FR2500474A1 - BASIC PEARLS DRIED BY ATOMIZATION AND THEIR APPLICATION IN DETERGENT COMPOSITIONS - Google Patents

Abstract

FREELY DRIED SPRAY PEARLS, WHICH ARE USEFUL AS A DETERGENT OR FOR THE MANUFACTURE OF A PARTICULAR SYNTHETIC NON-IONIC ORGANIC DETERGENT COMPOSITION CONTAINING DETERGENT ADJUVANTS, CONTAINING A WATER-SOFTENING ALUMINOSILICATE () BENTONITE AND A HYDROSOLUBLE DETERGENT ADJUVANT, AND MAY CONTAIN A HYDROSOLUBLE SYNTHETIC ORGANIC DETERGENT AND A SMALL PROPORTION OF HYDROSOLUBLE SILICATE, PREFERABLY EXCLUDED. BASIC PEARLS AND DETERGENT COMPOSITIONS THUS FORMULATED HAVE CHARACTERISTICS OF REDUCED ALUMINOSILICATE DEPOSIT, DUE TO THE PRESENCE OF BENTONITE AND THE ABSENCE OR LOW PROPORTION OF HYDROSOLUBLE SILICATE, THE COMPOSITION OF THE PEARLS MAINTAINED IN SPECIFIED RANGES.

Description

The present invention relates to basic pearls

  free flowing spray dried, which are in-

  interesting to use in the manufacture of a composite

  non-ionic, synthetic organic detergent, parti-

  cular, loaded. It also relates to compositions

  free flowing detergents spray dried.

  More particularly, the invention relates to such

  pearls and compositions which contain certain proportions

  tions (in the ranges indicated) of an aluminosilicate as a water softening agent, for example a

  zeolite, bentonite and a hydro- detergency builder

  soluble. The product obtained exhibits characteristics of lesser zeolite deposition in comparison with products of the prior art containing similar proportions of aluminosilicate as water softener. These products

  of the prior art also normally contain pro-

  notable portions of water-soluble silicate and generally

  they do not contain bentonite.

  In recent years, aluminosilica-

  your insolubles serving as water softeners, for example-

  full of hydrated zeolites, were used as adju-

  detergents of detergent compositions for laundry. Initially, a new one. interest in zeolites appears to have been stimulated by the need to produce

  detergent formulations not containing phosphates.

  Trisodium nitrilotriacetate and other acid salts

  of nitrilotriacetic acid (NTA), which have been suggested as potential substitutes for phosphates, in particular oentasodium tripolyphosphate, which have been used to a large extent in laundry detergent compositions containing detergency builders, have been suspected in some areas of 'be harmful, and

  as a result, for years, the compositions con-

  holding NTA have not been marketed in the United States.

  There has never been any serious doubt that the phos-

  phates are harmless to humans and recently

  The ban by the United States authorities on the use of NTA in detergents has been lifted. As a result, although some non-phosphate detergent formulations continue to be manufactured for use in areas near lakes and rivers, where phosDhate tends to provide a nutrient medium for algae growth and thus may cause some eutrophication of these waters, detergent compositions containing phosphate and / or NTA

are marketed again.

  Although zeolites, preferably zeolite A and better still hydrated zeolite 4A, have constituted detergency builder salts in detergent compositions without phosphate or NTA, they have now also been shown to be useful components of detergent compositions and pearl beads. improved base containing phosphate (s) and / or NTA. Typically, about 6 to 12% water-soluble sodium silicate has been used in blender mixtures from which spray dried base beads or detergent compositions are to be made. Silicate was used

  for its binding effect on the other components of the

  the, this bond ensuring the formation of stable pearls, and it was found that it favored the production of a structure of internal crosslinked pearls. It also serves as an anti-corrosion additive that prevents chemical attack on aluminum parts of washing machines and other devices with which the detergent solution may come into contact. However, in the proportions previously used, for example 8 to 10% O of the finished product, it has been observed that the combination of the water-soluble silicate and

  zeolite in the blender resulted in production

  tion of aggregates of these materials in spray-dried pearls, these aggregates having the disadvantage of

  deposit on washed items with a tendency to af-

  damaging the appearance of colors. Thanks to the pre-

  invention, using certain proportions of

  zeolite, bentonite and hydro- detergency builder

  soluble, with little or no water-soluble silicate,

  obtains spray dried beads having a sta-

  sufficient mechanical bility to be commercially

  acceptable and having zeolite deposition characteristics

  reduced tick (or reduced deposition characteristics of zeolitesilicate aggregate). Even in the presence of a small proportion of silicate, it seems that bentonite helps to

  neutralize the tendency of zeolite and silicate to react

  gir producing a larger particle than the zeolite normally present, and thus an undesirable deposit of

  zeolite or zeolite-silicate particles on the fabrics

  above washed is prevented or reduced. In addition, compositions containing bentonite disintegrate and disperse much more easily in the wash water, again

  it seems because of the presence of bentonite. An au-

  The advantage of the invention, when little or no silicate is used, resides in the fact that the formulations containing carbonate and / or bicarbonate do not require the presence of anti-gelling materials preventing

  excessive thickening of the mixer mixture. These addi-

  tifs are generally not necessary when the char-

  main detergent age is phosphate and when there is little or no carbonate and / or bicarbonate, but for phosphate-free compositions, which often contain appreciable amounts of carbonate and / or bicarbonate, the removal of anti-gelling materials is clearly advantageous in terms of manufacturing and

economic point of view.

  The prior art relating to deter-

  gentes, fabric softeners and composites

  softening detergent teaches that various detergent compositions can be made which contain one or more of the following ingredients: zeolite, bentonite, silicate, phosphate, NTA, compounds

  quaternary ammonium (fabric softeners), and other compounds

  generally with a synthetic organic detergent

  that, but although the descriptions contain enumerated-

  long rations of almost all the materials that have

  been used for any purpose, in the composi-

  detergent and softener, they do not contain clear indications or suggestions of the detergent compositions of the present invention, and this is particularly

  particularly true with regard to the compositions contained

  with little or no soluble silicate. Descriptions do

  seem not to recognize the importance of bentonite con-

  holding enough "lubrication" water between its plates, and they do not emphasize the combination of binding and disintegration effects attributable to

  "hydrated" bentonite. Likewise, a large number of the formu-

  those of "reference" contain appreciable proportions of sodium sulphate, an additive, perhaps to improve the physical properties of the particles produced, but this is useless for the manufacture of the compositions of the invention which, consequently, can include more

  high levels of active ingredients (including adjuvants

detergency).

  According to the present invention, dried pearls

  by free flowing atomization, useful as deter-

  gent or for the manufacture of a particulate synthetic nonionic organic detergent composition containing

  detergency builders, these detergents having

  characteristics of less particle deposition due to the presence of bentonite and a low content of water-soluble silicate or the absence of such a silicate in spray-dried pearls, include, by weight, 60% of aluminosilicate softening water, 2 to 40 X of bentonite, containing a sufficient quantity of moisture to facilitate the dispersion of the bentonite so as to inhibit the deposition of aluminosilicate on the washed linen, with 60% of water-soluble detergency builder or a mixture - mixture of such adjuvants, 0 to 30 0 of organic detergent

  water-soluble synthetic and 0 to 5% water-soluble silicate

  luble. The aluminosilicate can be a zeolite having a

  significant exchange capacity of the calcium ion, bento-

  nite has appreciable swelling power in water and

  contains a sufficient proportion of moisture to facilitate

  liter the disintegration of its connections between plates during-

  that the detergent beads, alone or as a mixture with other detergent components, are placed in water, the water-soluble detergency builder or the mixture of such builders is a polyphosphate, a nitrilotriacetate

  or a carbonate, and there is no water-soluble silicate.

  The invention also relates to detergent compositions

  made by spray drying pearls of the form

  mule indicated with the presence of an anionic detergent in the mixer mixture or by atomization of a nonionic detergent in liquid form on the beads free of

  detergent shaken or beads do not contain

  providing only relatively small amounts of detergent

  anionic or mixture of anionic detergents. Metals

  diapers of these compositions, mixed anionic and nonionic detergent compositions are also useful

  and may have better washing properties.

  The zeolites used include the crystalline, amorphous and mixed crystalline-amorphous zeolites, of natural or synthetic origin, which have a fairly rapid action and are effective enough to neutralize

  hardness ions due to calcium in the wash water.

  Preferably, these materials can react quickly enough with calcium ions so that, alone or in combination with other water softening compounds in the detergent, they soften the wash water before

  that harmful reactions of these ions with other com-

  components of the synthetic organic detergent composition

  do not appear. The zeolites used can be charac-

  terized as having a strong ion exchange capacity

  calcium, which is normally around 200 to 400 milli-

  equivalent grams or more of carbonate hardness

  cium per gram of aluminosilicate, preferably 250

  at 350 mg eq / g. Likewise, they preferably have a

  tesse of elimination of the residual hardness from 0.02 to 0.05 mg of CaCO3 / liter in one minute, preferably 0.02 to 0.03 mg / l and less than 0.01 mg / 1 in 10 minutes, these proportions being expressed on the basis of anhydrous zeolites. Although other ion exchange zeolites can also be used, normally the particles

  finely divided synthetic zeolite filler used

  Sees in the implementation of the invention have the formula: (Na20) x (A1203) y (SiO2) zW H20 in which x is equal to 1, y is between 0.8 and 1.2, preferably 1 approximately, z is between 1.5 and 3.5, preferably 2 to 3 or approximately 2, and w is between

  between O and 9, preferably 2.5 to 6.

  The zeolite must be a carbon exchange zeolite

  monovalent ions, i.e. it must be an aluminosilicate of a monovalent cation such as sodium, potassium, lithium (when possible) or other

  alkali metal, ammonium or hydrogen (sometimes). From Dréfé

  rence, the monovalent cation of the molecular sieve zeoliti-

  that is an alkali metal cation, especially sodium

  or potassium, preferably sodiumn.

  The crystalline types of zeolites which can be used as satisfactory ion exchangers in the invention, at least in part, include zeolites having the following crystal structure groups: A, X, Y, L,

  mordenite and erionite, types A, X and Y being preferred.

  Mixtures of these zeolitic molecular sieves can

  They can also be useful, in particular when there is a type A zeolite. These crystalline types of zeolites are well known in practice and are described more particularly in the work "Zeolite Molecular Sieves", by Donald W. Breck, published in 1974 by John Wiley & Sons. Commercially available standard zeolites having the above-mentioned structural types are listed in Table 9.6 on pages 747-749 of Breck's work. These zeolites are known in practice. Some, as well as other suitable zeolites, have been described in numerous patents in recent years

  to be used as fillers of deter-

  gentes. The zeolite used in the invention is usually synthetic and it is often characterized by a network of pores of substantially uniform dimensions between approximately 0.3 and 1.0 nm, often 0.4 nm (normal), this dimension being in particular determined

  by the unitary structure of the zeolitic crystal. Preferably

  rence, it is of type A or similar structure, in

  particular described on page 133 of the aforementioned book-

  born. Good results have been obtained using a type 4A zeolitic molecular sieve in which the

  the monovalent cation of the zeolite is sodium and the di-

  pore size of the zeolite is about 0.4 nm, these

  zeolites being preferred. These zeolitic molecular sieves

  which are described in U.S. Patent No. 2,882,243 which refers to it as Zeolite A. Zeolite molecular sieves having ion exchange and water softening properties can be made in a dehydrated or calcined form, which contains about 0 or 1.5% to about 3% moisture, or in a hydrated or water-loaded form, which contains

  additional binding water in an amount of

  about 4 to about 36% of the total weight of the zeolite, depending on the type of zeolite used. The hydrated water-containing form of the zeolitic molecular sieve (preferably hydrated to about 15 to 70%) is preferable in the noise of the present invention when a crystalline product is to be used. The manufacture of these crystals is well known in practice. For example, in the preparation of Zeolite A, indicated above, the hydrated zeolitic crystals which are formed in the

  crystallization medium (for example an alumino gel

  hydrated amorphous sodium silicate) are used without undergoing dehydration at high temperature (calcination at a water content of 3% or less), which is normally carried out in the preparation of such crystals intended for

  be used as catalysts, for example cataly-

  cracked sisters. The crystalline zeolite, in fully or partially hydrated form, can be recovered

  filtered by crystals from the crystalline medium

  filtration, then air drying at room temperature.

  ambient temperature, so that their water content is between approximately 5 and 30%, preferably between approximately 10

  or 15 and 25%, Dar exemplifies 17 to 22%, for example 20%.

  However, the moisture content of the zeolite of the type of molecular sieve used may be lower, as previously described, in which case the zeolite may be hydrated during mixing and other treatments,

  Preferably, the zeolite must be in the fine state.

  ment divided, the final particle diameter reaching microns, for example 0.005 or 0.01 to 20 microns, preferably 0.01 to 15 microns, for example 3 to 12 microns, in particular 0.01 to 8 microns, for example 3 to 7 microns,

  if it is crystalline, and 0.01 to 0.1 microns, For example-

  ple 0.01 to 0.05 microns if it is amorphous. Although the final particle sizes are much smaller, the zeolite particles generally have sizes between 0.037 and 0.149 mm, preferably 0.044 and 0.105 mm. Zeolites with smaller dimensions often form a harmful powder and those with

  larger dimensions may not be fixed enough

  ment and correctly with carbonate, bicarbonate, phosphate and / or nuclei of particles based on NTA on which they can be distributed with bentonite, by

  example in gel or film state, during drying

  chage by atomization of a mixture to form the pearls

basic.

  The bentonite used is a colloidal clay

  (aluminum silicate) containing montmorillonite.

  Montmorillonite is a hydrated aluminum silicate in which approximately 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which

  varying amounts of hydrogen, sodium, potassium-

  sium, calcium, magnesium and other metals can combine more or less. The type of bentonite which is most useful for the manufacture of the basic pearls of the invention is that which is known as sodium bentonite (or bentonite from Wyoming or from the west) which is

  normally an intangible powder of light color to cream

  me which, in water, forms a colloidal suspension having strongly thixotropic properties. In water, the

  the bulking power of clay is usually com-

  taken between 3 and 15 ml / gram, preferably 7 to 15 ml / g, and its viscosity, at a concentration of 6% in water,

  is generally between 3 and 30 mPa.s, preferably

  rence 8 to 30 mPa.s. Preferred swelling bentonites of this type are sold under the registered trademark "Mineral Colloid", as industrial bentonites, by Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials which are the same as those previously sold under the registered trademark "Thixo-Jel" are selectively mined and enriched bentonites, and those which are considered to be the most useful are available under the designation "Mineral Colloid NO 101" etc, corresponding to the designations "Thixo-Jel NI 1, 2, 3 and 4 ". These materials have a pH (concentration of 6% in water) of between 8 and 9.4, a maximum content of free moisture of approximately 8% and densities of approximately 2.6, and as regards the sprayable qualities,

  about% pass through a sieve with an opening of 0.074 mm.

  We prefer the Wyoming bentonite enriched as a compound

  sant compositions of the present invention, but other

  very bentonites are also useful, especially when they constitute a minor proportion of the bentonite used. Although it is advantageous to limit the maximum free moisture content, as mentioned above, it is even more important to ensure that the bentonite used contains sufficient free moisture, most of which is considered to be present between the adjacent bentonite plates, to facilitate rapid disintegration of bentonite and all adjacent materials of the particles when these particles or detergent compositions containing them are brought into contact with water, e.g.

  washing. It has been found that at least about 2%, preferably

  at least 3% and more preferably 4% or more water must be present in the bentonite initially, before it is mixed with the other components of the pearls in the mixer, and this proportion must

  also be present after spray drying.

  In other words, overdrying to the point or bento-

  nite loses "internal" moisture can significantly reduce

  the usefulness of the compositions of the invention. When the te-

  bentonite humidity is too low, the ben-

  tonite can no longer prevent the formation of silicate aggregate

  cate-zeolite and it does not favor the unpleasant-

  gation of the pearls in the washing water. When the bento-

  nite has a satisfactory moisture content, it pre-

  feels a percentage of exchangeable calcium oxide

  taken between about 1 and 1.8 and, compared to magnesium oxide, this percentage is normally between 0.04 and 0.41. Typical chemical analyzes of these materials are 64.8-73.0% SiO2, 1.4-1.8% A1203, 1.6-2.7% MgO, 1.3-3.1% CaO, 2.3 to 3.4% Fe203, 0.8 to

  2.8% Na2O and 0.4 to 7.0% K20.

  The water-soluble detergency builder or a mixture of

  a range of such adjuvants can consist of one or more of the conventional materials which have been used

  as detergency builders or proposed for this purpose.

  These materials include inorganic and or-

  ganics, and mixtures thereof. Among the inorganic charges

  the ones we prefer are the various phosphates,

  preferably nolyphosphates, for example tripoly-

  phosphates and pyrophosphates, such as tripolyphosphate

  pentasodium and tetrasodium pyrophosphate. Nitrilo-

  trisodium triacetate (NTA) preferably used in the form of monohydrate, and other nitrilotriacetates,

  such as disrilic nitrilotriacetate, are adjuvants

  preferred water soluble detergents. Tripoly-

  sodium phosphate, sodium pyrophosphate and NTA can be used in hydrated form, but even when anhydrous compounds are used, bentonite and zeolite appear to inhibit caking due

  of subsequent hydration. Naturally, carbo-

  nates such as sodium carbonate, are adjuvants

  useful detergents and can be advantageously used

  lized, alone or in combination with bicarbonates, such as sodium bicarbonate. When using the

  polyphosphates, it may be better to have pre-

  sence of sodium pyrophosphate with sodium tripolyphosphate in a proportion of 1:10 to 10: 1, preferably 1: 5

  5: 1, the total proportion of the two adjuvants being

  about the same as that mentioned for the tripolyphos-

  sodium phate. Other hydro detergency builders

  soluble considered effective include the various other inorganic and organic phosphates, borates, e.g. borax, citrates, gluconates, EDTA and iminodiacetates. Preferably, the various fillers are in the form of their alkali metal salts, sodium or potassium salts, or mixtures of these salts,

  but sodium salts are normally more preferred.

  In some cases, for example when making neutral to slightly acidic detergent compositions,

  acid forms of detergency builders, in particular

  as organic detergency builders, can

  be beneficial, but normally the salts are

  neutral or basic. Silicates, preferably sodium silicate having a ratio of 1: 1.6 to 1: 3.0, preferably 1: 2 to 1: 2.8, for example 1: 2.35 or 1: 2, 4, also serve as detergency builder salts but because of their strong bonding properties and their characteristic of aggregation or agglomeration with

  zeolite particles, these are special cases of adjuvant

  vants and it is preferable not to use them in the compositions of the invention. However, given

  that they have anti-corrosion properties, particularly

  particularly important when the detergent solution must

  be used in washing machines or other appliances

  reils in contact with aluminum parts, they can sometimes be present in limited proportions. In such cases, it may be preferable that the hydrated sodium silicate particles are added after the fact, so that they do not react or agglomerate with the zeolite particles during mixing and spray drying. Although sodium sulfate and sodium chloride and other filler salts are not endowed with detergency builder properties, they can sometimes be used in detergent compositions for their filler characteristics. In addition to increasing the volume and weight of the product to facilitate measurement, they also sometimes improve the stability and physical properties of the beads.

  detergent composition in which they are incorporated.

  However, since the compositions of the invention

  are satisfactory without charges, these are pre-

  completely avoided or may be present

  at a minimum, usually at a practical minimum.

  In general, - the detergent (s) used are nonionic or anionic or both, but amphoteric or ampholytic detergents can also be used, in particular in combination with nonionic and / or

  anionics in the compositions of the invention. Of the-

  Cationic tergents can serve as fabric softeners in these products, but normally are not spray dried with anionic detergents, due to an unwanted interaction that may take place. These classes of materials are well known and have been described repeatedly in the detergent technique. Because they are not components

  preferred compositions of the invention, a description

  more detailed in this brief is considered

as inappropriate.

  Although various non-ionic detergents with satisfactory physical characteristics can be

  used, including the oxidation products of

  of ethylene and propylene oxide with each other and with hydroxylated bases, for example nonylphenol and alcohols of the Oxo type, it is very preferable that the nonionic detergent is a condensation product of ethylene oxide and a higher fatty alcohol. In these products, the fatty alcohol greater than 10 to 20 carbon atoms, preferably 12 to 16 carbon atoms, and the nonionic detergent contains approximately 3 to 20 or 30

  ethylene oxide groups per mole, of reference 6 to 12.

  More preferably, the nonionic detergent is a detergent in which the higher fatty alcohol has about 12 or 13 or 15 carbon atoms and which contains 6 or 7 or 11 moles of ethylene oxide. These detergents are manufactured by Shell Chemical Company and are available under the registered trademarks Neodol D 23-6.5 and 25.7. Among their particularly attractive properties, in addition to a

  good detergent power on oily stains from items

  washing keys, we can mention a relative melting point

  tively low, but noticeably higher than the temperature

  rature ambient, so that they can be atomized on the base beads in the form of a liquid which solidifies. Various anionic detergents, usually in the form of sodium salts, can be used, but those

  which are preferred are higher alkylbenzene sulfonates

  linear laughers, higher alkyldulfates and

  polyethoxylate sulfates of higher fatty alcohols. Befor-

  In the higher alkylbenzenesulfonate, the higher alkyl is linear and has from 12 to 15 carbon atoms, for example 13, and is a sodium salt. The alkyl sulphate is preferably a higher fatty alkyl sulphate of 10 to 18 carbon atoms, preferably of 12 to 16 carbon atoms, for example 12, and is also used as the sodium salt. The alkyl (sup) ethoxamersulfates likewise have 10 or 12 to 18 carbon atoms, for example 12, in the upper alkyl group, which is preferably a fatty alkyl, and the ethoxy content is normally from 3 to 30 ethoxy groups per mol, preferably 3 or 20. Again, sodium salts are preferred. Thus, it can be seen that the alkyl groups are preferably fatty or linear higher alkyl groups from 10 to

  18 carbon atoms, the cation is preferably the so-

  dium, and when a polyethoxy chain is present, the

  sulfate is at its end. Other anionic detergents

  that are useful include olefin sulfonates and higher paraffinic sulfonates, for example sodium salts in which the olefin or paraffin groups have 10 to 18 carbon atoms. Particular examples of the preferred detergents are tridecylbenzenesulfonate

  sodium, tallow-alcohol-polyethoxy (3 EtO) sodium sulfate-

  dium and sodium hydrogenated tallow alcohol sulfate.

  In addition to the preferred anionic detergents mentioned,

  others from this well-known group may also be pre-

  feeling, especially in secondary proportions only-

  ment, compared to those previously described. Likewise, mixtures can be used and, in some cases, these mixtures can be superior to detergents alone. The various anionic detergents are well known in the art and are described in detail on pages 25 to 128 of Surface Active ACents and Deterqents, Vol. II of Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, Inc. Various adjuvants may be present in the mixer mixture from which the base beads or detergent compositions may be spray dried, or these adjuvants may be added after the fact, the choice of the mode of addition being often determined by the physical properties of the adjuvant, its resistance to heat, its resistance to degradation in the aqueous mixture medium, and its volatility. Among

  the most important adjuvants, we can cite a poly-

  acrylate which has been shown to be useful in adjusting the

  pearls and the apparent density, present

* effects of dispersion, anti-deposition and anti-rede

  position on the compositions of the invention and favors

  maintaining the fluid and homogeneous mixer mixture.

  The polyacrylate, present in the preferred base beads of the present invention, is a polyacrylate

  low molecular weight, generally between

  about 1000 and 5000, preferably 1000 and 3000, and better still 1000 and 2000 or about 2000. The polyacrylate can be partially or completely neutralized, for example about half or a third being present in the form of

  sodium polyacrylate. Although polyacrylates modi-

  Since they are substituted for the sodium polyacrylate described, including certain other polyacrylates of alkali metals and hydroxylated polyacrylates, it is preferable that these substitutions are limited to a proportion

  secondary of the material and preferably polyacry-

  late is an unsubstituted sodium polyacrylate. These

  materials are sold by Alco Chemical Cor-

  poration under the trademark "Alcosperse". The poly-

  sodium acrylates are available in the form of

  liquids or powders of light amber color, their

  lutions with a solids content of around 25 to 40%,

  for example 30%, and the pH of these solutions or a so-

  30% aqueous solution of the powder lying between

  about 7.5 and 9.5, for example about 9. These materials are completely soluble in water and have been used as dispersants. They were found to have

  the ability to fix calcium ion and they have been used

  to prevent deposition of calcium compounds

  insoluble in aqueous solutions. In the drying process

  atomization of the invention, small amounts

  ties (or percentages) of these materials promote strength

  pearls with better porosity.

  When the mixture contains carbonate and / or

  bicarbonate and silicate, even if the amount of silicon

  cate is weak, the mixture may tend to freeze

  proud or "freeze" in the mixing device, in particular

  particularly if, due to manufacturing delays, the

  diaper is maintained longer than the normal 30 minutes

  males. In these cases, when the silicate is present,

  processing aids are also preferably pre-

  smells in the mixture (and consequently in the pearls

  base and detergent composition completed) in order to

  fish for premature solidification or gelation.

  Citric acid and magnesium sulfate are preferably present. Instead of citric acid, soluble citrates such as sodium citrate can be used and, although it is preferable to use anhydrous magnesium sulfate, one can also use

  its various hydrates, in particular the Epsom salts.

  Also, magnesium citrate can be substituted.

  Instead of the preferred anti-gelling system, other suitable means and systems can be used to

  maintain the fluid mixture, for example sesquicarbo-

  sodium nate, used in place of part of the carbo-

  nate or sodium bicarbonate. However, although these processing aids are useful in many cases, a feature of the present invention is that they do not need to be used in the manufacture of

  preferred base beads from which silicate is omitted.

  Although certain adjuvants, for example a fluorescent brightening agent, a pigment, for example ultramarine blue, titanium dioxide, and an inorganic filler salt may be added to the mixer, other adjuvants such as perfumes, enzymes,

  bleaching agents, certain dyes, bacteria

  fungicides, fabric softeners and favourants

  risking the flow can often be atomized or otherwise-

  mixed with the base pearls or the spray-dried detergent composition, provided that they are not adversely affected by temperatures

  spray drying and also

  tion that their presence in pearls dried by atomi-

  does not inhibit the absorption of the non-ionic detergent

  when it must be atomized afterwards on the pearls.

  However, for stable and normally solid adjuvants, mixing with the starting suspension in the mixer is also possible. So, we are considering

  as Pigments and fluorescent brighteners, when

  that they are used, are normally present in the mixture from which the basic pearls of the invention

  are atomized. The preferred coloring agent is blue

  tremer but other stable pigments and dyes can be used together or in its place. Because the spray-dried base beads of this

  invention can sometimes be without coloring, general-

  due to the use of natural mineral materials

  actual, the color from such a coloring agent may

  be adversely affected. It has been found that the incorporation

  tion of a small proportion of titanium dioxide in the mixture favored the maintenance of the desired color of the coloring agent and the presence of titanium dioxide does not seem to have a detrimental effect on the appearance of the laundry washed with the compositions detergents made from

  basic pearls containing it.

  Among the fluorescent brightening agents, the one that is preferred is Tinopal 5BM, in particular in the form

  extra concentrated. However, various other flight attendants

  cotton, for example those sometimes designated by CC / DAS brightening agents derived from the reaction product of cyanuric chloride and the disodium salt of diaminostilbene-disulfonic acid, can also be used, including their variants as regards

  the substituents on the triazine and aromatic rings.

  This class of optical brightening agents is known in

  detergent technique and is most often used

  when the final product does not contain any ingredients

  whitening health. When it is desired that the detergent composition contain a bleaching agent, for example sodium perborate or other oxidizing agent, the stable brightening agents are generally incorporated in the mixer mixture. Among these, mention may be made of benzidine-sulfone-disulfonic acids, naphthotriazolylstilbene-sulfonic acids and benzimidazolylic derivatives. Polyamide brighteners, which may also be present, include aminocoumarin and diDhenyl-pyrazoline derivatives, and polyester brighteners that can also

  be used, include naphthotriazolyl-stilbenes.

  These brightening agents are normally used under the

  form of their soluble salts, but they may be in-

  products in the form of the corresponding acids. Cotton brighteners generally contain dominant proportions of the brightening agent systems used.

  Enzyme preparations, which are normal-

  added afterwards to the basic pearls because

  that they are heat sensitive, can be any

  as various commercially available products, including Alcalase, manufactured by Novo

  Industri A / S, and Maxatase, both of which are protea

  its alkalines (subtilisin). We sometimes prefer Maxazyme

  375. Although alkaline proteases are the most common

  frequently used, amylotic enzymes such as

  alpha-amylase, can also be used. The ingredients

  Sections cited generally contain active enzymes.

  ves in combination with an inert powder vehicle such as sodium or calcium sulfate, and the proportion of active enzyme can vary widely, generally from 2 to 80% of the commercial preparation. In the present

  memory, the proportions designated are those of the prepa-

  enzymatic rations, not their only active part-

  is lying. The perfumes used, which are generally thermo-

  sensitive and may contain volatile substances, including a solvent, such as an alcohol, are normally made of synthetic perfumes, sometimes in mixture

  with natural components, and they generally include-

  alcohols, aldehydes, terpenes, fixatives and other normal components of perfumes. Flow promoting agents, for example special clays, which are sometimes added to detergent products, although often useful for improving the flowability and reducing the tackiness of the various compositions, are unnecessary in the present case, perhaps in part due to the presence of bentonite and the absence or

  the very limited presence of silicate. However, they can-

  can be added if desired to further improve flowability. Although it has been found that detergent compositions made from

  basic pearls of the invention did not require pre-

  sence of anti-corrosion additive to replace silicate

  missing, the invention contemplates using such materials.

  third and she prefers to use stable ones

  under the conditions of mixing and spray drying

  tion and which do not adversely affect these operations.

  These anti-corrosion or antioxidant additives can be organic or inorganic, inorganic materials being normally preferred, and they are preferably chosen for their ability to prevent corrosion of the aluminum parts of washing machines. If it is desired to use a silicate for such a purpose or to use a silicate for its effect of treating the hardness of magnesium ions, a powdered silicate is normally preferable, for example hydrated sodium silicate which is commercially available under the designation Britesil (manufactured by Philadelphia Quartz Co. (Na20:

  SiO2 = 1: 2.4), and is preferably added after the fact.

  However, other normally solid and solid silicates

  lubles, preferably of alkali metals, can also

  be added afterwards to the pearls of this invention

  tion, preferably after absorption of the non-detergent

ionic that needs to be performed.

  When we want the manufactured product to be gifted

  softening characteristics of fabrics,

  Third-party softeners, preferably in the form of dry powder, can also be added afterwards to the base beads in an appropriate manner. This class of materials

  is well known and most often these softening agents

  sants are cationic compounds, in particular quaternary ammonium compounds such as quaternary ammonium halides. We particularly prefer the

  (higher alkyl) - alkylaryl- chlorides and bromides

  and of arylalkyl- (lower alkyl) quaternary ammonium,

  for example distearyldimethylammonium chloride.

  Among the softening materials, that which is pre-

  fère in particular is sold under the registered trademark Arosurf TA-100, manufactured by Sherex Chemical Company, Inc. These compounds have antistatic and antibacterial properties but, if desired, other antibacterial adjuvants can also be used, preferably incorporating them into the product by addition after the fact. Naturally, water is present in the mixing apparatus to serve as a medium for dispersing the various other components of the pearls, and part of the water,

  in free and hydrated form, is in the product.

  During pearl drying, the initial moisture content

  midity, which is about 25 to 60%, can be reduced to

  about 5 to 15%, this moisture content being sufficient

  health so that the dried pearl bentonite contains

  at least 2% and preferably at least 4% humidity.

  It is preferable to use deionized water, so that its content of hardness ions can be very low and so that the metal ions which can promote decomposition of organic matter can be

  present in the mixture, the base pearls and the

  are minimized, but can be replaced

  place with tap water. Normally, the hardness content of this water is less than 150 ppm, as

  CaCO3, preferably the hardness content is lower

  less than 100 ppm and better still less than 50 ppm.

  The proportions of the various components of pearls

  base and beads of the detergent composition

  sprayed are such that they flow freely and, for the base beads, are sufficiently

  absorbent with a non-ionic detergent applied to them

  qué in the liquid state so that the deter-

  gentes flow freely satisfactorily. Likewise, of course, the detergent compositions are

  effective cleaning agents, adjuvants

  tergence present acting to help the detergent

  organic in its detersive effect in aqueous solutions

  its compositions, and it is important that the resulting products are such that they do not cause deposits

  pests of zeolite particles (or zeolite aggregates-

  silicate) on washed items. The particles of zeo-

  lite and bentonite particles, although insoluble,

  do not adversely affect color or lighten

  do not shine colored laundry as loaded, due

  of their small particle sizes, but these

  color rations can occur when approvals

  zeolitic gats form and are large enough to be retained in the tissues and also to be easily noticeable by the eye, especially when

  significant proportions are not removed from the ma-

  all washed by drying air exhaustion during automatic drying. It is also advantageous for the base beads and the detergent composition beads

  have an appropriate bulk density and color.

  It has been found that satisfactory beads can

  to achieve the above-mentioned goals contain by weight 5 to 60% of water-softening aluminosilicate (zeolite), 2 to 40% of bentonite (having the desired moisture content) and 5 to 60% of water-soluble detergency builder or mixing such adjuvants. A proDortion of 0 to 30% of water-soluble synthetic organic detergent and / or O

  5% water-soluble silicate May also be pre-

  feel good, but often we prefer not to use them. Preferably, the spray dried beads contain

  3 to 15% humidity, preferably 5 to 12%, and generally

  7 to 10%, including the water of hydration present.

  This water of hydration can be present in zeolite, NTA, Phosphate, carbonate, bicarbonate and magnesium sulfate, when it exists in the formula, in addition

  of the one between the bentonite plates.

  The moisture content shown includes hydro-

  tation even highly retained, for example that which is still retained by the zeolite even after several hours of distillation of a dispersion in toluene. In some cases, for example when the concentration of zeolite in the product is high, so that about

  12 to 15% humidity may be present in the zeo-

  lite as water of hydration, the moisture content of dried pearls Dar atomization can reach 20% and occasionally about 25%. However, normally, for good flowability of the product and to reduce the sticky nature and the formation of lumps, this upper limit is around 15%, in particular when the final detergent composition contains a

  significant proportion of non-ionic detergent. The percent

  The indicated zeolite level includes the hydration water therein. It is possible to make useful beads

  spray dried with a low moisture content

  less than 3% provided the bentonite has a sufficient quantity

  of water associated with it for the above reasons

  recently exposed, but due to the strong moisture attraction of the zeolite and due to the action of other hydratable materials which may be present, it has generally been found that a minimum of 3% of moisture is

  necessary to avoid loss of internal moisture

  bentonite syrup, which seems to "lubricate" the plates and facilitate their separation when a product which

  contains is dispersed in water. Likewise, when

  brick of anhydrous products, even when sufficient moisture is retained in bentonite, they may be physically unstable, pulverizing more easily and being subject to attrition and disintegration. The apparent specific mass of the spray-dried pearls can be between 0.2 and 0.9 g / cm

  Apparent specific masses located in the par-

  lower tie of this range are easier to get

  when there is no silicate in the mixture of

  spray dried gor and little or no detergent no

  ionic is only absorbed by the beads. The densities appear

  higher annuities appear when non-ionic detergent is applied to porous beads and when a

  a certain amount of silicate is present in the pearls.

  These lighter products have specific masses

3 3

  taken between 0.2 and 0.5 g / cm, often from 0.3 to 0.4 g / cm and the heavier particles have apparent specific masses of 0.6 to 0.9 g / cm, generally from 0 .6 to 0.8

  g / cm. The particle sizes of the pearls are generally

  generally between 0.149 and 2.00 mm (pass through a 2.00 mm sieve and remain on a 0.149 mm sieve), better still from 0.250 to 2.00 mm. In preferred formulations, the proportion of bentonite and zeolite is between 1: 4 and 1: 1, the adjuvant ratio of water-soluble detergency to zeolite is between 1: 2 and 3: 1 and the

  ratio of the bentonite to the hydro- detergency builder

  soluble is between 1:10 and 1: 1. More preferably, these ranges of ratios are from 1: 3 to 2: 3, 2: 3 to 2: 1 and from

  1: 6 to 1: 2, respectively. As a percentage, the composi-

  tions preferably contain 10 to 40% of a partially hydrated sodium zeolite, preferably containing

  15 to 25% by weight of water of hydration and having a capacity

  calcium ion exchange city of between 200 and 400 mg equivalent hardness of calcium carbonate per gram of anhydrous zeolite, 2 to 35% bentonite, which is of a type having a swelling power of 7 to 15 ml / g and a viscosity of between 8 and 30 mPa.s at a concentration of 6% in water, 10 to 50% of alkali metal salt adjuvant with water-soluble detergency or a mixture of these salts, O to 25% of detergent organic anionic

  synthetic water-soluble and O at 3% hydroso- silicate

  luble, this silicate, when present, being a sili-

  alkali metal cate having an al-

  hug: silicon dioxide between 1: 1.6 and 1: 3, preferably from 1: 2 to 1: 2.8. Pearl formulations

  most preferred include 15 to 35% zeo-

  lite A, 5 to 20% enriched Wyoming bentonite, 20 to% sodium salt, water-soluble detergency builder

  or mixtures thereof, O to 20% organic anionic detergent

  water-soluble synthetic nique and O% silicate of so-

  dium. Although carbonate and bicarbonate are useful as detergency builders in the manufacture of the base beads of the invention, particularly those over which a nonionic detergent is to be atomized, polyphosphate and / or nitrilotriacetate builders are often preferable for spray dried beads, whether or not they contain an anionic detergent, and whether or not a nonionic detergent is applied to them. Preferred formulas of NTA base beads as a single or main soluble detergency builder contain 15 to 35 or 40% hydrated zeolite, 5 or 10 to 20% bentonite and 20 to 50 or 60%

  from NTA. When a phosphate, for example tripolyphos-

  sodium phate, must be the hydro-detergency builder

  main soluble, the same proportions of zeolite and bentonite can be used, but generally a higher quantity of phosphate can be present (compared to NTA). Preferably, for the base pearls on which a nonionic detergent must be atomized or for comparable compositions based on carbonate or a mixture of bicarbonate and carbonate (having a carbonate: bicarbonate ratio in the base pearls dried by atomization between 1 and 3 approximately), there is no water-soluble synthetic organic detergent and little or no water-soluble silicate. When bicarbonate and carbonate are used together in these formulations, they make up a total of 20 to 40% of the base pearls and, when carbonate is used alone,

  it normally constitutes 10 to 30%.

  When an anionic detergent or other suitable organic detergent is introduced into the blender

  so as to form a spray-dried detergent product

  tion, its preferred proportions are from 3 or 5 to 30%, preferably 5 to 25%, and better still from 10 to 25% for example 10%, 15% of this product, and the detergent is preferably chosen from the group comprising a linear sodium alkylbenzenesulfonate in which the alkyl group contains 10 to 18 carbon atoms, a sodium fatty alcohol sulfate in which the alcohol has

  10 to 18 carbon atoms, and a fatty alcohol ethoxylate-

  sodium sulfate in which the fatty alcohol has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per mole, and mixtures thereof. Currently,

  preferred detergents are tridecylbenzene sulfo-

  linear sodium nate and alkyls preferably have

12 to 16 carbon atoms.

  When a non-ionic detergent is absorbed on the spray dried base beads (and sometimes a small proportion can be absorbed in the spray dried detergent beads), its proportions are generally between 5 or 8 and 30%, preferably 10 to 25%, for example 15%, 20%. In this case, the preferred nonionic detergent is a condensation product of 6 to 12 moles of ethylene oxide and a

  mole of a fatty alcohol greater than 12 to 16 carbon atoms

bone.

  When a polyacrylate is present in the compound

  detergent or basic pearls, its proportion

  normally varies between 0.05 and 1%, and its molecular weight

  the area is preferably between 1000 and 5000.

  Because the presence of anionic detergent in the spray-dried base beads can inhibit the production of a bead structure that absorbs a desired proportion of non-ionic detergent, it may be preferable to produce dried detergent beads

  by atomization of a type within the framework of the

  vention and mix them with the basic pearls of the in-

  on which a non-ionic detergent has been

  bet, so that a greater proportion of detergent

  non-ionic may be present in the finished product.

  To do this, we can use ranges of proportions,

  for example 1:10 to 10: 1, 1: 5 to 5: 1 and 1: 2 to 2: 1 of the com-

  posers mentioned, according to the characteristics that are desired for the final product. It is advantageous that the apparent specific masses of the beads before mixing are approximately the same, preferably 0.1 g / cm 3 and the particle dimensions must be approximately the same,

  normally 0.149 to 2.00 mm to prevent separation

tion of the final mixture.

  The proportions of adjuvants and milking agents

  basic pearls and atomically dried detergent

  are normally limited to 20%, preferably 1 to 10% and more preferably 3 to 7%. The proportions of processing aids, when magnesium sulfate and citric acid are used, are normally between 0.5 and 2% of magnesium sulfate, preferably 1 to 1.5%, and 0.1 to 0.5% sodium citrate, preferably 0.1 to 0.3%. Regarding fluorescent coloring, pigmentation and brightening agents,

  when present, their proportions go normal-

  ment of 0.05 to 0.6% of coloring pigment, for example ultramarine blue, preferably 0.2 to 0.4%, and 0.1 to 4% of fluorescent brightening agent, preferably 1 to 3%. The

  proportion of titanium dioxide (as a white pigment

  normally) 1 to 3%, preferably 1.5 to 2.5%. If a dyeing agent or agents are used in place of a coloring pigment, its proportions are generally from 1 to 50%, in particular from 5 to 20% of those of the coloring pigments. For the spray dried base beads preferred in the present invention, which may contain

  NTA or polyphosphate as additives with or without de-

  synthetic organic tergent, or may contain such a detergent with any of the filler salts

  preferred water-soluble mentioned above, the specific

  apparent specificity is between 0.2 and 0.8 g / cm3,

  aluminosilicate is hydrated zeolite A, bento-

  nite contains at least 3% moisture on the basis of anhydrous bentonite, the water-soluble silicate, if present, is sodium silicate having a Na20: SiO2 ratio of 1: 2 to 1: 2.8, and the moisture content of the pearls is 3 to 12%. When the pearls contain

  NTA or other sodium salt of nitrilotriaceous acid-

  tick, with or without synthetic organic detergent, the bentonite: zeolite ratio is from 1: 6 to 1: 2, that of NTA: zeolite is from 1: 2 to 2: 1, and that of bentonite: NTA is 1: 6 at 1: 2, and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, and silicate are respectively from 10 to 40%, 2 to 25%,

at 40% and O at 5%.

  When preferred NTA-containing beads also contain an anionic organic detergent

* synthetic, with the above-mentioned zeolite A, bento-

  nite and humidity, and with or without soluble silicate, they preferably contain 5 to 30% detergent

  synthetic anionic organic, which is an alkylbenzene-

  linear sodium sulfonate in which the alkyl- radical

  le has 10 to 18 carbon atoms, a fatty alcohol sulfate

  sodium in which alcohol has 10 to 18 carbon atoms

  bone, or a fatty alcohol sodium ethoxylate sulphate in which the fatty alcohol has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per mole, or a

  mixture comprising two or more of them, the adju-

  Before water-soluble detergency is a sodium salt of a-

  nitrilotriacetic acid (NTA), the proportion bentonite: zeolite is from 1: 6 to 1: 1, that of NTA: zeolite is from 1: 3 to 3: 1, that of bentonite: NTA is from 1:10 to 1: 1 , and that of the synthetic anionic organic detergent: zeolite is from 1: 1 to 1: 4, and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, detergent

  organic anionic synthetic and silicate are res-

  pectively from 10 to 40%, 2 to 25%, 10 to 40%, 10 to 25%

(preferred range) and 0 to 5%.

  For phosphate-containing pearls, with or

  without synthetic detergent, materials and

  ports are identical to the case of the corresponding pearls containing NTA, with substitution of pentasodium tripolyphosphate or tetrasodium pyrophosphate, or their mixture, with NTA, but the percentages are in the respective ranges of 15 to 35%, 5 to 20%, 15 at 40% and O at 5%. Similarly, for the beads containing a phosphate with the presence of an anionic detergent, the materials and ratios are the same as for the beads

  containing NTA and ranges of pros

  percentages are the same except for that concerning

  total oolyphosphate, which is 10 to 50%.

  The ranges of proportions of the various components of the basic pearls in the final detergent composition, when the nonionic detergent (possibly with

  other materials) is added afterwards can be done

  cilately calculated from those given for pearls

  base, subtracted from the proportions of the detergent and

  very materials which are added afterwards to the pearls.

  Conversely, the proportions of the components of the pearls (and

  from them, the mixing formula) can be cal-

  abutments according to the formulation of the final product. So, for example, by calculating the formulation ranges of the

  final product from the pearl ranges, if the com-

  final detergent position contains only a non-ionic detergent so that the final product contains 20%

  non-ionic detergent, according to the various ranges indicated

  As for the components of the base beads, the ranges of proportions in the final detergent composition obtained as a product can be calculated by multiplying

  by 0.8, i.e. (100-20) / 100. Likewise, when the propor-

  tion of non-ionic detergent (in the formulas in the-

  which is the only additive to pearls), is between

  8 and 25% of the detergent composition, the multiplicates

  teurs are from 0.92 to 0.75. The final percentage of

  gent nonionic in the product is 8 to 30%, pre-

  ference from 10 to 25%, and better still from 15 to 22%, for example around 20%, but in certain cases, for certain types of products, proportions of 8 to 13% may be preferable. Normally, the percentage of perfume in the final product is between 0.1 and 1 X, preferably 0.5 to 3%, better still 1 to 2%, and if a hydrated sodium silicate must be added afterwards, its proportion is

  generally not less than 1% and is preferably li-

  about 5%, although in some cases up to 10% can be used. When a fabric softener is

  present in the final product, its proportion is normal-

  from 3 to 12%, preferably from 5 to 10%.

  Basic beads and dry detergent beads

  the invention is spray dried

  wetting from an aqueous mixture originating from a mixture

  geur which normally contains 40 to 70% or about 75% of solids, preferably 50 to 65%, the rest being

  water, preferably deionized water, as before

  as described (but you can also use tap water. The mixture is preferably made by adding

  successively the various components in the assu-

  rant a suspension as miscible as possible, easily pumpable and not forming a deposit for spray drying. The order of addition of the materials may vary, as the case may be, but it is very advantageous to add the silicate solution (possibly) last, and if not last, at least after the addition of any combination

  materials or processing aids that prevent gelation

  or a "solidification", for example the above acid

  stick and magnesium sulfate. Normally, it is preferable that all or almost all of the water is added to the mixer first, preferably at about the manufacturing temperature, after which the processing aids (if any) and other secondary components , comprising the pigment and the fluorescent brightening agent, and the polyacrylate, optionally, are added, followed by the zeolite, the detergency builder

  water-soluble, anionic detergent (if any), bento-

  nite and silicate (if any). Generally, during these additions, each component is mixed thoroughly before the addition of the next component, but the modes of addition may vary depending on the case, so as to allow simultaneous additions when this is possible. Sometimes the additions of the components can be done in two or three parts and sometimes different components can

  be mixed beforehand before addition, in order to

  speed up the mixing process. Normally the speed and

  the mixing intensity is increased as the

  edition of materials. For example, low speeds can be used until the zeolite and the soluble additive have been mixed, after which the speed can be

  be increased to an average value and then to a high value

  vee, which is preferably before, during or after

  the addition of any silicate solution.

  The temperature of the aqueous medium in the mixer

  is usually room temperature or a tempera-

  high ture, normally 20 to 80C, preferably 30 to or 800C, better still 40 to 7o0C. Environmental heating

  of the mixer can promote the dissolution of hydro-

  soluble in the mixture and thereby increase the miscibility,

  but the heating, when carried out in the mixture

  geur, can slow down the production rates and can sometimes favor a hardening of the mixture. An advantage of the presence of processing aids in the mixture (in particular in the presence of soluble silicate)

  is that they ensure the formation of non-gel suspensions

  strong at higher and lower temperatures. Temperatures above 80WC (and sometimes those above 700C) are generally avoided due to the risk of decomposition of one or more of the components of the mixture, for example bicarbonate

  sodium. Likewise, in some cases, the temperatures

  solids in the mixer increase the upper limits of the solids content, probably

  due to the insolubilization of the components which

normally lifie or harden.

  The mixing times in the mixer for obtaining

  Good suspensions can vary widely, lasting as short as 5 minutes in small mixers and for suspensions with higher moisture content, up to 4 hours in some cases. The mixing times required to homogenize all of the components of the mixture in a medium can be as short as 10 minutes, but in some cases it may take

  hour, although 30 minutes is an upper limit

  appreciable laughter. Based on the initial mixing times, mixing periods normally range from 15 minutes to two hours, for example 20 minutes to 1 hour, but the mixture must be such that it is mobile, neither gel nor gel. hardens, for at least one hour, preferably two hours, and better still for 4 hours or more after the end of the manufacture of the mixture,

  and preferably it must be mobile for 10 to 30 hours

  res before being pumped into the atomization tower to

  face other cases o other manufacturing problems

cation may be encountered.

  The mixed suspension, with the various salts and other components dissolved or in the form of particles to

  the uniformly distributed state, is transferred from the ma-

  usual in an spray drying tower, which is normally located near the mixer. Suspension

  is brought from the bottom of the mixer to a displacement pump

  positive, which discharges it under high pressure into spray nozzles located at the top of a tower

  conventional tomization (against the current or against the current)

  in which the droplets of the suspension fall through a hot drying gas, generally the combustion products of fuel oil or natural gas

  o the droplets are dried in the form of pearls

  sirée. During drying, part of the bicarbonate may

  if present can be transformed into carbonate, with release of carbon dioxide which, jointly

  polyacrylate present in the mixture being dried

  ge by atomization, improves physical characteristics

  as pearls obtained, so that they better absorb liquids, for example the liquid nonionic detergent, which can be atomized afterwards on them thereafter. However, the zeolite, bentonite and polyphosphate (possibly present) of the base pearls also seem to promote the absorption of liquid and

  the production of a solid pearl, and the polvacrylate amé

  enhances the characteristics of the pearls and promotes

  faster, which increases the efficiency of the tower.

  After drying, the product is sieved

  desired dimension, for example 0.140 or 0.250 to 2.00 mm, and

  is ready to apply the non-ionic detergent by ato-

  bet, if it is a basic pearl formula, the

  pearls in the hot or cooled state (at the temne-

  ambient). However, the non-ionic detergent is generally at a high temperature, for example 30 to 600C, for example 50oC, to ensure that it is liquid;

  however, upon cooling-to am-temperature

  biante, it is advantageously solid, often resembling a waxy solid. Even if at room temperature, the non-ionic detergent is somewhat sticky, this characteristic does not lead to a final composition that does not flow well due to the fact that the detergent penetrates under (or into) the surface of the beads. Detergent no

  ionic, applied to mobile or shaken pearls of ma-

  known, in the form of a spray or drop-

  lettes, is preferably a condensation product of ethylene oxide and a higher fatty alcohol, as previously described, but other nonionic substances can also be used. The enzyme preparation (designated by "enzyme", although it is known that it contains

  also a support), hydrated silicate and other ad-

  powdered juices can be sprayed on the particles

  detergent, and a perfume and any other liquid to be added afterwards can be sprayed on them at a

  any time before or after the addition (s)

of the powder (s).

  Spray-dried detergent, pearls

  spray dried base and detergent compositions

  your obtained ones contain little or no sili-

  cate from the mixture, although some of the silicate

  in solid form can be added afterwards. The sili-

  powdered cate added afterwards, if used, do not

  not seem to react with the zeolite, so that

  Zeolite-silicate gats which tend to deposit on the washed articles are reduced, in comparison with such deposits coming from products in which the silicate is added in the mixer. Although in the absence of bentonite, silicate is normally used for its

  anticorrosive and pearl setting effects, the ingredients

  Detergent compositions of the invention give acceptable beads and have shown that they do not corrode aluminum parts. In addition, bentonite does not adversely affect the stability of the product and, in fact, appears to assist in holding the beads together, making them resistant to crushing and spraying during transmort and use. The presence of the

  bentonite greatly improves the properties of the compound

  final detergent position, ensuring higher rates of fixation of calcium ions and a lower

  deposit of zeolite on washed fabrics. When the poly-

  Low molecular weight acrylate is present, the base beads are more porous and better absorb non-ionic detergent in the liquid state, without excessively reducing the bulk density of the product. Considering that the

  bentonite is a clay and serves as a binder, we can expect

  tend to deposit formation and gelation. In

  consequence, the characteristics of least deposit, the ab-

  gence, and the rapid dispersion of the product are surprising, and constitute important results of the present invention. What is also considered to be important results of the presence of the low proportion of polyacrylate in spray-dried pearls is the best spray drying of

  basic beads of the invention and deter-

  gentes, and better absorption of non-io- detergent

  liquid nique by the basic pearls.

  The following examples illustrate the invention without

  limit it. Unless otherwise specified, all temperatures

  tures are expressed in OC and all parts are in

  weight in the examples and in the whole description

  tion. When the weights and proportions of zeolite are indicated, they relate to the normal hydrate used, since it is considered that the water of hydration of the zeolite does not leave the zeolite and is not part of the medium of

  aqueous solvent in the inventive mixed operations

  tion. Likewise, part of the water present in the per-

  the base and the detergent compositions is present in the form of water of hydration of the zeolite. Similarly, the humidity associated with bentonite can also be considered not to be free moisture, but because of the lower percentage present, this distinction

  can often be overlooked, in general.

  EXAMPLE 1 (Comparative) A charge of 100 parts of mixer mixture for spray-dried base pearls considered to be satisfactory for the subsequent transformation into

  a detergent composition by adding a detergent or-

  synthetic non-ionic ganic is carried out by introducing

  sant in the mixer 47 parts of deionized water at a temperature of about 270C, then successively, and first with -mixing at low speed, adding 1.04

  part of Tinopal 5BM Extra Conc. (Ciba-Geigy), 0.13 per-

  tie of powdered ultramarine blue, 0.07 part of poly-

  sodium acrylate (Alcosperse 107D), 21.11 parts of Linde hydrated zeolite 4A (20% water of crystallization), 6.25 parts of Mineral Colloid No 1 (bentonite), 15.75 parts of sodium bicarbonate industrial grade), 7.74 parts of sodium carbonate (natural anhydrous sodium carbonate) and 0.91 parts of titanium dioxide (anatase). During the mixing of the various components, the speed of the mixer is increased to an average value and finally to a high value and, after the addition of all the components, which takes about 15 minutes, the mixing is continued for about 1 hour ( in

  some cases for as long as 4 hours),

  in which one part of the water present, for example two to six parts, can be lost by evaporation and can be replaced if desired. During mixing, the suspension of the mixer is continuously mobile and does not gel or solidify. Because the bicarbonate partially decomposes into carbonate during spray drying, the proportions of bicarbonate and carbonate in the formulation may vary, depending on the operating characteristics of the spray tower. About five minutes after all the components of the mixture are present, the mixture is discharged from the mixer to a pump which nominates it at

  pressure of approximately 0.147 MPa at the top of an atomic tower

  counter-current in which the temperature initiates

  tial is around 4300C and the final temperature is

  about 1051C. The essentially mineral base pearls

  rales obtained have an apparent specific mass of approxi-

  ron 0.6 to 0.7 g / cm3, an initial adhesion less than Y, a particle size substantially between 0.250 and 2.00 mm (they are sieved in this

  range), and a fine characteristic of about 15%.

  The moisture content of the pearls is from 1 to 10%, normally closer to 10%, for example 8 to 10%. The base beads flow freely (flow rate of

  %), are non-sticky, suitably porous, however

  dant firm on their surfaces. They can easily absorb large proportions of non-detergent

  ionic liquid without becoming too sticky.

  Detergent products are made from spray dried beads, spray spray on

  the surface of the pearls subjected to shaking of a

  normally waxy nonionic tergent. Neodol 23-6.5 is used, but it can be replaced by Neodol 23-7 or Neodol 25-7. Non-ionic detergent is

  the heated liquid state (at a temperature of about 45 C).

  The atomized quantity is such that it forms a product

  final containing about 20% non-ionic detergent.

  A proteolytic enzyme (Alcalase 1.7T or Maxazyme 375) is applied in powder form to ensure a concentration of 1.5% in the product, and a perfume is sprayed onto the product to give a concentration of 0.25%. The resulting detergent compositions have an apparent specific gravity of approximately 0.7 to 0.8 g / ml and contain approximately 32.45% of zeolite (hydrated), 19.7% of the nonionic detergent, 18.5% of carbonate sodium

  (part of which is produced by decomposition of the bicar-

  sodium bonate), 13.5% sodium bicarbonate, 1.3%

  of free water, 1.4% of enzyme, 1.6% of brightening agent

  rescent, 0.25% fragrance, 0.2% ultramarine blue, 9.6% bentonite, 0.1% sodium polyacrylate and 1.4%

of titanium dioxide.

  The detergent produced, having the above formula, is an excellent detergent for heavily soiled laundry and is particularly useful for washing household laundry

  in automatic washing machines. It is physical-

  aesthetically advantageous and attractive because it does not form dust and flows extremely freely, which allows it to be packaged in glass and plastic bottles with necks

  narrow ol it flows easily to be used.

  The detergent compositions produced, containing hentonite, as described, have better rates of fixing calcium ions, but more importantly, they leave less zeolite residue on the laundry

  washed (in an automatic washing machine at concen-

  usual trations for such products and at temperatures

  normal washing), especially when this

  laundry is dried on a thread, that similar compositions

  milk containing less bentonite and with silicate

  sodium in the spray dried base pearls.

  This difference is accentuated when the wash water

  is very hard, for example 200 ppm, in the form of carbon

  calcium nate, that the wash water is cold, and that

  uses a moderate agitation cycle.

  Basic pearls and detergent composition

  performed are acceptable standards to which the

  very beads and detergent compositions described in the following examples can be measured and to which they compare favorably. Also, the methods of

  manufacturing are essentially the same and are consi-

found to be satisfactory.

  Following the normal process, blender mixes are prepared quickly and can be emptied from the blender also quickly sometimes in as little as five minutes and can be removed from the blender.

  blender in as short a time as ten minutes.

  However, it is often important that the mixtures of the invention can resist for at least an hour in the mixer without gelling or solidifying, because

  sometimes maintenance for such durations meet

  trent in industrial production. The described mixture can be maintained for four hours, and often much longer without gelling or solidifying, which is attributed, at least in part, to the bentonite content and the absence of silicate. This action of bentonite is unexpected because it also exerts a thickening effect on the mixer mixture, but although the mixture can thicken to an appreciable extent, it remains pumpable. Minor components of the melap, such as the fluorescent brightener and the pigment, can be removed and an enzyme and fragrance can be omitted from the final product, although it is very preferable that all of these materials are present. The temperature of the mixture can be modified, for example raised to 520 ° C., and the proportions of the various components can vary by + 10%, + 20% and + 30%, while still being within the ranges previously indicated, and it is possible to obtain usable mixtures which give the pearls and the detergent compositions desired. The solids contents of the mixture can vary within the mentioned range, for example 45 to 65%, and a suitable mixing and spray drying is obtained. Other addition orders in the component mixer can be used, but normally it is advantageous to add the silicate last or almost at the end, and it is preferable that the

  bentonite is also added late in the pro-

  yielded, preferably just before the silicate. In place

  of Zeolite 4A, Zeolites X and Y can be substituted

  killed, as well as other types of Zeolite A. Although it

  is preferable to use the hydrated Zeolite 4A

  about 80% (moisture content about 20%) of this example, various degrees of hydration of the zeolite are acceptable and, in some cases, anhydrous crystalline or amorphous zeolites can be used. By varying the amount of bentonite in the mentioned range, up to 7%, 13% and 19% in the basic pearl, for example, we still obtain interesting products, but those containing larger proportions of bentonite are generally more effective in promoting non-deposition of zeolite on laundry. In some cases, it may be desirable to use even higher percentages of bentonite, within the ranges indicated herein, taking care that the other components of the base beads are such that the beads are

  fluids and are effective detergents. The proportion of bentonite suitable for commercial use depends on

of a number of factors and

  it normally represents a compromise between the decrease

  desired zeolitic residue and the desired effect of

  detergency builder and other functional effects of other components of the detergent composition which are

  may incorporate instead of an increased amount of ben-

tonite.

  The improvement noted in the compositions

  tergentes of this example depositing less residue on the washed linen is verified by a test of the product described in comparison with a control product having essentially the same formulation, but not containing bentonite and containing approximately 8% of sodium silicate in the final product. In this estimate, a Whirlpool Suds Saver model washing machine is used, with periods of

  8 minute wash on a moderate wash cycle. The con-

  concentration of the detergent composition is 0.06%, the washing water has a mixed hardness due to calcium and magnesium, with a total hardness of 200 ppm, in the form of

  calcium carbonate and the water temperature is 240C.

  The washed items are: 100% cotton; 100% polyester 85% acetate and 15% "Nylon"; and 65% polyester and 35%

  cotton. Washing is observed in the wet state and after drying

  chage on a wire (drying on a wire generally gives

  a more visible residue than drying in an automatic dryer

  than). No residue is observed in either case.

  When the detergent composition having the control formula is tested, a moderate residue is observed on all of the

washed samples.

  The results of the practical residue formation test described above are verified by weighing the residue deposited on a cotton twill test material. In this test, the detergent composition of the present invention is filtered through a cotton twill sample, the detergent being in solution-suspension at a concentration of 0.12% in water with a hardness of 200 opm ( as CaCO3) at 240C, and note the weight

  of the residue on the garment, and the comparison is made.

  Thanks to this test, it can be seen that the percentage of

  compared to the witness, is about 75, which

  is considered to represent a significant difference in

Detect washed products.

  The adhesion test, previously mentioned, which measures the stickiness of the detergent product, is a

  test in which 10 g of base pearls (or of compound

  detergent, in some cases) are placed regularly.

  between two watch glasses, both having a diameter of 23 cm, with a weight of 500 g at the top of the upper watch glass (the two watch glasses being turned concave side up). After standing for five minutes, the weight and the upper watch glass are removed and the lower watch glass is inverted, after which the product remaining bonded to this watch glass is weighed. The adhesion percentage is the number of

  grams of product remaining on this multi-watch glass

folded by 10.

  The flow index is that resulting from a flow test in which the volumetric flows

  basic pearls (and in some cases of the fi-

  nal) and standardized Ottawa sand (+0.250 mm, -0.84 mm) are compared by measuring the time required to completely empty a 1 liter bottle of Mason through a circular hole with a diameter of 2.2 cm in a nozzle fixed at its end. The flow index expressed as a percentage is the time necessary for the sand to flow, divided by the time for the test product

flows, multiplied by 100.

EXAMPLE 2

  Basic pearls similar to those of the example

* 1, but containing NTA instead of part of the carbo-

  nate and bicarbonate are made primarily by

  the same process as described in this example. The formula-

  tion only varies by replacing 5 parts of

  zeolite, 12 parts of sodium bicarbonate and 3 parts

  parts of the sodium carbonate of the mixture with 20 parts of NTA in the form of the trisodium salt monohydrate. The NTA

  is added after the sodium carbonate during the operation

  tion of mixture. The basic pearls obtained are not as "dry" to the touch as those of Example 1, but

  flow freely enough. Unlike the com-

  final detergent position containing 19.7% of the detergent

  non-ionic, it suffices to retain 12%, the percent

  final stages of the other components being increased in con-

  sequence. The resulting product is a particular detergent.

  satisfactory area for heavily soiled laundry.

  By varying this formula, 2.5% hydrated sodium silicate is added after coating to the product to

  its anti-corrosion properties and for its ability to

  x the magnesium ions in the wash water. Provided that the silicate has roughly the same particle size

  and the same density, it does not separate from the other compounds

  detergent beads during transport and use

  shopping, and the product obtained meets the existing standards

  for a strong industrial detergent, but a small

  this proportion of zeolite-silicate aggregate can be obtained

served on washed materials.

  In another variant of the formula, 3% silica

  sodium cate having a Na20: SiO2 ratio of approximately 1: 2.4 is incorporated into the final product by adding its aqueous solution to the mixer, together with 1.5% of magnesium sulfate and 0.4% citric acid for

  prevent gelation or hardening in the mixture

  geur. The finished product is a satisfactory detergent

  for very dirty laundry, but it doesn’t deposit any more

  zeolite-silicate gat on the washed materials dried on

  a thread that a comparable formulation to which the sili-

  hydrated sodium cate was added afterwards.

EXAMPLE 3

  We repeat the process of example 2, but with

  replacement of NTA with pentasodium tripolyphosphate.

  The products obtained are good detergents, having an apparent specific mass of approximately 0.8 g / cm 3 (like those of Example 2), but these specific masses can

  vary by adjusting the conditions of the atomic tower

  sation and formulations, so as to be in the range of 0.7 to 0.9, and in some cases the densities can be lowered to 0.3. With the silicate added afterwards, the densities may be slightly higher, in particular in the case of the lower part of the range. The product flows more freely than that of Example 2, but is roughly equivalent as regards

concerns washing power.

  In the above formula and those of the previous examples, an additional proportion of bentonite

  can be added to the blender to obtain

  duits containing 15% (or more) of bentonite. These products

  have even better fixation effects, properties

  Dispersible tees and other better beneficial properties attributable to bentonite and are good preparations of detergents (and base beads). Also, the tripolyphosphate can be replaced, in whole or in part, for example half, by tetrasodium pyrophosphate, and similar satisfactory products are then obtained.

EXAMPLE 4

  A final detergent product is prepared essential-

  also by the method of Examples 1 and 2 containing 30 parts of the zeolite, 30 parts of NTA, 20 parts of the nonionic detergent, 10 parts of bentonite, 5 parts of sodium carbonate, 5 parts of water and 1.3 parts enzyme. This product has a density of approximately 0.5 g / cm3 and constitutes a satisfactory detergent. However, to improve the flowability of the product, it is advantageous that the content of nonionic detergent is reduced to 15% and preferably to 12%. To increase the bulk density to about 0.7, half of the bentonite can be replaced by sodium silicate (Na2o: SiO2 equal to 1: 2.4), added as the last component in the mixer as a 47.5% aqueous solution, and 1.5 parts of magnesium sulfate and 0.4 parts of citric acid can be added correspondingly as anti-gelling agents earlier

  during the manufacture of the mixture. The resulting product

  both has an apparent specific mass of about 0.7 g / cm3 and it can absorb about 20 parts of nonionic detergent without becoming sticky and without its ability to

  the flow is decreased. Although it deposits less

  zeolite-silicate gat that formulations with pro-

  conventional upper silicate portions, aggregates can be detected on the laundry washed with the product and

dried on a wire.

EXAMPLE 5

  Instead of making basic pearls which

  a detergent is applied to form a deter-

  gente, the composition can be spray dried directly from the mixer, a suitable synthetic organic detergent being included in the mixture. Using essentially the same processes as described in Example 1, a mixture is prepared which is dried by

  spray on detergent beads containing 16 parts

  ties of linear tridecylbenzenesulfonate, 20 parts of the zeolite, 12.5 parts of bentonite, 15 parts of NTA,

  parts of sodium carbonate and adjuvants classi-

  ques (dye, fluorescent brightening agent). The bulk density of the spray dried product is 0.3 to 0.8, normally in the lower portion of this range and sometimes as low as 0.2 g / cm. In the manufacturing process, organic detergent is normally added after water. Drying is generally carried out to a moisture content of approximately 8 to 12%. The resulting product preferably has 3 parts of hydrated sodium silicate added afterwards, as well as other normal adjuvants, such as an enzyme and a perfume. It constitutes a satisfactory and powerful detergent which does not deposit harmful amounts of

  zeolite or zeolite-silicate aggregate on washed fabrics.

  Due to the presence of bentonite, the detergent seems to disperse very quickly when added to the wash water and it is considered that at least in part

  this rapid dispersibility in association with the present

  that of bentonite, tends to inhibit the deposition of zeolite.

EXAMPLE 6

  The process of Example 5 is followed, but the NTA is replaced by an equal weight of sodium carbonate

  anhydrous. This product is also a detergent,

being satisfactory.

EXAMPLE 7

  We follow the process of example 5, but we in-

  pentasodium tripolyphosDhate product instead of NTA.

  The product obtained flows particularly freely and constitutes a good composition of organic detergent

  high power synthetic. Although when the sili-

  cate is present, it is preferable to add it afterwards in the form of a hydrated sodium silicate, up to parts of silicate can be added to the mixer, together with the appropriate proportions of magnesium sulfate and citric acid, as described

  in the previous examples, and we can get

  interesting detergent positions, although some

  zeolite-silicate deposition may occur.

  In addition to the conventional materials which can be added afterwards, it is possible to add to the product of this

  example (and to the products of the other examples), pro-

  softening portions of a cationic material, for example 8% dimethyldistearyl ammonium chloride, an amphoteric detergent, for example 5% Miranol C2M

  (1-carboxymethyl-1-carboxyethoxyethyl-2-cocoimidazoli-

  nium-betaine), or a bleaching agent, for example 15% sodium perborate (preferably activated). Naturally, the additions of these materials reduce the proportions of the other components of the final composition and thus change the properties of the compositions

  to some extent, sometimes requiring the use of

  tion of a greater quantity of product in the water of

  wash to achieve the same cleaning effect.

  In Examples 5 to 7, tridecyl-benzene-sul-

  linear fonate can be replaced by an equal weight of sodium lauryl sulfate or sodium lauryl polyethoxy sulfate (3 to 10 EtO) or mixtures of these materials in equal parts, and the products obtained are also

  interesting as detergent compositions. In an ana-

  logue, instead of NTA, we can substitute carbonate,

  a carbonate and a bicarbonate, and a polyphosphate, of the

  sodium trate and / or sodium gluconate, at least in part, for example 1/4 or 1/2, and this results in good detergents.

EXAMPLE 8

  The products of Example 1 and Example 7 (the primary products described first) are mixed in equal proportions to give a final product having

  the characteristics of these two constituent parts.

  Before mixing, the materials to be mixed both have about the same apparent density, about 0.5 g / cm3 and about the same particle size, in the range of 0.250 to 2.00 mm, so as to prevent separation during transport and storage. The

  mixed product is particularly interesting for eli-

  mine oil-based and clay-based soiling on the laundry and it flows freely, it is stable and

  attractive. In some cases, one of the particular subjects

  the starting areas can be dyed or pigmented and the other left in the natural color to obtain special aesthetic effects. In addition to the particle sizes and densities which are about the same, it is preferable that the moisture content is also about the same, for example about 10%, so that there is a slight migration of humidity between the different pearls. In the materials of Example 7, the anionic detergent may be, instead of sodium alkylbenzenesulfonate, a sodium alpha-olefin sulfonate (14 or 15

  carbon atoms in the olefin) or a paraffin-sulfo-

  sodium nate (12 to 15 carbon atoms in the paraf-

  fine), and the mixtures obtained also constitute

useful detergents.

EXAMPLE 9

  By substantially following the process described in Example 1, a mixture is prepared from 36.9 parts of water, 1.2 parts of fluorescent brightening agent (Tinopal BM, extra concentrated), 0.1 parts 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

  about 20%), 20.9 parts of nitrilotriacetate triso-

  monohydrate, 7.4 parts of a 47.5% solution of

  sodium silicate solids (Na20: SiO2 = 1: 2.4), 3.7 per-

  sodium bentonite ties (previously marketed

  under the designation Thixo-Jel N 2), 2.8 parts of carbon

  natural anhydrous sodium nate and 2.1 parts of a mineral compound, which can be used to increase the porosity of the pearls, and as a detergency builder. The mixture

  is spray dried in the same manner as above

  as described, the loss of moisture during drying

being around 45.2%.

  20 parts of Neodol 23-6.5 are sprayed on 78.4 parts of the spray-dried base pearls, with a particle size of between 0.149 and 2.00 mm (sieved). part of high activity proteolytic enzyme, and

  0.3 part of detergent perfume is sprayed on them.

  The final product has a zeolite content of 25%, a te-

  neur in NTA of 30%, a sodium bentonite content of 5% and a solids content of water-soluble sodium silicate of 5%. The moisture content is 5% and the content of active detersive ingredient (polyethoxylated higher fatty alcohol) is 20%. The apparent specific mass is approximately 0.7 g / cm3 and the pH of its 1% solution is

about 10.

  The detergent composition produced by this process is a satisfactory strong non-ionic detergent but it deposits a little more zeolite-silicate aggregate on the

  washed laundry dried on a thread that a corresponding composition

  dante obtained without water-soluble silicate. It is preferred-

  rable that this corresponding composition also contains

  approximately 0.1 to 0.5% of low molecular weight polyacrylate, of the type previously described in this specification. These two products wash the laundry well and are particularly effective for washing in cold water, at least in part due to the bentonite content and the almost instantaneous dispersion observed when

  detergent is added to the wash water (this disper-

  also reduces the reaction time between the sili-

  soluble cate and the zeolite tending to form harmful aggregates).

Claims (24)

  1 - Free flowing beads, dried by   atomization, useful as a detergent or for the manufacture   tion of a non-organic detergent composition   synthetic particle particle containing detergency builders, these detergents having characteristics of less deposition of particles due to the   presence of bentonite and a low sili-   water-soluble cate or the absence of this silicate in the spray-dried pearls, characterized in   what they contain, by weight, 5 to 60% of aluminum   nosilicate as water softener, 2 to 40% of   bentonite, containing a sufficient amount of moisture   tee to facilitate the dispersion of bentonite so as to inhibit an aluminosilicate deposit on the   washing during washing, 5 to 60% of additives   water-soluble tergence or a mixture of such adju-   0-30% synthetic organic detergent   water-soluble and 0 to 5% water-soluble silicate.   2 - Pearls according to claim 1, character-   that when the synthetic detergent hy-   drosoluble is not present, the detergent adjuvant   this water-soluble includes polyphosphate, pyro-   phosphate, orthophosphate, borate, nitrilo-   triacetate, gluconate or citrate or a mixture of two or more of them.   3 - Pearls according to claim 2, character-   laughed at in that they have an apparent specific mass   rent between 0.2 and 0.9 g / cm3 and dimensions   between 0.149 and 2.00 mm, aluminum   water softening minosilicate is a hy-   softening dratée of water containing 15 to 25% in   weight of water of hydration and having a capacity of   age of calcium ions between 200 and 400 milli-   equivalent grams of calcium carbonate hardness per gram of anhydrous zeolite, bentonite is a swelling clay with a swelling power in water of 3 to 15 ml / g, and a viscosity of 3 to 30 mPa.s at a concentration 6% in water, and contains at least 2% moisture relative to the weight of the   anhydrous bentonite, a water-based detergency builder   luble is present and consists of polyphospha-   te, pyrophosphate, orthophosphate, borate, nitrilotri-   acetate, citrate, gluconate, carbonate or bicarbonate, or a mixture of two or more of these, and   the water-soluble silicate is a metal silicate al-   hug (M) having an M20: SiO2 ratio between 1: 1.6 and 1: 3.   4 - Pearls according to claim 3, charac-   terized in that the proportion of bentonite to zeolite is between 1: 4 and 1: 1, the proportion of water-soluble detergency builder to zeolite is between 1: 2 and 3: 1, and the proportion of bentonite to the water-soluble detergency builder is between 1:10 and 1: 1.   - pearls according to claim 4, character-   risées in that they comprise 10 to 40% of zeoli-   te hydrated sodium, 2 to 35% bentonite, which is   of a type having a swelling power included in   tre 7 and 15 ml / g and has a viscosity between 8 and 30 mPa.s at a concentration of 6% in water, 50% of an alkaline salt adjuvant with water-soluble detergency or a mixture of such salts, 0 25% water-soluble synthetic anionic organic detergent   and 0 to 3% of water-soluble silicate.   6 - Pearls according to claim 5, charac-   terized in that they comprise 15 to 35% of zeo-   lite A, 5 to 20% enriched Wyoming bentonite, 50% sodium salt adjuvant water-soluble detergency, or a mixture of such salts, 0 to 20% synthetic anionic water-soluble organic detergent   and 0% sodium silicate, and in that the proportion   tion of bentonite: zeolite is between 1: 3 and   2: 3, that of water-soluble detergency builder: zeo-   lite is between 2: 3 and 2: 1 and that of bento-   nite: water-soluble additive is 1: 6 to 1: 2.   7 - Pearls according to claim 2, character-   in that the water-soluble detergency builder   is chosen from carbonate, bicarbonate, polyphos-   phate or nitrilotriacetate, or mixtures thereof, and bentonite contains at least 3% moisture compared to by weight of anhydrous bentonite.   8 - Pearls according to claim 7, charac-   in that the bentonite contains at least 4%   humidity ', the water-soluble detergency builder   takes nitrilotriacetate and no organic detergent   than water-soluble synthetic or water-soluble silicate- ble are present.   9 - Pearls according to claim 8, character-   in that they contain 15 to 40% of zeolite A   hydrated containing 15 to 25% by weight of hydra water   tation and having an ion exchange capacity cal-   cium which is between 200 and 400 milligrams equivalent hardness of calcium carbonate per gram of anhydrous zeolite, 10 to 20% of bentonite which is an enriched Wyoming bentonite having a power   swelling between 7 and 15 ml / g and a screw   cosity between 3 and 30mPa.s at a concentration   6% in water, and 20 to 60% NTA.   - Pearls according to claim 7, character-   laughs in that bentonite contains at least 4% moisture, the water-soluble detergency builder   includes polyphosphate and no organic detergent   Synthetic water-soluble or hydro-silicate soluble are present.   11 - Pearls according to claim 1, charac-   terized in that they contain 20 to 40% of hydrated zeolite A containing 15 to 25% by weight of water of hydration and having an calcium ion exchange capacity of between 200 and 400 milligrams equivalent of carbonate hardness calcium per gram of anhydrous zeolite, 10 to 20% bentonite which is an enriched Wyoming bentonite having a swelling power of 7 to 15 ml / g and a viscosity of 3 to mPa. s at a concentration of 6% in water, and   60% sodium tripolyphosphate.   12 - Pearls according to claim 2, charac-   terized in that they contain 5 to 30% deter-   gent organic synthetic water-soluble.   13 - Pearls according to claim 12, ca-   characterized in that the organic detergent synthesized   Water-soluble tick is an anionic detergent.   14 - Pearls according to claim 13, charac-   that the anionic detergent is an al-   sodium linear kylbenzene sulfonate in which the alkyl group has 10 to 18 carbon atoms, a fatty alcohol-sodium sulfate in which the alcohol has   10 to 18 carbon atoms, or an ethoxy fatty alcool-   sodium late sulfate in which fatty alcohol has   with 18 carbon atoms and which contains 3 to 30 groups   pes ethylene oxide per molecule or a mixture of two or more of them, and the proportion of this or these anionic detergents in the beads is from 5 to 25%.   - Pearls according to claim 7, charac-   -terized in that they contain 3 to 30% deter-   gent organic anionic synthetic water-soluble.   16 - Pearls according to claim 15, ca-   characterized in that the nonionic detergent is a linear sodium alkylbenzene sulfonate in which the alkyl group has 10 to 18 carbon atoms, a fatty alcohol sodium sulfate in which the alcohol has 10 to 18 carbon atoms, or a fatty alcohol sodium ethoxy sulphate in which the fatty alcohol has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per molecule or a mixture of two or more of them, and the proportion of this or of these   anionic detergents in the beads is 5 to 25%.   17 - Pearls according to claim 7, ca-   characterized in that they do not contain deter-   gent organic synthetic water-soluble nor water-soluble silicate.   18 - Pearls according to claim 2, charac-   terized in that they contain 0.05 to 1% of po-   lyacrylate of molecular weight between 1000 and 5000.   19 - Pearls according to claim 3, charac-   terized in that they have an apparent specific mass   2O yield of 0.2 to 0.8 g / cm3, the aluminosilicate is a hydrated zeolite A, the bentonite contains at least 3%   relative to the weight of anhy bentonite-   dre, the water-soluble detergency builder is a sodium salt of nitrilotriacetic acid, the soluble silicate, if present, is sodium silicate having a Na20: SiO2 ratio of 1: 2 to 1.2.8, the moisture content of the beads is 3 to 12%; the proportion   bentonite: zeolite is from 1: 6 to 1: 2, that of NTA: zeo-   lite is 1: 2 to 2: 1, and that of bentonite: NTA is 1: 6 to 1: 2, and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, and silicate are respectively 10 to 40%, 2 to 25%, at 40% and 0 to 5%.   20- Pearls according to claim 3, ca-   characterized in that they have an apparent specific mass of 0.2 to 0.8 g / cm 3, that they contain 30% of synthetic anionic organic detergent,   aluminosilicate is a hydrated zeolite A, ben-   tonite contains at least 3% moisture based on the weight of anhydrous bentonite, the detergency builder   water-soluble is a sodium salt of nitrilo- acid   triacetic, the synthetic anionic organic detergent   tick is a linear alkyl benzene sulfonate of so-   dium in which the alkyl group has 10 to 18 carbon atoms, a fatty alcohol sodium sulfate, in which the alcohol has 10 to 18 carbon atoms, or a fatty alcohol sodium ethoxylate sulfate in which the fatty alcohol has 10 to 18 carbon atoms and which contains 3 to   ethylene oxide groups per molecule, or a mixture   ge comprising two Qu several of them, the sili-   water-soluble cate, if present, is sodium silicate having a Na20: SiO2 ratio of 1: 2 to 1: 2.8, the moisture content of the pearls is 3 to 12%, the proportion bentonite: zeolite is from 1: 6 to 1: 1, that of NTA: zeolite is from 1: 3 to 3: 1, that of bentonite: NTA is from 1:10 to 1: 1 and that of synthetic anionic organic detergent: zeolite is 1: 1 to 1: 4 and the percentages of hydrated zeolite, bentonite, sodium nitrilotriacetate, organic detergent   synthetic anionic and silicate are respective-   10 to 40%, 2 to 25%, 10 to 40%, 10 to 25% and 0 to 5%.   21 - Pearls according to claim 3, ca-   characterized in that they have an apparent specific gravity of 0.2 to 0.8 g / cm3, the aluminosilicate is a hydrated zeolite A, the bentonite contains at least 3% moisture relative to the weight of the   anhydrous bentonite, the hydrosol detergency builder   luble is pentasodium tripolyphosphate or   tetrasodium pyrophosphate, or a mixture of these   niers, the water-soluble silicate, if present, is sodium silicate having a Na20: SiO2 ratio of between 1: 2 and 1: 2.8, the moisture content of the   pearls is 3 to 12%, the proportion bentonite: zêo-   lite is 1: 6 to 1: 2, that of total polyphosphate: zeolite is 1: 2 to 2: 1 and that of bentonite:   total polyphosphate is 1: 6 to 1: 2, and the pros-   percentages of hydrated zeolite, bentonite, poly-   total phosphate, and silicate are respectively   from 15 to 35%, from 5 to 20%, from 15 to A0% and from O to 5%.   22 - Pearls according to claim 3, ca-   characterized in that they have an apparent specific mass of between 0.2 and 0.8 g / cm3, they contain 5 to 30% of anionic organic detergent   synthetic, aluminosilicate is a zeolite A hy-   drenton, bentonite contains at least 3% moisture   relative to the weight of anhydrous bentonite, the adju-   Before water-soluble detergency is the tripolyphos-   pentasodium phate or tetrasodium pyrophosphate, or a mixture thereof, the organic synthetic anionic detergent is a linear sodium alkylbenzene sulfonate in which the alkyl group has 18 carbon atoms, a fatty alcohol sulfate   sodium in which alcohol has 10 to 18 carbon atoms   bone, or a fatty alcohol sodium ethoxylate sulphate in which the fatty alcohol has 10 to 18 carbon atoms and which contains 3 to 30 ethylene oxide groups per molecule, or a mixture containing two or more of them, the water-soluble silicate, when it is present, is sodium silicate having a Na20: SiO2 ratio of 1: 2 to 1: 2.8, the moisture content of the pearls is 3 to 12%, the proportion bentonite: zeolite is 1: 6 to 1: 1, that of total polyphosphate: zeolite is 1: 3 to 3: 1, that of bentonite; total polyphosphate is 1:10 to 1: 1, and that of synthetic anionic organic detergent : zeolite is 1: 1 to 1: 4, and the   percentages of hydrated zeolite, bentonite, poly-   total phosphate, anionic organic detergent syn-   thetic and silicate are respectively from 10 to   %, 2 to 25%, 10 to 50%, 10 to 25% and 0 to 5%.   23 - Detergent composition, characterized   in that it contains pearls according to the claim   tion 1, containing in the absorbed state a nonionic detergent, the percentage of this nonionic detergent   in the composition being 8 to 30%.   24 - Detergent composition which contains pearls according to claim 2, containing   the absorbed state, a non-ionic detergent, the   centering of this non-ionic detergent in the composition sition being from 8 to 30%.   - Detergent composition according to the re-   vendication 24, characterized in that the non-ionic detergent is a condensation product of 6 to   12 moles of ethylene oxide and a fatty alcohol   12 to 16 carbon atoms, and the proportion of this nonionic detergent in the composition is at 25%.   26 - Characterized detergent composition   in that it contains pearls according to the claim   tion 17, containing in the absorbed state a nonionic detergent the percentage of this nonionic detergent   in the composition being from 8 to 30%.   27 - Detergent composition according to the resale   dication 26, characterized in that the non-ionic detergent is a condensation product of 6 to 22 moles of ethylene oxide and of a higher fatty alcohol of 12 to 16 carbon atoms, and the proportion of this non-ionic detergent in the composition is 10 at 25%.   28 - Detergent composition characterized in that it contains a mixture of pearls according to claim 17 and a composition according to claim 26, having a particle size between 0.149 and 2.00 mm, in a proportion, by weight, of 1:10 to 10: 1 and the apparent specific masses of the pearls before mixing being 0.1 g / cm3 from each other and the apparent specific mass of   the final composition is 0.2.9 g / cm3.   the final composition is 0.2 to 0.9 g / cm