FR2524901A1 - SOFTENING DETERGENT COMPOSITION FOR THE WASHING OF LAUNDRY, METHOD FOR MANUFACTURING SUCH COMPOSITIONS AND A COMPONENT THEREOF - Google Patents

Abstract

A PARTICULAR SYNTHETIC ORGANIC DETERGENT COMPOSITION FOR WASHING LAUNDRY AND SOFTENING TEXTILES INCLUDES A COMBINATION OF ANIONIC AND NON-IONIC ORGANIC DETERGENTS, A DETERGENT ADJUVANT OR A MIXTURE OF SUCH ADJUVANTS, A LIBANCHIMENT OF OXYGEN AND AGGLOMERATED BENTONITE ESSENTIALLY FREE OF ABRASIVE PARTICLES OF DETERMINED PARTICULAR SIZE. THE PREFERRED COMPOSITIONS ALSO CONTAIN A HIGHER FATTY ACID SOAP, A FLUORESCENT OPTICAL BRENCHANT, A WATER-SOLUBLE ADDITIVE FOR THE ANIONIC DETERGENT, A COLOR, AN ENZYME AND A PERFUME. IN THESE PRODUCTS, AGGLOMERATED BENTONITE PREFERABLY HAS A PARTICULAR SIZE GREATER THAN THE PARTICLES OF THE OTHER COMPONENTS OF THE DETERGENT COMPOSITION (INCLUDING THE PARTICLES OF THE MIXED COMPONENTS) AND CAN BE ADVANTAGELY COLORED WITH A BLASTING AGENT. THE BENTONITE USED IS ESSENTIALLY FREE OF ABRASIVE PARTICLES THAT ARE SOMETIMES FOUND IN BENTONITE IN THE NATURAL STATE.

Description

The present invention relates to detergent compositions.

  relates more particularly to detergent owpositions in particles for washing linen and softening textile materials, intended to be used both for washing machine in the machine and in dwarf It also contains

  processes for preparing a caoposant of these compositions (the ben-

  agglomerated tonite essentially free of abrasive materials). Detergent compositions for washing clothes, useful in the machine washing of textile materials, are usual household products, widely used in the world for domestic washing. British patents Nos. 404 413 and 461 221 reveal that compositions for washing washing clothes, which contain bentonite, a synthetic anionic detergent and a detergency builder salt "give fabrics which are washed with these compositions a soft appearance and a

soft touch ".

  Bentonites have long been used in soaps and detergents as fillers and body-building agents, and it has also been established that tissues are softened by the deposition of bentonite from aqueous baths; see U.S. Patent No. 3,594,212 Several of these bentonite applications

  and other suitable clays have also been found

  written in the more recent patent literature.

  For example, various uses of softeners are described in British Patent Nos. 1,404,898; NO 1,401,726; No. 1,455,873; NO 1,460,616; No. 1,572,815 United States of America patents No. 3,936,537 No. 4,141,847; and the British patent application

  No. 2,063,289 However, some bentonites do not contain

  do not have appreciable proportions of exchangeable monovalent metal ions and, consequently, they do not -2

  are not suitable fabric softeners, and

  taines contain harmful proportions of abrasive material which makes them unacceptable in laundry detergents However, thanks to the present invention, these bentonites can be successfully used to prepare softening detergent components and detergent compositions can be prepared having

excellent features.

  According to the present invention, a composition

  particulate detergent for washing clothes and washing

  fabric softening, useful for washing with water

  linen contains 3 to 10% of a sodium salt of a

  synthetic organic anionic tergent chosen from the group comprising sulphonates and sulphates, 1 to 8% of a nonionic detergent, 0 to 10% of a water-soluble alkali metal soap, 20 to 75% of a detergency builder synthetic organic detergent, 5% of a bleaching agent which liberates oxygen in aqueous solution at high temperature, and 5 to 25% of agglomerated bentonite having a particle size

  between 0.149 and 2 mm In embodiments

  sation preferred of the invention, the anionic detergent is a (higher alkyl) sodium benzene sulfonate with linear alkyl group, the nonionic detergent is a condensation product of a higher fatty alcohol and polyoxyethylene, an acid soap hydrogenated tallow fat is present, the detergency builder salt is mainly pentasodium tripolyphosphate or NTA, or a mixture of the two (with the presence of a small proportion of sodium silicate), bentonite is a swelling bentonite having a content of humidity of at least 3%, and the bleaching agent is perborate

  sodium The invention also relates to methods of manufacturing

  cation of essential swelling bentonite agglomerates-

  free from abrasive particles and compositions

  detergents containing this bentonite.

  The synthetic organic detergents used are normally nonionic and anionic, in combination, but suitable amphoteric or ampholytic detergents can also be used, for example those sold under the trademark Miranol, together with the nonionic and anionic detergents of the compositions of the invention. invention Cationic detergents such as quaternary ammonium halides, for example those

  sold under the Arosurf trademark, may also

  Also serve as additional fabric softeners in these products, but normally they are not used

  not and, if you use them, you don't dry them by atomi-

  due to any anionic detergent due to

  of an unwanted interaction that may take place.

  These subject classes are well known and have been

  repeatedly described in the technique of

  tergents. Since these are not preferred components of

  compositions of the invention are considered unsuitable

  requested to describe them further in this submission.

  Various synthetic anionic organic detergents can be used, such as those characterized as sulfonates and sulfates, generally salts

  of alkali metals or sodium, but those that we pre-

  fere are the (higher alkyl) -benzene sulfonates to

  linear alkyl group, the (alkyl or higher fatty alcohols

  laughing) sulfates and poly (higher fatty alcohol)

  ethoxy or polyethoxylate sulfates Preferably, in (higher alkyl) benzene sulfonates, the upper alkyl is linear and has 10 to 14 carbon atoms, preferably it to 13, for example 12, and the sulfonate is a sodium salt L (alkyl sulfate is preferably an alkyl or higher fatty alcohol) sulfate of 10 to 16 carbon atoms, preferably of 12 to 14 carbon atoms, for example 12, and it is also used under

  form of the sodium salt Les (higher fatty alcohol) for

  lyethoxy sulfates also have 10 to 18 carbon atoms, preferably 12 to 16, for example 12, in the higher fatty alcohol moiety, the content of ethoxy moiety is

  preferably 3 to 30 ethoxy moieties per mole, of pre-

  ference from 3 or 5 to 20, and the detergent is a salt of

  sodium So we see that the alkyl fragments of sulfo-

  nates and sulfates are preferably linear or fatty upper alkyls of 10 to 18 carbon atoms, the cation is preferably sodium, and when there is a presence

  polyethoxy chain, the sulfate is at its end.

  Other useful anionic detergents include higher olefin sulfonates and paraffin sulfonates, for example

  example the sodium salts in which the ole-

  Finics or paraffinics have 10 to 18 carbon atoms.

  Particular examples of the preferred detergents are

  sodium dodecyl benzene sulfonate, the (tallow alcohol) po-

  lyethoxy (3 Et 0) sodium sulfate, and tallow alcohol

  hydrogenated) sodium sulfate In addition to anio-

  favorite picnics mentioned, others included in this

  well-known group may also be present, in par

  particular in secondary proportions only with respect to those previously described Similarly, mixtures can be used and, in some cases, these mixtures may be superior to the individual detergents The various anionic detergents are well known in practice and are described in detail on pages 25 to 138 of Surface Active Agents and Detergents, Vol II, by Schwartz, Perry

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

  Although various detergents may not be used

  ionic with satisfactory physical characteristics

  health, comprising condensation products of ethylene oxide and propylene oxide with one another and with hydroxylated aromatic and aliphatic bases,

-2524901

  such as nonyl-phenol and alcohols of the Oxo type,

  it is quite preferable that the detergent not io-

  either a (higher fatty alkoxy) poly (lower alkoxy

  (lower) lower alkanol, which can also be described as a condensation product of ethylene oxide (and: or propylene oxide) with a higher fatty alcohol In such products, the alkoxy moiety or

  fatty alcohol greater than 10 to 16 carbon atoms, from pre-

  has 12 to 15 carbon atoms, and the nonionic detergent contains about 3 to 20 lower alkoxy groups, preferably 5 to 15, and more preferably 9 to 13 groups

  ethylene oxide per mole, for example 11.

  The detergent builder for organic detergent

  than synthetic, which promotes the washing action of the

  tergent, is a soluble or insoluble detergency builder

  water-soluble or a mixture of both Naturally, it is also possible to use mixtures of water-soluble detergency builders, for example polyphosphate and NTA (salt of nitrilotriacetic acid, normally sodium salt), but among the insoluble adjuvants

  in water, generally only zeolites will be pre-

  smells, although mixtures of these zeolites may also be beneficial Although zeolites

  are useful components of the compositions of the

  vention, it is usually best to use one or

  several water-soluble detergency builders, and

  these are the only deter-

gence present.

  The water-soluble detergency builder or the mixture of such detergency builders used may consist of one or more conventional materials used as detergency builders or suggested therefor. These detergency builders include inorganic detergency builders and organic, and

  their mixtures Among the detergency adjuvants inordinate

  the most preferred are the various phos-

  phates, preferably polyphosphates, for example

  tripolyphosphates and pyrophosphates, such as tripoly-

  pentasodium phosphate and tetrasodium pyrophosphate.

  Trisodium nitrilotriacetate (NTA) used preferably

  in the form of monohydrate, and other nitrilo-

  triacetates such as disrilotriacetate sodium, are

  preferred organic detergency builders.

  The designation NTA, which normally represents nitrilotriacetic acid, is used in the present specification to also designate its various salts, preferably the alkali metal salts, and in particular the salt

  trisodium Sodium tripolyphosphate, pyrophos-

  sodium phate and NTA can be used in hydrated forms, which are often preferable, but

  can also use Natural anhydrous forms-

  ment, carbonates such as sodium carbonate, are useful detergency builders which can advantageously be used, alone or together with bicarbonates, such as sodium bicarbonate When using polyphosphates, it may be preferable that

  sodium pyrophosphate is present with the tripoly-

  sodium phosphate in a proportion of 1:10 to 10: 1, pre-

  1: 5 to 5: 1 relative to the latter, the proportion

  total of the two detergency builders being

  about the same as that mentioned for the tripolyphos-

  sodium phate Other hydro detergency builders

  soluble which are considered effective include the various other phosphates, inorganic and organic borates, for example borax, citrates, gluconates, EDTA and iminodiacetates Preferably, the various detergency builders are in the form of their alkali metal salts, i.e. the salts sodium or potassium either

  a mixture of the two, but the sodium salts are parti-

  especially preferred In some cases, for example when making neutral or slightly acidic detergent compositions, the acid forms of detergency builders, especially organic detergency builders, may be preferable, but normally the salts are neutral or basic in nature Silicates, preferably sodium silicate having a Na 2 O: Si O 2 ratio of between 1: 1.6 and 1: 3.0, preferably

  1: 2 to 1: 2.8, for example 1: 2.35 or 1: 2.4, are also used

  detergency builder salts, but only relatively small proportions are present When larger proportions of silicate in the detergent composition are desired, it may be preferable that the hydrated sodium silicate particles be added

  after-spray to spray dried particles

  the other detergency builder (s).

  Insoluble detergency builders in

  water, according to the expression used in this

  are the ones that promote the improvement of

  see detergent for synthetic organic detergents,

  particular of synthetic anionic organic detergents

  ticks, and in this case, the mechanism increasing the

  see detergent seems to be associated with softening effects

  charge water, eg disposal

  of the calcium and / or magnesium ion in the wash water, ha-

  usually by an ion exchange mechanism Although

  the invention contemplates the use of adjuvant deter-

  gence insoluble in water other than zeolites, in practice, at present, zeolites are the main insoluble detergency adjuvants of this

type that are used.

  The zeolites used include the

  crystalline, amorphous and mixed crystalline zeolites-

  amorphous, of both natural and synthetic origin.

  Preferably, these materials can react quickly enough with the calcium ions so that, alone or together with other water softening compounds contained in the detergent, they soften the wash water before reactions appear. harmful-

  these ions with other components of the compound

  tion of synthetic organic detergent The zeolites used can be characterized as having a high calcium ion exchange power, which is normally about 200 to 400 milligrams equivalent or more than

  hardness due to calcium carbonate per gram of aluminum

  minosilicate, preferably from 250 to 350 mg eq / g.

  Although other ion exchange zeolites can-

  also felt to be used, the zeolite particles

  finely divided synthetic as adjuvant

  gence used in the implementation of the present invention normally have the formula (: ia LO) (A 1103) (Si O 2) z% Hio in which x is equal to 1, y is between 0.8 and 1, 2, preferably about 1, z is between 1.5 and 3.5, preferably between 2 and 3 or about 2, and W is between O and 9, preferably between 2.5 and 6 La

  zeolite must be a mono- cation exchange zeolite

  valents, i.e. it must be an aluminosi-

  licate of a monovalent cation such as sodium or potassium-

sium.

  The crystalline types of zeolites which can be used as suitable ion exchangers in the invention, at least in part, include the zli From groups with

  following crystal structure: A, X, Y, L, mordé-

  nite and erionite, types A, X and Y being preferred

  blends The mixtures of these zeolites of the soft sieve type

  eyepieces can also be useful, especially

  when using type A zeolite These types

  tallins of zeolites are well known in practice, and

  are described in particular in the book Zeolite Mole-

  cular Sieves, by Donald W Breck, published in 1974 by John Wiley & Sons Examples of commercially available zeolites of the above-mentioned structure types

  are listed in Table 9 6 on pages 747-749 of the

  Breck vrage, this table being cited here for reference Also, appropriate zeolites have

  have been described in numerous patents in recent years.

  years to be used as adjuvants for

  emergence of detergent compositions.

  The crystalline zeolites having ion exchange and water softening properties which are

  prefer those which are in hydrated or char-

  water, containing bound water in a quantity of

  about 4% to about 36% of the total weight of zeolite, depending on the type of zeolite used, and preferably hydrated to about 15 to 70% of their capacities Normally, the water content is in the range of about 5 to 30 %, preferably around 10 or 15 to 25%, for example 17

at 22%, for example 20%.

  Preferably, the zeolite must be in the finely divided state, the final particle diameters being at a maximum of 20 micrometers, for example between 0.005 or 0.01 and 20 micrometers, better still from 0.01 to 15 micrometers, per example 3 to 12 micrometers, and in particular, most advantageously between 0.01 and 8 micrometers, for example 3 to 7 micrometers, in the case of crystalline zeolite, and from 0.01 to 0.1 micrometer,

  for example 0.01 to 0.05 micrometer, in the case of zeo-

  amorphous lite Although the final particle sizes are much smaller, the zeolite particles generally have sizes between 0.037 and

  0.149 mm, preferably between 0.044 and 0.105 mm However

  dant, they can sometimes be agglomerated, separately or with particles of detergent composition spray-dried, to dimensions similar to those of

  particles, for example + 10 or 25%.

  Although sodium sulfate and gilding

  sodium and other additive salts show no

  additive properties, they can sometimes be used in detergent compositions to obtain loading characteristics, and sodium sulfate is particularly useful as a processing aid In addition to increasing the weight and volume of the product to facilitate measurement, they improve sometimes the stability of the pearls and the physical properties of the pearls of detergent composition in which they are incorporated Nevertheless, since the compositions of the invention are satisfactory without the presence of fillers, these are often preferably avoided entirely, or their presence may be

minimized.

  softening clay which is an important component

  detergent compositions of the invention is of the ca type

  Characterized as "bentonite" Bentonites are colloidal clays (aluminum silicates) containing montmorillonite They have various compositions and can be obtained from natural deposits in many countries including Italy, Spain, l 'USSR, Canada and

  the United States (mainly Wyoming, Mississippi and Texas).

  The bentonites which are useful, according to the present invention,

  are those which have "lubricating" and dissipative properties.

  persion, which appear to be associated with the swelling power in water Although some bentonites, in particular those which can be characterized as calcium (or magnesium) bentonites, have a low or negligible swelling power, they can be transformed or

  "activated" so as to increase this swelling power.

  This transformation can be done by processing

  suitable with an alkaline material, preferably a solution

  aqueous sodium carbonate, in a manner known in

  convenient for introducing a monovalent metal, such as a

  tal alkaline, for example sodium (or potassium) in the

  structure of clay, instead of di-alkaline earth metal

  worth or magnesium In addition to improving the bulking power of bentonite, which improves their tissue softening and dispersing power, the treatment

  with the solution of alkaline material or carbonate of so-

  dium, alkali metal of non-swelling clay or poorly fluid clay replaces, for example, 5 to 100%, 10 to 90%, or 15

  at 50% of the calcium and / or magnesium that can be heated by so-

  3 o dium (or potassium), and thus improves the exchanging power

  Age of clay water hardness ions, for example those formed by calcium and magnesium The resulting by-products, calcium carbonate and magnesium carbonate, remain with bentonite and seem to have advantageous adjuvant properties in final products Any excess

  sodium carbonate can act as an adjuvant to deter-

  gence in the final detergent composition.

  Although the ion exchange power of bentonites has been mentioned in the patent literature as

  being associated with the softening power, a characteristic

  The tick of the present invention resides in the fact that a suitable softening of textiles can be obtained with sodium bentonites having ion exchange powers.

  comparatively weak than swelling bentonite (equal to

  mentally called sodium bentonite because in most cases the heatable metal is sodium, a clay

  of natural origin or is obtained by an alkaline treatment

  flax from a non-swelling or slightly swelling bentonite, it can be used in detergent softening compositions

  fabrics of the invention Italian bentonites processed

  particularly useful and are considered

  Derived as being particularly useful for products intended for the European markets For the American markets, the bentonite of Wyoming is often preferable and does not have to be treated because it already contains sodium ion in its structure and has properties of swelling L analysis of a typical Italian bentonite (after alkaline treatment) shows that it can contain 66.2% of Si O 2, 17.9% of A 1203, 2.80% of Mg O, 2.43% of Na 2 O, 1.26% Fe 203, 1.15% Ca O, 0.14% Ti O 2 and 0.13% K 20 A typical bentonite of

  Wyoming or the western United States (untreated) can con-

  hold 64.8 to 73.0% of Si O 2, 14 to 18% of A 1203, 1.6 to 2.7% of Yg O, 0.8 to 2.8% of Na 2 O, 2.3 at 3.4% of Pe 203, 1.3 to 3.1% of

  Ca O and 0.4 to 7.0% of K 20 Thus, it can be seen that the compounds

  bentonites are quite different although

  both types have swelling properties.

  dere that if the Na 20 content of the clay is at least about 0.5%, preferably at least 1%, and better still

  at least 2% (the equivalent proportion of K 20 may also

  be taken into account), the clay swells satisfactorily

  for the purposes of the present invention and has pro

  satisfactory properties of softening and dispersion in aqueous suspension (the swelling of the bentonite facilitates the disintegration of the bentonite agglomerate) Although it is expected that proportions of the various constituents of the swelling bentonites (which can designate here by

  sodium bentonites, whether natural or "active"

  vées ") falling within the ranges included in the analyzes

  typical data form useful components of the composi-

  tions of the invention, it is also considered that the percentages of the components of the natural swelling bentonite can be raised or lowered by about 10% and that the typical analysis of the treated bentonite can undergo a deviation of + 10% , bentonites falling into these ranges

  still being useful In addition, other bentonites gon-

  flowers can be substituted, at least in part

  general, useful bentonites have swelling powers

  ment of at least 1 or 2 milliliters per gram, preferably at least 5 or 10 ml / g Naturally, bentonites with

  greater bulking power are also helpful.

  Normally, the range of the bulking powers is

  between 5 and 30 ml / g, and often between 5 and 20 ml / g.

  Sodium bentonite or swelling bentonite is

  normally agglomerated before being mixed with the per-

  detergent loaded with dried detergency builder

  by atomization and all other adjuvants to be added after-

  coup This agglomeration is carried out in a con-

  naked, for example by applying a spray of moisture to the shaken bentonite powder, extrusion, tamping, agglomeration in mold or other technique However, it is very advantageous that the bentonite is in the form of finely divided powder before the agglomeration so that when the agglomerate breaks in the wash water, the bentonite particles are small enough to form effective lubricants, as deposited on the

  laundry So it is normally beneficial that essential-

  all of the bentonite powder, before agglomeration

  ration, passes through a 0.149 mm mesh sieve, at least 99% passing through such a sieve, and a proportion representing more than half passing through a 0.074 mm mesh sieve, preferably less than about 30% by weight of the particles being retained on this sieve, and preferably not more than% remaining on this sieve Naturally, the dimensions

  final particulates are lower.

  The moisture content of the bentonite is also important to promote rapid breakdown of the bentonite agglomerates and dispersion in the wash water, so

  that its small particles can adhere to tex fibers

  tiles to soften them Although it is advantageous to limit the free moisture content of the bentonite used to around 10%, moisture contents higher than 15%

  not normally used, it is even more important

  both to ensure that the bentonite contains enough

  free humidity, most of which is considered to be

  being present between the adjacent plates of the bento-

  nite, in order to facilitate rapid disintegration of the ben-

  tonite and all adjacent matter in the particles

  when these particles or detergent compositions contain them

  nant are brought into contact with water, for example washing water It has been found that at least about 2%, preferably

  at least 3%, and better yet, about 4% or more of water should

  may be present in bentonite (which will be referred to as "internal" moisture), and that bentonite should not be dried to the point that it temporarily contains less than these percentages of water In other words, excessive drying

  to the point where bentonite loses its internal moisture can di-

  greatly diminish the usefulness of the compositions of the

* note When the moisture content of the bentonite is too low, the bentonite does not adequately promote the swelling and disintegration of the beads agglomerated in

wash water.

  Preferred swelling bentonites of the types described above are sold under the trademarks Laviosa and

  Winkelmann, for example Laviosa AGB and Winkelmann G 13, both being treated Italian bentonites, and Mineral Colloid NO 101 (and other similar designations)

  corresponding to Thixo-Gels N O 1, 2, 3 and 4 (commercially

  Benton Clay Company, a subsidiary of Georgia Kaolin

  Co) As will be described below, the bentonites processed

  Tees are also preferably free of abrasive particles and have preferably been further processed by grinding into a fine powder before agglomeration Generally the commercial bentonite used has a pH in water (at a concentration of 6%) in the range of 8 to 9.4, one grade

  maximum in free humidity of around 8%, a density of

  about 2.6 and a viscosity, at a concentration of 10% in water, between 5 and 30 m Pa s, preferably from 10 to

m Pa s.

  Water-soluble soap, which is a preferred component

  geux detergent compositions of the invention and which has a useful action of limiting the foam in the water of

  washing, which is particularly advantageous in

  washing machines with horizontal or lateral loading, is nor-

  improperly a soap of higher fatty acid of alkali metal, for example of sodium or potassium, the sodium soaps being very particularly preferred These soaps are well known and will not be described in more detail Suffice it to say that they can be prepared from fats

  and natural oils, for example from ani-

  males and from vegetable oils or seeds, for example tallow, hydrogenated tallow, coconut oil,

  palm kernel oil and "natural" fatty acids and syn-

  corresponding thetics, and normally having 10 to 24

  carbon atoms, preferably 14 to 18 carbon atoms.

  Preferably, these soaps are soaps of hydrogenated tallow or hydrogenated tallow fatty acids, for example of stearic acid. The water-soluble soap which can be incorporated into the compositions of the invention is chosen from

  preferably so as to present a desired balance

  table of advantageous detergent properties, a foam reducing effect and other physical properties

  In particular, among these other properties

  Physical tees include a desirable hardness, a good binding effect and little or no tendency to produce adhesive gels under the conditions of use (as in the loading compartment of a washing machine). Bleaching agents are generally incorporated in all the detergent compositions of the present invention intended for use in automatic washing machines of the "European type"

  using very hot water (close to the boiling

  tion), because under these conditions an effective and safe bleaching is obtained, which provides washed articles having a greater whiteness When the temperature of the washing water of the automatic washing machine is sufficiently high, sodium perborate constitutes the bleaching agent of choice because the high temperature, in particular above 800 ° C., in particular

  from 90 to 950 C, can cause decomposition of the

  borate and release bleaching oxygen so

  under these conditions, the sodium perborate which is

  wind designated by sodium perborate tetrahydrate or sodium borate perhydrate, and which generally has an active oxygen content of at least about 10%, releases this oxygen without the need for an activating agent or decomposition catalyst When undertaking automatic washing at a lower temperature, or if the product is intended to be used outside the washing machine, in cold water or in hot water, for example at temperatures of 20 to 600 ° C., the perborate of sodium generally does not decompose enough to adequately bleach textiles and, in this

  case, an activator or other bleaching agent is used

  appropriately, usually also with an activator.

  Many of these systems have been described in the literature, most of which belong to the class

  peroxygen compounds, for example persulfu- acid

  risk, peracetic acid, performic acid, perphthalic and perbenzoic acid, and their salts, such as

  alkali metal or alkaline earth metal salts

  red, for example sodium and magnesium salts.

  * Various activators for these compositions are known to promote the controlled release of oxygen in the

  Hot and cold water systems Among these activa-

  Mention may be made of heavy metal salts, such as copper salts, and various inorganic compounds.

  and organic which have been described in the art.

  Among the low temperature bleaches, the preferred one is magnesium dimonoperoxyphthalate. Naturally, various other oxygen-releasing materials can be used, for example hydroperoxides and, under suitable conditions, can be incorporated into the detergent compositions of the invention of chlorine-releasing bleaching materials Although in some cases it may be considered unnecessary to incorporate a bleaching agent into

  the detergent composition is normally used.

  In particular in the compositions of the invention, comprising agglomerated bentonite particles, the perborate can exert a bleaching effect on the bentonite, sometimes of a dirty white, which otherwise can

  be very dirty white due to the dimensions

  larger agglomerated dots Even if the agglomerated bentonite is intentionally colored, the

  per-compound can help "purify" the color by eliminating

  the lack of color of the base.

  Various adjuvants may be present in the mixer mixture from which the pearls

  base or detergent compositions can be dried

  chées par atomisation, or these adjuvants can be added after the fact, the choice of the mode of addition being

  often determined by the physical properties of the ad-

  juvant, its resistance to heat, its resistance to degradation in the aqueous medium of the mixer and its volatility. Among the adjuvants often used, mention may be made of enzyme powders or pellets, which are normally added afterwards to the base pearls because they are sensitive to heat They can be made up of a variety of commercially available products, including Alcalase, manufactured by Novo Industri, A / S and Maxatase, both of which are alkaline proteases (subtilisin) Among the specific enzymatic preparations which can be used, there may be mentioned Novo Alcalase 2 M (2 units

  Anson per gram) and Maxatase P 444,000 Among the pro-

  most often used alkaline teases, we can

  cite amylolytic enzymes, e.g. alpha-

  amylase The compositions mentioned usually contain

  of active enzymes in combination with an inert powdered vehicle, for example sodium or calcium sulphate, and the proportion of active enzyme can vary widely, generally between 2 and 80% of the preparation of commerce. the proportions indicated are those of the preparations

  enzymatic, and not of their active part.

  Among the fluorescent brighteners, the most commonly used are those of the stilbene type, for example Tinopal 5 BM, in particular in super concentrated form. Among the stilbene compounds, mention may be made of the brighteners of cotton, such as than those sometimes designated by CC / DAS optical brightening agents, coming from the reaction product-chloride

  cyanuric and disodium salt of diaminostil-

  bene disulfonic acid, including their variants with regard to the substituents on the triazine rings

  and aromatic This class of brightening agents is

  naked in the detergent technique and is most often used when the bleaching components are not present in the final product When it is desired that the detergent composition contain a bleaching agent, such as sodium perborate or other bleaching agent oxidizing agent, optical brightening agents can be incorporated into the mixer mixture

  stable bleaching agents in the presence of a bleaching agent

  among them we can mention acids

  benzidine-sulfone-disulfonic, naphthotria- acids

  solylstilbene-sulfonic and benzimidazoly derivatives-

  Polyamide brightening agents, which can

  also be present, include derivatives of ami-

  nocoumarin or diphenylpyrazoline, and the agents

  polyester brightener, which can also be used

  ser, include naphthotriazolyl stilbenes These optical brightening agents are normally used in the form of their soluble salts, for example sodium salts, but they can be introduced in the form of acids.

  agents The brightening agents for cotton

  generally kill a dominant proportion of systems

brightening agents used.

  When you want the product to be completely

  or partially colored, various colo-

  rants and dispersible pigments When blue dyes are used, for example Acilan blue, or pigments such as Overseas blue, they can have the double effect of serving to color part or all of the particles of the detergent composition. ,

  or particles of the components of the composition

  tergent, and to help give the washed laundry an interesting bluish or azure tint

  bentonite particles agglomerated by colo-

  rants or suitable pigments may be particularly

  highly advantageous because natural bentonite can

  sometimes be dirty white, so the clumps

  merats can be transformed from particles that look dirty to particles that are

color and a pleasant appearance.

  The perfumes used, which are generally sensitive to heat and may contain volatile materials, comprising a solvent, for example an alcohol or a glycol, a polyol or a suitable hydrocarbon,

  are normally synthetic fragrances sometimes mixed

  diapers with natural components, and they usually include alcohols, aldehydes, terpenes, fixing agents and / or other normal components

perfumes, known in practice.

  In addition to the additives mentioned, it can also

  presence of flow promoting agents, anti-hardening materials used to prevent premature gelation of the mixer mixture, dispersing aids, anti-deposition agents

  and, in some cases, additional softeners

  but for example cationic softeners such as quaternary ammonium halides, for example dimethyldioctadecylammonium chloride However, as indicated above, cationic softeners are not normally used and, if

  are, they are added afterwards.

  Naturally, water is present in the mixture

  the mixer from which the spray-dried component of the composition of the invention is made; it serves as a medium for dissolution or dispersion

  of the various components of the spray dried beads.

  Therefore, a certain amount of water, in free and hydrated form, is found in the product of a

  similarly, water can be used to agglo-

  merize bentonite and perborate powder Although 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 favor

  risking the decomposition of any organic matter

  Before being present are kept to a minimum, tap water or tap water can be used at the

  place and sometimes, for reasons of economy or convenience.

  provisioning, we use this water exclusively.

  Normally, the hardness content of this water is not more than about 300 parts per million, under

form of calcium carbonate.

  The proportions of the various components in the final product of the present invention are such that these components are effective as an effective detergent

  fabric softening, cleaning and whitening

  chastise. The proportion of anionic detergent normally represents 3 to 10% of the final product, preferably 3 to 7%, and better still 4 to 6%, for example 5%. Generally, the content of nonionic detergent is between 1 and 8%, preferably between 2 and 5%,

for example between 3 or 4%.

  The detergency builder content is generally

  20 to 75%, preferably 30 to 50% (this detergency builder often being preferably a fully water soluble detergency builder salt) and better still from 30 to 40%, for example around 35% As previously indicated , sodium tripolyphosphate and NTA are the preferred water-soluble detergency builders and may be the only detergency builders used When used in admixture, the blend preferably contains 10 to 90% of one 'them, the rest consisting of the other detergency builder and, in these ranges, the preferred proportions

  can be 20 to 80% and 40 to 60%, and percent

  additional stages whose total is equal to 100 Des

  analogous ranges of percentages are applicable when

  that the detergency builder is a mixture of a water-soluble detergency builder salt and an adjuvant of -

  detergency insoluble in water, such as a zeolite.

  The bentonite content of the softening detergent

  for textiles, in the form of a particulate agglomerate

  more finely divided bentonite powder scraps,

  is a proportion having a satisfactory effect of a-

  softening, which is between 5 and 25%, preferably

  between 10 and 20%, better still between 14 and 18%, for example around 16% The proportion of bleaching agent is between 5 and 35%, preferably between 15 and 25%, for example 20% However, we must

  remember that these proportions are based on user-

  sation of sodium perborate and should be changed when using other oxidizing agents, so as to have roughly the same bleaching effect (or active oxygen content) In the presence of a fatty acid soap, its proportion is generally not more than 10% A preferred range of soap contents is 2 to 6%, preferably 2 to 4% The moisture content of the product, which does not include moisture as

  hydrate which cannot be removed during heating

  classic fage at 1050 C, for two hours, is nor-

  wrongly from 3 to 20%, the highest percentages being admissible when a significant proportion, at least

  a quarter, and preferably at least half, of the hum

  moisture is in the form of hydrate A preferred moisture content is from 5 to 17%, and better still, this content is from 10 to 15%, for example 10% Any moisture

  which cannot be eliminated by the classic mention- test

  born above is considered part of the com-

  laid in which it is present in the form of a hydrate,

for example a zeolite.

  The total proportion of the various adjuvants

  also before being present in the deter-

  generally not more than 20%, pre-

  ference it is limited to 15% and better still to 10%.

  Because the water-soluble sodium silicate has detergency builder properties, particularly with regard to its action against magnesium ions

  in hard water, its proportion is included in the te-

  total neur in detergency builder However, since it also acts as a binder, its proportion

  is mentioned with the other adjuvants for the

  positions of the invention Generally, it does not constitute more than 8% of the product, a normal range being

  1 to 5%, preferably 2 to 4%, for example 3%.

  Sometimes, to improve fluidity, especially when the silicate content exceeds 3 or 4%, the rest is added afterwards, in the form of silicate

  hydrated The salt content of the filler, for example the sul-

  sodium fate when present, is normally also limited to a maximum of 10%, and it normally constitutes 0.5 to 5%, preferably 0.5 to 2%, for example 1 or 1.5% of the product The percentage of proteolytic enzyme used normally ranges from 0.1 to 2%, from

  preferably 0.2 to 1%, for example 0.3%, and the

  centering of optical brightening dye ranges from 0.1 to 2%, preferably from 0.1 to 0.5%, for example around 0.2% The fragrance content normally ranges from 0.05 to 2 %, preferably from 0.1 to 1%, and better still from 0.2 to

  0.5%, for example around 0.3% Among other adjutants

  However, it can sometimes be advantageous to introduce small quantities of specific sequestering agents and of agents promoting flow. Among these materials, a preferred sequestering agent is the magnesium salt of diethylenetriamine-pentaacetic acid, but

  can replace it with other diethylene acetates-

  triamine Magnesium silicate is a preferred flow promoting agent, which can also serve as a vehicle for the sequestrant A mixture of such products is commercially available and contains 15% of magnesium DTPA and 85% of Mg Si O 3 and, when used, its proportion is preferably 0.1 to 1%, pre-

  ference from 0.1 to 0.5%, for example 0.2% The propor-

  the sequestrant (or stabilizer) may be

  0.01 to 0.2%, preferably 0.02 to 0.1%, and the

  Mg Si O 3 concentrations are in the range of 0.1 to 0.9%, preferably 0.2 to 0.5% The amounts of the other adjuvants used are such as to ensure

  the role they should play in determining the composition

  but these proportions are normally not higher than

  less than 1 or 2%, and generally 0.05

at 1%.

  In addition to the detergent composition containing

  a synthetic organic detergent, a detergent adjuvant

  gence, bentonite and a bleaching agent, and soap and adjuvants, the present invention also relates to detergent compositions in which

  bentonite is a bentonite whose abra-

  harmful sives have been eliminated and also from

  ference, it is a bentonite which has been transformed into an alkali metal bentonite, for example sodium bentonite, by treatment of a bentonite containing a replaceable magnesium and / or calcium content, with an alkaline substance, for example a sodium carbonate solution The bentonite used is characterized by the

  fact that it is essentially free of abra-

  sives, which means that it contains less than 1% of abrasive particles The essentially abrasive free bentonite used normally contains less than 0.4% of hard palpable abrasive particles, which are insoluble in water and which are difficult to crush when placed on a hard surface and struck with a normal hammer blow Preferably still, it contains less than 0.1% of these abrasive particles, and this bentonite can be described as "free of abrasive particles" In the bentonite

  gross, as it is used, the share content

  abrasive cules can reach 15%, in some cases, although generally it is less than 5% A

  treatment of bentonite to drive out the parts

  abrasive cules is carried out in conjunction with the

  allowing to increase its content of mono- cations

  exchangeable valents, which is preferably brought to at least 2% (as Na 20) by such treatment The treatment process and its advantages will be described

  in detail later when describing the

  methods of the present invention.

  To manufacture the products of this invention

  tion, we can use known techniques of mixing, agglomeration and spray drying (preferably all three) Because these techniques do not

  are not considered as important peculiarities

  of the invention, we will only describe them briefly.

  In spray drying, a grinding mixture

  containing the various constituents of which it is desired to pre-

  sence in spray dried beads and sufficient

  stable enough to withstand mixing and spray drying operations, for example a detergent, a detergency builder and suitable builders is spray dried from an aqueous grinding mixture, which normally contains about 40 to 70% or% solids, preferably 50 to 65%, the remainder being water The grinding mixture may contain the anionic detergent and some or all of the nonionic detergent, although generally there is no more than 5 % of non-ionic detergent (based on final product) in the blender (any remainder added after the fact) All of the detergency builder or detergency builder mixture is normally added to the grinder, although this is not essential The bentonite is preferably agglomerated separately and is added afterwards to the product dried by

  atomization, often in the form of colored beads (pre-

  reference in blue). An aqueous silicate solution, a stable fluorescent brightening dye, soap and a filler salt are usually added to the mixer along with any stable pigment and other dyes that can be used. Instead of introducing a neutralized detergent, the

  mixer can be used as a neutralization container

  tion in which the detergent organic acid is neutralized with an aqueous caustic solution This acid, for example, can be dodecylbenzenesulfonic acid containing approximately 45 to 50% of active ingredient which can be neutralized with an aqueous solution of sodium hydroxide , containing for example 38% Na 20 If the acidic detergent is produced by sulfonation of alkylbenzene with sulfuric anhydride, the active ingredient content of the acid can be as high as 99% A mixture of higher fatty acids can also be neutralized in the blender with detergent acid to produce a desired mixture of detergent and

higher fatty acid soap.

  The mixer mixture can be spray dried

  sation in a conventional atomization tower, using

  a flow with parallel currents or against the current.

  Normally, the mixture is at a temperature of 20 to 80 OC, preferably 40 to 700 C, and it is spray dried

  in a tower in which the drying air is at a tem-

  temperature from 200 to 4000 C, to produce dried pearls

  by atomization with a particle size between 0.149 and 2.00 mm.

  All particles whose dimensions are located outside

  the desired range can be eliminated by sieving

  and can be re-treated The pearls obtained have an apparent density of 0.3 to 0.6 g / ml, for example 0.5 g / ml They have a moisture content in the range

  about 3 to 20%, but normally about 10 to 15%.

  After production of the spray dried portion -

  sation of the compositions, other components can be mixed with the beads or atomized on them (and on the other components of the product, when desired) In general, it is preferable that the bentonite, the enzyme, the agent bleaching agents, and other particulate products, such as those in the form of powder, agglomerate or pellets which are to be added afterwards to the spray-dried pearls, are mixed with them, after which any liquid to be added afterwards can be atomized on the mixture However, the order of post-addition of the components can be varied and sometimes part of the particulate matter can be added afterwards after a

  or more liquids Two particulate matter or more

  can be mixed before the post-ad-

  mixtures and, similarly, mixtures of liquids can also be formed Solvents can be used for the various components to be applied as liquids and, in some cases, emulsions can be used In some cases, it can be advantageous to dilute the perfume

  with a suitable solvent, for example a relative alkylate-

  odorless (hydrocarbon) When the non-ionic detergent

  that is added afterwards (and it is sometimes preferable that all of the nonionic detergent is added to the blender, it can be sprayed or suitably applied 2524 e OI in some other way to the surface of the spray dried beads before mixing with the other particulate components Similarly, as previously indicated, the nonionic detergent, in liquid form, can be mixed with the perfume to be sprayed on the product, in which case it

can act as an emulsifier.

  The apparatus intended for carrying out the various mixtures and atomizations is known in practice and, consequently,

  we will not describe it in detail The atomization can be done

  kill using conventional nozzles, usually

  sation capable of forming a broad atomization, but other types of atomization apparatus can also be used Mixing apparatuses can have various shapes, but preferably they are rotating inclined tubes or drums, inside which the atomization can be carried out However, V-mixing devices, in particular those designed for continuous introduction, and other commercial powder mixers can

also be satisfactory.

  The various mixing and atomizing operations normally take place at approximately room temperature, but operations between 10 and 400 ° C., preferably between 20 and

  300 C, are preferable The particle size of the materials

  res during mixing is generally analogous to that of the final product, between 0.074 or 0.149 and 2 mm (the ranges for perborate and the enzyme can go up to

  0.074 mm) The particles of agglomerated bentonite are

  those resulting from the agglomeration or settlement of the more finely divided particles, for example those of which a proportion

  more than 50% pass through an open sieve

0.074 mm.

  These particles are essential sodium bentonites

  partially free from abrasive particles.

  bet with an appropriate dye or pigment, for example,

  Bleu Acilan Brillant FFR and various other dyes suitable for

  required can be applied Sometimes, the bentonite agglomerates can be larger than the other particles of the product, for example 10 to 50% larger, to accentuate their difference Although the bentonites of

  Western USA or Wyoming to make agglomerations

  rats, in many cases, the bentonite agglomerates preferably consist of bentonite treated with sodium carbonate (this treatment improves the color of the clay of a blarcsale) and contains magnesium carbonate and / or

  calcium carbonate, following this treatment.

  Bentonite sodium carbonate treatment

  The raw is undertaken when the sodium content exchanged

  ble of bentonite is less than the desired value for softening and satisfactory dispersing action

  bentonite agglomerates when its agglomerated pearls

  are added to the wash water For the bentonite con-

  containing exchangeable and insufficient calcium and / or magnesium

  containing exchangeable sodium, for example less than 0.5% in the form of sodium oxide, the crude clay, containing in

  many cases of abrasive particles, is ground or otherwise

  highly disaggregated and treated with an appropriate alkaline material

  required such as aqueous sodium carbonate which can have a concentration of 5 to 20% After contact with clay

1524 M 1

* for an appropriate time, which may be 0.5 to 24 hours, the mixture, which still contains a little excess free sodium carbonate (normally an excess of 10 to 50% is used to replace calcium and magnesium exchangeable), is dried Generally, this material often dried in large cakes, having a moisture content included

  between 2 and 15%, is disaggregated and then crushed in partial form

  circular, the particles having diameters between

  0.8 and 8 mm In this state, bentonite can be commercially

  read for applications in which the content of

  abrasive particles is unimportant However, when bentonite contains undesirable amounts of particles

  abrasive, it is further reduced from the point of view of the dimensions

  Particulate ions up to particles smaller than 0.149 mm, at least 50% of which are smaller than 0.074 mm These are then subjected to separation by centrifugation or other separation technique sensitive to density, for example a deposit by gravitation, but preferably a cyclone separator is used. The abrasive particles are eliminated and their concentration in the product is reduced to less than 2%, for example less than 0.4%.

  bentonite, now essentially free of particles

  abrasives and containing enough exchangeable sodium to be a useful component in detergents

  softeners of the present invention, is agglomerated in par-

  tiles of the desired size, by an appropriate process, such as

  than one of those previously described.

  The products and methods of the present invention offer numerous advantages, several of which have already been mentioned. With regard to the products, the detergent compositions obtained constitute excellent bleaching detergents for laundry and they effectively soften washed laundry, such as have shown comparative tests on analogous compositions not containing bentonite The products flow freely, do not form dust and have a desired apparent density as well as an appearance

  pleasant Bentonite tends to make laundry washed with a touch

  expensive softer but do not cause hydro-

  harmful phobes in the washed material It has been shown

  that bentonite can sometimes even increase ab-

  sorption of moisture from tissues, and it acts as a detergency builder for detergents and can contribute

  to impart soil suspension properties

  res For example, it appears that nine parts of bentonite

  equivalent to about a part of tripolyphosphate of so-

  dium, as an additive for organic detergents Apparem-

  Because of its plate-like structure, the par-

  final bentonite particles which are retained by the

  of linen, are used to lubricate these fibers in their

rant thus a soft touch.

  Due to the very small size of the particu-

  them and apparently because of their opti-

  only advantageous, they do not fade or discolour

  tissues to which they adhere, and their deposits do not accumulate

  slow on fabrics to a detrimental extent despite repeated washing with detergent compositions containing

bentonite.

  Bentonite agglomerates dissociate easily-

  in wash water, especially in very water

  hot, and this dissociation can be favored by the li-

  oxygen bleaching of the bleaching agent, for example sodium perborate Agglomerates can absorb water, compared to the per-compound, without sticking to others

  particles of the detergent composition, at least in the presence

  that of relatively small amounts of outside moisture.

  In this regard, bentonite agglomerates can help stabilize the per-compound and prevent solidification of these materials and spray dried beads in which most of the other components of the product are present, although it may sometimes be desirable. that the perborates and the enzyme be coated with other materials, so as to be stabilized and prevent their interaction

  with the other components of the detergent composition,

  this was not necessary in the compositions of

  the invention In addition, the bentonite found in the par-

  agglomerated particles, which do not contain the other compounds

  product, is more available for absorbing moisture, and apparently has a greater effect on avoiding

  solidified than it would be if it had been se-

  sprayed with the other components of the detergent.

  Also, when the bentonite is spray dried with the other components of the detergent composition, it-

  the may lose some of its softening power, and this-

  This often makes the present invention preferable. However, in some cases it may be desirable to use a portion of the bentonite, for example up to half, in the mixer mixture, in which case it is present in the dried beads. atomization and can promote their rapid disintegration in the wash water.

  found that these spray dried beads did not contain

  no bentonite dissociates quickly enough when they have the particle size mentioned in the present invention, so that the "internal" bentonite

  is unnecessary perborate, co-detergent and adjuvant

  tergence can apparently interact with bentonite for

  prepare the sites on the fabric for softened particles

  health These sites are thus physically and chemically cleaned, which can improve their retaining power vis

  with respect to bentonite Thus, we see that the various components

  sants of the compositions of the invention can interact in order to improve their softening, cleaning and

bleaching.

  The following examples illustrate the invention without limiting it Unless otherwise specified, all parts

  are expressed by weight and all temperatures in C.

EXAMPLE 1

  A mixer mixture totaling 100 parts is

  made by reacting 11.38 parts of dodecylben- acid

  zenesulfonic (Dobane JNQ l 48.8% active ingredient, 7 and, 22 parts of hydrogenated fatty acids (16 to 18 carbon atoms per fatty acid molecule) with 1.47 part of caustic soda (38 % Na 20) in an aqueous medium containing an appropriate proportion (to maintain the reaction) of 29.75 parts of city water (with a hardness of 300 ppm, in the form of Ca CO 3) The rest of this water is used to cool the reaction mixture, as necessary, and to dilute the other components of the mixer mixture Then 7.56 parts of aqueous silicate solution of

  sodium (Na 20: Si 02 = 1: 2.4) at a concentration of 44.1% in ma-

  solid, 0.23 part of an optical brightening agent of the stilbene type, 0.22 part of Sydex 808 (85% of

  Mg Si O 3 and 15% magnesium-DTPA), 39.14 parts of tripoly-

  hydrated sodium phosphate (TPP "H"), 1.69 parts of sulfate

  anhydrous sodium (99.5% pure) and 33.34 parts of a deter-

  nonionic gent which can be considered as the condensation product of 11 moles of ethylene oxide with one mole of higher fatty alcohol having from 12 to 15 carbon atoms

per molecule.

  The mixer mixture is heated for about an hour, with stirring, so that its temperature rises

  at around 55 C, after which it is pumped into a drying tower

  chage by atomization where it is atomized at a high temperature

  through multiple spray nozzles in drying air at a temperature of about 300 C I 1

  the result is particles having a moisture content of

  about 12%, most of which are between

  0.149 and 2 mm Particles coming out of this size range

are removed by sieving.

  Then 63, lg parts of the spray-dried powder (of an apparent density of approximately

  0.4 g / ml) with 0.3 part of proteolytic enzyme in tablet

  (Alcalase of 2 Anson units per gram, although we can-

  instead of Maxatase P 400,000), 20 parts of granular sodium perborate and 16 parts of bentonite

  All these powders have a particular dimension.

  re included in the particle size range of the com-

  laying spray-dried detergent composition, but smaller enzyme and perborate particles can also be used, down to about 0.074 mm The bentonite particles consist of 82.3 parts of anhydrous bentonite, 16, 1 parts of water, 1.5 parts

  sodium silicate (previously described) and 0.06 per-

  tie of brilliant Acilan Blue dye, the dye being applied

  on the surface of the particles Bentonite particles can be obtained by agglomeration of particles of

  finely divided bentonite (Laviosa AGB) with the solu-

  diluted sodium silicate (in water) after which

  they are colored The bentonite used is a bentonite

  which has been treated with sodium carbonate to replace the calcium and magnesium it contains with sodium

  and of which a natural content of abrasive material has been eliminated

  born, after treatment, by separation by centrifugation.

  These processes for treating bentonite will be described 1 o later in this example. The moisture content of the

  suitable agglomerated bentonite may vary and may also be

  as low as 3% when mixed with other components

  of the softening detergent of the invention.

  A mixture of spray dried beads, enzyme, perborate and colored bentonite particles is mixed in an inclined drum mixer.

  0.5 part of the non-ionic detergent and 0.25 part of the

  smoke for detergent Spraying is adjusted so that the atomized liquid evenly covers the particles in the mixer or the shaking drum to give approximately

uniform product parts.

  The final product has a specific particle size

  is between 0.250 and 2 mm, an apparent density of approx.

  ron 0.5 g / ml, and a moisture content of approximately 12% (although it can be reduced to approximately 8 to 10%) The particulate detergent for softening the fabrics obtained does not

  no dust, it flows freely and looks attractive

  milking and presenting particles of agglomerated bentonite

  slightly larger blue (on average 20 to 200% above

  contrasting with the other white particles.

  Although the spray dried beads and bentonite agglomerates are distinct, the perborate and the enzyme, especially when their particles have dimensions at the lower end of the mentioned range, may appear to mix with the other beads, which improves the appearance of the enzyme However, they are not agglomerated and if they are not separated, they are easily separable from these other particles and some

others.

  When the product described is subjected to a practical test

  tick on the laundry, it is found that it constitutes an excellent detergent having advantageous properties of softening of fabrics. As an alternative to the above process, the anionic detergent is replaced by equal weights, respectively

  sodium lauryl sulfate, hydrogenated tallow alcohol,

  sodium sulfate and polyethoxy tallow alcohol (3 Et O) sulfa-

  sodium te As a variant, mixtures are used together

  of these materials, for example equal parts of dodecyl-

  sodium benzene sulfonate and hydrogenated tallow alcohol

  sodium sulfate In all these cases, the composition

  gente final is an excellent detergent for laundry and

  fabric softener

  analogous results when, instead of the anionic detergent, the non-ionic detergent is modified by replacing it with a

  block copolymer of propylene oxide and ethylene oxide

  lene, e.g. Pluronic L-44 or L-62, nonylphenol-po-

  lyoxyethylene (12 Et O) glycol or a C 12 -C 15 fatty alcohol condensation product with 3 to 7 moles of ethylene oxide per mole, or with a mixture of two or more of these detergents, for example in equal parts When half or all of the sodium tripolyphosphate is replaced

  by NTA, the final product also constitutes a deter-

  satisfying gent with softening properties.

  When the soap is removed from the formula, a reduction in foam control is obtained, but on the other hand, the product is acceptable and is identical to those previously described When the sodium perborate is replaced by other bleaching agents, such as than sodium persulfate, sodium perisophthalate or magnesium dimonoperoxyphthalate, it is still possible to obtain satisfactory bleaching and cleaning by the product when the bleaching agent is

  removed, the detergent composition obtained does not white

  does not chill laundry or remove stains as well When known activators for oxidizing agents are present, bleaching can be performed using the composition at temperatures below those near boiling (which are normally used in the procedures in this example

  to get maximum bleaching activity).

  When it is desired to incorporate more silicate into the product, its quantity is doubled by post-addition

  of hydrated sodium silicate particles of size

  analogous to other particulate solids added afterwards In a treatment variant, only the perfume is atomized on the mixture, the detergent

  nonionic being fully incorporated in the mixture

  geur. The bentonite agglomerates used

  in this example are substantially regular spheres

  lières consisting essentially of bentonite with a small proportion of binder silicate and a whitening dye on its surface To obtain them, an Italian clay, with low exchangeable sodium content, is treated to increase the sodium content, the swelling power and the softening effects First of all, this

  clay, which contains a minor proportion, for example-

  about 3% full, hard, black, abrasive mineral material is crushed and its dimensions are reduced so that its particles pass through a 4.76 mm mesh screen, after which they are treated with an excess, for example an excess of 50%, of sodium carbonate solution, for example of a concentration

  about 10% The mixture is allowed to stand, mixing

  managing intermittently, for an appropriate reaction time, for example about four hours, at which point sufficient ion exchange takes place between the exchangeable calcium and magnesium in the clay so that its typical analysis is that given for bentonite Italian (after alkaline treatment) at the beginning of this memo Thanks to this treatment, the Ca 20 content of the clay is significantly increased (approximately 2%) and the Mg O and Ca O content has been reduced in corresponding proportions Clay

  is then dried, for example to a moisture content

  about 5%, after which its size is reduced to particles which are advantageously less than 0.149 mm (although sometimes larger particles may be present), and it is subjected to air separation by centrifugation in a cyclone separator (although 1: 5 can also use separation techniques by

  dimension) to remove abrasive particles.

  Bentonite free of abrasive particles, contains

  containing less than 0.1% of abrasive particles, having a swelling power of approximately 5 ml / g and a viscosity of approximately 15 m Pa s, at a concentration of 6% in water, and a moisture content d '' about 7%, is then agglomerated by the process described above, the dilute sodium silicate solution being atomized on the surfaces of the moving particles, while they are shaken in an inclined drum Shaking is continued until the particles

  acquire the desired dimension and be suitable-

  rounded at the end of the shaking period, which can last up to an hour, on average, one

  diluted dye solution is atomized on the

  to color them and they are then ready for

  be mixed with the other ingredients to make

kill a final detergent product.

EXAMPLE 2

  We prepare an effective softening detergent

  this analogous to that of the first formula of the example-

  ple i from a mixer mixture of 10.24 parts of dodecylbenzene sulfonic acid, 2.81 parts of hydrogenated fatty acid, 0.81 part of caustic soda, 26.54 parts of water, 37.2 parts of pentasodium tripolyphosphate (hydrated), 6.8 parts of sodium silicate solution, 0.21 part of fluorescent optical brightener, 1.46 part of sodium sulfate

  and 3.0 parts of the non-ionic detergent, successively added

  This mixture is spray-dried by the method described in Example 1 to produce 62.5 parts of a product of similar bulk density and particle size. The spray-dried particles are then mixed with 0.3 parts of proteolytic enzyme, 20.0 parts of the sodium perborate granules, 16.0 parts of agglomerated bentonite and 0.2 parts of Sydex 808, and

  the powdered mixture subjected to shaking is atomized

  ge, a mixture of 0.3 part of the detergent perfume

  and 0.4 part of a linear C 10 _ 13 alkylate.

  When in place of an agglomerated Italian bentonite treated with sodium carbonate from which the abrasive particles have been removed, as in Example 1, a competitive product of the swelling clay type is used

  free of abrasive particles (Winkel agglomerate-

  mann) or a bentonite of the Wyoming type, for example that sold under the brand Mineral Colloid NO 101 (previously Thixogel No 1), analogous final products are obtained which constitute good softening detergents When the dye Blue Acilan, used to color the agglomerates of bentonite, is replaced by ultramarine blue, we also get good

coloring and brightening effects.

EXAMPLE 3

  When the proportions of the various compo-

  sants in the previous examples are modified by 10%, 20% and 30%, being maintained within the ranges indicated above and maintaining the ratios of the anionic detergent to the nonionic detergent

  in the range of about 1: 1 to 3: 1, the ratio of the te-

  total detergent neur to the detergency builder content in the range of about 1: 3 to 1: 8, and the ratio of sodium bentonite to total detergent

  in the range of about 1: 1 to 2: 1, results are obtained

  products having properties similar to those of the

  duits described in Example 1 This is also the case

  when the adjuvant salt (s)

  lubles of Example 1 are replaced by zeolite A (hydrated to 20%) and when a mixture of various synthetic anionic and nonionic detergents is used, possibly with an amphoteric detergent such as a detergent of the Miranol type Also, the composition detergent with bentonite agglomerates and its components may have densities (0.2 to 0.9 g / ml)

  and dimensions (preferably 0.42 to 2 mm) dif-

férentes.

Claims (10)

R E V E N D I C A T I O N S   1 Detergent composition in particles for bleaching laundry and softening textiles intended for washing laundry with water, which contains 3 to 10% of a sodium salt of a synthetic organic anionic detergent chosen from sulfonates and sulfates, 1 to 8% of a deter-   gent nonionic, 0 to 10% of an alkali metal soap hydro-   soluble, 20 to 75% of a detergency builder for deter-   synthetic organic gent, 5 to 35% of a bleaching agent which liberates oxygen in aqueous solution at high temperature, and 5 to 25% of agglomerated bentonite of dimensions   particles between 0.149 and 2 mm.   2 A detergent composition according to claim 1, in which the sodium salt of the anionic detergent is chosen from sodium alkyl benzene sulfonates having a linear alkyl group in which the alkyl group greater than from 10 to 14 carbon atoms, higher fatty alcohol) sodium sulfates in which fatty alcohol greater than 10 to 16 carbon atoms, and (higher fatty alcohol) sodium polyethoxysulfates in which fatty alcohol greater than 10 to 18 carbon atoms   carbon and which contain 3 to 20 ethoxy groups per molar   cule, and their mixtures, the non-ionic detergent is a   (higher fatty alkoxy) -poly (lower alkoxy) lower alkanol   In which the fatty alkoxy group greater than 10 to 16 carbon atoms, and the lower alkoxy and alkanol groups have 2 or 3 carbon atoms and which contains 3 to 20 lower alkoxy groups per molecule, the soap is a soap of fatty acids having from 10 to 24 carbon atoms per molecule the detergency builder is chosen from water-soluble and water-insoluble detergency builders and their mixtures, the bleaching agent is sodium perborate and bentonite has a moisture content   at least 3% and swells in water, its power to swell- being at least 1 ml / g.   3 A detergent composition according to claim 2, which comprises 3 to 7% of (higher alkyl) sodium benzene sulfonate with linear alkyl group, having from 11 to 13 carbon atoms, 2 to 5% of a (higher fatty alkoxy ) lower poly (lower alkoxy) alkanol in which the fatty alkoxy moiety greater than 12 to 15 carbon atoms, the lower alkoxy and lower alkanol moiety have 2 carbon atoms, and the molar ratio of the higher fatty alkoxy moiety to the lower alkoxy moiety is 1: 5 to 1:15, 2 to 6% sodium soap of higher fatty acids having 14 to 18 carbon atoms per mole, 30 to 50% of adjuvant salt of water-soluble detergency, 15 to 25% of perborate sodium and 10 to 20% sodium bentonite.   4 A detergent composition according to claim 3, in which the particles have a size of between 0.149 and 2 mm, the (higher alkyl) sodium benzene sulfonate, the soap and the detergency builder salt together form substantially homogeneous particles dried by atomization from the same mixer mixture, sodium perborate is in separate or separable particles, and bentonite is in separate particles. 5 detergent composition according to claim 4,   wherein the higher alkyl group of (higher alkyl   laughing) sodium benzene sulfonate with linear alkyl group is dodecyl group non-ionic detergent is a condensation product of a higher fatty alcohol having from 12 to 15 carbon atoms and from 9 to 13 moles of ethylene oxide per mole of higher fatty alcohol, the soap is a sodium soap   hydrogenated tallow fatty acids, the adjuvant salt of deter-   gence is mainly pentasodium tripolyphosphate   and the bentonite particles are in the form of agglomerates   merats obtained after treatment with sodium carbonate of bentonite containing magnesium and / or calcium for "5249-0   produce sodium bentonite, thereby containing   magnesium carbonate and / or calcium carbonate.   6 A detergent composition according to claim 5, which contains from 1 to 5% of sodium sulfate, from 0.1 to 2% of optical brightening dye and from 0.1 to 1% of proteolytic enzyme, the particles of agglomerated bentonite having an average particle size greater than the average particle size of the spray-dried particles   and perborate particles, and being colored differently   so they are easily identifiable in the detergent composition.   7. A detergent composition according to claim 6, in which the sodium bentonite has a swelling power of 5 to 30 ml / g and a viscosity, in dispersion at 10% in water, of 5 to 30 m Pa s, and is a agglomerate of smaller particles of ground sodium bentonite, the particles of which   abrasives were removed after grinding and before agglomeration-   ration. 8 A detergent composition according to claim 7, which contains about 5% of sodium dodecylbenzenesulfonate with linear dodecyl group, about 3% of nonionic detergent of the type (higher fatty alkoxy) poly- (lower alkoxy)   lower alkanol in which the higher fatty alkoxy moiety   lower than 12 to 15 carbon atoms, the lower alkoxy moiety and the lower alkanol moiety have 2 atoms   carbon, and the molar ratio of the fatty fatty alkoxy moiety   laughing at the lower alkoxy fragment is about 1:11, approxi-   ron 5% sodium soap of hydrogenated tallow fatty acids, about 20% sodium perborate, about 16% sodium bentonite, about 35% hydrated pentasodium tripolyphosphate, about 3% sodium silicate, about 0.3 % proteolytic enzyme, about 0.6% fragrance, about   0.2% optical brightening agent, and approximately 9% moisture.   9 A detergent composition according to claim 1, in which the bentonite particles are in the form of agglomerated particles obtained after treatment, with sodium carbonate, bentonite containing magnesium and / or calcium to replace this magnesium and / or this calcium   with sodium, and consequently containing magnesium carbonate sium and / or calcium carbonate.   A detergent composition according to claim 9, wherein the sodium bentonite agglomerate has a   bulking power of 5 to 30 ml / g and a viscosity, in dispersed   sion at 6% in water, from 5 to 30 m Pa s, and is an agglomerate of smaller ground sodium bentonite particles, from which the abrasive particles have been removed after grinding and before agglomeration.   11 Method for manufacturing a particulate detergent composition for washing clothes and softening textiles intended to be used for washing clothes with water, containing 3 to 10% of the sodium salt of an organic anionic detergent synthetic or a mixture chosen from the group comprising sulphonates and sulphates, 1 to 8% of a nonionic detergent, 0 to 10% of a water-soluble alkali metal soap, 20 to 75% of a detergency builder for synthetic organic anionic detergent, 5 to 35% of a bleaching agent which liberates oxygen in aqueous solution at high temperature, and 5 to 25% of agglomerated bentonite, this process consisting in treating a clay of the bentonite type containing magnesium and / or calcium and abrasive particles with sodium carbonate to transform at least part of the calcium and / or magnesium present in sodium, the magnesium carbonate and / or calcium carbonate thus obtained accompanying bentonite s odium produced, to reduce the particle size of the resulting product, to remove abrasive particles therefrom, to agglomerate the product free of abrasive particles, to spray-dry a mixer mixture comprising the sodium salt of synthetic organic anionic detergent, the soap optionally present and the detergency builder and mixing the bleach in particulate form and the agglomerated bentonite with the spray dried particles   thus obtained to obtain a product as described.   12 Method according to claim 11, characterized in that the particles of agglomerated bentonite are larger than the particles of spray-dried detergent composition, and the particles of bentonite   agglomerates are colored blue so as to distinguish them   removes particles of detergent and bleach and so as to have a brightening effect on the washed laundry with the detergent composition.   13 Process for manufacturing a detergent composition   te particulate for washing clothes and softening textiles for washing clothes with water, containing a detergent proportion of a synthetic organic detergent chosen from anionic detergents and not   ionic, an effective proportion of a deter-   agency for synthetic organic anionic detergent,   and a proportion of agglomerated bentonite with a softening effect   tissue, this process of reducing the size   bentonite containing abrasive particles, to separate the bentonite whose dimensions have been reduced from the abrasive particles by a separation process based on the dimension or dependent on the density, to agglomerate the separated bentonite free of the abrasive particles at particle sizes between 0.149 and 2 mm and mixing the bentonite particles with particles   spray dried which contain the synthetic detergent   tick and detergency builder and which have dimensions within the same range as that of agglomerated bentonite. 14 Process for the manufacture of agglomerated bentonite particles suitable for being mixed with spray-dried particles containing a synthetic organic detergent selected from anionic and nonionic detergents, and a detergency builder for anionic detergent, in order to prepare detergent compositions for softening textiles, this process consisting in reducing the size of natural bentonite containing an exchangeable divalent metal chosen from calcium and magnesium, and their mixtures, in reacting it with an alkaline substance to replace at least part of it divalent metal with a monovalent metal chosen from sodium and potassium, to dry the resulting bentonite, to reduce its size, with the abrasive material it contains, to then separate the bentonite from the abrasive material and to agglomerate the bentonite into particles of   dimension between 0.149 and 2 mm.