undesired pulverization thereof, which in other cases can sometimes occur especially in the case of anhydrous compositions. The preferred weight ratio of sodium carbonate: sodium bicarbonate in the product is in the range of about 1-3, the beads may have a bulk volume in the range of 0.6 - 0.9 g / cc, preferably 0.6 or 0.7 to 0.8. g / cc, and the particle size of the beads is in the range No. 10 - 100 (through No. 10 and at No. 100) according to the US sight series, preferably No. 10 - 60 10 15 20 25 30 soà 089 "| '§ \' 1 | i | "l 17 in this series. Other preferred levels of the components are 20-27% by weight sodium carbonate, 14-21% by weight sodium bicarbonate, 20-50% by weight hydrated zeolite, 0% sodium silicate, 5-20% by weight bentonite and 1-5% by weight. % water, excluding zeolite hydrated water. In these preferred products, the weight ratio of sodium carbonate: sodium bicarbonate is in the range of 1 to 2. When silicate is present in this bead material, it is convenient to limit its content to 2% by weight and preferably to 0.5 - 1% by weight. Other preferred ranges for contents of important components according to the invention are 35 - 45% by weight of hydrated zeolite and S - 15% by weight and even better 10 - 15% by weight of bentonite.

When a polyacrylate is included in such a bead material composition, its content should generally be in the range of 0.05 - 0.5% by weight, preferably 0.05 - 0.3% by weight and in particular 0.01 - 0.2% by weight. -%. The levels of adjuvants and processing aids and fillers, if any, in the bead material should generally be limited to 20% by weight thereof and preferably be 1 to 10% by weight thereof or more preferably 3 to 7% by weight thereof, and the levels should be equal to those previously specified. Although it has been found that detergent compositions prepared from the bead material in question do not require the presence of any anti-corrosion additive in exchange for the silicate, it is possible within the scope of the invention to use suitable such materials, and preferably such which are stable under the mixing and spray-drying conditions and which do not adversely affect these work stages. The anti-corrosion additives or antioxidants may be organic or inorganic, with inorganic materials generally being preferred, and preferably those which are suitable for preventing corrosion of the aluminum parts of the washing machine are selected. If it is desired to continue using silicate for this purpose or to insert silicate due to its effect on hardness caused by magnesium ions, a powdered silicate, such as anhydrous sodium silicate, which is commercially available under the tradename Britesil and is generally preferred. is produced by Philadelphia Quartz Co (Na 2 O: SiO 2 = 1: 2.4) and this is added afterwards. Other, normally solid, soluble silicates, preferably of alkali metals, can also be added to the bead material according to the invention after it has absorbed the nonionic detergent.

If it is desired that the product produced should have the ability to make the laundry softer, plasticizers, preferably in the form of dry powder, can also be added to the bead material in a suitable manner afterwards. This class of material is well known, and very often the plasticizers are cationic compounds, especially quaternary ammonium compounds such as quaternary ammonium halides. Particularly preferred are the higher alkyl, alkylaryl and arylalkyl-lower alkyl quaternary ammonium chlorides and bromides, such as distearyl dimethylammonium chloride. Of the commercial plasticizers, the most preferred are those sold under the trademark Arosurf TA-100, manufactured by Sherex Chemical Company, Inc. These compounds also have antistatic and antibacterial properties, but if desired, other antibacterial adjuvants may also be used, which are also preferably the product is added afterwards.

It is an important feature of the present invention that an effective detergent detergent composition based on nonionic detergent alone can be prepared in a commercially suitable manner, but it may sometimes be desirable to also have an anionic surfactant component or The detergent component present in the final product, generally because it promotes the foaming properties of the product and its cleansing effect. In general, it is preferable not to add any or all of the detergent component. some anionic detergent materials to the mixer, but if such or such materials are to be used, this is preferably by post-addition to the spray-dried bead material, and generally the addition is carried out afterwards after the beads have absorbed the liquid nonionic detergent. anionic detergents, preferably wholly in powder form and / or in some cases in admixture with detergents materials, can be used, the linear higher alkyl benzene sulfonates, higher fatty alcohol sulphates and polyethoxylated higher fatty alcohol sulphates are preferred. In these products, the higher alkyl and higher alcohol moieties normally have 8 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and the detergents should be present in the form of their water-soluble alkali metal salts, preferably in the form of sodium salts. The ethoxylated alcohol sulfate generally contains 3 to 20 moles of ethylene oxide per mole of fatty alcohol.

The ranges of the contents of the various bead components in the final detergent composition can be readily calculated from the contents given for the bead material itself minus the levels of detergent and other materials subsequently added to the beads. If only nonionic detergent is added to the final detergent composition, so that the final product contains 20% nonionic detergent, the contents can be calculated on the basis of the different ranges given for the components in the bead material itself by multiplying by 0.8, ie (100 Similarly, when the content of nonionic detergent (in the compositions where this is the only additive in the beads) can vary between 8 and 25% of the detergent composition, the multiplier should be between 0.75 20 25 30 35 502 0š9 f; 20 and 0.92. In general, the final percentage of non-ionic detergent in the product should be in the range of 8 - 25%, preferably 15 - 22% and more preferably about 20%, but in some cases for some types of products levels in the range of 8 - 13% may be to prefer. Usually the percentage of perfume in the final product should be in the range 0.1 - 1%, preferably 0.2 - 0.4%, the percentage of enzyme should be between 0.5 and 3%, preferably 1 or 1.5 to 2.5 %, and the percentage of flow-improving agents which can be added afterwards should be less than 2% and preferably less than 1%. In order to calculate the contents of the bead components in the final composition, in addition to basing these calculations on the percentage of nonionic, one must. detergent in the final product (additive afterwards), of course also take into account the percentages of other adjuvants added afterwards. In addition, if some additives are made afterwards with the use of aqueous solutions of the additives, this also affects the moisture content, which should often be in the range 1 - 12% but can sometimes extend to 15%.

When polyacrylate is used and bentonite is omitted, the ranges for the contents of the various components of the detergent composition are 13 - 28% by weight of sodium carbonate, 8 - 18% by weight of sodium bicarbonate, 15 - 35% by weight of water-softening aluminum silicate, 3 - 40 wt% sodium silicate, 0.1 - 1.6 wt% polyacrylate, 8 - 30 wt% nonionic detergent and 1 - 10 wt% water. Preferably these ranges are 16 - 21% by weight of sodium carbonate, 10 - 15% by weight of sodium bicarbonate, 22 - 32% by weight of hydrated zeolite, 8 - 13% by weight of sodium silicate, 0.5 - 1.5% by weight of sodium polyacrylate, 3 - 6% by weight (sometimes 3 - 10% by weight) of water and 10 - 22 or 25% by weight of nonionic active detergent. The percentages of process aids, bleaches and dyes in the final composition should be approximately the same as in the bead material itself, and preferably in the range of 0.2 - 0.6% by weight for sodium ggoz 089 | '; 1'h 21 citrate (resulting from the addition of citric acid) and 1 - 2% by weight for magnesium sulphate, 0,1 - 0,3% by weight for triturate and 1.5 - 2% by weight for the: fluorescent The enzyme content should be in the range 0.5 - 3% by weight, usually 1 - 2% by weight, and the perfume content should be 0.1 - 1% by weight, preferably 0.2 - 0.4% by weight.

The ranges of the contents of the various bead components in the spray dried portion of the final detergent composition when a small quantity or no silicate is present can be calculated in the manner previously described. In the case of subsequently added components, the percentage of nonionic active detergent should be the same as before, the percentage of perfume in the final product should be in the range 0.1 - 1% by weight, preferably 0.2 - 0.4% by weight. , the percentage of enzyme should be between 0.5 and 3% by weight, preferably 1-2% by weight, and if an aqueous silicate is added afterwards, the amount thereof should generally be 2 - 10% by weight and preferably 3 - 8% by weight, eg about 5% by weight. When a plasticizer is present in the final product, the amount thereof should generally be in the range of 3 to 12% by weight, preferably 5 to 10% by weight, and when one or more anionic detergents are used, the amount thereof should be limited to no more than the nonionic detergent. and the total weight of anionic detergent: and nonionic detergent in the final product shall be within the ranges previously indicated for nonionic detergent only. If anionic detergent is used, the present quantity thereof should generally be in the range of 0.2 to 0.8 times the weight of the nonionic detergent. In order to calculate the levels of the bead components in the final composition, in addition to basing these calculations on the percentage of nonionic detergent in the final product (additive subsequently added), one must of course also take into account the percentages of others afterwards. 25 30 502 §_s9 i, VX 22 added adjuvants. In addition, if some additives are made afterwards using aqueous solutions of the additives, this also affects the moisture content, but this must generally be kept within the range 1 - 12% by weight for the final product, which range can sometimes extend to 15% by weight.

The carrier material in the form of beads according to the invention is spray-dried starting from an aqueous mixture, which should generally contain from about 40 to about 70 or 75% solids, preferably 50-65% thereof, the residue being water, preferably deionized water as described earlier, but tap water can also be used. The contents of the components in the mixture can be calculated on the basis of the areas for the composition of the desired bead material based on the moisture contents in the bead material and in the mixture. For example, in a mixture containing S0% water, and from which mixture beads containing S% water are to be produced (excluding the hydrated water of the zeolite), the percentages of the components of the bead material must be multiplied by 10/19, ie ÅTOO / 2 (10O - 517. The calculations above are satisfactory for components which do not decompose during spray drying, but it is known that a portion of the bicarbonate is converted to carbonate when dried at elevated temperatures in a spray drying tower, knowing the properties of the tower and the drying conditions, so that the degree of decomposition of the bicarbonate It is thus possible to calculate the levels of carbonate and bicarbonate to be included in the mixture, for example, if it is desired to produce a product containing about 22% sodium carbonate and about 16% sodium bicarbonate and in this case about a third of bicarbonate. the bonnet is decomposed into carbonate in the drying tower (whereby two parts of carbonate are obtained from three parts of split bicarbonate), then you could invest 24% bicarbonate and 17% / “\ 10 15 _20 25 30 šsoz us ßW ~ q 23 carbonate in the mixer (dry base).

Regarding the different compositions and calculations, it should be taken into account that the zeolite in the mixture and in the spray-dried pearl material and the detergent composition is hydrated to about 20% hydrate water, but it should be mentioned that the degree of hydration can vary. For the consistency and purpose of the calculations, however, such a degree of hydration must be taken into account.

The mixture of which the bead material of the present invention is preferably prepared by spray drying is a substantially inorganic mixture, and the content of organic material is generally limited to 10%, preferably 7% and in particular 4%, based on solids.

Organic materials that may be present are citric acid materials (citric acid and soluble citrates), fluorescent whitening agents, polyacrylates, dyes and pigments. Other organic materials may also be present, such as hydrotropic salts, chelating agents and polyelectrolytes, but as is clear, the mixture must mainly consist of inorganic materials and water.

For polyacrylate-containing beads, without bentonite, based on 100% solids, the mixture should generally contain about 10 - 25% sodium carbonate, 15 - 30% sodium bicarbonate, with a weight ratio of sodium bicarbonate: sodium carbonate in the range 0.5 - 2, 20 - 40% water-softening aluminum silicate, 4 - 18% by weight of sodium silicate and 0.1 - 2% by weight of polyacrylate. When process aids are present, their levels should, on the same basis, generally be 1 - 3% magnesium sulphate and 0,2 - 1% sodium citrate. In these slurries of the mixture the content of sodium polyacrylate should preferably be between 0.5 and 1.5% and, when process aids and dyes are also present, the contents thereof should be 1.5 - 2.5% magnesium sulphate, 0.2 - 0 502 (899 '(1 24% sodium citrate, 0.2 - 0.4% ultramarine blue and 1.5 - 3% fluorescent whitening agents, based on solids.

The mixture is preferably effected by sequentially adding the various components therein in a manner which results in a visibly miscible, easily pumpable and non-solidifying slurry intended for spray drying.

The order in which the various components are added may vary, depending on the circumstances, but it is highly desirable that the silicate solution (if any) be added last, and if not last, at least after the addition of any gelation or solidification inhibitor. combination of materials or process aids. It is generally preferred that all or almost all of the water be added to the mixer first, preferably at the operating temperature, after which the processing aids (if any) and other secondary components, including pigments and fluorescent whitening agents, and polyacrylates (if any) are added, followed by bentonite (if any), zeolite, bicarbonate, carbonate and silicate (if any). Usually in the additives each component must be thoroughly mixed before the addition of the next component, but the additive methods may vary depending on the circumstances, so that simultaneous additives may be allowed when appropriate. In some cases, the component additive, such as the silicate additive, may be divided into two or more parts. Different components can be pre-mixed before the addition to speed up the mixing process. Normally, the mixing speed and ability increase as the materials are added. For example, low speeds can be used until the last of the bentonite or zeolite is mixed in, after which the speed can be increased to medium speed and then to high speed before, during and after the addition of any silicate solution.

The temperature of the aqueous medium in the mixer should generally be as follows; 089 'pwmr. » Be about room temperature or elevated temperature, generally in the range 20 - 80 ° C, preferably 30 - 7S ° C and in particular 40 - 70 ° C. Heating the medium in the mixer can promote the dissolution of the water-soluble salts in the mixture, thereby increasing the miscibility, but the heating if it takes place in the mixer can also reduce the production rate and promote the solidification of the mixture. An advantage of having process aids present in the mixture is because these guarantee that you get the desired, non-gelling slurries both at lower and higher temperatures. Temperatures higher than 80 ° C (and sometimes 70 ° C) should generally be avoided due to the possibility of decomposition of one or more of the components of the mixture, eg sodium bicarbonate. In some cases, even lower temperatures in the mixer also raise the upper limits of the solids content of the mixture, probably due to the insolubilization of normally gelling or solidifying components.

Mixing times to obtain good slurries can vary widely, from as little as 5 minutes in small mixers and for slurries with higher water contents, to as much as 4 hours in some cases. The mixing time required for mixing all components of the mixture into a substantially homogeneous medium can be as short as 10 minutes, but in some cases up to 1 hour is required, although 30 minutes is the preferred upper limit. Including any such initial mixing time, the mixing periods should generally be between 15 minutes and 2 hours, eg 20 minutes to 1 hour, but the mixture may be mobile, without gelation or solidification, for at least 1 hour, preferably 2 hours and more preferably during 4 hours or longer, after completion of the preparation of the mixture, and it can also be mobile for as long as 10 - 30 hours before it is pumped out to the spray tower, if you encounter other manufacturing problems. The slurry in the mixer, with the various salts and the other components dissolved or in finely divided form evenly distributed therein, is transferred in the usual way to a spray tower, which is generally located near the mixer.

The slurry is allowed to fall from the bottom of the mixer to a feed pump, which at high pressure presses the mixture through spray nozzles at the upper end of a conventional spray tower (co- or countercurrent), in which the droplets of the slurry fall down through a hot drying gas, generally consisting of combustion products of fuel oil or natural gas, the droplets being dried to the desired absorbent material in the form of beads.

During drying, a portion of the bicarbonate (often 1/4 to 1/2), eg 1/3) can be converted to carbonate while releasing carbon dioxide, which in conjunction with the polyacrylate, which may be present in the mixture which is spray-dried, can be improve the physical properties of the bead material produced so that it better absorbs liquids, such as liquid nonionic detergent, which is subsequently sprayed onto it. However, the zeolite and bentonite components in the bead material produced also appear to have a beneficial effect on the absorption of liquid, and the polyacrylate also contributes to faster drying, thereby increasing the tower's capacity.

After drying, the products are sieved to the desired size, eg 10 to 60 or 100 according to the US sieve series, and are then ready to be sprayed with nonionic detergent, the bead material being either hot or cooled (to room temperature). However, the nonionic detergent should generally have an elevated temperature, such as 30 DEG-60 DEG C., for example SO2 DEG C., to ensure that it has a liquid form; after cooling to room temperature, however, it is desirable that it be a solid, often wax-like substance. Although the nonionic detergent is slightly tacky at room temperature, it does not cause the free flow of the final product to deteriorate as the detergent penetrates below the bead surface or into the beads. The nonionic detergent which is applied in a known manner to moving or tumbling beads in the form of a spray mist or as droplets is preferably a condensation product of ethylene oxide and a higher fatty alcohol, as previously described, but other nonionic substances are also useful. called the enzymes although it also includes a carrier), aqueous silicate and other powdered adjuvants to be added afterwards can be powdered over the detergent particles, and perfume and other liquids may be sprayed on them at any convenient time, before or after the addition of the powder ( powder).

The spray-dried bead material and the detergent compositions prepared therefrom may include a small quantity, or no, silicate derived from the mixture, in which case solid silicate may be added afterwards.

The subsequently added powdered silicate, if used, does not appear to react with the zeolite as much, so that the amount of zeolite-silicate agglomerates with a tendency to deposit on washed articles is reduced. Although silicate, even when bentonite is not present, is generally used at least because it has an anti-corrosion effect, it has not been found that the detergent compositions in question have a corrosive effect on aluminum objects, not even in the absence of silicate. Furthermore, bentonite does not have a negative effect on the stability of the product, but in fact seems to help hold the beads together and make them resistant to crushing and pulverization during transport and use. The presence of bentonite and / or polyacrylate markedly improves the properties of the final detergent composition, with the bentonite achieving higher bonding rates with respect to the calcium ions resulting in a smaller amount of zeolite being deposited on washed fabrics. . When low molecular weight polyacrylate is present, the beads become more porous and better absorb the nonionic detergent in liquid form, without excessively reducing the bulk volume of the product. Given that bentonite is a clay that can be expected to create deposition and gelation problems in itself, the reduced deposition of zeolite and the absence of gelation are surprising and constitute important results of the present invention.

The following examples illustrate but do not limit the invention.

Unless otherwise indicated, all temperatures refer to ° C, and all parts in the examples and description refer to parts by weight. When weights and contents of zeolite are given, these refer to the use of the usual hydrate, since the hydrolyte water of the zeolite probably does not leave the zeolite and does not become part of the aqueous solvent in the mixing processes in question, and also since some of the water present in the bead material and in the detergent compositions is present in the form of the hydrated water of the zeolite.

Example 1.

A 4536 kg batch of a mixture, intended to be spray dried to bead material according to the present invention and to be converted into a detergent composition, was prepared by introducing into the mixer 1832 kg of deionized water at a temperature of about 27 ° C, and then mixing it under low mixing speed in that order with 51.3 kg of anhydrous magnesium sulphate (10S, 5 kg of epsom salt can be used instead, in which case the water initially charged is reduced to 1777.4 kg), 12.7 kg of citric acid, 57.6 kg Tinopal SBM Extra Conc. (CIBA-Geigy). 68 kg ultra-navy blue powder, 169.6 kg Thixo-Jel No. 1 (bentonite), 914 Linde hydrated zeolite 4A (20% crystalline water), 636.9 kg of sodium bicarbonate and 456.3 kg of sodium carbonate (calcined soda). The mixing speed was then increased to a high speed (in some cases it can be increased to an average speed at an earlier time if the components are not mixed to the desired extent), after which 189.6 kg of sodium silicate with the Nazmsioz compound equal to 1 = 2.4 inbianaaaes' ( in a farm of 399.2 kg of a 47.5% aqueous solution). The stirring of the whole batch was then allowed to continue for about 1 hour (in some cases a mixing time as long as 4 hours can be used), during which time about 90.7 - 272.2 kg of water could disappear by evaporation and this water could, if so desired, supplemented. During the mixing time, the mixture was kept in continuous motion, and it did not gel, solidify or bake. Since the bicarbonate partially decomposes to carbonate during spray drying, the quantities thereof may vary depending on the properties of the spray tower.

Starting S minutes after all the components were added to the mixture, it was caused to fall from the mixer down to a pump which at high pressure, which was 21 kg / cm 2, pumped the mixture to the top of a countercurrent spray tower in which the initial temperature was about 430 ° C and the final temperature was about 10S ° C. The resulting, substantially inorganic bead material had a bulk volume of about 0.6 - 0.7 g / ml, an initial adhesion of about 40%, a particle size mainly in the range of 10 - 100 mesh according to the US sieve series (they were sieved to this size ) and a characteristic fineness (through U.S. sieve No. 50) of about 15%. The moisture content of the beads was about 7%. The bead material was found to be free-flowing, non-sticky, satisfactorily porous but still hard on the surface, and it was able to easily absorb significant quantities of liquid nonionic detergent without becoming impermissibly sticky.

Detergent products were prepared from the spray-dried bead material by spraying on the surface of the tumbling beads a normally waxy, nonionic detergent, either Neodol 23 -6.5 or Neodol 23-7. , in a heated liquid state, in such a quantity that the resulting final product obtained a content of 20% nonionic detergent, and proteolytic enzyme (Alcalase) was applied in powder form to a content of 1.99% in the product . Perfume was sprayed on the product to a content therein of 0.25%.

The resulting detergent products had a bulk volume of about 0.7 or 0.8 g / ml, and they contained 27.3% zeolite (hydrated), 20.1% nonionic detergent, 11.8% sodium carbonate (of which a part formed by decomposition of the bicarbonate), 12.7% sodium bicarbonate, 5.6% sodium silicate, 5.45% water, 2.0% enzymes, 1.7% fluorescent whitening agents, 1.5% magnesium sulphate, 0.4% citric acid (in citrate form), 0.25% perfume, 0.2% ultramarine blue and 5.0% bentonite (Thixo-Jel). The detergent prepared with the above composition was an excellent, very effective washing detergent, especially suitable for washing household laundry in automatic washing machines. These physical and aesthetic properties were appealing and advantageous, as they were non-dusting and extremely free-flowing, which made it possible to pack them in narrow-necked glass or plastic bottles, from which it easily flowed out during dosing. The detergent compositions according to the invention, containing bentonite, have, as mentioned, been found to have markedly improved calcium ion binding rates, but what is even more important is that they leave less residue on laundry washed therewith (in an automatic washing machine at general product concentrations). and at normal washing temperatures) than is the case with similar compositions which do not contain bentonite. This difference is accentuated when the washing water has a high hardness, eg 200 ppm in the form of calcium carbonate, the washing water is cold and the stirring is done carefully. In a control experiment, beads were prepared, excluding the bentonite from the mixture and replacing it with the same amount by weight of sodium carbonate and sodium bicarbonate and the total amount of the added materials corresponded to the excluded bentonite. weight. The mixture was spray dried and converted to a detergent composition in the same manner as used in the preparation of the detergent composition of the invention. Although this "control" product was useful as a detergent, it resulted in a greater amount of residue being deposited on the laundry than with the test product of the invention, and it had a lower calcium binding rate. the control beads were increased to 10.7%, and the levels of sodium carbonate and sodium bicarbonate were reduced to compensate for the increase in the silicate, so the deposition of residue was even greater for the control product.

During a normal process, the mixtures must be prepared quickly and can be taken out of the mixer just as quickly, whereby they are sometimes produced within as short a period as 5 minutes and pumped out of the mixer in as short a time as 10 minutes. However, it is often important that the mixtures in question can withstand at least 1 hour in the mixer without gelling or solidifying, since one can sometimes expect such long delays in commercial production. The mixture described can be retained for as long as 4 hours, and often considerably longer, without gelling or solidifying, which is at least partly attributed to the content of magnesium sulphate and citric acid in the form of process aids. However, other process aids intended to prevent gelation and solidification of the mixture may be used instead, and under certain conditions the quantities thereof may be reduced, and one or both may be omitted.

Likewise, other minor components of the mixture, such as the fluorescent bleach and pigment, may be excluded therefrom, and enzymes and perfumes may be excluded from the final product, although it is highly desirable that all these materials are present. The temperature of the mixture can be modified, such as by raising to 52 ° C, and the quantities of the various components can vary by 1 10%, in 20% and 1 30% and still be kept within the limits given above, while it is possible to obtain processable mixtures which give the desired bead material and the desired detergent compositions.

Instead of using anhydrous magnesium sulphate, an equivalent quantity of epsom salt may be added, and various other components may be used in the form of aqueous solutions, provided that the amount of water added to them is subtracted from the water introduced into the mixer. The order may be different at the time of addition, but in general it is desirable that the processing aids be used early in the preparation and that the silicate be added last or near the end thereof. Instead of Zeolite 4A, Zeolites X and Y can be used, as can other types of Zeolite A. Although the use of hydrated Zeolite 4A is preferred according to this example, different degrees of hydration of zeolite are acceptable, and in some cases almost anhydrous crystalline zeolites or amorphous zeolites can be used. A change in the amount of bentonite within the given range to, for example, 3% and 10% still gives useful products, but those that contain higher levels of bentonite are usually more effective in preventing the deposition of zeolite on the laundry. The quantities used commercially depend on a number of factors and are often a balancing act between the desired reduction of zeolite residues and the desired washing activity as well as other functional effects of other components in the detergent composition.

Example 2 A product similar to that of Example 1 was prepared but with the addition of the mixture of a low molen polyacrylate with a cooling weight (MV = 1000 to 2000), which was added at an early time, before the bentonite, to give a comparable product containing 1% polyacrylate (Alcosperse 107D). The only change in the composition to compensate for the addition of the polyacrylate was that the amount of sodium bicarbonate in the mixture was reduced by the same weight.

Furthermore, this batch was smaller when an experimental mixer was used. The bead material obtained in the spray drying, carried out in the same manner as previously described in Example 1, was converted into a final detergent product of the same type as in Example 1, with the exception of the addition of polyacrylate.

The composition was tested and its properties were noted. It proved to be an excellent free-flowing detergent, with less zeolite residues on the laundry than for the control experiments of Example 1. Furthermore, the presence of Alcosperse considerably improved the absorption properties of the beads produced so that they more readily absorbed liquid D ° akt j ° 0aktiV-Åë. §SsIgeQt @ which could be of the ethoxylated alcohol type or of another type mentioned in the description. However, the bulk volume of the beads and the product did not decrease appreciably, which is important when it is desired to produce a concentrated particulate detergent with a comparatively high bulk volume. It has been observed that when the described polyacrylate is present in the mixture, the spray drying is better and less material is lost by depositing it on the walls of the spray tower, which advantages in production are significant in terms of increasing commercial production and avoiding losses. and reprocessing materials that are not the right size.

As in Example 1, the contents of the components can also be varied in this example, within the limits given in the description, to give bead material and detergent compositions with improved properties. Although it appears that about 1% of the polyacrylate described is an optimally useful concentration in the detergent compositions, between 0.1 and 2% thereof may have good effects, whereby the use of the larger amounts results in a greater improvement in the porosity of the beads. Instead of 1%, for example, 0.5% and 1.5% are also desirable levels of the polyacrylate. In some cases it may be desirable to use polyacrylates with higher molecular weights within the given limits, for example 4000 - 5000, but in most cases the lower molecular weights within the range are preferred. As in Example 1, in some cases process aids, perfumes, enzymes, fluorescent whitening agents and pigments may be excluded or replaced, but in all these cases said zeolite, carbonate, bicarbonate, silicate and bentonite, together with the polyacrylate , are present in the given quantities in the bead material, and likewise nonionic detergent should be present in the final detergent composition, which like the others is of the non-phosphate type.

Example 3 Using a pilot plant, detergent bead material containing 23.37% sodium carbonate, 16.60% sodium bicarbonate, 34.74% zeolite 4A, 13.64% sodium silicate (Na 2 O: SiO 2 ratio 1: 2.4) was prepared. , 0.26% ultra-navy blue, 2.20% Tinopal SBM Extra Conc. (CIBA Geigy), 1.95% magnesium sulphate, 0.32% oitric acid (present in the form of sodium citrate), 1.29% sodium polyacrylate with a molecular weight in the range 1000 - 2000 (Alcosperse 107D) and 5.64% water. The product was prepared by spray drying a mixture prepared in the test plant containing 50% solids and 50% water, including water added via the aqueous silicate solution and together with the polyacrylate (when an aqueous solution thereof, such as Alcosperse 107, was used) and together with the epsom salt, if used. The other solid components- 10 15 20 25 30 suction 989, V! V! I. 35 comprised the remaining SO% of the mixture and were present at the same relative levels as indicated for the bead material, with the exception of the sodium carbonate and sodium bicarbonate of which, provided that 1/3 of the bicarbonate decomposed into carbonate, 24 , 90 parts sodium bicarbonate (proportional) and 17.84 parts sodium carbonate (proportional).

The water charged to the mixer was deionized water and had a temperature of 27 ° C. The magnesium sulphate introduced was anhydrous, although an equivalent amount of epinephrine salt could be used instead. After the addition of water and magnesium sulphate, citric acid, Tinopal SBM Extra Conc., Ultramarine blue powder and Alcosperse 107D were introduced into the mixer, generally at a relatively low speed in the mixer, after which Linde hydrated zeolite 4A (20% crystal water), sodium bicarbonate and sodium mixed carbonate could be charged. low speed or medium speed. The mixing speed was then increased to high speed and the sodium silicate was added in the form of a 47.5% aqueous solution. The mixing of the whole batch was then allowed to continue for about 1 hour (in some cases as long a mixing time as 4 hours could be used), during which time a considerable quantity of water, in some cases 2 - 6% could evaporate. This water could, if desired, be compressed. During the mixing time, the slurry was in continuous motion and did not gel, solidify or bake.

Since the decomposition of the bicarbonate may vary depending on the conditions of the spray drying, the quantities of bicarbonate and carbonate may be varied accordingly to obtain the desired composition of the bead material. 10 15 20 25 30 II 502 08 36 Starting about 5 minutes after all components were present in the mixer, the mixture was brought down from the mixer to a pump which, at a pressure maintained at about 21 kg / cm 2, pumped it to the top. of a countercurrent spray tower, in which the initial temperature was about 430 ° C and the final temperature was about 105 ° C. The resulting, mainly organic bead material had a bulk volume of about 0.6 - 0.7 g / ml, low adhesion, a particle size mainly between 10 and 100 mesh according to the US screen series (they were screened to this size), and it did not contain any disturbing part finer particles. The moisture content of the beads was about 5.6%. The beads were found to be free-flowing, non-sticky, satisfactorily porous but still had the desired physical strength, and they were able to rapidly absorb increased amounts, eg 2 - 5% more, of liquid nonionic detergent sprayed on them, without therefore becoming impermissibly sticky.

In addition to the desired properties of the bead material produced, it was noted that the growth of product on the inner walls of the spray tower was less, often about 20-50% less, than when polyacrylate was not included in the composition. The capacity of the tower increased and it turned out that the content of too fine-grained material in the product decreased. The reduction in growth and in fine-grained material meant that a considerably smaller part of the product needed to be returned.

Detergent products were prepared from the spray-dried beads by spraying on the surface of the tumbling beads a normally waxy nonionic detergent, either Neodol 23-6,5, or Neodol 23-7, in a hot state in such a quantity that a final product was obtained. containing 20.7% nonionic active detergent, and proteolytic enzyme (Alcalase) was applied in powder form to a content of 1.32% in the product. Perfume was sprayed on the product to a content therein of 0.25%. The resulting detergent products had a bulk volume of about 0.7 g / ml, and they contained 27.0% zeolite (hydrate), 20.7% nonionic active soz 089 k fl vw 37 detergent, 18.17% sodium carbonate (part of which is formed by decomposition of sodium bicarbonate), 12.9% sodium bicarbonate, 10.6% sodium silicate, 4.39% water, 1.32% enzymes, 1.71% fluorescent bleach, 1.51% magnesium sulphate, 0.25% citric acid (in citrate form), 0.25% perfume, 0.2% ultramarine blue and 1.0% sodium polyacrylate. The detergent prepared with this composition was an excellent reinforced washing detergent, especially suitable for washing household laundry in automatic washing machines. It was physically and aesthetically attractive and advantageous because it was non-dusting and extremely free-flowing, which made it possible to pack it in narrow-necked glass and plastic bottles, from which it flowed easily during dosing. In comparative experiments with similar compositions which did not contain polyacrylate, the compositions of the invention were found to have improved dirt and stain removal ability when tested for different types of dirt and stains on a wide variety of sample fabrics, including cotton, polyester-cotton blends. , polyesters and other synthetic materials. When it comes to stain removal, it has often been found that the polyacrylates are usually more effective against the stains than larger quantities of expensive enzymes, which are generally more specific in terms of stain removal ability and therefore not as effective against the combinations of stains that often precede - comes in the laundry. Compositions according to the invention containing polyacrylate also have an excellent anti-redeposition effect, whereby loosened dirt is prevented from sticking to the laundry again.

The preparation methods may be the same as described in Example 1, and various process aids and adjuvants may be used, as set forth in that Example. Some adjuvants may also be excluded, as mentioned in Example 1. The temperature of the mixture in the mixer may be modified, for example by raising to 52 ° C, and the quantities of the various components may vary by 1 10%, in 20% and in 1 30% and nevertheless retained within the limits given above, it being possible to obtain workable mixtures which give the desired bead material and the desired detergent compositions. Various compounds can be added in the form of aqueous solutions, provided that the amount of water added to them is subtracted from the water introduced into the mixer. The order may be different when investing. Instead of Zeolite 4A, Zeolites X and Y can be used, as well as other types of Zeolite A. Although the use of hydrated Zeolite 4A according to this example is preferred, different degrees of hydration of the zeolite are acceptable, and in some cases almost anhydrous crystalline geolites or amorphous zeolites be used. A change in the amount of polyacrylate in the given range, for example to 1.0 and 1.7% in the bead material, still results in useful products, but those containing the larger amounts of sodium polyacrylate are usually more effective with respect to the cleaning for - mågan, - the absorption of nonionic detergent and the improvement of the process in the spray tower. It is generally not desirable to use more than about 2% polyacrylate, as its efficiency decreases at higher concentrations and the benefits obtained are not economically sought after.

Example 4 A product similar to that of Example 3 was prepared, but using Alcosperse 107, a sodium polyacrylate solution in which the polyacrylate had a molecular weight of about 1000 or 1000 - 2000, and which consisted of a clear amber liquid containing 30% solids. The content of Alcosperse 107 inserted was equivalent to the amount of Alcosperse 1070 used in Example 1 with respect to the solids content. Instead of Alcosperse 107, corresponding amounts with respect to the solids content of Alcosperse 104 (25% solids) and 149 (40% solids content) could be used, but the results obtained with the type 107 product were better and Alcosperse 107 is preferred. because. No other significant changes were made in the composition, compared to Example 3 nor with respect to the preparation procedure. The pearl material resulting from the spray drying of the mixture was converted to the final product in the manner described, with Neodol 23- 6.5 was used as a nonionic detergent. The product obtained with Alcosperse 107 was an excellent, non-phosphate detergent, useful as a reinforced highly active detergent, which was effective against a wide variety of blemishes, including liquid cosmetic make-up and synthetic sebum (Spangler type). A test panel of 10 members clearly preferred this product over a comparable product in which the Alcosperse 107 had been excluded. The advantages have also been shown in instrumental examinations of washed materials. The experiments described were performed on cotton, dachron cotton and nylon fabrics, and the experimental conditions included machine washing in water with a hardness of 150 ppm, with a detergent composition concentration of 0.07% by weight and with a water temperature of 49 ° C.

The same advantages as mentioned in Example 3 in the manufacturing process were observed, including excellent dispersion of the materials in the mixer and excellent spray drying of the product. The beads had a measurably greater porosity than the comparison material (without polyacrylate). However, the volume of shrinkage did not fall by more than a few percent, eg 3%, which is important for such concentrated products. Similar results could be obtained by varying the content of the composition of the various other main components by 1 15% and 1 30%, while keeping the quantities thereof within the specified ranges. The same results could be obtained when other zeolites A were used, which had different degrees of hydration, eg 15 and 22%, and when polyacrylates with molecular weights in the range 1000 - S000 were used.

Preferably the polyacrylates should be sodium neutralized, either completely or at least to about 50%, but those which are less neutralized can also be used. 10 15 20 25 30 35 i fl: I .soz É9 40 Results similar to those reported here are also obtained when fluorescent whitening agents, perfumes, enzymes and processing aids (citric acid and magnesium sulphate) are excluded, but in this case care must be taken that the spray drying out is carried out shortly after the preparation of the mixture so that it does not solidify in the mixer. The individual contributions from the excluded materials are of course lost, but the product remains a good washing detergent, as described, the mixture becomes easily dispersed and easily dried, and the bead material acquires improved porosity.

Example 5 A 4536 kg batch of a mixture, intended for spray drying to bead material according to the present invention, which did not contain water-soluble silicate, was prepared by introducing into a mixer 2132 kg of deionized water at a temperature of about 27 ° C, and then This was mixed in the order mentioned and from the beginning the mixing speed was 47.2 kg Tinopal SBM Extra Conc, (CIBA-Geigy), 5.9 kg ultramarine blue powder, 3.2 kg sodium polyacrylate (Alcosperse 107D), 957.5 kg Linde hydrated zeolite 4A (20% crystal water), 283.5 kg Thixo-Jel No. 1 (bentonite), 714.4 kg of sodium bicarbonate (industrial quality), 351.1 kg of sodium carbonate (natural calcined soda) and 41.3 kg of titanium dioxide (Anatase). During the mixing of the various components, the mixing speed was increased to medium and finally to high speed, and after adding all the ingredients, which took about 15 minutes, stirring was continued for about 1 hour (in some cases the mixing time can be as long as 4 hours). during which time some of the water present, for example about 90.7 to 272.2 kg, could disappear by evaporation, and this water could be supplemented, if desired. During the mixing time, the mixture was kept in continuous motion and it did not gel, solidify or bake. Since the bicarbonate partially decomposes to the carbonate during spray drying, the quantities of bicarbonate and carbonate in the mixture can be varied depending on the properties of the spray tower. u / Å 10 15 20 25 30 35 g§_o2 089 b fi vw 41 Beginning 5 minutes after all components were added to the mixture, it was caused to fall from the mixer to a pump, which at a pressure of 21 kg / cm 2 pumped the mixture to the top of a countercurrent spray tower, in which the initial temperature was about 430 ° C and the final temperature was about 105 ° C. The resulting, mainly inorganic beads had a bulk volume of about 0.6 to 0.7 g / ml, an initial adhesion of less than 10%, a particle size mainly in the range of 10 to 60 mesh according to the US sieve series ( they were sieved to this size), and a characteristic fineness (through U.S. sieve No. SO) of about 15%. The humidity of the beads was in the range of 1 - 10%. The bead material was found to be free-flowing (80% buoyancy), non-sticky, satisfactorily porous but still hard on the surface, and it had the ability to easily absorb significant quantities of liquid nonionic detergent without becoming impermissibly tacky.

Detergent products were prepared from the spray-dried bead material by spraying a normal waxy, nonionic detergent on the surface of the tumbling beads. Neodol 23 - 6.5 was used but this can be exchanged for Neodol 23 - 7 or Neodol 25 - 7. The nonionic detergent was in heated liquid form (with a temperature of about 45 ° C). The quantity injected was such that a final product was obtained containing about 20% of nonionic active detergent. Proteolytic enzyme (Alcalase) was applied in powder form to a content of about 1.5% in the product, and perfume was sprayed on the product to a content therein of 0.25%. The resulting detergent products had a bulk volume of about 0.7 to 0.8 g / ml, and they contained 32.45% zeolite (hydrated), 19.7% nonionic detergent, 18.5% sodium carbonate (of which part is formed by decomposition of the sodium bicarbonate), 13.5% sodium bicarbonate, 1.3% free water, 1.4% enzymes, 1.6% fluorescent whitening agent, 0.25% perfume, 0.2% ultramarine blue, 9.6% bentonite (Thixo-Jel), 0.1% sodium polyacrylate and 1.4% titanium dioxide. The detergent prepared with the above composition was an excellent, very effective laundry detergent, suitable for washing household laundry in automatic washing machines.

It was non-dusty and extremely free-flowing. Detergent compositions similar to that of this example and containing bentonite, as described, have been found to have markedly improved calcium ion binding rates, but more importantly, they leave less zeolite residue on laundry washed therewith in an automatic washing machine, in especially when this is dried on a clothesline, than is the case with similar compositions containing less bentonite and co-sodium silicate present in the spray-dried bead material. This difference is accentuated when the washing water has a high hardness, eg 200 ppm in the form of calcium carbonate, the washing water is cold and the stirring is done carefully.

Various preparation methods may be used, as described in Example 1, and certain adjuvants may be excluded, as mentioned therein. The quantities of the various components can be varied by I 10%, I 20% and 1 30% and still be kept within the limits given above, it being possible to obtain machinable mixtures which give the desired bead material and the desired detergent compositions.

The content of solids in the mixture can vary within the given range, for example to 45% and 65%, whereby good mixing and spray drying can be obtained. Instead of using Zeolite 4A, Zeolites X and Y can be used, as can other types of Zeolite A. Although the use of hydrated Zeolite 4A is preferred according to this example, different degrees of hydration of the zeolite are acceptable, and in some cases may almost anhydrous crystalline zeolites or amorphous zeolites are used. A change in the amount of bentonite in the given range to, for example, 10 and 17% still yields useful products, but those that contain the higher levels of bentonite are usually more effective in preventing the deposition of zeolite on the laundry. 10 15 20 25 30 02 089 'H fl í I | "| Ü' Im: I. 43 The noted improvement of the detergent compositions according to the invention containing low soluble silicate or no silicate, which means that less residue is deposited on the laundry has been verified. by testing the described product in comparison with a control product with essentially the same composition, but without the presence of bentonite and containing about 8% sodium silicate.In this comparison experiment a Whirlpool Suds Save model washing machine was used and the washing periods were 8 minutes at a gentle The concentration of the detergent composition - was 0.06%, the washing water had a mixed calcium and magnesium hardness of a total of 200 ppm, in the form of calcium carbonate, and the water temperature was 24 ° C.

The laundry consisted of: 100% cotton; 100% polyester; 85% acetate and 15% nylon; and 65% polyester and 35% cotton. The laundry was inspected in a wet state and after drying on a clothesline. No residue was observed in any of the cases. When the control detergent was tested, a moderate residue was observed on all specimens.

The results of the practical experiment described above for residues were verified by weighing the residue deposited on a sample of denim fabric. In this experiment, the detergent composition of the invention was filtered through a sample of denim material, the detergent being in a solution suspension with a concentration of 0.12% in water with a hardness of 200 ppm (as CaCO 3) and at 24 ° C . The weight of the residue on the fabric was noted and compared with it in the control experiment.

In this trial, the percentage remaining, compared with the control trial, was about 75%, which can be considered a significant improvement.

The adhesion test, as previously mentioned and in which 10 15 20 25 30 502 éše -l VF ”. 44 measures the tackiness of the detergent products, is a test in which 10 g of the bead material (or detergent composition in some cases) is placed evenly between two watch glasses which both have a diameter of about 23 cm, with a weight of 500 g on top of the upper watch glass (both glasses with the concave side UP).

After standing for about 5 minutes, the weight and the upper watch glass are removed, and the lower watch glass is turned upside down, after which the product that remains adhering to this watch glass is weighed. The percentage adhesion is the number of grams of the product left on the watch glass, divided by 10 and multiplied by 100.

Flow index is obtained by a flow test in which the volumetric flow rate of the bead material (and in some cases the final product) and of standardized Gttawa sand (-20 +60, US sieve series) is compared by measuring the times required to completely empty a 1.9 liter Mason can via a hole with a diameter of 2.2 cm in a nozzle attached to the lid of the can. The index is the time of sand flow divided by the time of flow of the test product, expressed as a percentage.

Example 6 The experiment of Example 5 was repeated on a reduced scale, without the presence of polyacrylate in the mixture. The rate of passage through the spray tower decreased markedly and also the ability of the bead material to absorb nonionic detergent decreased (or the product produced became slightly stickier if the same quantity of nonionic detergent was applied). However, the mixture did not solidify in the mixer, the bead material could be prepared by spray drying and the resulting detergent composition was still, even if it had a lower content of nonionic detergent, eg 17% nonionic detergent, to maintain flowability and non-stick properties, a useful product with satisfactory flow properties. Example 7 The procedure described in Example 5 was repeated, adding 2% sodium silicate with a Na 2 O: SiO 2 ratio of 1: 2.4 to the mixer in the form of a 47, S% aqueous solution of solids. The product produced did not gel in the mixer in normal manufacturing processes, but it is desirable to use magnesium sulphate and citric acid as process aids to prevent gelation or solidification if the residence time is longer than normal. The detergent composition produced left more residue on the laundry, which became clearer when the laundry had a dark color.

Example 8 The procedure described in Example 5 was repeated, adding 5% sodium bicarbonate powder (Britesil) subsequently together with the enzyme powder. The subsequently added silicate did not appear to adversely affect the deposition of zeolite on washed material to a significant extent, and it acted as a corrosion inhibitor with respect to aluminum parts in the washing machine, and also as a water softener and detergent.

Example 9 The procedure described in Example 5 was repeated with only water, zeolite, bentonite, sodium carbonate, sodium bicarbonate and sodium polyacrylate present in the mixture and in the bead material, and with only nonionic detergent applied thereafter. The resulting product had satisfactory cleaning properties but was not commercially acceptable for aesthetic reasons due to the lack of perfume therein. Nor was the cleaning ability as good due to the absence of enzymes, and the product did not have the bluish effect and the color luster effect that ultramarine blue and fluorescent agents contributed in other compositions. v-Pïfs:

Claims (6)

10 15 20 25 30 35 47 Ésoz 089 P a t g_n t k r a v Detergent composition, characterized in that it consists of a bead material containing about 15 - 30% by weight of sodium carbonate, about 10 - 22% by weight of sodium bicarbonate, about 10 - 50% by weight of water-softening aluminum silicate, about 0 - 18% by weight of sodium silicate and about 1 - 20% by weight of bentonite and / or 0.05 - 2% by weight of polyacrylate with a molecular weight in the range 1000 - 5000, in which bead material is absorbed a nonionic detergent, so that the content of the nonionic active the detergent in the composition is in the range of 8 - 30% by weight. Detergent composition according to claim 1, characterized in that the nonionic detergent is a condensation product of 6 - 12 moles of ethylene oxide and a higher fatty alcohol having 12 - 16 carbon atoms, the nalt of the nonionic detergent in the composition being in the range 15 - 22 % by weight, and which detergent composition also comprises 0.5-3% by weight of an enzyme. Detergent composition according to claim 1, characterized in that it consists of a bead material with a bulk density of 0.6 - 0.8 g / ml, which contains 0.05 - 0.5% by weight of sodium polyacrylate with the molecular weight within range 1000 - 5000, and that the bentonite consists of processed Wyoming bentonite with a swelling in the range 7 - 15 ml / g and a viscosity in the range 8 - 30 cP at 6% concentration in water, in which a nonionic detergent is absorbed, so that the percentage of the nonionic detergent in the composition is in the range of 8-25% by weight. Detergent composition according to claim 1, characterized in that it consists of a bead material with a bulk volume of 0.6 - 0.9 g / ml and the particle size in the range 0.149. 2.0 mm, the aluminosilicate being a hydrated water-curing sodium zeolite containing between 15 and 25% by weight of hydrate water and having a calcium ion exchange capacity in the range of 200 to 400 milligram equivalents of calcium carbonate hardness per gram of anhydrous zeolite, the sodium silicate having a Na , 0: SiO 2, ratio in the range 1: 1.4 - 1: 3, and the weight ratio sodium carbonate: sodium bicarbonate is in the range about 1 - 3, in which a nonionic active detergent is absorbed, so that the percentage of the nonionic active detergent in the composition is in the range of 8 - 25% by weight. Detergent composition according to claim 1, characterized in that it contains 13 - 28% by weight of sodium carbonate, 8 - 18% by weight of sodium bicarbonate, 15 - 35% by weight of water-softening aluminum silicate, 3 - 14% by weight of sodium silicate , 0.1 - 1.6% by weight of polyacrylate with a molecular weight in the range 1000 - 5000 and 8 - 30% by weight of a nonionic detergent. Detergent composition according to Claim 5, with a bulk volume of 0.6 to 0.9 g / ml and particle sizes in the range 0.149 to 2.0 mm, characterized in that the aluminosilicate consists of hydrated zeolite A containing between 15 and 25% by weight of hydrate water, the sodium silicate has a Na3: SiO2 ratio in the range 1: 1.4-1: 3, the polyacrylate is sodium polyacrylate with a molecular weight in the range 1000 - 3000, the weight ratio of sodium carbonate: sodium bicarbonate in the range 1 to 2, the nonionic detergent is a condensation product of 5 to 12 moles of ethylene oxide and 1 mole of a higher fatty alcohol having 12 to 16 carbon atoms, and which composition contains water, excluding the hydrated water of the zeolite, the percentages of the components is within the range of 16 to 21 weight percent sodium carbonate, 10 to 15 weight percent sodium bicarbonate, 22 to 32 weight percent hydrated zeolite, 8 to 13 weight percent sodium silicate, 5 - 1.5% by weight of sodium polyacrylate, 3 - 6% by weight of water one and 10 - 22 weight-S: nonionic detergent.