DK159933B - Free-flowing spray-dried particulate detergent - Google Patents

Description

DK 159933 B

The present invention relates to a free flowing spray dried cleaner comprising spray dried base beads. The product produced has reduced zeolite deposition compared to previously known products containing similar 5 amounts of the water softening aluminum silicate. These previously known products would normally also have contained appreciable amounts of water-soluble silicate and would generally not have contained bentonite.

In recent years, water softening insoluble aluminum silicates such as hydrated zeolites have been used as builder ingredients in laundry detergents. Initially, the renewed interest in zeolites seemed to be stimulated by the necessity of producing detergents that did not contain phosphates. Trisodium nitrilotriacetate and other salts of 15 nitrilotriacetic acid (NTA), which have been suggested as possible replacements for the phosphates, especially for pentane sodium = tripolyphosphate, which has been widely used in built up laundry detergents, have been suspected of being harmful in some circles, and Therefore, over several years, funds containing NTA were not negotiated in the United States. There has never been any serious doubt that phosphates are safe for humans and, most recently, the United States authorities' condemnation of the use of NTA in cleansers has been withdrawn. Therefore, although certain phosphate-free detergents will continue to be prepared for use in areas located near lakes and rivers, in which phosphate tends to provide necessary nourishment for algae growth, and may therefore cause some eutrophication of these streams , detergents containing phosphate and / or NTA are again negotiated.

Although the zeolites, preferably Zeolite A and especially preferably hydrated Zeolite 4A, had been builder salts in phosphate-free and NTA-free detergents, they have now also been found to be useful components of improved detergents and basic bead compositions containing phosphate and / or NTA.

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Normally, approx. 6 - 12% water-soluble sodium silicate in mixtures from which spray-dried foundation beads or cleaners were to be prepared. The silicate has been used for its bonding effect to the other components 5 of the bead, which results in stable beads, and have been found to help produce a net-shaped inner bead structure. It also acts as an anti-corrosion additive which prevents chemical attack on aluminum parts in washing machines and other equipment with which the detergent solution may come into contact. In the quantities previously used, e.g. 8-10% of the finished product, however, it was noted that the combination of water-soluble silicate and zeolite in the mixer led to the production of aggregates of these materials in spray-dried beads, which were adversely deposited on washed materials and were tend to have a detrimental effect on the appearance of the color of the materials. By the present invention using certain amounts of zeolite, bentonite and water-soluble builder with no or only a small amount of water-soluble silicate 20, spray-dried beads with sufficient mechanical stability to be commercially acceptable are obtained and these have reduced zeolite deposition properties. (or decreased deposition of zeolite and silicate aggregate). Even when a small amount of silicate is present, 25 bentonite appears to help counteract any potential tendency of the zeolite and the silicate to react to form a particle of a larger size than that of the normally present zeolite. thereby preventing or reducing unwanted deposition of zeolite or zeolite silicate particles on washed fabrics. In addition, the bentonite-containing agents more easily decay and disperse in the wash water, again apparently due to the presence of bentonite therein. Another advantage of the invention when no silicate or little silicate is used is that compositions containing carbohydrate and / or bicarbonate do not require the presence of anti-gelling materials to prevent excessive thickening of the mixture in the mixer. . Such additives are generally

DK 159933 B

3 not necessary * when the main builder for the detergent is a phosphate / and when no or only a small amount of carbonate and / or bicarbonate is present, but for agents without phosphate which will often contain significant amounts of carbohydrate = per night and / or bicarbonate, the exclusion of anti-gelling materials is definitely an advantage, both in terms of processing and from an economic point of view.

The prior art on cleansers, plasticizers and cleansers provides the teachings that various 10 cleansers can be prepared containing one or more of zeolite, bentonite, silicate, phosphate, NTA, quaternary ammonium compounds (plasticizers), and other components, usually together with synthetic organic detergent, but although the descriptions contain extensive publications (sometimes called "laun-15 dry lists") of almost all materials used for any purpose in detergents and emollients, they do not contain any clear teachings or hints of the detergents of the present invention, and this is especially true for those agents which contain no soluble silicate or only a high amount of soluble silicate. The prior art descriptions do not appear to recognize the importance of bentonite containing sufficiently "lubricating" water between the plates and do not appear to understand the combination of binding and disintegrating effects attributable to the "hydrated" bentonite. Many of the compositions disclosed also contain significant amounts of sodium sulfate, a filler, possibly to improve the physical properties of the product particles, but this is not necessary for 3q to prepare the compositions of the invention which may therefore have higher content of active ingredients (including builder).

The cleaning agent according to the invention is characterized in that the base beads by weight contain 5-30% water-soluble synthetic organic surfactant, 5-60% water-soluble builder or a mixture of such builders, 5-60% ion-exchanging zeolite and 2-40% bentonite, optionally nonionic surfactant present is one

DK 159933 B

4 condensation product of a higher fatty alcohol of 12-16 carbon atoms with 6-12 moles of ethylene oxide per mole of alcohol applied to the surface of the beads after spray drying. Hereby, due to the presence of bentonite instead of 5, a binding amount of water-soluble silicate is obtained, leaving smaller amounts of deposits on laundry after washing, and the spray-dried cleaning beads sufficiently hard and effectively bonded to be free flowing and resistant to rupture. , and the resulting particulate brine detergent is an effective detergent.

The zeolites used include crystalline, amorphous and mixed crystalline-amorphous zeolites of both natural and synthetic origin, which have sufficiently rapid and sufficiently effective activities to counteract calcium hardness ions in wash water. Preferably, these materials are capable of reacting rapidly enough with the calcium ions to soften the wash water alone or together with other water-softening compounds before detrimental reactions of these ions with other components of the synthetic organic detergent. The zeolites used can be characterized as having a high ion exchange capacity for calcium ion, which is usually from ca. 200 to 400 or more mg equivalents of calcium carbonate hardness per

g of aluminum silicate, preferably 250-350 mg equivalent per

They also preferably have a degree of reduction of hardness to a residual hardness of 0.02 - 0.05 mg CaCO 2 / liter in 1 minute, preferably 0.02 - 0.03 mg per minute. per liter, and less than 0.01 mg per liter. liter of 10 minutes, all based on anhydrous zeolite.

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Although other ion-exchange zeolites may also be used, the finely divided synthetic zeolite builder particles used in the practice of the invention will usually be of the formula (Na 2 °) x, (Al 2 O 3), (SiO 2) z, wH 2 O, where x is 1, y is from 0.8 to 1.2, preferably approx. 1, z is from 1.5 to 3.5, preferably 2-3 or ca. 2, and w is from 0 to 9, preferably 2.5 to 6.

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The zeolite must be a monovalent cation exchange zeolite, i.e. it must be an aluminum silicate of a monovalent cation such as sodium, potassium, lithium (where possible) or other alkali metal, ammonium or hydrogen (sometimes). Preferably, the monovalent cation of the zeolite molecular sieve is an alkali metal cation, especially sodium or potassium, and preferably crystalline types of zeolites which can be used as good ion exchangers for the invention, at least in part, include '0 zeolites of the following crystal structure groups: A, X, Y, L , mordenite and erionite, of which types A, X and Y are preferred. Mixtures of these molecular sieve zeolites may also be useful, especially when type A zeolite is present. These crystalline types of zeolites are well known and are more specifically described in the text Zeolite Molecular Sieves by Donald W.Breck, published in 1974 by John Wiley & Sons. Typical commercially available zeolites of the aforementioned structural types are listed in Table 9.6 on pages 747 - 749 in Breck's text. These zeolites are well known. Other suitable zeolites have been described in many patents in recent years for use as builders in detergents.

The zeolite used according to the invention is usually synthetic and is often characterized by a network of pores of substantially uniform size in the range of from ca. 3 to 10 angstroms and is often approx. 4 Å (normal), which size is determined solely by the unit structure of the zeolite crystal. Preferably, it is of type A or similar structure, particularly described on page 133 of the aforementioned text. Good results have been obtained when using a type 4A molecular sieve zeolite in which the monovalent cation of the zeolite is sodium and the pore size of the zeolite is approx. 4 Å, and such zeolites are preferred. Such zeolite molecular sieves are described in U.S. Patent No. 2,882,243 which describes them as zeolite A.

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Molecular sieve zeolites with ion-exchange and water-softening properties can be prepared in either dehydrated or calcined form, containing from ca. 0 or approx. 1.5% to 5 approx. 3% moisture, or in a hydrated or urinated form containing additional bonded water in an amount of from approx. 4% and up to approx. 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% of capacity) is preferred for carrying out the present invention when using a crystalline product. The preparation of such crystals is well known. In the manufacture of e.g. In the above mentioned zeolite A, the hydrated zeolite crystals formed in the crystallization medium (such as an aqueous amorphous sodium aluminum silicate gel) are used without undergoing the high temperature dehydration (calcination to 3% or less water content) which is usually practiced in the preparation of such crystals for use as catalysts, e.g. cracking catalysts. The crystalline zeolite, either in fully hydrated or partially hydrated form, can be recovered by filtering the crystals from the crystallization medium and drying them in air at ambient temperature, so that their water content is in the range of approx. 5 to 30%, preferably about 10 or 15 to 25%, such as 17 to 22%, e.g.

20%. However, the moisture content of the molecular sieve type zeolite used may be lower, as previously described, in which case the zeolite may be hydrated during mixing in the mixer or during other processing.

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Preferably, the zeolite should be in a finely divided state where the final particle diameter is up to 20 microns, e.g. 0.005 or 0.01 - 20 microns, preferably 0.01 to 15 microns, e.g. 3-12 microns, and most preferably from 0.01 to 8 microns average particle size, e.g. 3-7 microns, if crystalline, and 0.01 - 0.1 microns, e.g. 0.01 -0.05 micron if amorphous. Although the final particle sizes are much lower, the zeolite particles generally will

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7 have sizes ranging from 100 to 400 mesh, preferably 140 to 325 mesh. Smaller sizes of zeolites will often become too dusty, and those of larger sizes may be insufficiently bonded to carbonate, bicarbonate, phosphate and / or NTA-5 basic particle cores on which they can be distributed together with the benzonite, such as in a gel-like or film state. during spray drying a mixture to form base beads.

The bentonite used is a colloidal clay (aluminum silicate) containing montmorillonite. Montmorillonite is a hydrated aluminum silicate in which ca. 1/6 of the aluminum atoms may be replaced by magnesium atoms and with varying amounts of hydrogen, sodium, potassium, calcium, magnium and other metals loosely bonded. The type of bentonite most useful for preparing the base beads of the agent of the invention is that known as sodium bentonite (or Wyoming or western bentonite), which is usually a lust for cream colored intractable powder which forms in water a colloid suspension with strong thixotropic properties. In water, the swelling ability of the clay 20 will generally be in the range of 3 to 15 ml. g, preferably 7-15 ml per ml. g, and its viscosity at a concentration of 6% in water will generally be in the range of 3-30 centipoise, preferably 8-30 centipoise. Preferred swelling bentonites of this type are traded under the trademark MINERAL COLLOID 25 as industrial bentonites by Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials, similar to those previously sold under the THIXO-JEL trademark, are selectively mined and concentrated bentonites, and those considered to be the most useful are available as MINERAL 30 COLLOID No. 101, etc. to THIXO-JEL Nos. 1, 2, 3 and 4. These materials have pH values (6% concentration in water) ranging from 8 to 9.4, maximum free moisture content of approx. 8% and a density of approx. 2.6, and for the powdered quality, approx. 85% through a 200 mesh, US sieve-35 standard. Concentrated Wyoming bentonite is preferred as a component of the present agents, but other bentonites are also useful, especially when they form a minor part of the used

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8 bentonite. Although it is desirable to limit the maximum free moisture content, as mentioned, it is even more important to ensure that the bentonite used contains sufficient free moisture, most of which is considered to be present between 5 neighboring plates in the bentonite to facilitate rapid decay of the bentonite and any adjacent materials in the particles when these particles or cleaners containing them are contacted with water such as wash water. It has been found that at least approx. 2%, preferably at least 3% and most preferably about 2%. 4% or more water must be present in the bentonite from the beginning before it is mixed with the other bead components in the mixer, and this amount must also be present after spray drying. In other words, drying to the point where the bentonite loses its "internal" moisture can mean a diminished utility of the present means. When the moisture content of the bentonite is too low, the bentonite does not prevent the formation of agglomerates of silicate and zeolite, nor does it help to disintegrate the beads in the wash water. When the bentonite has a satisfactory moisture content, it exhibits an interchangeable calcium oxide percentage in the range of from about. 1 to 1.8, and with respect to magnesium oxide, this percentage is usually in the range of 0.04 to 0.41. Typical known assays of such materials are from 64.8 to 73.0% SiO 2, 1.4 - 1.8% Al 2 O 3, 1.6 - 2.7% MgO, 1.3 - 3.1% CaO, 25 , 3 - 3.4% Fe 2 O 3, 0.8 - 2.8% Na 2 O and 0.4 - 7.0% K 2 O.

A preferred embodiment of the detergent according to the invention is characterized in that the zeolite contains from 15 to 25% by weight of hydration water and has an ion exchange capacity for calcium ions in the range of 200-400 mg. equivalents of calcium carbonate hardness per gram of anhydrous zeolite, that the bentonite is a swelling clay with a swelling capacity in water of about 3-15 ml per g and a viscosity of 3-30 cents in poise at a concentration of 6% in water and contains at least 2% moisture calculated on anhydrous bentonite.

The water-soluble builder or mixture thereof may be one or more of the usual materials used.

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9 as builders or proposed for this purpose. These include inorganic and organic builders and mixtures thereof.

Among the inorganic builders, the preferred are the various phosphates, preferably polyphosphates, e.g. tripolyphosphates = 5s and pyrophosphates such as pentane sodium tripolyphosphate and tetrasodium pyrophosphate. Trisodium nitrilotriacetate (NTA), which is preferably used as the monohydrate, and other nitrilotriacetates such as disodium nitrilotriacetate, are preferred water-soluble builders. Sodium tripolyphosphate, sodium pyrophosphate, and NTA can be used in hydrated forms / but although anhydrous compounds are used, the bentonite and zeolite appear to prevent baking as a result of subsequent hydration. Of course, carbonates such as sodium carbonate are useful builders and can be used alone or in combination with carbonates such as sodium bicarbonate. When the polyphosphates are used, it may be preferable to have sodium pyrophosphate present with sodium tripolyphosphate in an amount of 1:10 -10: 1, preferably 1: 5 - 5: 1 relative thereto, with the total amount of both builders being about the same as mentioned for sodium = 23 umtripolyphosphate. Other water-soluble builders which are considered to be effective include the various inorganic and organic phosphates, borates, e.g. borax, citrates, gluconates, EDTA and iminodiacetates. Preferably, the various builders will be in the form of their alkali metal salts, either the sodium or potassium salts or a mixture thereof, but sodium salts are usually preferred. In some cases, e.g. when neutral or slightly acidic cleaners are produced, acidic forms of the builders, especially the organic builders, may be preferred, but usually the salts will be either neutral or basic. The silicates, preferably sodium silicate, with a Na 2 O: SiO 2 ratio in the range of 1: 1.6 - 1: 3.0, preferably 1: 2 - 1: 2.8, e.g. 1: 2.35 or 1: 2.4 also serve as builder salts, but due to their strong bonding properties and their ability to promote aggregation or agglomeration with zeolite particles, they are a special class of builders and are preferred to be omitted. of the present means. Since they have anti-corrosion properties, which are especially important when cleaning

DK 159933 B

Although the semideal solution must be used in washing machines or other appliances in contact with aluminum parts, they may sometimes be present in limited quantities. In such cases, it is preferred that hydrated sodium silicate particles be added afterwards so that they do not react with or agglomerate with zeolite particles in the mixture or spray drying. Although sodium sulphate and sodium chloride and other filler salts have no build-up properties, they are sometimes used in detergents because of their satisfactory properties. In addition to increasing the volume and weight of the product to facilitate measurement, they also sometimes improve the bead stability and physical properties of the detergent in which they are incorporated. However, because the present compositions are satisfactory without fillers, these are preferably avoided altogether, or any part thereof minimized, as a rule, to a practical minimum.

As a rule, the surfactant (s) used will usually be nonionic or anionic or both, but amphoteric or ampholytic surfactants may also be used, especially with nonionic and / or anionic agents in the present agents. Cationic surfactants may serve as fabric softeners in these products, but will not normally be spray dried with anionic surfactants due to an undesirable reaction which may occur. These classes of materials are well known and have been repeatedly described in the prior art. As they are not preferred components of the present compositions, no further description thereof is given in the present disclosure.

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Although various nonionic surfactants having satisfactory physical properties can be used, including condensation products of ethylene oxide and propylene oxide with one another, and with hydroxyl-containing bases such as nonylphenol and oxo-type alcohols, it is much preferred that the nonionic surfactant be a condensation product of ethylene oxide and higher fatty alcohol. In such products, the higher fatty alcohol has 10-20 carbon

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11 atoms, preferably 12 to 16 carbon atoms, and the nonionic surfactant contains from ca. 3 to 20 or 30 ethylene oxide groups per mole, preferably from 6 to 12. Most preferably, the nonionic surfactant will be one in which the higher fatty alcohol has about 5%. 12 to 13 or 15 cow 1 substance atoms and containing from 6 to 7 or 11 moles of ethylene oxide. Such surfactants are manufactured by Shell Chemical Company and are available under the trade name NEO-DOL® 23-6.5 and 25.7. Among their particularly appealing properties, in addition to good cleaning performance against oil marks on clothes to be washed, is a relatively low melting point, yet considerably above room temperature, so that they can be sprayed onto foundation beads as a solidifying liquid.

Various anionic surfactants, usually as sodium salts, may be used, but those most preferred are linear higher alkylbenzenesulfonates, higher alkyl sulfates and higher fatty alcohol polyethoxylate sulfates. In the higher alkylbenzene sulfonate, the higher alkyl is preferably linear and having 12 to 15 carbon atoms, e.g. 13, and is a sodium salt. The alkyl sulfate is preferably a higher alkyl sulfate having 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms, e.g. 12, and is also used as the sodium salt. Similarly, higher alkyl ethoxamer sulfates will have 10 or 12 to 18 carbon atoms, e.g. 12, in the higher alkyl which is preferably a fatty alkyl, and the ethoxy content will normally be from 3 to 30 ethoxy groups per Thus, it will be seen that the alkyls are preferably linear or fatty higher alkyls having 10-18 carbon atoms and that the cation is preferably sodium and the sulfate is at the end when 30 a polyethoxy chain exists. Other useful anionic surfactants include the higher olefin sulfonates and paraffin sulfonates, e.g. the sodium salts in which the olefin or paraffin groups have 10 to 18 carbon atoms. Particular examples of the preferred surfactants are sodium tridecylbenzenesulfonate, sodium tallow alcohol polyethoxy sulfate (3 EtO) and hydrogenated tallow alcohol sulfate sodium salt. In addition to said preferred anionic surfactants, others of this well-known group may also be present

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12, especially in only small quantities compared to those previously described. Mixtures thereof may also be used, and in some cases such mixtures may be better than single surfactants. The various anionic surfactants are well known and are described on pages 25-138 of the text Surface Active Agents and Detergents, Volume II, by Schwartz, Perry & Berch, published in 1958 by Interscince Publishers, Inc.

Various additives may be present in the mixture from which the base beads or cleaners can be spray dried, or these additives may be added afterwards, the decision of the additive being often determined by the physical properties of the additive, its resistance to heat, its resistance to degradation in the aqueous medium. in the mixing apparatus as well as its volatility. Among the more important additives is a polyacrylate which has been found to be useful in regulating the bead properties and mass space weight, has dispersing effects, antifouling and re-depositing effects in the present agents, and helps to keep the mixture in the mixer is liquid and homogeneous.

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The polyacrylate found in preferred primer beads is a low molecular weight polyacrylate, with the molecular weight generally being in the range of from about. 1,000 to 5,000, preferably 1,000 - 3,000, 25 and best 1,000 - 2000 or approx. 2000. The polyacrylate may be partially neutralized or completely neutralized, e.g. ca. half or 1/3 present as sodium polyacrylate. Modified polyacrylates may be used in place of the described sodium polyacrylate, including some other O Λ alkali metal polyacrylates and hydroxylated polyacrylates, but it is preferred that such replacements be limited to a minor portion of the material, and preferably the polyacrylate will be entirely sodium polyacrylate. These materials are available (5) from Alco Chemical Corporation under the name ALCOSPERSE Na = the tri polyacrylates are available as clear amber liquids or powders, solutions of which have approx. 25 - 40% solids content, e.g. 30%, and the pH of these solutions or of

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13 a 30% aqueous solution of the powder is in the range of approx.

7.5 to 9.5, e.g. ca. 9. These materials are completely soluble in water and have been used as dispersants. It has been shown that they have the ability to bind calcium ions, and have been used to prevent the deposition of insoluble calcium compounds from aqueous solutions. In the present spray drying process, small amounts thereof help to give the resulting beads improved porosity.

When the mixture in the mixer includes carbonate and / or bicarbonate and silicate, although the amount of silicate is small, the mixture may tend to gell or "freeze" in the mixer, especially if the mixture is held longer than the process due to delays in the process. normal 30 minutes or 15 minutes or so. In such cases, when silicate is present, processing aids are also preferably present in the mixture (and therefore in the finished beads and cleansers) to prevent premature solidification or gelling. Preferably, they include citric acid and magnesium sulfate.

20 instead of citric acid, soluble citrates such as sodium citrate can be used, and although it is preferred to use anhydrous magnesium sulfate, various hydrates such as epsom salt may be used. Instead, magnesium citrate can also be used. Instead of the preferred anti-gelling system, other agents and suitable systems can be used to keep the mixture in the mixer liquid, such as sodium sesquicarbonate used to replace some of the sodium carbonate and sodium bicarbonate.

These processing aids are useful in many cases, but it is a feature of the invention that they are not required to make the preferred base beads from which silicate is omitted.

Although some additives such as fluorescent brightener, pigment, e.g. ultramarine blue, titanium dioxide and inorganic filler salt can be added to the mixer, others such as perfumes, enzymes, bleaches, some staining agents, bactericides, fungicides, fabric softeners and flow promoters.

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14 agents are often sprayed or otherwise mixed with the base beads or spray-dried cleanser together with any nonionic detergent and / or independently thereof, so that they are not adversely affected by the elevated temperatures during the spray operation, and also thus, that their presence in the spray-dried beads does not prevent the absorption of non-ionic surfactant when it is subsequently to be sprayed onto the beads. For stable and usually solid additions, mixing in the slurry in the mixer is also possible. Thus, it is within the scope of the invention that pigments and fluorescent clarifiers, when used, will normally be present in the blend of the blender from which the present beads are sprayed. The preferred coloring agent is ultramarine blue, but other stable pigments and dyes can be used in conjunction with this or to replace it. Since the spray-dried foundation beads of the invention can sometimes have a discoloration, usually due to the use of naturally occurring minerals, the color nuance of such a coloring agent 20 can be adversely affected. It has been found that incorporating a small amount of titanium dioxide into the mixture in the mixer helps maintain the desired color tint of the coloring agent, and the presence of titanium dioxide does not appear to have any detrimental effect on the appearance of laundry washed with the detergents made from the primer beads. that contains it.

Among the fluorescent detergents, the most preferred is TINOPAL 5BM, especially in extra concentrated form. However, various 30 1 other cotton clearing agents such as those commonly referred to as 'CC / DAS clearing agents derived from the reaction product of cyanuric acid chloride and the disodium salt of diaminostilben =' disulfonic acid may also be used, including variations thereof with respect to substituents on The triazine ring and the aro-35 "mathematical rings. This class of detergents is known in the art of the detergent and is often used when bleaching agents are not present in the final product. When it is desired that

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If the detergent contains a bleach such as sodium perborate or other oxidizing bleach, bleach stable clarifiers will usually be incorporated into the blend in the blender. These include the benzidine sulfone disulfonic acids, naph = 5 thotriazolylstilbenzulfonic acids and benzimidazolyl derivatives. Polyamide clarifiers / which may also be present / include aminocoumarin or diphenylpyrazoline derivatives, and polyester clarifiers which may also be used include naphthotriazolylstilbenes. These clarifiers are usually used as their water-soluble salts, but can be added as the corresponding acids. The cotton clearing agents will usually constitute the majority of the system of clearing agents used.

Enzyme preparations that are usually added afterwards to the base beads because they are heat sensitive can be any of various industrially available products, including ALCALASE, manufactured by Novo Industri A / S, and MAXATASE, both of which are alkaline proteases (subtilisin). ΜΆΧΑΖΥΜΕ 375 20 is sometimes preferred. Although the alkaline proteases are most heavily used, amylotic enzymes such as α-amylase can also be used. Said agents generally contain active enzymes in combination with an inert powdered carrier such as sodium or calcium sulfate, and the amount of active enzyme can vary widely and is generally from 2 to 80% of the industrial composition. In the present disclosure, the amounts referred to are the amounts of the enzyme preparations, not the active portion thereof. Perfumes used which are generally heat sensitive and may contain volatiles, including a solvent such as alcohol, are usually synthetic perfumery materials sometimes mixed with natural components, and will generally include alcohols, aldehydes, terpenes, fixatives and other normal perfume components. . Flow enhancers such as special clays, sometimes added to detergent products, are often useful for improving the flowability and for reducing the tackiness of various agents, but are unnecessary in the present case, possibly partially as

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16 due to the presence of the bentonite and the absence of silicate or the very limited presence of silicate. However, they may be added, if desired, to further promote flowability. It has been found that detergents according to the invention do not require the presence of any anti-corrosion additive to replace the omitted silicate, but it is within the scope of the invention to use such suitable materials, and it is preferred to use those which are stable during mixing and mixing. spray drying conditions and which have no detrimental effect on these operations. Such anti-corrosion additives or antioxidants may be organic or inorganic, with inorganic materials being usually preferred and they will preferably be selected for their suitability to prevent corrosion of aluminum parts on washing machines. If one wishes to continue using a silicate for this purpose or to use a silicate for its effect in treating magnesium ion hardness, a powdered silicate is usually preferred, such as aqueous sodium silicate commercially known as BRITESIL®, manufactured by Philadelphia Quartz Co.

20 (Na 2 O: SiO 2 = 1: 2.4), and this will preferably be added afterwards. However, other normally solid soluble silicates, preferably of alkali metals, may also be added afterwards to the beads, preferably after absorption of nonionic surfactant.

When the manufactured product is desired to have textile softening properties, softening materials, preferably in dry powder form, may also be added afterwards to the base beads appropriately. This class of materials is well known and most commonly these emollients are cationic compounds, especially quaternary ammonium compounds such as 30 quaternary ammonium halides. Particularly preferred are the higher alkyl, alkylaryl and arylalkyl lower alkyl quaternary ammonium chlorides and bromides such as distearyldimethylammonium chloride. Among the industrial softening materials, what is most preferred is that traded under the trade name AROSUKF TA-100, manufactured by Sherex Chemial Company, Inc. These compounds also have antistatic and

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17 antibacterial properties, but if desired, other bacterial additives may also be used which are preferably also incorporated into the product upon addition afterwards.

Of course, water is present in the mixer to serve as a medium for dispersing the various other bead components, and some water, both in free form and in hydrate form, is present in the product. During drying of the beads, the initial moisture content thereof, which will be approx. 25 - 60%, 10 is reduced to approx. 5 to 15%, this moisture content being sufficient for the bentonite in the dried beads to contain at least 2% and preferably at least 4% moisture. It is preferred to use deionized water so that the hardness ion content thereof can be very low, and so that metal ions which can promote decomposition of any organic materials which may be present in the mixture, the beads and the detergent are reduced. but tap water can usually be used instead. Usually, the hardness content of this will. water will be less than 150 ppm, such as CaCO 2, and preferably the hardness content will be less than 100 ppm, and most preferably will be less than 50 ppm.

The amounts of the various components in the base beads and in the spray-dried cleaner beads are such that they result in the beads being free flowing and, for the base beads, sufficiently absorbent for nonionic surfactant applied thereon in liquid state, thus that the detergents will be satisfactorily free-flowing. Of course, the detergents will also be effective detergents, since the 30 builters present act to support the organic surfactant in its purifying action in aqueous solutions of the agents, and it is important that the resulting products be such that they do not cause harmful deposition of zeolite particles (or aggregates of zeolite and silicate) on washed 35 materials. Although the zeolite particles and bentonite particles are insoluble, they will not adversely discolor or brighten colored laundry due to their small particle size.

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However, such discoloration can occur when zeolite assemblies are formed which are sufficiently large to be retained on fabrics and readily visible, especially when substantial amounts thereof are not removed from the washed materials by being removed with the drying air under automatic drying. It is also desirable that the prepared primer beads and cleanser beads made therefrom have appropriate room weight and color.

Preferably, the spray-dried beads will contain from 3 to 10 15% moisture, preferably from 5 to 12%, and generally from 7 to 10%, including optionally hydration water. This hydration water may be present in the zeolite, NTA, phosphate, carbonate, bicarbonate and magnesium sulfate when present in the composition, in addition to that found between the plates in the bentonite. Said moisture content also includes strongly bonded hydration water such as that still retained by the zeolite, even after several hours of distillation of a toluene dispersion. In some cases, when the concentration of zeolite in the product is high, so that there can be up to approx. 12 20 - 15% moisture present in the hydration water of the zeolite, the moisture content of the spray dried beads may be as high as 20% and may occasionally go up to approx. 25%. However, in order to obtain good flowability of the product and to reduce stickiness and clumping, the upper limit will normally be approx. 15%, 25 especially if the final detergent contains a known amount of nonionic surfactant. The percentage of zeolite quoted includes the hydration water therein. It is possible to make useful spray-dried beads having a moisture content of less than 3%, provided the bentonite is associated with sufficient water for the aforementioned reasons, but because of the high tendency of the zeolite to attract moisture and because of the effects of the other hydrating materials which may be found in the product have generally been found to require a minimum of 3% moisture to avoid the loss of the desired internal moisture in the bentonite, which appears to "lubricate" the plates and facilitate their separation when a product containing them is dispersed in water. When water is produced,

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19 free products, even when sufficient moisture is retained in the bentonite, they also tend to be physically unstable, pulverize more easily, and are subject to tearing and disintegration.

5

The mass weight of the spray-dried beads may range from 0.2 to 0.9 g / ml. cm. Room weights at the lower end of this range are more easily obtained when there is no silicate in the mixer in the mixer which is spray-dried and when no 10 or little surfactant is absorbed by the beads. The higher bulk weights appear when nonionic surfactant is applied to porous beads and when some silicate is present in the beads. These lighter products have mass space weights in the range of 0.2 -0.5 g / kg. , often from 0.3 to 0.4 g / cm and the heavier particles have mass space weights in the range of 0.6 - 0.9 g / cm cm, 3 1 rule 0.6 - 0.8 g per cm. The particle sizes of the beads will generally be in the range of # 10 to # 100 (pass # 10 and retained at # 100), US sieve series, preferably from 10 to 60, US sieve series. In preferred compositions, the ratio of the amount of bentonite to zeolite is in the range of 1: 4 - 1: 1, the ratio of the amount of water-soluble builder to zeolite is in the range of 1: 2 to 3: 1, and the ratio of the amount of bentonite and water-soluble builder are in the range of 1:10 to 1: 1. Preferably, these intervals are 1: 3 - 2: 3, 2: 3 - 2: 1 and 1: 6 - 1: 2, respectively. Percentage, the agents preferably comprise from 10 to 40% partially hydrated sodium zeolite, preferably containing from 15 to 25 wt% hydration water, and having an ion exchange capacity for calcium ion in the range of 200-400 mg 30 equivalents of calcium carbonate hardness per liter. g of anhydrous zeolite, 2 - 35% bentonite, which is of a type having a swelling capacity in the range of 7 - 15 ml per ml. g and a viscosity in the range of 8-30 centipoise at a concentration of 6% in water, 10 - 50% water-soluble alkali metal builder salt or mixture thereof, 0-25% water-soluble synthetic anionic organic detergent and 0-3% water-soluble silicate, which silicate , when present, is an alkali metal silicate having a ratio

DK 159933 B

Between alkali metal oxide and silica in the range of 1: 1.6 to 1: 3, preferably 1: 2 to 1: 2.8. More preferred bead compositions contain 15 - 35% zeolite A, 5-20% concentrated Wyoming bentonite, 20 - 50% water-soluble sodium builder salt or mixture thereof, 0-20% water-soluble synthetic anionic organic surfactant and 0% sodium silicate.

Although carbonate and bicarbonate as builders are useful in the preparation of base beads on which nonionic surfactant is to be sprayed, polyphosphate and / or nitrilotriacetate builders are often preferred to the spray dried beads, whether or not containing anionic surfactant. Preferred compositions of base beads based on NTA as the sole or most important soluble builder contain from 15 to 35 or 25 40% hydrated zeolite, 5 or 10 - 20% bentonite and 20 - 50 or 60% NTA. When a phosphate such as sodium tripolyphosphate is to be the main water-soluble builder, the same ratio of zeolite to bentonite may be used, but as a rule more phosphate may be present (than NTA). For 20 base beads to be sprayed with nonionic surfactant or for carbonate-based or a mixture of bicarbonate and carbonate (where the ratio of carbonate: bicarbonate in the spray dried base beads is in the range of about 1 to 3), preferably no be any soluble synthetic organic surfactant and no or only slightly soluble silicate present. When bicarbonate and carbonate are used together in such compositions, they will generally be in total from 20 to 40% of the base beads, and when carbonate is used alone, there will usually be from 10 to 30% thereof.

When an anionic surfactant or other suitable organic surfactant is included in the mixer in the mixer to produce a spray-dried cleaner product, preferred amounts thereof are 3 or 5-30%, especially 5-25% and best 10-25%, e.g. 10%, 15%, 15% of such a product and the surfactant is preferably selected from the group consisting of linear alkylbenzenesulfonate sodium salt, wherein the alkyl has 10 to 18 carbon atoms, fatty alcohol sulfate sodium.

DK 159933 B

21 sodium salt, wherein the alcohol has from 10 to 18 carbon atoms, and the fatty alcohol ethoxylate sulfate sodium salt, wherein the fatty alcohol has from 10 to 18 carbon atoms and containing from 3 to 30 ethylene oxide groups per liter. moles and mixtures thereof. Currently, the most preferred of the surfactants is linear tridecylbenzenesulfonate sodium salt, and the alkyls preferably have 12-16 carbon atoms.

When a non-ionic surfactant is absorbed into the spray-dried ground beads (and sometimes a small amount can be absorbed into the 10 spray-dried beads, the amount thereof will usually be in the range of 5 or 8 to 30%, preferably 10 to 25%, e.g. In these cases, the preferred nonionic surfactant is a condensation product of 6 - 12 moles of ethylene oxide and 1 mole of a higher fatty alcohol of 12 - 16 carbon atoms.

When polyacrylate is present in some, of the cleansers or primer beads, there will usually be from 0.05 to 1% thereof, and its molecular weight is preferably in the range of 1,000 to 5,000.

20

Because the presence of anionic surfactant in the spray dried detergent beads may impede or inhibit the production of a bead structure which is absorbent for a desired amount of nonionic surfactant, it is preferable to prepare spray-dried surfactant beads and mix them with ground beads upon which nonionic surfactant such that a greater amount of nonionic surfactant may be present in the finished product. To do this, varying ranges of the amounts, e.g. 1:10 - 10: 1, 1: 5 - 5: 1 and 1: 2 - 2: 1, of the 30 components mentioned, depending on the characteristics desired by the final product. It is convenient that the mass weight of the beads prior to mixing is approximately the same, preferably at the end of 0.1 g / ml. cm3 apart, and party in the larger size The ice should be about the same and is usually from # 10 to #.

35 100, US sieve series, to prevent separation of the final product.

22

DK 1S9933 B

Amounts of additives and processing aids in the base beads and spray-dried surfactant will usually be limited to 20% thereof and are preferably 1 - 10% and especially 3 - 7%. The amounts of processing aids when using magnesium sulfate and citric acid will usually be from 0.5 to 2% of magnesium sulfate, preferably 1 - 1.5% thereof, and 0.1 - 0.5% sodium citrate, preferably 0.1 - 0.3% thereof. In the case of color, pigmentation and fluorescent brighteners, when present, the amounts will normally be from 0.05 to 0.6% staining pigments such as ultramarine blue, preferably 0.2-0.4%, and 0.1%. - 4% fluorescent brightening agent, preferably 1-3% thereof. The amount of titanium dioxide (a whitening pigment) will usually be from 1 to 3%, preferably 1.5 to 2.5%. If a dyeing dye or substances is used in place of a dyeing pigment, the amounts will generally be 1 - 50%, especially 5 - 20% of the amounts of dyeing pigments.

For preferred spray-dried beads which may contain NTA or polyphosphate formers, with or without synthetic organic surfactant, or which may contain such surfactant with any of the aforementioned preferred water-soluble builder salts, the room weight is in the range of 0.2 to 0. 9 g per cm3, the aluminum silicate is hydrated zeolite A, the bentonite contains at least 3% moisture, calculated on anhydrous bentonite, and the water-soluble silicate, if present, is sodium silicate with a Na 2 O: SiO 2 ratio in the range of 1: 2 - 1: 2 , 8, and the moisture content of the beads is from 3 to 12%. When the beads contain NTA or other sodium salt of nitrilo-acetic acid, with or without synthetic organic surfactant, the amount ratio of bentonite to zeolite is in the range 1: 6 -1: 2, the ratio of NTA to zeolite is in the range 1: 2 -2: 1, and the ratio of bentonite to NTA is in the range of 1: 6 - 1: 2, and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate and silicate are in the ranges of 10 - 40%, 2 - 25%, 10 - 40, respectively. % and 0 - 5%.

When the preferred NTA-containing beads also contain a synthetic anionic organic surfactant together with the aforementioned zeolite

DK 159933B

23A, bentonite and moisture, and with or without soluble silicate, preferably comprise from 5 to 30% of synthetic organic anionic surfactant which will be linear alkylbenzene = sulfonate sodium salt, wherein the alkyl has from 10 to 18 carbon atoms, fatty alcohol sulfate sodium salt wherein the alcohol has 10 to 18 carbon atoms, or fatty alcohol ethoxylateSulfate sodium salt, wherein the fatty alcohol has 10 to 18 carbon atoms and containing from 3 to 30 ethylene oxide groups per liter. mole, or a mixture comprising 2 or more thereof, and the water-soluble builder is a sodium salt of nitrilotriacetic acid (NTA), the ratio of bentonite to zeolite is in the range 1: 6 to 1: 1, the ratio of NTA to zeolite is in the ratio of 1: 3 to 3: 1, the ratio of bentonite to NTA is in the range of 1:10 to 1: 1, and the ratio of synthetic organic anionic surfactant to zeolite is in the range of 1: 1 to 1: 4, and the percentages of hydrated zeolite, bentonite, sodium nitrilo triacetate, synthetic anionic organic surfactant and silicate are in the ranges 10 - 40%, 2 - 25%, 10 - 40%, 10 - 25% (most preferred range) and 0 - 5%, respectively.

20

For phosphate-containing beads, with or without synthetic surfactant, the materials and proportions are the same as for the corresponding NTA-containing beads when pentane sodium tripolyphosphate or tetrasodium pyrophosphate or a mixture thereof is used instead of NTA, but the percentages are in the range of 15 - 35% , 5 - 20%, 15 - 40% and 0 - 5%. For phosphate-containing beads containing anionic surfactant, the materials and ratios are similarly the same as for the corresponding NTA-containing beads, and the percent ranges 30 are the same except for the total amount of polyphosphate which is 10 - 50%.

The intervals for amounts of the various basic bead components in the final detergent when nonionic surfactant (optionally with other materials) is added afterwards can be easily calculated by those listed for the basic beads, reduced by the amounts of the surfactant and other materials

DK 159933 B

24 which is then added to the beads. Conversely, the amounts of components in the beads (and hence the composition of the mixture in the mixer) can be calculated by the composition of the final product. For example, when calculates the intervals of the composition in the final product from the intervals in the bead, if the final detergent has only added nonionic surfactant such that the final product contains 20% nonionic surfactant from the various intervals listed for components in the base beads, for quantities thereof ^ 3 in the final detergent is calculated by multiplying by 0.8 which is (100 - 20) / 100. Similarly, when the amount of nonionic surfactant (in compositions where it is the only additive to the beads) can range from 8 to 25% of the detergent, the factors will be from 0.92 to 0.75. The final percentage nonionic surfactant in the product will be in the range of 8-30% and is preferably 10-25% and especially 15-22%, e.g. ca. 20%, but in some situations for certain types of products, quantities in the range of 8 - 13% may be preferred. Typically, the percentage of perfume in the final product 20 will be in the range of 0.1 to 1%, preferably 0.2 to 0.4%, the percentage of the enzyme will be from 0.5 to 3%, preferably 1-2%, and if if an aqueous sodium silicate is to be added afterwards, the amount thereof will usually be not less than 1% and is preferably limited to approx. 5%, although in some 25 cases as much as 10% can be used. When a plasticizer is present in the final product, the amount thereof will usually be in the range of 3 - 12%, preferably 5 - 10%.

The base beads and spray-dried cleaner beads of the invention are spray-dried by an aqueous mixture which will normally contain from ca. 40 to approx. 70 or 75% solids, preferably 50-65%, the remainder being water, preferably deionized water, as previously described (but tap water can also be used). The mixture in the mixer is preferably prepared by adding in order of various components thereof in a manner which results in the most mixture.

DK 1599X3 B

bare, easily pumpable and non-solidifying slurry for spray drying. The order of addition of the materials may be varied, depending on the circumstances, but it is highly desirable to add a possible silicate solution last, and if not last, then at least after the addition of any gel antifreeze or antifreeze combination of materials or processing aids. such as citric acid and magnesium sulfate. Usually it is preferred,

1 Q

that all the water or almost all the water is added to the mixing apparatus first, preferably at approx. the processing temperature, after which the processing aids (if used) and other minor components including pigment and fluorescent brightening agent and polyacrylate (if used) are added, followed by the zeolite, water-soluble builder, anionic surfactant (if used), bentonite and silicate (if used). During such additions, each component will generally be thoroughly mixed prior to addition of the next component, but the addition methods may be varied depending on the circumstances, so that simultaneous additions may also occur where possible. Sometimes additions of components may be in two or more parts, and sometimes different components may be pre-mixed prior to addition to expedite the mixing process. Usually, the shaking speed and force will increase as the materials are added. For example, low rates may be used until after admixing the last zeolite or soluble builder, after which the rate can be increased to medium speed and then to high speed, which it will preferably be at during and after the addition of any silicate solution.

The temperature of the aqueous medium in the mixer will generally be around room temperature or elevated temperature.

DK 159933 B

26 and is usually in the range of 20 - 80 ° C, preferably from 30 to 75 or 80 ° C and preferably from 40 to 70 ° C. Heating the medium in the mixer can promote dissolution of the water-soluble salts of the mixture, thereby increasing the mixing steam, when heating is carried out in the mixer, it can slow down the production rate and sometimes promote solidification of the mixture. An advantage of having processing aids present in the mixture (especially if soluble silicate is present) is that they ensure that at higher and lower temperatures non-gelling slurries will appear. Temperatures higher than 80 ° C (and sometimes higher than 70 ° C) will generally be avoided due to the possibility of decomposing one or more of the ingredients in the mixture, e.g. sodium bicarbonate. In some cases, lower temperatures in the mixer also increase the upper limit of solids content in the mixer, probably due to insolubilization of normally gelling or solidifying components.

Mixing times in the mixer to get good slurries can vary greatly, from as little as 5 minutes in small appliances and to higher moisture slurries to as much as 25 to 4 hours in some cases. The mixing times required to bring all the components of the mixture substantially homogeneously together in a medium may be as short as 10 minutes, but in some cases may take up to 1 hour, although 30 minutes is a preferred upper limit. Taking into account such initial mixing times, the normal periods in the mixer will be from 15 minutes to 2 hours, e.g. 20 minutes- 35

DK 159933 B

27 hours - 1 hour, but the mixture in the mixer must be such that it is movable, not gelled or solidified for at least 1 hour, preferably 2 hours, and especially 4 hours or more, after completion of the preparation of the mixture and it will preferably be movable for as long as 10 - 30 hours before being pumped to the spray tower to take into account situations where other manufacturing problems may arise.

10

The slurry in the mixer with the various salts and any other components thereof, dissolved or in particulate form, uniformly distributed therein, is conventionally transferred to a spray drying tower normally located near the mixer. The slurry falls from the bottom of the mixer to a positive displacement pump which forces it at high pressure through spray nozzles at the top of a conventional spray tower (countercurrent or co-current), where the droplets of the slurry fall through a hot drying gas, usually the combustion fuel or petroleum products. natural gas in which the drops are dried to the desired bead shape. During drying, a portion of the bicarbonate, if present, may be converted to carbonate with carbon dioxide release, which, together with any polyacrylate present in the mixture, which is spray dried, improves the physical properties of the beads produced. so that they become more absorbent of liquids such as liquid nonionic detergent, which can subsequently be sprayed on them. However, the zeolite, bentonite, and polyphosphate components (when used) in the base beads may also appear to promote fluid absorption and production of a strong bead, and the polyacrylate improves bead properties and promotes rapid drying, thereby increasing tower production.

After drying, the product is sieved to the desired size, e.g. 10 - 60 or 100, US standard sieve series, and is prepared for application of nonionic surfactant in the case of a basic bead composition, the beads being either hot or

DK 159933 B

28 cooled state (room temperature). However, the nonionic surfactant will generally have an elevated temperature such as 30 - 60 ° C, e.g. 50 ° C to ensure that it is liquid. However, upon cooling to room temperature, it will be convenient to have a solid which often resembles a waxy solid. Although the nonionic surfactant at room temperature is somewhat sticky, this property does not render the final product poorly flowing because the surfactant penetrates below the bead surface. The nonionic surfactant applied to upturned or moving beads in known manner in the form of a spray liquid or as a dropper is preferably a condensation product of ethylene oxide and higher fatty alcohol, as previously described, but other nonionic substances may also be used. The enzyme preparation (referred to as enzyme in the present description, although also containing a carrier material), the anhydrous silicate and any other powdered additives can be dusted on the cleanser particles, and perfume and any other liquids to be added afterwards can be sprayed. at another time, before or after adding the powders.

20

The spray-dried cleaner contains no or only a small amount of silicate from the mixture in the mixer, although some solid silicate may be added afterwards.

Afterwards, the addition of powdered silicon = 25 kt does not appear to react as much with the zeolite, so that agglomerations of zeolite and silicate that are prone to deposited on washed articles are reduced compared to deposits from products in which the silicate was added in the mixer. Although silicate without the presence of 30 bentonite would normally be used for its bead regulating and anti-corrosive effects, the present cleansers provide acceptable beads and have not been found to cause corrosion of aluminum objects. Furthermore, the bentonite has no detrimental effect on the stability of the product 35 and in fact appears to help hold the beads together and make them resistant to crushing and pulverization during shipping and use. The presence of the bentonite

29 DK 159933 B

significantly improves the properties of the final detergent, resulting in higher calcium ion binding capacity and less zeolite deposited on washed substances. When the low molecular weight polyacrylate is present, the primer beads become more porous and better absorb the liquid ionic surfactant without reducing the bulk weight of the product too much. Given that bentonite is a clay species and serves as a binder, it could be expected to create deposition and gelling problems per se. Therefore, the decreased deposition properties, the absence of gelling and the easy dispersion of the product are surprising and are important results of the present invention. Important results of the presence of the small amount of polyacrylate in the spray dried beads are also considered to be the improved spray drying of the present cleansers and the improved sorption of liquid nonionic surfactant by the base beads.

The following examples illustrate the invention. Unless otherwise stated, all temperatures are in ° C and all parts are by weight in the Examples and in the specification. When 20 weights and amounts of zeolite are listed, these are for the normal hydrate form because it is believed that the hydration water of the zeolite does not leave the zeolite and does not become part of the aqueous solution medium in the mixture. Part of the water found in the foundation beads and cleansers is also present as hydration water in the zeolite. Similarly, the moisture content associated with the concrete can also be considered as not free moisture, but due to the lesser percentage present, this distinction can often be neglected for practical reasons.

EXAMPLE 1.

(Comparative Example).

A batch of 100 parts mixture is prepared for spray drying of ground beads which are considered satisfactory for

DK 159933 B

30 subsequent conversion to a detergent by adding synthetic nonionic organic surfactant thereto, by adding 47 parts of deionized water at a temperature of approx. 27 ° C and then sequentially and initially at a low mixing rate to mix 1/04 parts TINOPAL 5BM / extra concentrated (Ciba-Geigy) / 0.13 parts ultramarine blue powder, 0/07 parts sodium polyacrylate (ALCOSPERSE 107D), 21 times parts Lime hydrated zeolite 4A (20% crystal water), 6.25 parts MINERAL COLLOID # 1 (bentonite), 15.75 parts sodium bicarbonate: 0 (industrial grade), 7.74 parts sodium carbonate (natural anhydrous sodium carbonate), and 0.91 parts titanium dioxide (anatase). While mixing the various components, the speed of the mixer is increased to medium and eventually to high, and after addition of all the components, which takes approx. 15 minutes, 15.

the mixture is continued for approx. 1 hour (in some cases mixing may take as long as 4 hours), during which some of the water present, e.g. 2 - 6 parts, can be lost by evaporation and can be replaced if desired. During the mixing period, the slurry in the mixer is continuously agitated and does not gel, solidify or bake together.

Because bicarbonate partially decomposes to carbonate during spray drying, the amounts of bicarbonate and carbonate in the composition of the mixer may be varied, depending on the characteristics of the spray drying tower.

25

Starting approx. 5 minutes after all the components of the mixture are present, the mixture falls from the apparatus into a pump which pumps it at a pressure of approx. 21 kg per cm into the top of a countercurrent spray drying tower wherein the initial temperature is approx. 430 ° C and the final temperature is approx. 105 ° C.

The resulting inorganic base beads have a mass 3 room weight of approx. 0.6 - 0.7 g per an initial adhesion less than 10%, a particle size range substantially between # 10 and # 60 mesh, US sieve series (sieved to this range), and a quantity of fine material (through US sieve # 50) of ca. 15%. The moisture content of the beads is in the range of 1 - 10% and is usually closer to 10%, e.g. 8 - 10%.

31

DK 1599 * 53 B

The ground beads are found to be free flowing (80% flow rate), non-sticky, satisfactorily porous, yet solid on the surface. They can readily absorb substantial amounts of liquid nonionic surfactant without becoming too sticky.

Cleanser products are made from the spray-dried beads by spraying a normally waxy non-ionic surfactant on the surface of the upturned beads. NEODOL 10 23-6.5 is used, but NEODOL 23-7 or NEODOL 25-7 (and sometimes NEO

DOL 45-11) can be used instead. The nonionic surfactant is in the heated liquid state (at a temperature of about 45 ° C). The amount sprayed is such that it results in a final product containing approx. 20% non-ionic surfactant. Proteolytic enzyme (ALCALASE 1.7T or MAXAZYME 375) is applied in powdered form, resulting in a concentration of approx. 1.5% in the product and perfume is sprayed on the product to give a concentration of 0.25% therein. The resulting detergents have a mass space weight of approx. 0.7 - 0.8 g per ml and contains approx. 32.45% zeolite (hydrated), 19.7% non-ionic surfactant, 18.5% sodium carbonate (some of which was produced by sodium bicarbonate decomposition), 13.5% sodium bicarbonate, 1.3% free water, 1 , 4% enzyme, 1.6% fluorescent clarifier, 0.25% perfume, 0.2% ultramarine blue, 9.6% bentonite, 0.1% sodium polyacrylate and 1.4% titanium dioxide.

The fabricated cleaner of the above composition is an excellent powerful laundry detergent and is particularly useful for washing household laundry in automatic washing machines. It is physically and aesthetically advantageous and appealing because it is not dusty and is extremely free-flowing, allowing it to be packaged more easily in glass and plastic bottles with narrow necks from which it can easily flow out.

The bentonite-containing detergents prepared, as noted, have improved calcium ion binding capacity, but more importantly they leave less zeolite residue on washed clothing (in an automated

DK 159933 B

32 washing machine at usual concentrations for such products and at normal washing temperature), especially when the laundry is dried on a leash, than similar agents containing less bentonite and with sodium silicate in the spray-dried beads. This difference is emphasized when the wash water has a high hardness, e.g. 200 ppm, like calcium carbonate, the wash water is cold and gentle stirring is used.

* 0 The prepared beads and the cleanser have an acceptable standard against which the other beads and cleaners described in the following examples can be measured and with which they can be compared. The methods of preparation are also essentially the same and are considered to be satisfactory.

15

Following the normal procedure, mixtures will be prepared quickly and may be discharged by the mixer as quickly and sometimes produced in as short a time as 5 minutes and pumped out of the mixer in as short a time as 20 minutes. Nevertheless, it is often important that the present compositions be able to withstand at least 1 hour in the mixer without gelling or solidifying because sometimes such holding times occur in industrial production. The mixture described in the mixer can be kept for as long as 4 hours and often considerably longer without gels or solidifying, which is attributed, at least in part, to the content of bentonite and the absence of silicate. This effect of the bentonite is unexpected, because it also has a thickening effect on the mixture, but although the mixture 30 can significantly thicken, it remains pumpable. Smaller components of the mixture such as fluorescent brightening agent and pigment can be omitted therefrom and enzyme and perfume are omitted from the final product, but it is highly preferred that all of these materials be present. The temperature of the mixture i

3 5 O

the mixer can be changed, e.g. at elevation to 52 ° C, and the amounts of the various components can be varied -10%, -20% and -30% and still remain within the previously stated ranges and machinable mixtures can be obtained,

DK 159933 B

33 which results in the desired beads and cleansers. The solids content of the mixture in the mixer may be varied within said range, e.g. to 45% and 65%, and good mixing and spray drying results. Other sequences 5 of addition to the mixer of components may be used, but usually it is desirable to add optionally as late or towards the end, and it is preferred that the treatment is also added late in the process, preferably just before the silicate. Instead of using zeolite 4A, zeolite X and Y can be used, as can other types of zeolite A.

It is preferred to use approx. 80% hydrated zeolite 4A (about 20% moisture content), but different degrees of hydration of the zeolite are acceptable and in some cases almost anhydrous crystalline zeolites or amorphous zeolites can be used. Variation of the amount of bentonite within the indicated range to 7%, 13% and 19% in the base bead results, e.g. still in useful products, but those containing the larger amounts of bentonite will usually be more effective in helping prevent the deposition of 2o laundry. In some cases, it may be desirable to use even higher percentages of bentonite within the ranges set forth in the present disclosure, taking care that the other components of the base bead are such that the beads are free flowing and effective cleaners. The 25 amount of bentonite suitably used industrially depends on various factors and will usually represent a balance between the desired reduction of zeolite residue and the desired build-up and other functional effects of other detergent components which could be incorporated in place of an increased amount of bentonite.

The improvement observed in the cleaners in this example, which consists in depositing less residue on washed clothing, is confirmed by testing the product described for 3g a control product of substantially the same composition, with no bentonite present and containing ca. 8% sodium silicate in the final product. This rating uses a Whirlpool

DK 159933 B

34 washing machine with the washing program set to 8 minutes and gentle washing. The concentration of detergent is 0.06%, the wash water has a mixed calcium and magnesium hardness of 200 ppm as calcium carbonate, and the temperature of the water is 24 ° C.

5 The items washed are: 100% cotton, 100% polyester, 85% acetate and 15% nylon, and 65% polyester and 35% cotton. The wash is observed wet and after drying on a leash (drying on a leash usually results in a more visible residue than drying in an automatic dryer). No residue is observed in any case.

10 When the cleaning composition of the control composition is tested, moderate residue is observed on all the washed pieces.

The results of the practical residual test described above are confirmed by weighing the residue deposited on a denim test material. In this test, the detergent according to the invention is filtered through a sample of denim material, the detergent being in solution suspension with a concentration of 0.12% in water with a hardness of 200 ppm (as CaCC> 3) at 24 ° C, and the weight of the remainder on the fabric is noted and compared. At this test, the percentage of residue compared to the control is approx. 75%, which is considered to represent a significant difference in the appearance of washed products.

The adhesive test previously mentioned, which measures the tackiness of the detergent product, is a test in which 10 g of basic beads (or in some cases detergent) are applied uniformly between two watches, both 23 cm in diameter and weighing 500 g. , on top of the upper watch glass (both glasses with the concave side facing up). After standing for 5 minutes, the weight and upper watch glass are removed and the lower watch glass is inverted, whereupon the product remaining sticky on the watch glass is weighed. The percent adhesion is the number of g of product remaining on the watch glass multiplied by 10.

The flow index obtained by a flow test by which the volumetric flow rate of basic beads (and in some cases final product) and standardized Ottawa sand (-20 + 60, DS sieve standard) is compared by measuring the time,

DK 159933 B

35 required to complete discharge of a 1.9 liter Mason jar through a 2.2 cm diameter circular hole in a nozzle attached to the cap. The flow index percentage is the time it takes for the sand to flow out, divided by 5 times the test product times 100.

EXAMPLE 2.

Base beads like those in Example 1, but with NTA instead of some of the carbonate and bicarbonate, are prepared in substantially the same manner as described in Example 1. The composition is changed only by replacing 5 parts of the zeolite, 12 parts of the sodium bicarbonate and 3 parts. of the sodium carbonate in the 20 parts NTA mixture as trisodium salt monohydrate. i5 NTA is added after the sodium carbonate during mixing. The resulting beads are not as brittle as those of Example 1, but are satisfactory free flowing. Instead of the final detergent containing 19.7% of the non-ionic surfactant, it is sufficient that it contains 12%, 2o as the final percentages of the other components are increased accordingly. The resulting product is a satisfactorily powerful particulate cleaner.

Upon variation of this composition, 2.5% aqueous sodium silicate is added afterwards to the product for its anti-corrosion properties and its usefulness to bind magnesium ions in the wash water. Assuming the silicate has approx. the same particle size and density, it does not differ from the other components of the detergent bead during shipment and storage, and the resulting product satisfies the requirements of a powerful industrial detergent, but a small amount of zeolite-silicate aggregate can be observed on washed materials.

In another alternative composition, 3% sodium silicate [with a Na 2 O: $ 10 1: 2.4 to the final product at

DK 159933 B

36 addition of an aqueous solution thereof in the mixer together with 1/5% magnesium sulfate and 0/4% citric acid to prevent gelling or solidification in the mixer. The finished product is a good powerful cleanser / but it deposits more zeolite-silicate aggregate on washed materials / which is wiped dry than a comparable composition to which the aqueous sodium silicate is added afterwards.

EXAMPLE 3.

1 o -

The procedure of Example 2 is repeated, but penta = sodium tripolyphosphate is used instead of NTA. The products obtained are good cleansers with a mass space weight of approx. 0/8 g 3 .r pr. cm (as in Example 2), but these room weights can be varied by setting the conditions in the spray tower and by setting the compositions to range from 0/7 to 0.9 and in some cases the room weights can be reduced to 0 , third With the added silicate afterwards, the room weights may be slightly higher, especially for those in the lower range. The product is more free flowing than that of Example 2, but is approximately equivalent to this in terms of washing power.

In the above composition and in the compositions of the foregoing examples, an additional amount of bentonite can be added to the mixture in the mixer to produce products containing 15% (or more) bentonite. These products are even better in terms of bonding effects, dispersibility and other desirable properties attributable to bento = nineteen, and are good detergents (and primers). The tripoly = phosphate can also be replaced, in whole or in part, e.g. half, with tetrasodium pyrophosphate, and equally good products appear.

35

DK 159933 B

EXAMPLE 4.

A detergent product is prepared essentially in the manner described in Examples 1 and 2 containing 30 parts of zeolite, 30 parts of NTA, 20 parts of nonionic surfactant, 10 parts of bentonite, 5 parts of sodium carbonate, 5 parts of water and 1, 3 parts

ISLAND

enzyme. This product has a space weight of approx. 0.5 g per cm and is a satisfactory cleanser. However, to improve the flowability of the product, it is desirable that the content of nonionic surfactant be reduced to 15% and preferably to 12%. To increase the mass space weight to approx. 0.7, half of bentonite tea can be replaced with sodium silicate (Na 2 O: SiC> 2 ratio of 1: 2.4) added as the last component of the * 5 mixer as a 47.5% aqueous solution, and 1.5 parts of magnesium sulfate and 0.4 parts of citric acid may similarly be added as anti-gelling agents earlier in the preparation of the mixture in the mixer. The resulting product has a 3 mass compartment weight of approx. 0.7 g per cm and can absorb approx. 20 de-20 le of non-ionic surfactant without becoming sticky or diminishing in flowability. It deposits less agglomerate of zeolite and silicate than compositions with usual larger amounts of silicate obtained by addition to the mixer, but agglomerate can be detected on clothes washed with the product 25 and dried on leash.

EXAMPLE 5.

Instead of preparing base beads on which detergent is applied to form a detergent, the agent can be spray dried directly by the mixture from the mixer, where a suitable synthetic organic surfactant is added to the mixture.

Using essentially the same procedure as described in Example 1, a mixture is prepared in the mixer which is spray dried to cleaner beads containing 16 parts of linear tridecylbenzenesulfonate, 20 parts of zeolite,

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38 12.5 parts bentonite, 15 parts NTA, 10 parts sodium carbonate and usual additions (color, fluorescent clarifier). The mass weight of the spray-dried product will be in the range of 0.3 - 0.8 and is usually at the lower end of this range and sometimes as low as 0.2 g / ml. cm. In the manufacturing process, the organic surfactant is usually added after the water. Drying will usually be to a moisture content of approx. 8 - 12%. Preferably, the resulting product has approx. 3 parts aqueous sodium silicate added afterwards with other normal additives such as enzyme and perfume. It is a satisfactory powerful cleanser that does not deposit harmful amounts of zeolite or aggregate of zeolite and silicate on washed fabrics. Due to the presence of the bentonite, the detergent is found to disperse * c1 very quickly when added to the wash water, and it is believed that at least part of this rapid dispersibility, together with the presence of the bentonite, tends to inhibit zeolite deposition.

EXAMPLE 6.

The procedure of Example 5 is followed, but NTA is replaced with an equal amount of weight of anhydrous sodium carbonate. This product is also a satisfactorily powerful cleanser.

EXAMPLE 7.

The procedure of Example 5 is followed, but penta = 30 sodium tripolyphosphate is added instead of NTA. The product produced is particularly free-flowing and is a well-acting synthetic organic cleanser. Although it is preferred when silicate is to be added afterwards as an aqueous sodium silicate, up to 5 parts of 35 silicate may be added to the mixer together with the appropriate amount of magnesium sulfate and citric acid, as described in the preceding examples, and will occur. useful detergents, although some zeolite-silicate deposition will occur.

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In addition to the usual materials which may be added afterwards, softening amounts of a cationic material, e.g. 8% dimethyl distearyl ammonium chloride, an amphoteric cleaner, e.g. 5% MIRANOL C2M (1-carboxymethyl-1-carboxyethoxyethyl-2-coconutimidazolinium betaine) or a bleach, e.g. 151 sodium perborate (preferably activated). Of course, the addition of these materials 10 will reduce the amounts of the other components of the final agent and will therefore slightly change the properties of the agent, so that sometimes more use of the product in the wash water is required to achieve the same purification effect.

In Examples 5-7, the linear tridecylbenzenesulfonate can be replaced with an equal weight amount of sodium lauryl sulfate or sodium lauryl polyethoxy sulfate (3-10 EtO) or mixtures of such materials in equal amounts of weight, and the resulting products are also useful as detergents. In a similar manner at 2C, instead of: NTA, carbonate or carbonate and bicarbonate, polyphosphate, sodium citrate and / or sodium gluconate can be used, at least in part, e.g. 1/4 or 1/2, and good cleansers are obtained.

EXAMPLE 8.

The products of Example 1 and Example 7 (the primary products first described) are mixed in equal amounts to form an end product with the properties of both the incoming parts. Before mixing, both mixed materials have approx. total mass weight, approx. 0.5 g per cm, and approx. the same particle size in the range from No. 10 to No. 60, US Sieve Series, to prevent separation during shipment and storage.

The blended product is particularly useful for removing the go-35 oil-based and clay-based laundry molds and is free-flowing, stable and appealing. In some cases, one of the particulate starting materials may be dyed or pigmented, and the other left naturally in color to thereby have special effects in appearance. In addition to the particle sizes and room weights being approximately the same,

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It is preferred that the moisture contents are also about the same, e.g. ca. 10%, so that there is little moisture migration between the different beads.

In the materials used in Example 7, the anionic surfactant can be changed from sodium alkylbenzenesulfonate to a sodium α-olefin sulfonate (14 to 15 carbon atoms in the olefin) or to sodium paraffin sulfonate (12 to 15 carbon atoms in the paraffin fin) and the mixtures prepared will also be useful cleansers.

EXAMPLE 9.

Following essentially the procedure described in Example 1, a mixture is formed in a mixer of 36.9 parts of water, 1.2 parts of fluorescent clarifier (TINOPAL 5BM, extra concentrated), 0.1 parts of ultramarine blue, 2.1 parts of magnesium sulfate (heptahydrate), 0.3 parts of sodium citrate, 22.4 parts of zeolite 4A powder (partially hydrated to a moisture content of about 20%), 20.9 parts of trisodium nitrilotriacetate = monohydrate, 7, 4 parts of a 47.5% solution of sodium silicate (Na 2 O: SiO 2 = 1: 2.4), 3.7 parts of sodium bentonite (previously negotiated as THIXO-JEL # 2), 2.8 parts of natural anhydrous sodium carbonate and 2 1 parts of a mineral-type compound which may act to increase the porosity of the bead and as a builder. The mixture from the mixer is spray dried in a similar manner as previously described, with the moisture loss on drying being approx. 45.2%.

30 On 48.4 parts of the spray dried base beads having a particle size from No. 10 to No. 100 (sieved), 20 parts of NEODOL 23-6.5 are sprayed, after which the beads are mixed with 1.3 parts of high-active proteolytic enzyme and 0.3 part cleaning medium perfume thereon. The final product has a zeolite content of 25%, an NTA content of 30%, a sodium bentonite content of 5% and a water-soluble sodium silicate content of 5%.

Claims (5)

A free-flowing spray-dried particulate cleaner comprising spray-dried primer beads, characterized in that the primer by weight contains 5-30% water-soluble synthetic organic surfactant, 5-60% water-soluble builder or a mixture of such builders, 5-60% ion-exchange zeolite and 2-40% bentonite, with any nonionic surfactant present being a condensation product of a higher fatty alcohol of 12-16 carbon atoms with 6-12 moles of ethylene oxide per mole of alcohol applied to the surface of the beads after spray drying. Purifier according to claim 1, characterized in that the zeolite contains from 15 to 25% by weight of hydrated water and 35 has an ion exchange capacity for calcium ions in the range 200-400 mg. equivalents of calcium carbonate hardness per gram of anhydrous zeolite, that the bentonite is a swelling clay with a swelling capacity in water of about 3-15 ml per g and a viscosity of 3-30 centipoise at a concentration of 6¾ in water and contains at least 2 % humidity calculated on anhydrous bentonite. Purifier according to claim 2, characterized in that the ratio of bentonite to zeolite is in the range 1: 4 -1: 1, the ratio of the amount of water-soluble builder to zeolite is in the range 1: 2 to 3: 1, and the ratio between bentonite and water-soluble builder is in the range of 1:10 - 1: 1. Purifier according to claim 1, characterized in that it contains 10-40% hydrated sodium zeolite, 2-35% bentonite, which has a swelling capacity in the range of 7-15 ml per g and a viscosity in the range of 8-30 centipoise. at a concentration of 6% in water, 10-50% water-soluble alkali metal salt or a mixture thereof, and 0-25% water-soluble synthetic anionic organic detergent. 20 Purifier according to claims 1-4, characterized in that the bentonite is a concentrated Wyoming bentonite having a nitrogen capacity in the range of 7-15 ml per gram and a viscosity in the range of 3-30 centipoise at a concentration of 6% in water. 25 30 35