FR2611213A1 - SOLID DETERGENT AND SOFTENING COMPOSITIONS WITHOUT PHOSPHATE FOR LAUNDRY WASHING, CONTAINING DIAMONIC COMPOUND - Google Patents

Abstract

THE INVENTION CONCERNS A SOLID DETERGENT AND SOFTENING COMPOSITION WITHOUT PHOSPHATE FOR WASHING LAUNDRY. THE COMPOSITION INCLUDES A DIAMMONIUM COMPOUND TYPE SOFTENER, SUCH AS N-DIMETHYL-N- CHLORIDE (SUIF ALKYL) -N-TRIMETHYL-PROPYLENE-DIAMMONIUM, AND A MINERAL SOFTENER OF THE CLAY TYPE, SUCH AS A SMALL CLAY , WHICH ARE INTIMATELY MIXED WITH PEARLS OR GRANULES OF DETERGENT COMPOSITION WITHOUT PHOSPHATE DRIED BY ATOMIZATION. THE FINAL COMPOSITION OFFERS IMPROVED SOFTENING PROPERTIES EVEN AT LOW LEVELS (EXAMPLE LESS THAN 2.5) OF DIAMMONIC COMPOUND, WITHOUT ADVERSE EFFECTS ON THE CLEANING OR BLEACHING ACTION. IN A TYPICAL PHOSPHATE-FREE DETERGENT AND SOFTENING COMPOSITION, THE ATOMIZED-DRIED PEARLS INCLUDE A (LINEAR ALKYL) BENZENE SULPHONATE OR OTHER ANIONIC SURFACTANT, AN ADJUSTING SALT FOR MINERAL AND OR ORGANIC DETERGENCE, AND OTHER PHOSPHATE ADDITIVES, AND OTHER PHOSPHATE ADDITIVES STABLE TO HEAT, AS WELL AS OTHER INGREDIENTS ADDED AFTER-STROKE WITH SOFTENING AGENTS, SUCH AS A NON-IONIC SURFACTANT, ENZYME, PERFUME, BLEACHING AGENT AND OTHER ADDITIVES WHICH MAY BE SENSITIVE TO PH OR BY HEAT, INSOLUBLE IN WATER OR REACTIVE TO ONE OR MORE CONSTITUENTS OF ATOMIZED DRIED PEARLS. FIELD OF APPLICATION: DETERGENT PRODUCTS FOR WASHING LAUNDRY.

Description

The present invention relates to a phosphate-free softening detergent

for washing clothes,

  that is to say a softening and deter-

  base of a softening clay and an agent

  diametric cationic softener. This invn-

  more particularly concerns a composition

  phosphate-free detergent powder for laundry

  holding a detergent surfactant, a softening clay

  te and a softening agent of the diammonium salt type,

  the process of preparing the composition and its use

  washing for textile materials.

  Detergent powder compositions containing

  a detergent surfactant (anionic, nonionic, etc.) with a softening agent and a fabric softener

  cationic agent and / or an antistatic agent, such as

  quaternary ammonium salt, a di (ammonium

  quaternary), etc., are known in the art. Examples

  Representative examples of the patent literature in this field are United States patents

  No. 3,862,058; N 3 886 075; No. 3,915,882; No. 3,948,790;

  No. 4,203,851; the British patent application

  GB 2 141 152 A. Other patents relating to

  clay treatments for the treatment of

  take the patents of the United States of America

  N 3 594 212 and N 4 062 647. The use of benton

  for the softening of textile materials is known from British Patents N 401 413 and

N 461 221.

  While satisfactory cleaning and softening performance has been obtained with known softening clay detergent compositions, it would be desirable to decrease the amount of softening clay without adversely affecting the softening and cleaning performance of the softening clay. compositions. In addition, polyphosphates were

  contained in laundry detergents to be

  responsible for the unfavorably high phosphate content of surface water. It has been found that a higher phosphate content of surface water contributes to increasing the growth of algae, which

  causes a detrimental change in the biological balance

logic of water.

  Legislation has recently been introduced in some countries to reduce the amount of polyphosphate present in laundry detergents, and in some countries o polyphosphates

  posed a problem, to require that the deter-

  clothes do not contain adjuvants

detergency of the polyphosphate type.

  Therefore, a purpose of this invention

  is to provide a phosphate-free, clay-softening detergent composition containing an agent

  softener of the diammonium compound type.

  Another object of the invention is to provide a polyphosphate-free detergent composition for laundry, in the form of spray-dried beads, wherein the spray-dried beads are mixed with a softening diammonium compound and a fabric softening clay, and one

  process for the preparation of this composition.

  Another object of the present invention is to provide a detergent powder composition with softening clay, reinforced with a detergency adjunct, without polyphosphate, the clay content of which is softened.

  health is reduced without negative effects-on the performance

  cleaning, bleaching or softening

composition.

  Yet another object of the present invention is to provide a powdered detergent composition for

  softening clay, without polyphosphate, in the

  that the cationic salt softening agent of the diammonium salt type and the softening clay may be added afterwards to the dried pearls or granules

atomization.

  These objects of the invention as well as others

  will emerge from the following detailed description

  preferred embodiments being obtained using as a cationic softener compound a

  diammonium salt of formula (I) below.

R2 R4

R-N - R7 N R.2X (I)

1 7 1 5

R3 R6

  wherein R 1 is an aliphatic hydrocarbon radical having from about 12 to about 30 carbon atoms; each of R 2, R 3, R 4, R 5 and R 6 is independently selected from aliphatic hydrocarbon groups having 1 to 22 carbon atoms, with the proviso that the total number of carbon atoms in all aliphatic hydrocarbon groups, including R 1 not more than about 75, and with the additional proviso that not more than two of R 2 to R 6 have more than 12 carbon atoms, R 7 is -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -; and

  X is an anion forming a water-soluble salt.

  The diammonium compounds of formula (I) can be dispersed in an organic or aqueous vehicle and

  be atomized on the granules or detergent beads.

  It is also possible to heat the diammonium compounds at a temperature above their melting temperature and to atomize them on the detergent granules or beads. Alternatively, the diammonium compounds can, in the form of an aqueous dispersion, an organic solution.

  or melt, be added to the clay soften

  and then mixed with the granules or detergent beads. According to the present invention, the desired degree of softening can be achieved by using lower levels of softening clay and without deleteriously affecting the other properties of the detergent composition, including cleaning and bleaching performance. Another advantage

  composition is to be low foaming.

  The softening diammonic compounds are soluble in the usual organic solvents and / or form stable dispersions in water. The composites

  softening diammonics are generally unsafe

  in the water. Since agents soften

  of the diammonium salt type of formula (I) are available or can be prepared in organic solutions or aqueous dispersions, they can be

  easily and safely handled in

  intended for the treatment of powders and they are

  can be easily atomized on the compositions de-

  Powdered or granular tergents reinforced for heavy laundry or mixed with another

way with these compositions.

  In a preferred embodiment of the invention

  Diammonical relaxation and softening clay

  The ingredients are premixed and then incorporated as a postaddition ingredient to the spray-dried granules or powder laundry detergent composition. A representative example of formulation of

  dried pates by reinforced atomisation for large

  of laundry including the softening agent

  sant of formula (I) and a softening clay may contain the following ingredients: Proportion (% by weight) Ingredients; Coeposition Dried Beads Total by atomisatin Detergent Surfactant Composition 1-95 10-60

Organic detergency adjuvants

  2-80 15-90 Softening Clay 1-50 0 Formula Softener (I) 0.2-5 O Fillers 0-25 0-10 Bleach and Bleach Additives 0-25 0- 5 Optical brighteners, pigments, dyes 0-10 0-8 Defoamers, suds suppressors, etc. 0-10 0-8 Enzymes 0-5 O pH adjusting agents, buffers, etc. 0-10 0-8 Agent antiredépositiaon, perfume, etc. 0-5 0-3 Water the rest In a preferred method of preparation of the detergent composition reinforced with powder or granules for heavy duty washing, the ingredients are mixed heat-stable, pH-insensitive detergents in a blender and spray-dried to form spray-dried beads, and then uniformly blended or spray-coated with the

  diammonic compound softener of formula I and half

  clay mineral softener and with the ingredients of

  formulation that are sensitive to pH and / or sensitization

  heat-resistant or otherwise able to react with the anionic surfactant or other component of the spray-dried beads or granules. As examples of ingredients added after the fact to be mixed with the spray-dried beads, there may be mentioned, for example, a bleaching agent, enzymes, a perfume, a nonionic surfactant, etc. The diammonic compound softener of formula I can, as

  mentioned above, be premixed with the clay as-

  soft and mixed with pearls or granules

  spray dried. The procedures of pre-

  paration of the composition are well known in the

  technique and those skilled in the art will be able to determine

  with ease the optimum conditions for preparing

  tion. Synthetic organic detergent compounds

  The laundry detergent compositions can

  to contain one or more surfactants chosen fromanionic, nonionic detergents,

  ampholytic and zwitterionic. Organic detergents

  The synthetic materials used in the practice of the invention can be any of a variety of such compounds which are well known and are described in detail in the "Surface Active Agents and Detergents", Volume II, of Schwartz, Perry and Berch, published in 1958 by Interscience Publishers. The total proportion of the detergent surfactant compound (s) can be as high as% by weight of the total detergent composition, although preferred portions are in the range of about 1 to 70% by weight, particularly 5 to 50% by weight, and more preferably from about 5 to

  % by weight of the total detergent composition.

  The detergent compositions of this

  invention preferably use one or more

  posed anionic detergents as primary surfactants. The anionic detergent may be supplemented, if desired, by another type of surfactant, preferably a nonionic detergent, particularly when it is

  used in combination with an adjuvant salt of

tergence.

  Anionic surfactants Among the anionic surfactants useful in the present invention, there may be mentioned surfactant compounds which contain a hydrophobic organic group containing about 8 to 26 carbon atoms and, preferably, about 10 to 18 carbon atoms in their molecular structure and at least one solubilization group in water selected from groups

  sulfonate, sulfate, carboxylate, phosphonate and phosphorus

  D phate, so as to form a water-soluble detergent.

  Examples of suitable anionic detergents

  required include soaps such as hydro-

  soluble (eg sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 atoms

  carbon and preferably 10 to 18 carbon atoms.

  Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example tallow, fat, coconut oil and mixtures thereof. The sodium and potassium salts of the coconut oil-tallow fatty acid mixtures, for example coconut sodium soap and tallow potassium soap, are of particular interest. The class of anionic detergents comprises

  sulphated and sulphonated detergents

  soluble compounds having an aliphatic radical, preferably

  of about 8 to 26, and preferably

  this is about 12 to 22 carbon atoms. (The term "alkyl"

  includes the alkyl portion of the higher acyl radicals).

  Examples of the sulphonated anionic detergents are

  alkylated monocyclic aromatic sulfonates

  such as (higher alkyl) benzenesulfonates whose higher alkyl group contains about 10 to 16 carbon atoms in a chain configuration

  straight or branched, such as for example

  benzene-sulfonates, (higher alkyl) toluene-

  sulfonates and (higher alkyl) -phenol-sulfonates

sodium, potassium and ammonium.

  Other suitable anionic detergents are olefin sulfonates including long-chain alkene sulfonates, long-chain hydroxyalkanesulfonates, and long-chain hydroxyalkanesulfonates.

  chain, or mixtures of alkene-sulphonates and hydro-

  xyalcane sulfonates. The olefin can be

  sulfonates in a conventional manner by reacting sulfuric anhydride (SO3) with

  long chain containing about 8 to 25, and preferably

  about 12 to 21 carbon atoms, these olefins

  formula RCH = CHR1 where R represents a higher alkyl group of about 6 to 23 carbon atoms and R1 represents hydrogen or an alkyl group containing

  about 1 to 17 carbon atoms, to form a

  a mixture of sulfones and alkene sulphonic acids which is then treated to convert the sulphones to sulphonates. Other examples of sulfated or sulfonated detergents are paraffin sulfonates containing about 10 to 20 carbon atoms, and preferably about 15 to 20 carbon atoms. Primary paraffin sulfonates are prepared by reacting long chain alpha-olefins and bisulfites. Paraffin sulfonates whose sulfonate group is distributed along the paraffinic chain are described in U.S. Patent Nos. 2,503,280; N 2,507,088; No. 3,260,741; N 3 372 188 and in the

German Patent No. 735,096.

  Other suitable anionic detergents are sulphated ethoxylated higher fatty alcohols of formula RO (C 2 H 4 O) m SO 3 M, where R represents a fatty alkyl group of 10 to 18 carbon atoms, m is 2 to 6 (preferably a value of from at half the number of carbon atoms of the group R) and M is a salt-forming solubilising cation, such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino cation. The proportion of ethylene oxide in the sulfated polyethiolated higher alkanol is preferably from 2 to 5 moles of ethylene oxide groups per mole of anionic detergent,

  a quantity of three moles being particularly preferred.

  especially when the higher alkanol has

  11 to 15 carbon atoms. In order to maintain the

  desired hydrophilic-lipophilic port, when the number of carbon atoms of the alkyl chain is in the lower part of the range of 10 to 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about two moles per

  mole, while in the upper part of the

  when the higher alkanol has from 16 to 18 carbon atoms, the number of oleoic oxide groups can be increased to 4 or 5 and in some cases

  value as high as 8 to 9. Similarly, we can modify

  Prove the salt-forming cation in order to achieve the best solubility. It can be any metal or a suitably solubilizing radical, but it is most often an alkali metal, for example sodium or ammonium. If lower alkylamine or alkanolamine groups are used, the alkyl and

  alkanol generally contain 1 to 4 carbon atoms.

  and the amines and alkanolamines may be mono-, di- and trisubstituted, as in the case of monoethanolamine, diisopropanolamine and trimethylamine. Preferred polyethoxylated alcohol sulfate as a detergent is available from Shell Chemical Company and sold under the trade name Neodol®-3S.

  Anionic water-soluble detergent compounds

  which are very preferable are (higher alkyl)

  benzene-sulfonates, olefin-sulfonates and ammonium and ammonium

  substituted (for example mono-, di- or triethano-

  alkaline metals (eg sodium and potassium) and alkaline earth metals (eg calcium and magnesium). Of the above-mentioned anionic detergents, those which are most preferred are sodium (linear alkyl) benzene sulfonates (ALBS), and in particular those in which the alkyl group is a straight chain alkyl radical of 12 or

13 carbon atoms.

  Anionic surfactant is usually the most important

  detergent component and can constitute approximately

  30 to 100% of all the surfactant ingredients

  assets. Preferably, the anionic surfactant

  at least 50%, preferably at least 60%, more preferably at least 70%, and at most about 99%, preferably at most about 90%, more preferably at least

  plus about 80% of the total ingredients

sio-active detergents.

  The anionic surfactant compound is generally

  and preferably incorporated as a component of the spray-dried beads and is added to the mixer mixture in the form of an aqueous solution or dispersion, and preferably in the form of a

  highly concentrated aqueous suspension.

  Non-ionic surfactants The next class of detergent surfactant ingredients in order of preference is synthetic organic detergent compounds.

nonionic.

  Nonionic synthetic organic detergents are characterized by the presence of a group

  hydrophobic organic and a hydro-organic group

  and are typically produced by the condensation of an aliphatic or alkyl aromatic aromatic hydrophobic compound with ethylene oxide (of hydrophilic nature). Virtually any hydrophobic compound carrying a carboxy, hydroxy, amido or amino group with a labile hydrogen atom attached to nitrogen may be condensed with ethylene oxide or

  with its polyhydration product, polyethylene-

  glycol, to form a nonionic detergent. The length of the hydrophilic polyoxyethylene chain can be easily adjusted to achieve the ratio

  desired between the hydrophobic and hydrophilic groups.

  The nonionic detergent used is preferably

  a lower alkoxy polyalkoxylated alkanol, wherein the alkanol has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and o the number of moles of lower alkylene oxide (2 or 3 carbon atoms) is from 3 to 20. Among these materials, it is preferable to employ those whose higher alkanol is a higher fatty alcohol of 11 to 15 carbon atoms and which contain 5 to 13 lower alkoxy groups per mole. Preferably, the lower alkoxy group is ethoxy but in some cases it may be advantageously mixed with the propoxy group which, if present, is often only a minor component (less than%). Representative examples of such compounds are those whose alkanol has from 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per molecule, for example Neodol (registered trademark) 25-7 and Neodol 23-6, Which are products manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide. and the second is a mixture where the number of carbon atoms of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups per mole is on average

  about 6.5. The higher alcohols are alkalis

  primary soils. Other examples of such detergents include Tergitol (registered trademark)

  -S-7 and Tergitol 15-S-9 which are both ethos

  Secondary linear alcohol xylates manufactured by Union Carbide Corporation. The first is a mixed ethoxylation product of a secondary linear alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide and the second is a similar product but

  nine moles of ethylene oxide reacted.

  Nonionic surfactants which are very preferable for their utility in the present compositions are

  higher molecular weight nonionic detergents

  such as Neodol 45-11, which are similar products of ethylene oxide condensation on

  higher fatty alcohols, the higher fatty alcohol

  14 to 15 carbon atoms and the number of groups

  ethylene being about 11 per molecule. These

  Dukes are also manufactured by Shell Chemical

Company.

  Based on all of the detergent surfactant ingredients contained in the detergent composition, the nonionic surfactant may be present in amounts of up to about 70% by weight, preferably about 50%, more preferably

  about 40%, and in particular about 15%. In general

  In general, the nonionic surfactant, when used, is at least 1%, preferably at least 10%, and especially at least 30% of the combined weights of all the detergent surfactant ingredients. On the

  basis of the totality of the detergent composition

  softening agent, the nonionic surfactant is generally

  present in the range of about 0.1 to 20%, preferably

  15%, and more preferably 0.6 to 10% by weight.

  Since nonionic surfactants are often difficult to dissolve in water or

  form viscous solutions or gels when

  they are added to water they are usually presented as solutions in a solvent

  organic, for example, in ethanol or isopropanol

  nol, alone or with water. Therefore, when the nonionic surfactant is available in the form of its

  solution in an organic solvent, it is not

  It will not be added to the mixer mixture to form the spray-dried granules or beads, but instead it will be added after-the-fact to the already dried spray-dried beads. In addition, even when using the nonionic surfactant in its pure liquid form (most nonionic surfactants being liquid at ambient temperatures) or in the form of an aqueous solution, it is still preferable to add after-the-fact the nonionic surfactant

spray dried beads.

  Zwitterionic detergents are also

  such as betaines and sulfobetaines

to the following formula:

9

R8_N R1 1 X = 0

R $

R10 L O

  wherein g 8 represents an alkyl group containing about 8 to 18 carbon atoms, R 9 and R 10 each independently represent an alkyl or hydroxyalkyl group containing about 1 to 4 carbon atoms.

  carbon, R11 represents an alkylene or hydro-

  xyalkylene containing 1 to 4 carbon atoms, and X represents a carbon atom or an S: O group. The alkyl group may contain one or more intermediate links such as amido, ether or polyether links or nonfunctional substituents such as the hydroxyl group or a halogen which do not affect

  not significantly the hydrophobicity of the group.

  When X represents a carbon atom, the detergent is called a betaine; and when X is S: O, the detergent is called a sulfobetaine

or sultaine.

  Ampholytic detergents are also

  appropriate in the invention. Ampholytic detergents

  are well known in the art and a large number of usable detergents of this class are described

  by Schwartz, Perry and Berch in the book

  "Active Agents and Detergents". of the

  Examples of suitable amphoteric detergents include

  are: alkyl-beta-imino-dipropionates, RN (C2H4COOM) 2; alkyl-beta-aminopropionates, RN (H) C 2 H 4 COOM; and long-chain imidazole derivatives of the general formula: CH 2

N CH2

He 1

R - C N CH2CH2OCH2COOM

OH CH2COOM

  in each of the above formulas, R represents a hydrophobic acyclic group containing about 8 to 18 carbon atoms and M is a cation

  used to neutralize the charge of the anion. Some deter-

  Particularly useful amphoteric moieties include the disodium salt of undecylcycloimidinum acid

  (ethoxyethanoic) -2-ethanoXque, the dodecylbeta;

  alanine and the internal salt of 2-trimethylamino

lauric.

  The amounts of synthetic organic detergent

  The rionic and synthetic ampholytic organic detergent optionally present in the cpDsitim of the invention are not particularly critical and may be selected depending on the desired results. In general, one or the other can be used

  or these two classes of detergent ingredients to replace

  place all or part of the detergent anionic organic surfactant and / or non-organic surfactant

  ionic detergent within the limits of the above-mentioned

  mentioned. As in the case of anionic and nonionic surfactants, those skilled in the art will readily be able to determine whether to include zwitterionic and ampholytic surfactants as a component of the blender mixture for forming the dried or granulated beads. atomizing or subsequently adding these compounds to the spray-dried beads to form the final reinforced detergent composition for heavy laundry operations. Briefly, when in the form of aqueous solutions, they are preferably added to the mixer mixture and when in organic solvents they are added to the spray-dried beads after the fact. Clay Softening Agents Clay softener may be selected from any softening clay known in the art to provide flexibility to washed fabrics in their presence. The preferred clays are the clays of

  smectite type, and those with a

  ion exchange city of at least about 50 meq / 100 g of clay (50 milliequivalents per 100 grams of clay). The smectite clays useful in the present invention are three-layer clays

  characterized by the ability of the structure to

  to increase its volume by several

  expanding or diluting in the presence of water to form a thixotropic gelatinous substance. There are two distinct classes of smectite-type clays: in the first class, aluminum oxide is present in the crystalline silicate lattice; in the second class, magnesium oxide is present

  in the crystalline silicate lattice. A substitute

  of atoms by iron, magnesium, sodium,

  potassium, calcium, etc., may exist within the

  crystalline lattice of smectite-type clays. It is customary to distinguish clays according to

  their predominant cation. For example, a sodic clay

  what is a clay in which the predominant cation

is sodium.

* The cation exchange capacity of a mineral

  clay is linked to factors such as

  clay swelling properties, the burden of the ar-

  which are in turn determined at least in part by the structure of the network etc. The ion exchange capacity of clays varies over a wide range of about 2 meq / 100 g for kaolinites

  to about 150 meq / 100 g and over for some

  the ones of the variety montmorillonite. The illite type clays have an ion exchange capacity located in the lower part of the range, that is to say around 26 meq / 100 g for a clay of the type.

average illite.

  It has been determined that illite and kaolinite clays, with their relatively low ion exchange capacities, are not useful as, or only marginally, softening clay. In fact, these illite and kaolinite clays are a major component of clay soils and, as mentioned above, are removed from the tissue surface by means of the compositions of the present invention. However, smectites such as nontronite, having an ion exchange capacity of about 50 meq / 100 g, saponite, which has an ion exchange capacity of about 70 meq / g, and montmorillonite which has an ion exchange capacity greater than 70 meq / 100 g, have been found to be very useful softening agents in that they deposit on the tissues by exerting the desired softening effects. Therefore, preferred clay minerals useful herein can be characterized as clays of the smectite type to

  three layers, expandable, with a capacity of

  Ie ions of at least about 50 meq / 100 g. A smectite-type clay, known as "fooler clay", found in a relatively thin vein above

  from Black Hills, (USA), also presents the

  Required Ion Exchange Drives characteristics of

  useful clays here and this clay is also in

  globeted by the expression "smectite-type clay",

as used here.

  The smectite clays used in the compositions of the invention are all commercially available. These clays include, for example, montmorillonite, volchonskoite, nontronite,

  hectorite, saponite, sauconite and vermicul-

  lite. These clays are available under various

  such as Thoxogel N 1 (also "Thixo-Jel") and Gelwhite GP of Georgia Kaolin Company, Elizabeth, New Jersey; Volclay BC and Volclay N 325 from American Colloid Company, Skokie, Illinois; Black Hills Bentonite BH450 from International Minerals and Chemicals; and Veegum Pro and Veegum F by R. T. Vanderbilt. It should be noted that these type minerals

  smectite obtained under the trade marks

  above may comprise mixtures of the various discrete mineral entities. These smectite mineral mixtures are suitable for use in the invention. While any of the smectite clays having a cation exchange capacity of at least about 50 meq / 100 g are particularly useful herein, some clays are preferable. For example, Gelwhite GP clay is a very form

  smectite type of clay and is therefore preferable

  if it is desired to prepare deter-

  white granular gentes. Volclay BC, which is a

  clay mineral of the smectite type, whose crys-

  tallin contains at least 3 percent iron (expressed as Fe 2 O 3) and has a very high ion exchange capacity, is one of the most effective clays for use in laundry compositions and is prefers from the point of view of product performance.

  Suitable clay minerals can be selected

  requested by virtue of the fact that smectites have a

  14A X-ray diffraction pattern true. This spec-

  This characteristic, taken in combination with the exchange capacity measurements performed in the manner mentioned above, provides a basis for the selection of the particular smectite-type minerals for use in the granular detergent compositions described herein. In the compositions of the present invention,

  the softening clays that one prefers all

  particularly important are aluminum silicates in

  which sodium is the predominant cation, such as clays of the bentonite type. Among the bentonite-type clays, those from Wyoming (generally known as bentonites from the western United States of America or Wyoming) are particularly preferred.

  Preferred swelling bentonites are sold

  under the trademark Mineral Colloid, as industrial bentonites, by Benton Clay Company, a subsidiary of Georgia Kaolin Company. These

  which are the same as those

  sold under the trademark THIXO-JEL,

  are selectively extracted and enamelled bentonites

  chies, and those considered the most useful are available under the designation Mineral Colloid N 101, etc., corresponding to THIXO-JEL N 1, 2, 3 and 4. These materials have a pH (concentration of 6% in water) in the range of 8 to 9.4, maximum free moisture levels of about 8% and densities of about 2.6, and in respect of the quality sprayed, at least about 85 % (and preferably 100%) pass through a sieve of 74 microns mesh. Preferably, the bentonite is in such a form that substantially all of its particles (i.e., at least 90% of the particles, preferably more than 95%) pass through a mesh screen.

  44 micrometers and, better still, all the

  These cells pass through such a sieve. The swelling capacity of bentonites generally corresponds to a capacity

  water absorption rate of 3 to 15 ml / gram and their visco-

  at a concentration of 6% in water, is generally

typically about 8 to 30 mPa.s.

  Instead of using THIXO-JEL or Mineral Colloid bentonites, products such as

  that sold by American Colloid Company, Indus-

  Trial Division, under the name "General Purpose Bentonite Powder, 325 mesh", of which a minimum fraction of 95% has a particle diameter of less than 44 micrometers (wet particle size) and a fraction of at least 96% has a diameter particle size less than 74 micrometers (particle size

  dry). Such hydrated aluminum silicate is

  predominantly montmorillonite (90% minimum), with lower proportions of feldspar, biotite and selenite. A typical "anhydrous" analysis is 63.05% silica, 21.5% alumina, 3.3% ferric ion (expressed as FeO), 0.4% ferrous ion. (expressed as FeO), 2.7% magnesium (expressed as MgO), 2.6% sodium and potassium (expressed as Na O) and 0.7% calcium (as CaO), 5.6% of water of crystallization (expressed in HO) and 0.7% of elements present in

the state of traces.

  Although bentonites are preferred in the western United States of America, it is also possible to use other bentonites, such as those which can be made by treating Italian bentonites or the like with proportions

  relatively small amounts of monovalent metals exchanged

  (sodium and potassium) with alkaline substances

  lines such as sodium carbonate, to increase

  the cation exchange capacities of these products.

  It is believed that the Na2O content of the bentonite should be at least about 0.5%, preferably at least 1%, and more preferably at least 2%, so

  that the clay swells properly and has good

  properties of softening and dispersion in

  aqueous suspension. Swelling bentonites preferable

  of the types described above are sold under the

  trademarks Laviosa and Winkelmann, for example

Laviosa AGB and Winkelmann G-13.

  Of course, any other clay minerals that are substantive to textile materials and are

  able to give them "flexibility".

  The preferred clays used herein are "imalpable", i.e. they have a particle size that can not be perceived by touch. Impalpable clays have particle sizes of less than about 50 micrometers; the clays used here have a particle size ranging

  from about 5 microns to about 50 microns.

  The softening agents of the clay type are

  present in the detergent compositions in

  3 portions of about 1 to about 50 percent, preferably

  from about 2 to 30%, more preferably from about 4 to

  % by weight, relative to the totality of the

  sition. In the present invention, it is preferable that the softening clay and the softening diammonium compound be added afterwards to the pearls or

  spray dried granules. The diammonium compound

  that softener is preferably dissolved in an organic solvent or dispersed in an aqueous liquid and mixed with the particles of the clay mineral. The

  diammonium softener compound and the clay mineral

  The softener is then intimately and uniformly mixed with the spray dried beads or granules.

  The diammonium softening compound and the

  the softener are present in the compositions

  detergents of the invention in a sufficient proportion

  to give the desired softening effect when

  that the composition is used in usual doses for a laundry detergent composition, for example from about 1/8 to 1/2 cup of detergent

by washing load.

  DETERGENT ADDITIVES The detergent compositions of the invention optionally contain, and preferably, at least one commonly used detergency builder.

  used in detergent compositions. The adjutants

  useful detergents include all the salts

  classic water-soluble mineral detergents,

  such as silicates, carbonates, bicarbonates

  water-soluble nates, borates, sulphates, etc. Organic detergency builders include

  Dolyhydroxy-sulfonates, polyacetates, aminopolyaceas

  tates, carboxylates, polycarboxylates, succinates,

phytates, Ptc., water-soluble.

  Specific examples of adjuvants for deter-

  non-phosphorus-containing minerals include carbon

  hydrosoluble minerals, bicarbonates and silicates

  ble. Carbonates, bicarbonates and silicates of alkali metals, for example sodium and potassium

are particularly useful here.

  Crystalline and amorphous aluminosilicates

  zeolitics are particular detergency builders

  useful. Generally, the zeolites have the general formula: (bO) x- (Al 2 O 3) y (SiO 2) z WH 2

  where x is 1, y is 0.8 to 1.2 and preferably

  1, z is 1.5 to 3.5 or more and preferably 2 to 3, west to 9 and preferably 2.5 to 6, and M is preferably sodium. A typical zeolite is a type A zeolite or similar structure, the type

  4A being particularly preferred. Aluminosilicones

  Preferred calcium ion exchange capacities are about 200 milliequivalents per gram or

more, for example 400 meq / g.

  Various zeolites (i.e. alumino

  Crystalline silicates which can be used are described in British Patent No. 1,504,168, U.S. Patent No. 4,409,136 and Canadian Patents Nos. 1,072,835 and 1,087,477. An Example of Useful Amorphous Zeolites here can be

  find in Belgian Patent No. 835,351.

  Hydroso organic detergency builders

  lubles are particularly useful. For example,

  acetates, carboxylates, polycarboxylates and polyhydric

  alkali metal, ammonium and substituted ammonium droxy-sulfonates are detergency builders useful in the compositions and methods of the present invention.

  present invention. Specific examples of

  detergents of the acetate and polycarboxy type.

  include the sodium, potassium, lithium, ammonium and substituted ammonium salts of

  ethylene-diaminetetraacetic acid, nitrilotri-

  acetic acid, benzene-polycarboxylic acids (i.e.

  penta- and tetracarboxylic acids), carbohydrate

  xymethoxysuccinic and citric acid.

  Other organic adjuvant salts of detergent

  Useful herein are the polycarboxylates disclosed in U.S. Patent No. 2,264,103, including alkali metal salts.

  water-soluble mellitic acid. Hydroso-

  polycarboxylic polymers and copolymers, such as those described in US Pat.

  No. 3,308,067, are also useful here.

  Particular detergent builder organic salts which can be used include

  alkali metal salts of polymers of hydro-

  xyacrylic, preferably the sodium and potassium salts. A particular detergency builder

  preferred is an alpha-hydroxy-acrylic acid polymer

  that or its sodium salt; the hydroxy acid polymer

  acrylic or its salt which may be used as an adjunct

  Detergent contains monomeric units of the formula:

R OH

1 l

C C

_ 12 OOM

not

  wherein R1 and R2 may be the same or different

  and each represents hydrogen or an alkyl group of 1 to 3 carbon atoms, such as methyl, ethyl and propyl. The preferred R 1 and R 2 substituents are both hydrogen. M represents hydrogen or an alkali metal such as sodium or potassium, or an alkaline earth metal such as calcium, magnesium

  or barium. The preferred substituent M is sodium.

  The terminal or end groups of the polymer

  are not very important and can be H, OH, CH-.

  or a hydrocarbon chain. The degree of polymerisation

  ticon, i.e., the value of n, is generally determined by the limit compatible with the solubility of the polymer in water. The hydroxy-acrylic acid polymer or its salt may, for example, have a weight

  from 2000 to 20000. See, for example,

  United States of America No. 3,920,570 and No. 4,107,411, which describe manufacturing processes.

polymers.

  Another class of useful organic detergency builder salts include metal salts

  alkaline or ammonium carboxymethyloxy

  succinic, preferably the trisodium salt. The salts of carboxymethyloxy-succinic acid which can be

  used in the detergent compositions of the present invention.

  invention correspond to the following general formula:

boasts:

MOOC-CH-COOM-

CH3O-CH-COOM

  wherein M is selected from hydrogen and alkali metal and ammaluminum cations, and at least one M is an alkali metal or ammonium. The preferred alkali metals are sodium and potassium, more preferably sodium. The mono-, di- and trisodium salts can be used, the trisodium salt being

the most appreciated.

  Another organic salt adjuvant detergence

  which can be used is an adjuvant salt of deter-

  alkali metal organic acid of po! ycarboxy-

  lower level. This class of organic salts

  detergents includes the alkali metal salts

  lower polycarboxylic acid inserts, for example having two to four carboxyl groups

  Sodium and potassium salts of polycarboxylic acids

  Preferred lower salts are the citric acid and tartaric acid salts. Sodium salts of

  citric acid are the most popular, especially

  bind the trisodium citrate. Other organic detergency additives that

  can still be used are polymers and co-

  polymers of polyacrylic acid and polymeric anhydride

  and their alkali metal salts. More specifically

  firstly, these builder salts may consist of a copolymer which is the product of the reaction of an approximately equal number of moles of acid

  methacrylic acid and maleic anhydride, having been

  completely neutralized to form its sodium salt.

  This detergency builder is available in the com-

  merce under the trademark Sokalan CP5. This

  detergency adjuvant serves, even when used

  in small amounts, to inhibit incrustation.

  Examples of organic adjuvant salts of

  alkaline sequestering detergents that can be used

  with the alkali metal builder salts of lower polycarboxylic acids or

  mixture with other organic detergency adjuvants

  Examples of these are aminopolycarboxylates of alkali metals, ammonium and substituted ammonium, for example sodium and potassium ethylenediaminetetraacetate (EDTA), nitriloacetates (NTA) of

  sodium and potassium and N- (2-hydroxyethyl) nitr -

  lodiacetates of triethanolamine. Mixtures of these

  aminopolycarboxylates are also suitable.

  Other suitable detergency builders

  organic type include polyacetal carboxylates

  your. Polyacetal carboxylates and their use in detergent compositions are described, for example, in United States Patents.

  Nos. 4,144,226, 4,315,092 and 4,146,495.

  Mixtures of adjuvants can be used

  organic and / or mineral detergents. It must be

  However, for reasons of economy, the varieties whose cations are alkali metals are preferred to inorganic polyvalent anionic detergency salts and mineral salts. described

  above, the water-soluble salts of ammonium, alkanol-

  ammonium, for example triethanolammonium, diethanolammonium, etc., all anions of adjuvants

  detergents described above are useful herein.

  Adjuvant detergency salts, comprising both organic detergency builder salts and

  minerals, are conveniently added to the mixture of

  langer to be incorporated with the anionic surfactant

  that, etc., in the spray-dried beads or granules such that they are present at about 75%, preferably about 20 to 60%, more preferably about 22 to 55% by weight detergency builder salts. on the basis of the weight of the spray-dried beads, and this proportion will generally be chosen so as to obtain in the finished composition,

  after mixing with the ingredients added after

  about 2 to 80%, preferably 10 to 70% and more preferably 20 to 50%, of builder salts

the basis of the total composition.

  Softening agent of the diammonium compound type

  The softening agents used in the pre-

  invention are diammonic compounds which

  are characterized by their general insolubility dals 1'e.

  The diammonic compounds useful here for improving

  to improve the relaxation performance of the

  are compounds of the general formula (1):

R2 R4

R1 N -R7 N -R5. 2X (I)

  Wherein R 1 is an aliphatic hydrocarbon group having about 12 to about 30 carbon atoms; each of the symbols R2, R3, R4, R5 and R6 is independently selected from hydrocarbon groups

  aliphatic compounds of 1 to 22 carbon atoms, with the con-

  the total number of carbon atoms of all aliphatic hydrocarbon groups, including R1,

  not be greater than about 75 and with the condition

  that not more than three of R2 to R6 have more than 12 carbon atoms; R7 is -CH2CH2- or -CH2CH2CH2-; and

  X is an anion forming a water-soluble salt.

  Preferred compounds of formula (I) are

  those containing only 1 or 2, and preferably only

  1, long carbon chain group, that is to say having 12 or more carbon atoms. Therefore, in formula (I), the preferred definitions of R 1 to R 6 are: R 1 is an aliphatic hydrocarbon group, which may be straight chain or branched chain, and saturated or unsaturated (i.e. linear or branched alkyl, alkenyl or alkynyl group) having 16 to 22 carbon atoms, for example 18 to 20 carbon atoms; R2 to R6 are independently selected from alkyl and alkenyl groups having 1 to 16, preferably 1 to 12, more preferably 1 to 6 carbon atoms, with the proviso that the total number of carbon atoms of all aliphatic hydrocarbon groups R1-R6 is not greater than about 50, preferably not

  greater than about 35, and with the additional condition

  that not more than 2, preferably not more than 1, and more preferably R2 to R6 has no more than 12 carbon atoms; R7 is -CH2CH2- or -CH2CHCH2-, preferably -CH2CH2CH2-; and X is an anion forming a water-soluble salt such as, for example, halide, for example bromide, chloride or iodide, sulfate, methosulphate, ethosulphate,

  hydroxide, acetate, propionate, or other mono-

  are worth similar organic or mineral solubilizer.

  Examples of preferred R1 groups include

  Stearyl groups, tallow, hydrogenated tallow, eicosyl, soy, etc.

  Examples of alkyl and alkenyl groups

  represented by R2 to R6 include the groups

  methyl, ethyl, propyl, isopropyl, n-butyl, tert-

  butyl, n-butyl, octyl, 1-octenyl, etc. Particularly preferred are methyl, ethyl, propyl

  and isopropyl, and at best the methyl and ethyl groups.

  Specific examples of compounds of formula (I) that are commercially available or

  which can be easily manufactured by

  Typical examples include: CH 3 CH 3 (1) tallow CH 2 CH 2 CH 2 N CH 3 Cl 2

CH3 CH3

(Adogen 477) (Adogen 477)

CH2CH3 CH2CH3 1

(2 tallow N CH 2 CH 2 CH 2 N CH 3.

CH3 CH

CH 1+

  (3) starylN - CH2CH2CH N ± CH3.2CH3SO4

I 222 1 334

CH3 CH3

CH3 16H37

CH3 CH3

  (5) C16H37 - N - CH2CH2CH2 - NCH3 2CH3SO4

C3H8 CH

* etc. and ethosulfates, halides, acetates, etc.

corresponding water-soluble

  Compound (1) above, namely the dichloid

  dimethyl-N- (tallow alkyl) -N'-trimethyl-

  propylene diammonium is particularly preferred.

  This compound is commercially available under the

  Adogen 477 denomination of Rewo Company. We can pre-

  parer this compound in the usual way, for example in

  reacting 1 mole of N-methyl-N-tallow-N'-methyl-

  propylene diamine with 3 moles of methyl chloride and then quaternizing the resulting compound with

methyl sulfate.

  The pearls or granules can be impregnated with the softening diammonium compound without the use of a solvent or carrier liquid. However, it is

  aGenerally preferable to dissolve the diamino compound

  monique softening agent in an organic solvent or disperse the softening diam-nic compound in an aqueous liquid vehicle. The diammonic softening compound is preferably premixed with the softening clay mineral and the mixture is added to the

  spray dried beads or granules.

  A solution and / or dispersion is mixed together.

  aqueous solution of pH-insensitive heat-stable ingredients, such as one or more detergency builders, fillers, anionic surfactant, pH adjusting agent, water, etc., to form the mixture of the mixer and then the mixture is dried

  atomization according to usual techniques.

  The spray-dried beads are then intimately intimately mixed with the softening diammonium compound and the softening clay, and the remaining ingredients, for example the non-ionic surfactant, the bleaching agent, the enzymes, the fragrances and other heat-sensitive ingredients. or at pH and / or insoluble in water, to prepare the

  final detergent-softening composition. The pro-

  portion of the spray dried beads and

  ingredients added after the fact is such that the

  The final statement contains the following proportions of the essential ingredients: I__ __ Ed_ __ i Proportion (% on <oic

Ingredient Iarn T.g, rp -.mA-

  Detergent 1-95 5-50 5-30 Detergent Adjuvants 2-80 10-70 20-50 Softening Clay 1-30 2-20 4-10 Ammonium Salt0; 25-10 0 5-5 1O0-2jS (Compound of formula (I)) 0 Acids for detents, Ar: es, 0-60 2-50 5-30 of Hhamdate eT.-t ama = a x.tiissen / .i_.c. - 10: 1 to 1: 1 6: 1 to 3: 1 The remainder, if any, of the composition is occupied by conventional additives for detergents, fillers

and moisture.

  Optional Components The use of an inert water-soluble filler salt is desirable in the laundry compositions of the invention. A preferred filler salt is an alkali metal sulfate such as

  potassium or sodium, the latter being particularly

  favorite. The proportion of charge generally reaches

  about 5%, for example 0.1 to 2%, preferably

  0.3 to 1% by weight of the composition.

  Various additives may be included in the laundry detergent compositions of the present invention. They usually include

  perfumes, dyestuffs such as pigments

  solubles and soluble dyes, agents of

  such as sodium perborate, activators

  bleaching agents, bleach stabilizers, antiredeposition or soil suspension agents such as the alkali metal salts of carboxymethylcellulose, optical brighteners such as anionic, cationic or nonionic brighteners, foam stabilizers such as alkanolamides, reinforcers

  moss, germicides, antitumour agents,

  pH adjusting agents, enzymes, etc., all of which are well known in the tissue lavace art as to their use in detergent compositions. Also commonly used flow promoting agents may be used

  Dar flow adjuvants, to maintain the components

  particulate matter in the form of loose beads or powder. Starch derivatives and special clays are commercially available as additives improving the flowability of otherwise sticky or tacky particulate compositions, two of these clay additives being

  currently marketed under the trade marks

  "Satintone" and "Microsil". Detergent compositions may also contain bound water

  and free water in minor quantities which

  It does not adversely affect the flowability of the granular or powdery compositions. Moisture proportions are normally from 1 to 15%, preferably from 5 to 12% and most preferably from 8 to 12% of the total composition. Within the limits of these proportions

  A granular, powdery or

  ticular, which flows satisfactorily and that one can prevent being too dusty by acting

  particle size and hXmi-

  ity. Suitable ranges of detergent additives are: 2% enzymes, in particular 0.2 to 1%; corrosion inhibitors about 0 to 15%

  and preferably 2 to 8%; antifoams and

  foam pressers - 0 to 15%, preferably 0 to 8% For example 0.1 to 5%; suspending agents

  or antiredeposition of dirt and anti-agents

  yellowness - 0 to 10%, preferably 0.3 to 3%; dyes, perfumes, brighteners and brighteners - in total 0% to about 2%, and preferably 0% to about 1%,

  var 0.2 to 0.8%; pH modifiers and tamper

  pH range - 0 to 5%, preferably 0 to 2%; bleaching agent - 0% to about 40% and preferably 0% to about 25%; for example 2 to 20%; stabilizers of the bleaching agent and activators of the bleaching agent - 0 to about 15%, preferably 0 to 10%, for example 0.1 to 8%. We will choose the additives

  so that they are compatible with the prin-

  components of the detergent composition.

  Whatever the form of the laundry detergent, its use in the washing process is essentially the same. The particulate composition is generally added to the wash water in a

  automatic washing machine so that its

  concentration in the wash water can be approximately

  0.05 to 1.5%, generally 0.1 to 1.2%. The water to which the composition is added is preferably of medium or low hardness, for example a

  hardness of 30 to 120 mg / l, expressed as calcium carbonate

  but we can usefully use more

soft and hard.

  The temperature of the water may be from 20 ° C to 100 ° C, and is preferably from 60 ° C to 100 ° C where the textile material or the laundry can withstand high temperatures without degradation or color fading. When it is desired to carry out a washing at low temperature, the temperature can be maintained

between 20 and 40 C.

  At the concentrations of detergent composition mentioned, the pH of the washing water is generally on the alkaline side, for example from 7 to 12, preferably from 8 to 11, in particular from 9 to 10. The weight ratio of the laundry to the washing water is usually

  from about 1: 4 to 1:30, preferably from 1:10 to 1:30.

  The following examples illustrate the invention without limiting it. Unless otherwise specified, all parts and percentages are expressed in

weight.

Example 1

  The following composition is prepared by first forming the spray-dried beads (A)

  then adding the components (B) afterwards.

  "A" (Spray dried pearls) Parts Tap water 6.8 Fatty acids tallow oil or oil of 2.8 hydrogenated fish NaOH (35.7%) 1, 3 Tap water 11.5 Silicate Sodium (40%) (Na2O: SiO2) 9.9 Anionic surfactant (1) 16.0 Optical brightener (2) 0.2 Sodium carboxymethylcellulose 0.7 Zeolite (mineral adjuvant salt) 33.9 Sulfate Sodium (Anhydrous) 0.7 Subtotal: 83.8 (4) Ingredients added after (B) Parts Sodium Perborate 15.0 Blue Bentonite Agglomerate 16.0 Adogen 477 (3) 2.5 Enzyme 0 Mixture n 2 magnesium silicate WDTPA 0.2 Potassium methyl-siliconate (50%) 0.6 Nonionic surfactant (5) 3.0 Duet 787 (Fragrance) 0.5 Subtotal 38.3 Spray dried beads (A) 61.7, -1 (linear dodecyl) benzenesulfonate-as an aqueous solution.

  2. Stilbene N 4 brightener, highly concentrated granules.

  3. Adogen 477 is N- (tallow alkyl) -N- (CH3) 2-CH2CH2CH2-N'-

(CH3) 3.2C1.

4. 61.7 parts after drying.

  5.C14-C15 fatty alcohol ethoxylated with 11 moles of oxide

of ethylene per mole.

  The spray dried beads (A) are mixed with the added ingredients (B) to obtain the product 1 (invention). The concentration of the clay mineral softener in the final composition is 16% and the concentration of the Plissant Adogen 477 in the final composition is

  2.5% in product 1 (invention).

  By way of comparison, we prepare the same

  except that we do not use Adogen 477. The

  second composition, product 2 (comparative),

  has a concentration of clay mineral softening

  16% and does not contain Adogen 477.

  Products 1 and 2 are used to wash

  test tissues at 60 C using three cycles.

  Evaluation of relaxation, cleaning

  and bleaching achieved by the product 1 (inven-

  A + B shows that there is no negative effect on the performance parameters as a result

  the addition of Adoqen 477 to the composition, by

  parison with the product 2 A + B (without agent as-

folding Adogen 477).

  The efficacy of product 1 (inven-

  for the removal of dirt with that of product 2 (comparative) and it is found that the products

1 and 2 are almost equivalent.

  The qualities of flexibility

  test fabrics by Products 1 and 2, and

  product 1 (invention) is superior to

duit 2 (comparative).

  We compare the whiteness and the effect of antire-

  deposition of soiling obtained with the products 1

  and 2 on polyester-polyester blend test fabrics

  cotton, cotton and nylon, washed with these products, and the product 1 (invention) is superior to

  product 2 (comparative), in the three comparisons.

  It is found that the washing liquor containing

  product 1 (invention) does not produce a com-

  relative to product 2 (comparative) which produces

the foam.

  Example 1 shows that the addition of Adogen 477 to the composition makes it possible to obtain an elimination of soils approximately. equivalent, while ensuring superior properties of flexibility and whiteness.

  antiredeposition and low foaming.

Example 2

  Following the same general procedure as in Example 1, the following composition was prepared: "A" (Spray dried beads) Percent by weight Sodium tridecylbenzenesulfonate 15.0 Zeolite (Mineral detergency adjuvant salt) 39.3 Sodium silicate (lNa2O: 2.4 SiO2) 7.0 Sodium sulphate 4.0 Optical brightener (Tinopal 5BM) 0.2 Sodium carboxymethylcellulose 0.25 NaOH (40%) 1.75 Subtotal: 67.5 t . 39 Ingredients added afterwards (B) Percent by weight ArQile Thixogel N 1 10.0 Adocen 477 2.5 Sodium perborate 15.0 Enzyme 0.5 Potassium methylsiliconate 0.6 Nonionic surfactant (1) 3.0 10 Magnesium silicate / DTPA (N 2 mixture) 0.3 Duet 787 (fragrance) 0.6 Subtotal: 32.5 Total: 100.0 1. Fatty alcohol C12 - C14 condensed with 9 moles

of ethylene oxide per mole.

  In the product 3 (invention) of Example 2,

  the concentration of softening clay in the

  final concentration is 10 per cent by weight and the

  Adogen 477 concentration in the final composition is 2.5%. For comparison, we prepare a

  second composition (product 4) in which the

  clay softener concentration is 16 to

  percent by weight and no Adogen 477 is used.

  The soil removal efficiency of product 3 (invention) and product 4 (comparative) is compared and it is found that products 3 and 4

are almost equivalent.

  The qualities of flexibility

  tissues by products 3 and 4, and the

  duit 3 (invention) is superior to product 4 (comparative).

  We compare the whiteness and the effect of antire-

  deposition of the soils obtained with the products 3 and 4 on cotton / nylon polyester / cotton blend test fabrics, washed with these products, and the product 3 (invention) is superior to the product 4 (comparative) on the Cotton and nylon and products 3 and 4 are about as effective on the polyester / cotton blend. Product 3 (invention) does not produce foam compared to product 4 (comparative) which

produces foam.

  Example 2 shows that the addition of Adogen 477 to the composition allows a significant reduction in the amount of softening clay required to obtain the desired softening performance, while still ensuring equivalent efficiency or

  superior to the elimination of soil

  safety, whiteness / anti-redeposition and

foaming.

Claims (14)

  1. A phosphate-free detergent and softener composition, in solid form, for washing clothes, comprising spray-dried beads consisting of a homogeneous mixture of: one or more heat and pH-insensitive detergent compounds selected from the group consisting of: synthetic anionic detergents, synthetic nonionic detergents, synthetic ampholytic detergents, synthetic zwitterionic detergents and mixtures thereof; one or more inorganic or organic detergency builder salts insensitive to heat and pH; a mineral softening agent of the agile type;   a softening agent of the diammo compound type   selected from compounds of the formula; R R4 R1 - + R7 N - R5. 2X (I) i i I5 R3 R6   wherein R 1 is an aliphatic hydrocarbon radical having from about 12 to about 30 carbon atoms, each of R 2, R 3, R 4 R 5, and R 6 is independently selected from aliphatic hydrocarbon groups having 1 to 22 carbon atoms, with the proviso that the total number of carbon atoms in all aliphatic hydrocarbon groups, including R1, is not more than about 75, and with the additional proviso that no more than two R 2 to R 6 groups have more than 12 carbon atoms R7 is -CH2CH2- or -CH2CH2CH2-, and X is an anion forming a water-soluble salt; and optionally one or more additives for   detergents insensitive to heat and pH, and humidity.   2. A phosphate-free detergent and softener composition according to claim 1, characterized in that the detergent compound (s) comprise a synthetic anionic detergent and said one or more   adjuvant detergency salts include an adjuvant salt   mineral detergency or an adjuvant salt of organic tergence.   3. A phosphate detergent and softener composition according to claim 1, characterized in that, in the formula (I), R1 is a linear or branched alkyl, alkenyl or alkynyl group having 16 to 22 carbon atoms, R2 to R6 are each independently selected from alkyl and alkenyl groups having 1 to 16 carbon atoms, with the proviso that the total number of atans   carbon in all aliphatic hydrocarbon groups.   ticks R1 to R6 are not greater than about 50 and with the additional condition that no more than two   from R2 to R6 have no more than 12 carbon atoms.   4. A phosphate-free detergent and softener composition according to claim 2, characterized in that R2 to R6 are each independently an alkyl or alkenyl group of 1 to 6 carbon atoms, provided that the total number of carbon atoms in all the aliphatic hydrocarbon groups R1 to R6 do not not more than about 35.   5. A phosphate-free detergent and softener composition according to claim 1, characterized in that it comprises about 10 to about 60% by weight of the detergent compound (s); about 15 to about 90% by weight of the builder salt (s); about 0.25 to about 10% by weight of the diammonium compound softening agent; about 1 to 30% by weight of the clay mineral softening agent; and about 0 to about 50% by weight of additives for detergent, fillers and moisture.   6. A phosphate-free detergent and softener composition according to claim 4, characterized in that it comprises, on a weight basis, approximately 15 to approximately 40% of anionic detergent.   synthetic type (linear higher alkyl) benzene-   sulfonate; about 25 to 65% of a zeolite-type mineral detergency builder; about 0.5 to 5% of said diammonium compound softening agent: about 2 to 20% of said clay type softening agent; and about 5 to 40% of one or more materials   selected from the additives for insensitive detergents   pH-stable and heat-stable, the charges, the humidity and their mixtures.   7. A phosphate-free detergent and softener composition according to claim 6, characterized in that the linear (higher alkyl) benzene sulfonate   is a dodecylbenzene sulfonate, the adjuvant   mineral is a zeolite, and the compound diammnr & n. is the compound of formula: CH3 CH3   Tallow - N - CH2CH2CH2 - N CH3. 2C1 f I CH3 CH3   8. A phosphate-free detergent and softening composition, characterized in that it comprises   a clay softening agent and an auxiliary agent   of the diammonic compound type in admixture with the detergent composition of   atomization for washing the laundry of the 1.   9. A phosphate-free detergent and softener composition for washing laundry in the form of   granules or powders flowing freely, including   (a) about 1 to about 95% by weight of one or   several detergent compounds selected from   synthetic anionic tergents, synthetic nonionic detergents, amphoteric detergents   synthetics, synthetic zwitterionic detergents   ticks and mixtures thereof; (B) about 2 to about 20% by weight of a clay mineral softening agent: (C) about 2 to about 80% by weight of one or more detergency builders;   (D) about 0.5 to 5% by weight of an agent   pleating of the diammonic compound type corresponding to the formula: R2 R1 N R7- R5 2X () I t R3 R6   wherein R 1 is an aliphatic hydrocarbon group having about 12 to about 30 carbon atoms, each of R 2, R 3, R 4, R 5 and R 6 is independently selected from aliphatic hydrocarbon groups having 1 to 22 carbon atoms, with the proviso that the total number of carbon atoms in all aliphatic hydrocarbon groups, including R1, is not more than about 75, and with the additional proviso that not more than three of R2 to R6 have more than 12 carbon atoms, R7 is -CH2CH2- or -CH2CH2CH2-, and X is an anion forming a water-soluble salt, and   (E) 0 to about 50% by weight of one or more   selected from among the additives to gent, loads and moisture.   10. Phosphate-free composition according to the claim   9, characterized in that it comprises   spray-dried beads consisting of an over-   anionic filler, a detergency builder salt and one or more materials selected from   for detergent insensitive to pH and stable on the   their charges and their mixtures, and that the   said diammonium compound is premixed with clay   softener and the premix is evenly   mixed with the spray dried beads.   11. Phosphate-free composition according to claim   9, characterized in that, in formula (I), R 1 is a linear or branched alkyl, alkenyl or alkynyl group having 16 to 22 carbon atoms; and R2 to R6 are independently selected from alkyl and alkenyl groups having 1 to 16 carbon atoms, with the proviso that the total number of atoms   carbon in all aliphatic hydrocarbon groups.   ticks R1 to R6 is not greater than about 50, and with the additional condition that no more than two   from R2 to R6 have no more than 12 carbon atoms.   12. Phosphate-free composition according to   claim 11, characterized in that, in formula (I), R2 to R6 are each independently an alkyl or alkenyl group of 1 to 6 carbon atoms, with the proviso that the total number of carbon atoms in all groups hydrocarbons R1 to R6 are not not greater than about 35.   13. A phosphate-free composition according to claim 9, characterized in that the softening agent of the diammonium compound type has the formula: CH3 CH3 tallow - N CH2CH2CH2 -N - CH3. 2C1- CH3 3H   14. Phosphate-free composition according to the   13, characterized in that the agent relaxes   clay-like mineral constitutes about 10% of the composition and the softening agent of the compound type   diammonium constitutes about 2.5% of the composition.