SE444953B - PHOSPHATE-FREE PARTICULATE HIGH-EFFECTIVE DETERGENT COMPOSITION AND SET FOR ITS PREPARATION - Google Patents

Description

Forms 92-9 to form free-flowing particles containing 40-90% by weight of said mixture of carbonate and bicarbonate, 10-30% by weight of nonionic detergent and 3 to 15% by weight of moisture. The detergent compositions can be prepared by spraying the nonionic detergent on a moving bed of spray dried cores.

The products of the present invention are excellent phosphate-free particulate detergents with comparatively high bulk density and acceptably large particle sizes, which makes it possible to use small volumes thereof, eg 50 - 125 ml, for an average wash in an automatic washing machine.

The alkali metal carbonate and the alkali metal bicarbonate used can be charged in a so-called "crutcher" mixer or other suitable mixer as separate particles, with both the carbonate and the bicarbonate included in the same individual grains or double salts or as a mixture of these materials. Thus, while normal powders, such as those having a particle size in the range 0.149 - 0.84 mm, can be used, even powders having particle sizes up to about 4.76 mm and as fine as 0.074 mm can be used provided that they are easily dissolved and / or dispersed in the aqueous mixture of the crutcher mixer. Salts such as sodium sesquicarbonate and Wegscheider's salt can be used as well as various hydrates of carbonates and bicarbonates. Although both the sodium and potassium salts are preferred by the alkali metal salts, the sodium salts, carbonate and bicarbonate are those which are best used in mixtures, but only bicarbonate can be added in the process. desired proportion of carbonate is obtained by decomposition.

The nonionic detergents are listed in large size in McCutcheon's Detergents and Emulsifiers, 1973 Annual and in Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (rnterscience Publishers, less), to which the literature figures are hereby referred. These detergents can be liquid, pasty or waxy solids at room temperature (20 ° C) and are usually either sufficiently water soluble to dissolve directly in water or will melt rapidly at the temperature of the wash water (and 'for crutches'). the mixer), such as when this temperature is above 30 - 40 ° C. The nonionic detergents used are usually those which are liquid at room temperature, but those which are meltable at elevated temperature, eg 35 - 70 ° C or 40 - 60 ° C, at which temperature they can be applied to the grains and absorbed by them, are also useful. The liquid nonionic detergents are often preferred because they are very fast in the grains very quickly, without the need to heat either the detergent or the grains. .

One of the unexpectedly valuable properties of the grains produced is that they absorb and retain comparatively large amounts of liquid nonionic detergent without the grains becoming sticky and without gaining long-lasting shelf life, not even after long storage time. The pasty or solid nonionic detergents, once penetrated into the interior of the carbonate-bicarbonate particles, are also useful in the preparation of free-flowing and non-sticky products, but to promote this initial penetration they must be converted to liquid form. , which requires heating and in some cases also heats the base grains on which they are sprayed.

Typical useful nonionic detergents are the poly (lower alkenoxy) derivatives, which are usually prepared by the condensation of lower (2-4 carbon atoms) alkylene oxide, e.g. ethylene oxide, propylene oxide (with sufficient ethylene oxide to obtain a water-soluble product), together with a compound having a hydro-, .- ___..- _ .. ~ ........... > ...._ .. _....._........-..........-_., ...._ .._. _ ...., ..........-....._ .. 7soas92-9 p ¿Q fob hydrocarbon chain and containing one or more active hydrogen atoms, such as higher alkylphenols, higher -fatty acids, higher-fat- mercaptan or higher-fatty amines and higher-fat polyols and -alcohols, e.g. fatty alcohols having 8 to 20 or 10 or 12 to 18 carbon atoms in an alkyl chain and alkoxylated with an average of about 3 to 30, preferably 3 to 20 and more preferably 5 to 12 lower alkylene oxide units, e.g. ethylene oxide.

Preferred nonionic detergents are those represented by the formula R 0 (C 2 H 4 O) n H wherein R is the residue of a linear saturated primary or secondary alcohol (an alkyl) having 10 to 18 carbon atoms and n is an integer from 3 to 20 or 5 to 12. The preferred nonionic detergents may be referred to as higher fatty alcohol polyoxyethylene ethanols (the end-of-ethanol portion of these ethers is included in the number of oxyethylene groups calculated in moles of the nonionic detergent). Typical commercial nonionic surfactants suitable for use in connection with the invention include Neodolium 23 - 6.5, which is an ethoxylating product containing the drugs 6.5 moles of ethylene oxide per mole of a fatty alcohol having a chain of 12 - 13 carbon atoms, - Neodo R 25 - 7, which is a fatty alcohol with a chain of l2 - l5 carbon atoms and which has been ethoxylated with an average of 7 ethylene oxide units, Neodo§à 45 - ll, which is an ethoxylation product (which has an average of about ll ethylene oxide units) of a fatty alcohol with a carbon chain of on average 14 - 15 carbon atoms, and of these materials the first two are the most preferred (all of these materials are manufactured by Shell Chemical Company). Thus, the fatty alcohol is preferably a carbon atom and thus the polyoxyethylene has 5 to 8 moles of ethylene oxide per mole of fatty alcohol.

The alkali metal silicate which may be included in the compositions of the present invention is preferably sodium silicate having a Na 2 O: SiO 2 ratio ranging from 1: 1, 6 to 1: 3.2, preferably 1: 1, 8 - 1: 3 and most preferably about 1: 2 - - 1 = 2.4, sex. 1 = 2.35. Such a silicate may be added to the aqueous crutcher mixture as an aqueous solution, usually containing about 40% sodium silicate as a solid; Alternatively, another usable silicate may be used, such as aqueous sodium silicate (such a product is sold under the working name Britesil, which is manufactured by the Philadelphia Quartz Company and which normally has a Na 2 O: SiO 2 ratio of about 1: 2 and with 20 - 24% moisture).

The silicate usually has particle sizes (effective diameters) in the range of 10 - 150 mesh according to US Standard Sieve and essentially all, 97% or more are in the range of 0.149 - - 2.00 mm. When aqueous sodium silicate is used, it can often be mixed with the carbonate-bicarbonate grains before spraying the mixture of the liquid nonionic detergent thereon, but it can be added afterwards to the carbonate-bicarbonate grains after they have absorbed the detergent.

In addition to the mentioned components of the finished product, a number of different additives can also be included in the preferred compositions. To improve the cleaning, e.g. a proteolytic enzyme or equivalent enzyme is added afterwards (normally such a component is not incorporated into the crutcher mixture because spray drying has an inactivating effect on such enzymes. Such enzymes are described in Principles of Biochemistry by White, Handler, Smith and Stetten (1954)). .

Another preferred component of the present detergent is a fluorine. The fluorescent whitening agents are compounds of a well-known class in the detergent field and usually constitute the reaction products of cyanuric acid chloride and the disodium salt of diaminostilbene disulfonic acid, benzidinesulfonic disulfonic acid, aminocoumarins, diphenylpyrazoline derivatives or naphthobenylene derivatives. Such materials are described in the article Optical Brighteners and Their Evaluation by Per S Stensby, a reprint of articles published in Soap and Chemical Specialties during April, May, July, August and September 196, especially pages 3 - 5. Among such whitening agents is TinopaiR SBM (Geigy ), TinopašE> RBS, SOF (Ciba), and one known as Stilbene No. 4, disodium 4,4'-bis- (4-anilino-6-morpholin-s-triazina-2-ylamino) -2,2'-stilbene disulfonate. 7863892-9, 6 ~ Of these, Tinopaí is generally preferred:> 5BM.

A variety of other ingredients and additives may be included in the "crutcher" mixture or may be added afterwards, including defoamers, defoamers, fungicides, antioxidants, hygienic agents, stabilizers, gelling agents, soil suspending agents, contaminants. color materials (pigments and dyes), bleaches and perfumes.Such materials are well known in the art and do not need to be listed to any great extent here.

The proportion of alkali metal carbonate relative to alkali metal bicarbonate should be in the range of 2: 1 - 1: 5, preferably 2: 1 - 1: 3, more preferably about 11.8 - 1: 3 and most preferably about 1: 1. The sum of the weights of carbonate and bicarbonate is normally 40 ~ 90% by weight of the product, preferably 50 - 75% by weight, more preferably 55 - 65% by weight and most preferably about 60 or 52% by weight of the weight of the product, while the content of nonionic detergent is from 10 - 30% by weight, preferably 15 to 25% by weight, more preferably 18 to 22% by weight and most preferably about 20% by weight thereof. In some cases, it may even contain as much as 35-40% nonionic detergent, usually as a normal solid detergent in such cases. The silicate content, although it may be as high as 25%. In some cases, is normally from 3 or 5 - 20% preferably 5 - 15% and most preferably about 10%, while the moisture content, although variable to suit particular circumstances, normally 2 - 12%, preferably 2 - 10%, more preferably 3 - 6% and most preferably about 4 - 5%. The total amount of additives, including fluorescent whitening agents, proteolytic enzyme, antifoulants, when included, etc., usually does not exceed 10% of the product and is preferably less than 5% and more preferably less than 3%, the percentages of individual components being less than 3% or less than 1 or 2% for each. The content of fluorescent whitening agent is thus normally in the range 0.05 - 3%, preferably 7 - 78% - 2.5%, the content of proteolytic enzyme (including the normal carrier for such an enzyme) is from 0.5 - 3%. %, preferably 1 - 2 a, the content of pigment is from 0.1? 0.4% and the perfume content is from 0.1 - 0.4%, when such components are present. m as desired, the percentage of anti-redeposition agent may be as high as 3%, but normally this percentage, if this agent is used, is from 0.5 - 2%.

If a bleaching detergent is desired, as much as 30% sodium perborate, usually as the usual hydrate, NaBO2-H2O2-3H2O or NaBO3-4H2O, termed sodium perborate tetrahydrate, may be included and the proportions of other materials previously described may be reduced accordingly. . Preferably, the constituent proportion is perborate from 18 - 25%.

Due to the heat sensitivity of the perborate, it should be added afterwards to the spray-dried carbonate-bicarbonate particles, either before or after the spraying of the nonionic detergent, and the perborate has a similar particle size, e.g. 0.149 - 4.76 mm. Instead of perborate, you can also use other compatible bleaches in similar or otherwise suitable amounts, e.g. sodium percarbonate, potassium persulfate, sodium dichloroisocyanurate.

The particulate and high bulk density detergent product of the present invention, consisting essentially of the aforementioned components, in the proportions described and with the said advantageous features, is usually in free-flowing rounded granular form similar to that of other spray-dried products. although the interior of the grains may be practically rare or hollow. The particle sizes of the grains are normally in the range 0.125 - - 4.76 mm, preferably 0.149 - 3.36 or 4.76 mm and more preferably 0.149 - 2.38 mm, with less than 10%, preferably less than 5 % and more preferably less than 1% of the product falls outside these ranges. The bulk density of the final detergent is normally at least 0.6 g / ml, preferably at least 0.65 g / ml and most preferably it is in the range 0.65 - 0.8 or 0.9 g / ml, e.g. 0.67 g / ml. The dispersibility of the products produced is excellent and is usually greater than 70% of the dispersibility of free-flowing sand with similar particle size, and is normally from 70-90% thereof and preferably 75-90% thereof.

In the manufacture of the invented detergent, it is important that a sorptive grain be prepared for rapid penetration of nonionic detergent and absorption of the detergent into the interior of the grain. Such sorption must be sufficient so that the nonionic detergent is retained in the interior of the grain, whether it is liquid, pasty or waxy, and therefore does not tend to cause sticky grains or poor dispersibility properties, regardless of long-term storage. Although sodium carbonate has sometimes been found to be a satisfactory sorbent for many nonionic detergents, products made with this material alone tend to be builder materials, at least in the quantities needed to achieve compositions of the type acceptable. detersive and sorptive, to obtain remarkably high pH values. The presence of bicarbonate together with the carbonate has a buffering effect and lowers the pH value satisfactorily. But even then, when the carbonate levels are too high, despite the lowering of the pH value due to the presence of the bicarbonate, the amount of carbonate available in the product can make it dangerous (can burn the esophagus), if the product is accidentally swallowed such as may occur in children or infants. At the special ratios of carbonate to bicarbonate previously stated, such as 1: 0, 8 - - 1: 3, it has been found that advantageous cleaning effects are obtained, compared with similar products in which carbonate was used exclusively, when no bicarbonate is present.

Some of the desirable physical properties of the product, including sorption properties, may be enhanced by the decomposition of a portion of the bicarbonate during the manufacture of the spray-dried carbonate-bicarbonate grains, with the consequent release of carbon dioxide from the product and / or neutralization of any excess or locally accumulated alkaline parts of the carbon dioxide released. The production of the base grains by spray-drying the carbonate-bicarbonate solution to give a product with certain proportions of carbonate and bicarbonate thus has desirable physical effects, produces an improved detergent composition and lowers the pH and toxicity of the product.

The bulk density of spray-dried carbonate-bicarbonate grains, with or without silicate and other heat-stable auxiliary materials contained therein, but added before the nonionic detergent is sprayed onto the grains, will normally be in the range of 0.5 - 0.7 g / ml. The moisture content of these grains is usually higher than the moisture content of the final product due to "dilution" of the final product with nonionic detergent and any other dry or drier post-added materials. When aqueous sodium silicate is subsequently added to the carbonate-bicarbonate granules, either before or after the spraying of the nonionic detergent, the moisture content contained therein is allowed. When significant additions of material are not made afterwards, the moisture content of the carbonate-bicarbonate grains is normally in the range 2.5 - or 3 - 15%, preferably 3.5 - 12%.

The crutcher mixture to be spray-dried normally comprises 40-75% solids and 25-60% water. The water content is preferably 25 - 50 elh fl: -55%, the remainder of the mixture being non-surfactant solids. Of the solids content, at least 80% and preferably at least 90% is a carbonate-bicarbonate mixture, the weight ratio of carbonate to bicarbonate being charged being in the range 1,8: 1 ~ 1: 10, preferably 1: 1 - 1: 6. The "crutcher" apparatus is usually provided with heat exchange means so that the temperature of the mixture can be controlled. Normally this temperature is within a range ranging from room temperature to 90 DEG C., preferably 20 DEG-70 DEG C. and most preferably 45 DEG-65 DEG C. The residence times in the crutcher mixer are usually in the range of 5 minutes to one hour, preferably 10 minutes to 30 minutes. When the silicate is present in the crutcher mixture, the carbonate, bicarbonate and water, plus any other non-surfactant components to be incorporated into the spray-dried base granules, e.g. fluorescent whitening agents, pigments, are mixed together initially, usually for a period of 1 to 10 minutes, preferably 3 to 7 minutes, and then the silicate can be added slowly, preferably as an aqueous solution of 20- ~ 50%, preferably 35-41 % solids, e.g. 40%, the addition being carried out for a period of about 2 to 10 minutes, usually about 3 to 7 minutes. By varying the mixing techniques, changing the mixing speeds, the degree of shear, the temperature, etc., the viscosity of the mixture can often be maintained within a machinable range, but if the mixture becomes extremely viscous it can be thinned ".

After the crutcher mixture has been completely treated in the crutcher mixer, it is atomized, preferably by pressing through a round nozzle having an inner diameter in the range of about 0.5 - 2 mm, at a pressure of about 10-- 50 kp / cm 2, into a spray tower, preferably a countercurrent spray tower, in which the drying air has a temperature of about 150 - 350 ° C. The conditions therein (temperature, size of the small spray droplets, air flow, residence time) can be controlled so that the desired degree of decomposition of bicarbonate 9 to carbonate, usually 10 - 70%, preferably 20 - 50 0, is not achieved. The resulting product has spherical particles which are substantially in the range of 0.105 - or 0.125 - 4.76 mm and have a moisture content of 2.5 - 15%, the product being sieved so that substantially all particles fall within this range or a narrower intervals, e.g. 0.149 - 4.76 or 0.149 - 2.38 mm.

After the base particles are prepared, and when they do not contain silicate, a particulate solid silicate, such as aqueous sodium silicate, preferably of the type sold by the Philadelphia Quarts Company as Britesil, having a Na 2 O: SiO 2 ratio of 1: 2 or 1 : 2,4 and a moisture content of 20 - 24% (although 10 - 40% is also possible), mixed with the base grains in an inclined drum or other mixing and / or tumbling device, which normally takes place over a period of 11_ ' 7808892-9 about 1 - 5 minutes, after which nonionic detergent, in a liquid state and at a temperature in the range 20 - 70 ° C (room temperature is preferred for normally liquid nonionic detergents), preferably 20 - GOOC, is sprayed on the tumbling the surfaces of the base grains (which had been premixed with subsequently added particulate silicate). The finely divided nonionic detergent beads may be of any suitable size, but are normally in a diameter range of 0.05 - 2 mm, preferably 0.1 - 1 mm. The application of the nonionic detergent to the tumbling particles normally takes place over a period of from 1 to 20 minutes, preferably from 2 to 10 minutes, and is preferably carried out by spraying, as described, but other forms of mixing and mixing can also be used, such as adding liquid to a fluidized bed of the base particles. After the addition of the nonionic detergent is completed, other materials may be added which are intended to be added afterwards, such as perfume and proteolytic enzyme.

Although the present detergent compositions can preferably be prepared by spray drying and subsequent spraying, as previously described, it is also possible to make useful products by applying the nonionic detergent to a mixture of bicarbonate and carbonate, preferably with Wegscheider's salt also included. One such product is a phosphate-free, free-flowing, heavy duty detergent having a bulk density of at least about 0.6 g / ml, moisture content below 10% and particle sizes in the range 0.149 - 4.76 mm. which detergent comprises core particles of mixed alkali metal bicarbonate and alkali metal carbonate, the ratio of bicarbonate to carbonate being in the range 1: 0.4 - 1: 0.8, and containing a normally liquid or pasty nonionic detergent in such a quantity that the percentage of this detergent in the product is from 15 - 22% and the proportion of nonionic detergent in relation to the total content of alkali metal bicarbonate and alkali metal carbonate is in the range 1: 2.5 - 1: 4. The mixture of alkali metal carbonate and alkali metal bicarbonate is preferably such a mixture in which both types of compounds are contained in the same individual granules or particles. Such particles have a size which is preferably 0.250 - 2.00 mm and most preferably about 0.42 - 0.84 mm.

The alkali metal (sodium or potassium preferred) carbonates and bicarbonates, most preferably the sodium salts, are substantially anhydrous in preferred embodiments of the invention, but partially hydrated builder salts of this type may be tolerated. Normally the moisture contents are less than 9%, preferably less than 7%, the weight ratio between alkali metal bicarbonate and alkali metal carbonate is generally in the range 1: 0.4 - 1: 0.8. The mixed product is preferably prepared by a method which results in a substantial content, e.g. 10 - 90%, of Wegscheider's salt, with any remaining part being carbonate and / or bicarbonate. Such a product has an excellent sorptive ability for liquid nonionic detergent and can be easily converted to a suitable base for coating a powder of zeolite builder, if it would be desirable to apply such a material * to the product.

In the preparation of certain preferred particulate starting mixtures of carbonate and bicarbonate, the method described in U.S. Pat. No. 3,944,500 can be used and the product obtained, designated by the trade name Snowlite and obtainable from Allied Chemical Corporation, is preferably use the product. A typical analysis of Snowlite I gives 35% Na2CO3, 58.5% NaHCO3 and 6.5% H2O, while an analysis of another such product, Snowlite II, gives 30.0%, 66.5% and 3.5% respectively . Sight analyzes (percentages of sieves with Nos. 10, 40, 50 and 100 according to American standards corresponding to 2.00, 0.42, 0.297 and 0.149 mm respectively) give the values 0.2, 67.6, 96.9, 99.0 and 0.7, 60.7, 90.7 and 97.0.

The bulk densities Kg / ml) are 0.51 and 0.48 (packed) and 0.42 and 0.38 (unpacked), respectively. The dispersibility is particularly low for Snowlite I (2.5%) according to a test Na 17-35 13 g 5,7808892-9 by Allied Chemical Corp.) so it is sometimes preferred. In some cases, other components of the final product may be incorporated into the mixture of bicarbonate and Wegscheider's salt, prepared by the method described in said patent, provided that they are stable and do not adversely react or interfere with the production of the carbonate bicarbonate product.

Normally the carbonate-bicarbonate particles contain at least 60%, preferably 70% and more preferably from 80-95% or more bicarbonate and carbonate and when such other types of auxiliary materials are included they constitute.5 - 15% sodium silicate and / or 0.1 - 5 % fluorescent whitening agent and / or 0.2 - - 1.5% anti-redeposition agent, sometimes also together with additional water to bring the water content of the products within the areas previously mentioned. Although the method according to the above-mentioned American patent specification is a preferred method, the mixed carbonate-bicarbonate grains can be manufactured by means of other techniques, provided that the final product is substantially the same. The other components of the detergent composition may be the same as previously described.

The proportions between bicarbonate-carbonate particles and nonionic detergent in the product now discussed should be chosen to give the composition a satisfactory cleaning ability and so that the particles become free-flowing and with the desired high bulk density. Such proportions are normally in the range of 15 ~ 22% nonionic detergent, the remainder being mixed bicarbonate-carbonate in granular form, complementary builder materials such as silicate (alkali metal silicate) e.g. sodium silicate, if included, and adjuvants and moisture. The alkali metal bicarbonate component, sodium bicarbonate, in Wegscheiderite or otherwise, is preferably 30-45%, more preferably 30-40%, the carbonate content, in Wegscheiderite or otherwise, is preferably 15-30%, more preferably 15-25 %, the moisture content is preferably 1 - 7%, more preferably 1 - 5%, the silicate content is 5 - 15%, preferably 8 - 12% and the total auxiliary content is 3 - 10%, preferably 4 - 8%. An especially preferred formulation comprises 20% nonionic detergent, 38% sodium bicarbonate, gg7snàs92-9 jelly 23% sodium carbonate, 10% aqueous sodium silicate, 5% auxiliary additive and 4% moisture. The moisture content is that which can be removed from the product when kept at 105 ° C in an oven for 5 minutes, but normally it excludes the water of hydration in the aqueous sodium silicate.

The manufacturing methods, including after-spray techniques, are essentially the same as those previously described for treating the spray-grained grains and the properties of the product are also similar. "The following examples illustrate the present invention, but without limiting it. parts parts by weight and all temperatures are in OC.

Example 1 Percent Neodoles3 - 6.5 (Shell Chemical Company) 20.0 NaHCO3 31.0 -0Na2co3 g 31.0 Sodium Music (Nazmsioz = 1 = 2.4) 100.0 Tinopagš% BM, fluorescent bleach 0.0 _ * Proteolytic enzyme (Protease) _ 1.5 Ultramarine blue, pigment 0.2 Perfume 0.3 Water _ 4.0 100.0 * Condensation product of higher fatty alcohol with an average of 12 - 13 carbon atoms and with about 6.5 moles of ethylene oxide per mole . A free-flowing, particulate detergent composition having a high bulk density is prepared from the above recipe and has substantially spherical or round particles, 99% of which have sizes (usually considered as diameters or effective diameters) in the range of 0.149-2. 38 mm. The product has a bulk density of 0.67 g / ml and flows at a rate of about 75% of the corresponding rate for dry sand of similar particle sizes, which material is the standard for comparative purposes. The product is an excellent heavy duty synthetic organic detergent composition that is useful for both hot and cold water when washing both synthetic and natural fiber textiles and leaves no residue on such textiles that could lead to remarks, nor does the composition make these textiles randi- as is sometimes observed after washing with detergents containing comparatively high percentages of sodium carbonate. The product does not undergo fractionation, does not become unacceptably sticky during prolonged storage under normal storage conditions and remains free-flowing and high-density during such storage.

The described detergent composition is prepared by mixing in a mixer for synthetic detergent or soap, at a temperature of 60 ° C (the water is initially preheated and the heat "on the mixer fcrutcher" mixer is maintained to reach and maintain such a temperature). of sodium carbonate and sodium bicarbonate plus stable auxiliary additives such as pigments and bleaches. The parts by weight used are 40 sodium bicarbonate, 22 sodium carbonate, 0.2 pigments, 2 bleaches and 59 deionized water. Alternatively, in some cases the deionized water is replaced with low tap water. hardness, less than 50 ppm calculated as calcium carbonate After about 5 to 10 minutes of mixing, 25 parts of aqueous sodium silicate solution containing 40% solids are added to the crutcher mixture.

Although the mixture becomes slightly thick during the mixing operation, the viscosity of the mixture is maintained, by increasing the mixing rate during the addition of the sodium silicate and by controlling the rate of addition, at a level at which the mixture is still obtained and the formation of gel material is reduced. to a minimum. Usually only about 5 or 6 minutes are taken for the mixing, of the sodium silicate in the other components of the "crutcher" mixture.

The "crutcher" mixture is spray-dried in a stream-operated spray tower, which is about 10 meters high and 3 meters in diameter, by pumping the mixture at a pressure of about 25 kp / cm 2 through a nozzle about 1 mm-in diameter into the dryer. air (with a temperature of about 30 ° C at the inlet and 11 ° C at the outlet) for au; form a product which is substantially or substantially in the range 0.125 - 4.76 mm, which product is cooled to around room temperature and sieved so that it will be substantially completely (above 99%) within said size range.

Alternatively, the screening is performed to particle sizes that are within the narrower ranges of 0.125 - or 0.149 - - 2.38 - or - 3.36 or - 4.76 mm. In all these cases the grains of the base detergent composition have a comparatively high bulk density, about 0.55 g / ml and are free-flowing, this free-flowing ability being about 80% or more of that of dry sand of comparable particle size.

On the base grains with a sieve size of 0.125 - 4.76 mm, 20 parts of Neodofså3 - 6.5 are sprayed in a liquid state at room temperature (25 ° C) while these base grains are kept in motion in an inclined cylinder mixer to constantly give new surfaces.

The particles on which Neodofs 23 - 6,5 are sprayed as a mist in the form of droplets with diameters of about 1 mm are initially at a temperature of about 25 ° C, but this temperature can be raised and the temperature of Neodo š 23 ~ 6.5 can also be raised, usually to about 35-45 ° C, to promote rapid penetration of the detergent into the interior of the porous and cellular globular particles. This spraying is carried out within a period of about 8 minutes, after which perfume is applied to the grains (by spraying) and a proteclytic enzyme powder with a particle size between 0.149 and 0.250 mm is dusted on the surfaces of the particles still kept in the mixing cylinder. , each of these procedures taking about 3 minutes. The grains are then cooled to room temperature or slightly above, but not more than 30 ° C, to avoid unnecessary loss of volatile perfume components by evaporation. The final product, which is sieved to a size of 0.125 - - 4.76 mm (or 0.149 - 2.38 mm), has the desired high bulk density and very good free-flowing properties and is "bottled", packaged and stored in a warehouse ready for distribution. When the product is tested after storage, it turns out to be a satisfactory household detergent, which is useful for washing in both hot and cold water, and leaves surprisingly little or no carbonate residue on the washed materials and does not make them hard (boardy) .The product remains free-flowing during storage. does not coalesce in any remarkable way and does not show poor dispersibility properties during storage.The pH of a 0.07% solution thereof in wash water is about 9.5, which is an ideal pH for proteolytic enzymatic action, which helps the detergent composition to clean and remove stains from washed fabrics, whether they are synthetic (nylon, polyester and blends of natural and synthetic materials with permanent pressure) or natural fabrics (cotton).

The product described is significantly superior to a number of other detergent compositions in which the ratios of carbonate to bicarbonate are outside the previously stated ranges. Thus, when instead of a ratio of carbonate to bicarbonate of 1: 1 (weight ratios) this ratio is increased to 3: 1, with the total content of carbonate plus bicarbonate, the cleaning ability of the composition in a standard test is with a 0.07% product concentration, using wash water with a hardness of 150 ppm, calculated as calcium carbonate (mixed magnesium and calcium hardness in a ratio of 2: 3), when washing test tissues soiled with a standard dirt, significantly inferior to the cleaning ability of the preferred compositions according to the invention, in which the same total amount of carbonate and bicarbonate is used and in which the ratios of carbonate to bicarbonate are 2: 1, 1: 1 and 1: 3, although the cleaning ability of said composition is better than that obtained with a detergent composition which is fortified with carbonate only. These results are obtained when the washing is done in hot water (49%) and in cold water (21%), but the improvements in cleaning ability are greater in hot washing water. When the carbonate content is 60% and there is no bicarbonate in the product (originally nothing was added to the crutcher mixer or all the bicarbonate added was decomposed into carbonate), and if the removal of dirt observed is taken as a basis, then at 45W% sodium carbonate and 15% sodium bicarbonate (with all the other components still present) increases by 6.8 cleaning units after washing the test tissues at 49 ° C and 1.3 units at 21 ° C; at 40% and 20% of the respective compound, these readings are +9.7 and +2.3, respectively; at 30% and 30% of the respective compounds, the readings are + 14, 1 and + 5.5; at 15% and 45% of the respective compounds they are +13, 1 and +2.0; _ and at 0% and 60% of the respective compounds these readings are +8.9 and +1.0.

In a variation of the above experiments, the silicate is omitted from the crutcher mixer and subsequently added as aqueous sodium silicate (Britesil H-20 containing 20% water) before the addition of the nonionic detergent (preferred), after the addition of the nonionic detergent or Some products before and some after.The products obtained are also good household detergents with a high bulk density and are sufficiently free-flowing to be commercially acceptable.In cases where the percentage of silicate, which it is desired to use in the preparation, is greater than 15% and V sometimes greater than 10%, at least a portion of the silicate is often added retrospectively due at least in part to problems with increased viscosity of the "crutcher" mixture containing the large proportions of silicate. 19 vsoasøz-9 Although it is preferred to add the nonionic detergent afterwards to the grains shortly after preparation and also to add any other components afterwards Enter of the product which is not present in the spray-dried base grains, this can also take place after aging of the base grains for a period of from 20 minutes to several days without losing their absorbency. In such cases it may be desirable to heat the grains prior to the application of the nonionic detergent, but the correct choice of nonionic detergent type with respect to melting point can be avoided.

In a modification of the example described above, instead of the sodium carbonate and sodium bicarbonate powders, sodium sesquicarbonate and Wegscheider's salt were used as an additive to the crutcher mixer, with additional sodium carbonate being added when Wegscheider's salt was used and sodium bicarbonate sodium bicarbonate being added. exploited.

The hydration water in the sodium sesquicarbonate is also taken into account when determining the amount of deionized water to be mixed with the carbonate and bicarbonate and other auxiliary additives in the crutcher mixer, so instead of charging 40 parts sodium bicarbonate and 22 parts sodium carbonate, when Wegsche salt was used, 53.3 parts of Wegscheider's salt and 8.7 parts of sodium carbonate (59 parts of deionized water) and when sodium sesquicarbonate was used such a batch constituted 52.3 parts of sodium sesquicarbonate (containing 8.3 parts of hydration water) and 18 parts of sodium bicarbonate , the water to be added to the "crutcher" mixer being reduced from 59 to 50.7 parts The products prepared using such different starting materials have the same characteristics as those previously described and produced by the same methods after the bet of the "crutcher" mixer.

Although silicate, enzyme, fluorescent bleach, pigment and perfume are desirable components of the present composition (and various other auxiliary additives, such as those previously mentioned, may also be included), they are not essential to the preparation of a useful detersive product. Thus, when left out, the grains produced by spray drying of a described "fragrance" mixture under said conditions have essentially the same characteristics, i. slightly more porous, and by spraying on them nonionic detergent they can be converted into a useful detergent. However, the product containing silicate shows greater grain strength and is better suited for commercial use. Instead of the silicate, a phosphate-free, silicate-free product may have included therein filler salts or other builder salts, such as sodium sulfate, sodium chloride or borax or other such materials and possibly in some additional quantities, up to the 30% previously mentioned for the sodium perborate content of bleach detergent, may be included. When such larger proportions are present, the proportions of other components are reduced in proportion thereto. The products produced still have the desired characteristics previously indicated.

Example 2 Products according to the recipe given in Example 1 are prepared by utilizing different initial proportions of sodium carbonate and sodium bicarbonate and by modifying the conditions of the drying tower accordingly so as to effect greater or lesser decomposition of sodium bicarbonate, e.g. -from 10 to 70%. Instead of using 40 parts of sodium bicarbonate and 22 parts of sodium carbonate, for example, these amounts can be changed to 45 and 17; sow and 12; 35 'and 27 or intermediate proportions, while the tower conditions (temperatures, residence time) are changed to increase or decrease the decomposition of the bicarbonate. The final products have essentially the same properties as those obtained for the preferred embodiment of the invention as described in Example 1. 21 I in 7308892-59 Example> 3 Percent a Nonionic Dotergent (condensation product of higher fatty alcohol having 12 to 13 carbon atoms with polyethylene oxide with 6 to 7 moles of ethylene oxide per mole of higher fatty alcohol 20.0 b Mixed sodium bicarbonate-sodium carbonate scrubber containing 66.5% sodium bicarbonate, 30% sodium carbonate and 3.5% water, comprising at least 10% Wegscheiderite 65.0 ^ c Aqueous sodium silicate (Na 2 O: SiO 2 = 1: 2, containing 18% H 2 O) 10.0 d Fluorescent white matter 2.0 Sodium carboxymethylcellulose 1.0 e Proteolytic enzyme 1.5 Ultramarine blue 0.2 Perfume _ 0.3 100.0 Va Neodog §23 - 6.5, manufactured by shell Chemical Company b šnowlite II manufactured by Applied Chemical Corporation in accordance with the procedure of U.S. Patent 3,944,500 c Britesil H20 manufactured by Philadelphia Quartz Corp. d Tinopag§5BM manufactured courtesy of Ciba ~ Geigy Corp. e Alcalase manufactured by Novo Industries, Inc.

The mixed sodium bicarbonate and sodium carbonate mixed particle salt particles having particle sizes previously described in this specification and containing ranges around 20% Wegscheiderite together with sodium bicarbonate 7808892-9 for 0220 r and sodium carbonate are charged at room temperature (2500) to the components of the product in an inclined drum or cylinder with an inclination of about 8 ° which rotates at a speed of about 40 revolutions per minute. The aqueous sodium silicate particles have sizes (effective diameters) in the range 0.149 - 4.76 mm, but the rest of the composition's content of particulate solids is more finely divided and is normally in the range 0.095 - 0.250 mm. in comparable experiments, however, the particulate auxiliaries, with the exception of the pigments, are also in the range 0.149 - 4.76 mm and similar results are obtained.

After the various particulate solid components of the product have been premixed for a period of about 1-3 minutes, the nonionic detergent is sprayed on the moving surfaces of the particles for a period of about 3 minutes, after which the mixing in the drum is allowed to continue for another 5 minutes. The nonionic detergent is sprayed in the form of droplets which are largely in the range 0.149 - 0.297 mm and at a temperature of 25 ° C, which conditions are sufficient for penetration of the grains on which the detergent is sprayed. The perfume is then sprayed on the product for a period of about 1 minute and the resulting detergent composition is packaged and stored ready for distribution and sale. The particles of the product are in the range 0.42 - 4.76 mm, its bulk density is about 0.7 g / ml in the unpacked state and the free flow rate is about 80% of that of sand with comparable particle size.

The stored composition does not bake in and does not form remarkable lumps during storage, and when the package is opened after 3 months of storage under average ambient conditions, the detergent easily drains out of the package and the bulk density is still found to be around 0.7 g / ml.

When the detergent composition is subjected to appreciation of actual properties and washing tests or practical washing tests, it is found that it is non-formative, free-flowing, non-caking and with acceptable cleaning ability for commercial uses, and shows more favorable in comparison with products containing tripolyphosphate as detergents and which have similar levels of active ingredients. The carbonate does not form excess alkalinity due to the presence of the bicarbonate, which buffers the carbonate and results in a wash water having a pH of about 9.5 at both 0.07% and 0.15% product concentrations. Due to the comparatively low content of carbonate, the product is also safe for commercial marketing and is not considered intolerably dangerous when swallowed by small children due to an accident.

In a comparative experiment, finely divided sodium carbonate and sodium bicarbonate powders with particle sizes in the range 0.053 - 0.088 mm are used and agglomerated to a particle size in the range 0.42 - 4.76 mm by a preliminary treatment with 5% by weight of a 20% cereal starch paste (aqueous) which is sprayed on moving particles of the powdered carbonate and bicarbonate in the same mixing drum as previously described for a period of about 3 minutes, the drum moving at low speed, e.g. 10 revolutions per minute. The resulting product is a useful detergent at the same concentration as used in the previous experiments (a quarter cup or about 45 g per 65 liters of washing water in the cylinder), when washing a batch of about 4 kilos of soiled clothes, but is not as free-flowing as the previously described detergent. When only sodium bicarbonate is used as a starting builder salt, the product does not wash as well as the described preferred product and when the carbonate alone is used, the product is more alkaline than desirable and is not as free-flowing. However, the carbonate-containing composition can be used as a detergent in applications where higher pH values can be tolerated, although it would not be as acceptable in the retail trade as the preferred products of the present invention due to its comparatively poor dispersibility properties, higher pH and relative toxicity when swallowed in an accident. 7soas92Ä9 'l 24 Example 4 Percent Snowlite I - 70.0 Aqueous sodium silicate (Na2O: SiO2 = 1: 2 containing 18% H2O) ° ~ 10.0 Neodo fi®25-7 "20.0 100.0 The snowlite particles are charged at room temperature to the inclined drum used in Example 3 or to comparable double-jacketed V-mixers or Patterson-Kelley mixers, and the aqueous silicate, preferably having approximately the same particle size, is added to the drum while mixing for a period of about 2 The mixture is allowed to proceed for a further minute to mix the silicate uniformly with the carbonate-bicarbonate particles. For a further period of 5 minutes, the nonionic detergent is then sprayed at a temperature of about 30 ° C on the moving surfaces of the particles. the product is an excellent concentrated high-performance phosphate-free detergent which is useful for washing laundry at a concentration of 0.05 - 0.2% in the washing water (0.07% and 0.15% was used for the most part). a in top-loading washing machines. The product has a bulk density of about 0.6 g / ml and is free-flowing after normal storage, having a free-flowing rate of about 80% of that of sand of similar particle size. Such a free-flowing rate is superior to that of most spray-dried high-performance detergent compositions commercially marketed today. Comparable products are prepared using NeodolÉä5-ll and Alfonic l6l8- -65 instead of NeodofÉÖ5-7, but these nonionic detergents are added at elevated temperatures, e.g. 45 ° C, to promote penetration into the interior of the base particles for reasons previously stated.

When the sodium silicate is omitted, attention is paid to the loss of its reinforcing effect as well as the loss of its anti-corrosion effect, but the product produced, with additional Snowlite I replacement silicate, is a useful detergent with acceptable dispersibility, bulk density and storage density. for a variety of uses.

Example 5 Percent Snowlite I ': 35.0 Snowlite II' 35.0 Neodol® 23 - 6.5 20.0 Aqueous sodium silicate (as in Examples 3 and 4) 10.0 100.0 The manufacturing procedure of Example 4 is followed by except for the two different Snowlite products are premixed for a period of about 2 minutes. The resulting product is an excellent high performance detergent, which is free-flowing, non-sticky, non-caking during storage and which has a desirable comparatively high bulk density (0.6 g / ml).

Example 6 The compositions of the products according to the preceding examples are varied É 10%, É 20% and É 30% within the limits or ranges provided and similarly the procedures are varied with respect to times and temperatures. The manufactured products are within the specified ranges for spreadability properties, bulk density and particle size and the products have satisfactory detersive properties for their intended uses.

Claims (6)

7808892-9 26 _; P a t e n t k r a v 1.; Free-flowing phosphate-free particulate high-performance detergent composition with a bulk density of at least 0.6 g / ml and a particle size in the range of 0.125 - 4.76 mm, characterized in that it comprises spray-dried particles, all containing alkali metal carbonate and alkali metal bicarbonate alkali metal carbonate to bicarbonate in the range of 2: 1 to 1-5 and having in these particles an absorbed detersive proportion of a normally liquid or pasty, water-soluble nonionic detergent containing polyoxyethylene groups on a compound having a hydrophobic hydrocarbon chain and one or more active hydrogen atoms, which composition contains 40 to 90% by weight of the mixture of alkali metal carbonate and alkali metal bicarbonate, 10 to 30% by weight of nonionic detergent and 3 to 15% by weight of moisture. Detergent composition according to claim 1, characterized in that said nonionic detergent is represented by the formula R0 (C2H4O) nH, where R is the residue of a linear saturated primary or secondary alcohol having 10 to 18 carbon atoms and n is a integers from 3 to 20, which alkali metal bicarbonate is sodium bicarbonate, the weight ratio of Na2CO3: NaHCO3 in the particles of mixed sodium carbonate and sodium bicarbonate is in the range of 1: 0.8 - 1: 3, and the weight proportions of the mixture of sodium carbonate and sodium bicarbonate and the nonionic detergent amounts to 50 - 75% and 15 - 25%, respectively. Detergent composition according to claim 2, characterized in that said nonionic detergent is a condensation product of a fatty alcohol having 10 - 18 carbon atoms and 5 - 12 moles of ethylene oxide, that the proportion of nonionic detergent is 18 22% by weight, the proportion of the mixture of sodium carbonate and sodium bicarbonate amounts to 55-65% by weight and that the proportion of moisture amounts to 3.5 -a 12% by weight. Detergent composition according to claim 2, characterized in that it further comprises »from 3 - 20% by weight of sodium silicate with a Na 2 O: SiO 2 ratio in the range 1: 1, 6 - 1: 3.2. 5. A process for preparing a free-flowing, phosphate-free, particulate, high-performance detergent composition having a bulk density of at least 0.6 g / ml and a particle size in the range of 0.125 - 4.76 mm, characterized by the steps of spray drying an aqueous mixture of alkali metal carbonate and alkali metal bicarbonate for the production of cores containing said carbonate and bicarbonate in a weight ratio of 2: 1 to 1: 5 and admixture in desia particles of a normally liquid or pasty, water-soluble, nonionic detergent containing polyoxyethylene groups on a compound with a hydrophobic hydrocarbon chain and one or more active hydrogen atoms, which detergent is in a liquid state so that the detergent can penetrate into the interior of the cores to form free-flowing particles containing 40-90% by weight of said mixture of carbonate and bicarbonate, 10 - 30% by weight of nonionic detergent and 3 - 15% by weight of moisture. 6. A method according to claim 5, characterized in that said nonionic detergent is sprayed on a moving bed of spray-dried cores.