LU87139A1 - SOLID PHOSPHATE FREE DETERGENT AND SOFTENER COMPOSITIONS FOR WASHING LAUNDRY, CONTAINING A DIAMMONIC COMPOUND - Google Patents

Description

88 / B 52 726

JT * 'fï “/ 3 ^” 10 GRAND-DUCHY OF LUXEMBOURG

O / * v ',. · "' Minister of February 1 ....... 1988 of the Economy and the Middle Classes„. „Intellectual Property Service

Title issued ................................................ ...... LUXEMBOURG

Patent Application .....................................-______________________________________________________________________— (1) I Request

The company known as: COLGATE-PALMOLIVE COMPANY, 300 Park Avenue / 2) NEW YORK, NY ........ 10022. (United States ...... United ...... & '. America represented ... ......

............ by Monsieur ...... Jaqques ...... de. üuyser, ..acting „in -quality-of- - ............. agent ....................... .................................................. .................................................. ................._...............----------------- -------------------------------------------- (3) deposit) this nineteen ............. February. 1900 eighty ...... eight_________________________________ (4) to ................. ............. hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent of invention concerning: ... .......... "Compositions ...... detergents.-and ...... softeners-solids --------- (5) ....... ............ without ...... phosphate .for .washing ...... washing ...... laundry, ... ..- containing a ....................- ................. compound ...... diammonic. "_____________________________________________________________________________________________________________________ - 2. description in language £? .SU.Ç a ise__________ _________________________ from pinVention in triplicate; 3. .............. / · ................................ ............. drawing boards, in triplicate; 4. the receipt of the taxes paid to the Luxembourg Registration Office on .18 ...... February 1988; 5. the delegation of power, dated ..........__.............................. .......................................... the------- ---------------------------------------------------------- --------------; 6. the successor document (authorization); declares (s) assuming responsibility for this declaration, that the inventor (s) is (are): (6) ............ “Viviane DAFFE, .... .... 7A. rue d 'Ans, ....... B-.4420 ...... ROCQURT (Belgium) ________________________ ................. Marcel .GILLIS, .. ...... 26 ...... Alley ...... des ...... Cherry trees, _ 3 = 453-1. ARGENTEAU -------- ......................... (Belgium) ______________________________________________________________________________________________________________________________________________________________________________ claim) for the above patent application the priority of one (s) request (s) for (7) .......... patent ___________________________________________________________________________ filed (s) in (8) aux.Hats-Un.is ..... of America on (9) 20 February 1987 ................................................ .................................................. .............................

under N ° (10) 016> 826 ........................................ ..'_______________________________________________________________________________________________________________________ — .................................— on behalf of (he) of the inventors ... .................................................. .................................................. .................................................. ....... ............

elect (elect) domicile for him / her and, if designated, for his / her representative, in Luxembourg__________ - ______________

Jb boulevard Royal _ _ _ _ _ {Ώ) request) the grant of a patent for the subject described and represented in the abovementioned appendices, with adjournment of this issue to Ç. ____________________________________________________________________________________________________________________month. (13) ^ JLe-depqsantr / agent: ........................................ .................................................. ...................................... ............ .......................... ......... ..... (14) jyl 0 0 O y 0 jl / f R · Deposit Report

The request from OTevet ^ J ^ aiseQjion was filed with the Ministry of the Economy and the Middle Classes, Property Services InteHegi & eSe'â Îtp ^ èmbourg, dated: February 19, 1988 / f f t '. · S Pr. The Minister of Economy and Movennes Classes.

15 î. · \ JS | , at ............__ hours I ^ j p. d.

X 'C ·' f / The head of the intellectual property department, "'' vv, A 68007___ f A f EXPLANATIONS RELATING TO THE DEPOSIT FORM.

î | f \ 111 Ml will take place “Request for certificate of addition to the main patent, at the main patent request Ne -......... of ..........." (2i write the names. Name. Pr ^ icsN.or.

v * 4 * - address of the applicant, when the latter is a private individual or company name, legal form, address of the head office, when the applicant is a legal entity-T. :: (es nom. nrennm . address of the authorized representative of the industrial nmnnere council, provided with a special nnuvmr if he goes uh. * represented nar .......... acting in Quality fle m <mca: a.is *. '88 / B 52 726

CLAIM OF PRIORITY

of the patent application / utility model IN THE UNITED STATES OF AMERICA OF FEBRUARY 20, 1987 (NO. 016.826) Brief Description filed in support of an application for

PATENT

at

Luxembourg on behalf of: colgate-palmolive company NEW YORK, N.Y. 10022 (United States of America) for: "Solid phosphate-free detergent and fabric softener compositions for washing clothes, containing a diammonium compound." 4 *, SOLID DETERGENT AND SOFTENING COMPOSITIONS WITHOUT PHOSPHATE FOR THE WASHING OF LAUNDRY, CONTAINING A DIAMMONIC COMPOUND.

The present invention relates to a softening detergent without phosphate for washing clothes, that is to say a softening and detergent composition based on a softening clay and a cationic diammonic softening agent. The present invention relates more particularly to a phosphate-free powder detergent composition for laundry containing an active detergent surfactant, a softening clay and a softening agent of the ammonium salt type, the process for preparing the composition and its use for the washing of textile materials.

Powder detergent compositions containing a detergent surfactant (anionic, nonionic, etc.) with a softening clay and a cationic softener and / or an antistatic agent, such as a quaternary ammonium ocrrpo - se, a compound of di (quaternary ammonium), etc., are known in the art. Representative examples of the patent literature in this area are US Pat. Nos. 3,862,058; No. 3,886,075; No. 3,915,882; No. 3,948,790; No. 4,203,851; British patent application 25 GB 2,141,152 A. Other patents relating to clay compositions for the treatment of fabrics include the patents of the United States of America., 1.

»· * .- 2 No. 3,594,212 and No. 4,062,647. The use of bento-nites for the softening of textile materials is known from British patents No. 401 413 and No. 461 221.

5 Although performance t has been obtained.

Satisfactory cleaning and softening 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 compositions.

Furthermore, the polyphosphates contained in laundry detergents have been accused of being responsible for the unfavorably high phosphate content of surface waters. Higher phosphate content in surface waters has been found to increase the growth of algae, which adversely affects the biological balance of the water.

20 Legislative measures have recently come into force in some countries to reduce the amount of polyphosphates present in laundry detergents, and in some countries where polyphosphates have been a problem, to require that detergents for laundry should not do not contain detergency builders such as polyphosphate.

It is therefore an object of the present invention to provide a phosphate-free detergent composition to the softening clay, containing a softening agent of the diammonic compound type.

Another object of the invention is to provide a polyphosphate-free detergent composition for laundry, in the form of spray-dried pearls, in which the spray-dried pearls are mixed with a fabric softener and a clay-softening mineral ?, and a ' . 1 ““ *, **: * 3 process for preparing this composition.

. Another object of the present invention is to provide a softening clay detergent powder composition, reinforced by a polyphosphate-free detergency builder, the softening clay content of which is reduced without negative effects on the cleaning performance of bleaching or softening of the composition.

Yet another object of the present invention is to provide a softening clay powder composition, polyphosphate-free, in which the cationic softener of the ammonium salt type and the softening clay can be added afterwards to the beads. or spray dried granules.

These and other objects of the invention will become apparent from the detailed description which follows of preferred embodiments being obtained by using as the cationic softening compound a diammonic salt of formula (I) below.

I! ; R __N + -R - N -R, .2X ~ (I) 1 I 7 I 5 r3 r6 25 wherein R.j is an aliphatic hydrocarbon radical having about 12 to about 30 carbon atoms; each of the symbols R2, R3, R4, R ^ and R ^ is independently chosen 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, y inclusive R. |, is not more than about 75, and with the additional condition that not more than two of ^; * '* 4 groups R2 to Rg have more than 12 carbon atoms, R7 is -CH2CH2- or ~ CH2CH2CH2- ,; and X is an anion forming a water-soluble salt.

The diammonic compounds of formula (I) can be dispersed in an organic or aqueous vehicle and atomized on the detergent granules or beads. The diammonic compounds can also be heated to a temperature above their melting temperature and atomized on the detergent granules or beads. As a variant, the diammonic compounds may, in the form of an aqueous dispersion, of organic solution or of melt, be added to the softening clay and then mixed with the detergent granules or beads. According to the present invention, the desired degree of softening can be achieved by using lower levels of softening clay and without adversely affecting the other properties of the detergent composition, including cleaning and bleaching performance. Another advantage of the composition is that it has low foaming properties.

The softening diammonic compounds are soluble in the usual organic solvents and / or form stable dispersions in water. Fabric softeners are generally insoluble in water. Since softening agents of the diammonium salt type of formula (I) are available or can be prepared in organic solutions or aqueous dispersions, they can be handled easily and without risk in installations intended for the treatment of powders and they can be easily atomized on powdered or granular detergent compositions reinforced for heavy laundry work or otherwise mixed with these compositions.

In a preferred embodiment of the invention the softener and the softening clay are premixed and then incorporated as a post-addition ingredient into the spray-dried granules or the detergent composition. 5 powder for laundry.

A representative example of a spray dried pearl formulation for heavy duty laundry operations comprising the softening agent of formula (I) and a softening clay may contain the following ingredients:

Proportion (% by weight)

Ingredients Composition Dried pearls

Total by atomization - 15 ---

Detergent surfactant compound 1-95 10-60

Organic and mineral detergency builders 2-8015-90

Softening clay 1-50 0

Softening agent of formula (I) 0.2-5 0

Charges 0-25 0-10 20 Bleach and bleach additives 0-25 0-5

Optical brighteners, pigments, dyes 0-10 0-8

Anti-foaming agents, foam suppressants, etc. 0-10 0-8

Enzymes 0-5 0

PH adjusting agents, buffers, etc. 0-10 0-8

Anti-deposition agent, perfume, etc. 0-5 0-3

Water the rest

In a preferred method of preparing the softened detergent composition reinforced with powder or granules for heavy laundry work, the heat-stable, pH-insensitive detergent ingredients are mixed in a blender and spray dried. to form spray dried beads, then these beads are uniformly mixed * 1 * 6 or spray coated with the softening diammonic compound of formula I and the softening clay mineral and with the ingredients of the formulation which are sensitive to pH and / or heat-sensitive or which may react otherwise with the anionic surfactant or other component of the spray-dried pearls or granules. As examples of the after-added ingredients to be mixed with the spray-dried beads, there may be mentioned, for example, a bleach, enzymes, perfume, nonionic surfactant, etc. The fabric softener compound of formula I can, as mentioned above, be premixed with the fabric softener clay and then mixed with the spray dried beads or granules. The procedures for preparing the composition are well known in the art and those skilled in the art will be able to easily determine the optimal conditions for preparation.

20 Synthetic organic detergent compounds

The laundry detergent compositions may contain one or more surfactants chosen from anionic, nonionic, ampholytic and zwitterionic detergents. The synthetic organic detergents used in the practice of the invention may be any of a wide variety of such compounds which are well known and are described in detail in the book "Surface Active Agents and Detergents ", Volume II, de Schwartz, 30 Perry and Berch, published in 1958 by Interscience

Publishers. The total proportion of the detergent surfactant compound (s) can be as high as 95% by weight of the total detergent composition, although preferred portions are in the range of about 1 to 70% by weight, particular>> * 7 from 5 to 50% by weight, and better still from about 5 to 30% by weight of the total detergent composition.

The detergent compositions of the present invention preferably use one or more anionic detergent compounds as primary surfactants. The anionic detergent can be supplemented, if desired, by another type of surfactant, preferably a nonionic detergent, particularly when used in combination with an adjuvant detergency salt.

. Anionic surfactants Among the anionic surfactants useful in the present invention, mention may be made of surfactant compounds s which contain a hydrophobic organic group 15 containing approximately 8 to 26 carbon atoms and, preferably, approximately 10 to 18 atoms. carbon in their molecular structure and at least one water solubilization group selected from the sulfonate, sulfate, carboxylate, phosphonate and phosphorate groups, so as to form a water-soluble detergent.

Examples of suitable anionic detergents include soaps such as water-soluble salts (e.g. sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids: or resin salts containing from about 8 to 20 carbon atoms 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. Of particular interest are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, for example coconut sodium soap and potassium tallow soap. The class of anionic detergents comprises 35 also sulfated and sulfonated hydro detergents. 1 ", ï 4 1 t * * 8 soluble having an aliphatic radical, preferably alkyl, containing about 8 to 26, and preferably about 12 to 22 carbon atoms. (The term "alkyl" includes the alkyl portion of the higher acyl radicals).

Examples of the sulfonated anionic detergents are the higher alkyl monocyclic aromatic sulfonates such as the (higher alkyl) benzene sulfonates whose higher alkyl group contains about 10 to 16 carbon atoms in a straight or branched chain configuration, such as for example (higher alkyl) benzene sulfonates, (higher alkyl) toluene sulfonates and (higher alkyl) -phenol-sulfonates of sodium, potassium and ammonium.

Other suitable anionic detergents are olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkane sulfonates, or mixtures of alkene sulfonates and hydroxyalkane sulfonates. The olefin sulfonates can be prepared in a conventional manner by reacting sulfuric anhydride (SO3) with long chain olefins containing about 8 to 25, and preferably about 12 to 21 carbon atoms, these olefins react - corresponding to the formula RCH = CHR where R represents a higher alkyl group of approximately 6 to 23 carbon atoms and 25 R represents hydrogen or an alkyl group containing approximately 1 to 17 carbon atoms, to form a mixture of sulfones and alkene sulfonic acids which are then processed to transform the sulfones into sulfonates. 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. The primary paraffin sulfonates are prepared by reacting long chain alpha-olefins and bisulfites. Paraffin sulfonates of which the sulfonate group is '* ·, **' * * · * *>> 9 distributed along the paraffinic chain are described in US Pat. Nos. 2,503,280; No. 2,507,088; No. 3,260,741; No. 3,372,188 and in German Patent No. 735,096.

Other suitable anionic detergents are the sulfated ethoxylated higher fatty alcohols of the formula R0 (C 2 ^ 0) ^ 0 ^, where R represents a fatty alkyl group of 10 to 18 carbon atoms, m is 2 to 6 (of preferably a value ranging from one fifth to one half of the number of carbon atoms in group R) and M is a salt-forming cation, such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino cation. The proportion of ethylene oxide in the sulfated polyetoxylated higher alkanol is preferably from 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, an amount of three moles being particularly preferred, in particular when 1 ' higher alkanol has 11 to 15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic ratio, when the number of carbon atoms in the alkyl chain is in the lower part of the range from 10 to 18 carbon atoms, the content of ethylene oxide detergent can be reduced to about two moles per 25 moles, while in the upper part of the range, when the higher alkanol has 16 to 18 carbon atoms, the number of ethylene oxide groups can be increased to 4 or 5 and, in some cases, as high as 8 to 9. Likewise, the salt-forming cation can be modified to achieve the best solubility. It may be any metal or 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

"I

The alkanol generally contains 1 to 4 carbon atoms, and the amines and alkanol amines can be mono-, di- and trisubstituted, as in the case of monoethanolamine, diisopropanolamine and trimethylamine. A polyethoxylated alcohol sulfate pre --- fere as detergent is available from the Shell Chemical Company and sold under; the name Neodol (registered trademark) 25-3S.

The water-soluble anionic detergent compounds which are very preferable are the (higher alkyl) benzene sulfonates, olefin sulfonates and (higher alkyl) ammonium and substituted ammonium sulfates (e.g. mono-, di- or triethanola- 15), alkali metals (eg sodium and potassium) and alkaline earth metals (eg calcium and magnesium). Among the above-mentioned anionic detergents, the 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.

The anionic surfactant is generally the main detergent component and can constitute about 30 to 100% of the total surfactant ingredients. assets. Preferably, the anionic surfactant represents at least 50%, preferably at least 60%, better still at least 70%, and at most about 99%, preferably at most about 90%, more preferably at most about 80% of all the detergent surfactant ingredients.

The anionic surfactant is generally, and preferably incorporated as a component of the spray dried beads and is added

* 1T

JM »Λ * 11 to the mixture of the mixer in the form of an aqueous solution or dispersion, and preferably in the form of a highly concentrated aqueous suspension.

Non-Ionic Surfactants 5 The class of detersive surfactant ingredients which comes next in order of preference is that of compounds, non-ionic synthetic organic detergents.

Non-ionic synthetic organic detergents are characterized by the presence of a hydrophobic organic group and a hydrophilic organic group and are typically produced by the condensation of an aliphatic or alkyl aromatic hydrophobic organic compound with the oxide d ethylene (hydrophilic in nature). Almost any hydrophobic compound carrying a carboxy, hydroxy, amido or amino group with a labile hydrogen atom attached to nitrogen can be condensed with ethylene oxide or with bran. polyhydration product, polyethylene-20 glycol, to form a nonionic detergent. The length of. the polyoxyethylene hydrophilic chain can be easily adjusted to achieve the desired ratio between the hydrophobic and hydrophilic groups.

The nonionic detergent used is preferably a higher alkanol polyalkoxylated by a lower alkoxy group, where the alkanol has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and where the number of moles d the lower alkylene oxide (with 2 or 3 carbon atoms) is from 3 to 20. Among these 30 materials, it is preferable to use those in which the 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 the ethoxy group, but in some cases it may advantageously be 12 *. * * * I * '* mixed with the propoxy group which, if present, is often not as a minor constituent (less than 50%). Representative examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethvlene oxide groups per molecule, for example Neodol ( 25-7 and Neodol 23-6.5 which are products manufactured by Shell Chemical Company,

Inc. The first 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 corresponding mixture where the the number of carbon atoms in the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups per mole is on average about 6.5. Higher alcohols are primary alcohols. Other examples of such detergents include Tergitol (registered trademark) 15-S-7 and Tergitol 15-S-9 which are both secondary linear alcohol ethoxylates produced by "Union Union Carbide Corporation. 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 where nine moles of ethylene oxide have reacted .

Very preferred nonionic surfactants for their utility in the present compositions are higher molecular weight nonionic detergents, such as Neodol 45-11, which are similar condensation products of ethylene oxide on higher fatty alcohols , the higher fatty alcohol having 1 4 to 15 carbon atoms and the number of ethylene oxyy groups being approximately 11 per molecule. These products are also manufactured by Shelli Chemical 35 Company.

»» V,

-I

* <♦ * 13

On the basis of all of the detergent surfactant ingredients contained in the detergent composition, the nonionic surfactant may be present in proportions of at most about 70% by weight, preferably about 50%, more preferably about 40%, and in particular about 15%. In general, the nonionic surfactant, when used, represents at least 1%, preferably at least 10%, and in particular at least 30% of the combined weights of all detergent surfactant ingredients. Based on the entire detergent-softening composition, the nonionic surfactant is generally present in proportions ranging from about 0.1 to 20%, preferably 0.3 to 15%, and more preferably from 0.6 to 10% by weight.

Since nonionic surfactants are often only sparingly soluble in water or form viscous solutions or gels when added to water, they are generally presented in the form of solutions in a solvent. organic, for example, in ethanol or isopropanol, alone or with water. Consequently, when the nonionic surfactant is available in the form of its solution in an organic solvent, it will not be incorporated into the mixer mixture intended to form the spray-dried granules or pearls, but on the other hand, add it afterwards to the spray dried beads already formed. In addition, even when the nonionic surfactant is used 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 afterwards blow the nonionic surfactant to the spray dried beads.

J ",, P '* 14

Zwitterionic detergents are also useful, such as betaines and sulfobetaines corresponding to the following formula: 5 s9

R8 -N-R11- X = O

R10 IL-0 in which R 8 represents an alkyl group 9 10 10 containing approximately 8 to 18 carbon atoms, R and R each independently represent an alkyl or hydroxyalkyl group containing approximately 1 to 4 carbon atoms, R 11 represents an alkylene group or hydro-xyalkylene containing 1 to 4 carbon atoms, and X 15 represents a carbon atom or an S: 0 group. The alkyl group may contain one or more intermediate links such as amido, ether or polyether links or non-functional substituents such as the hydroxyl group or a halogen which do not substantially affect the hydrophobicity of the group.

When X represents a carbon atom, the cletergent is called a betaine? and when X represents an S: O group, the detergent is called a sulfobetaine or sultaine.

__ Ampholytic detergents are also

Zo suitable 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 above-mentioned book "Surface Active Agents and Detergents". Examples of suitable amphoteric detergents include: alkyl-beta-imino-dipropionates, RN (C2H4COOM) 2; alkyl-beta-amino-propionates, RN (H) C0H.COOM> and long chain imidazole derivatives of general formula: t · t t * 15 ch9 / \ N CH2

5 R - C - N- CH-CH-OCH ^ COOM

/ \

OH CH2COOM

where, 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. Specific amphoteric detergents for use include the disodium salt of undecylcycloimidinum (ethoxyethanoic) -2-ethanoic acid, dodecyl-beta-alanine and the internal salt of 2-trimethylamino-lauric acid.

The amounts of 7.witte-rionic synthetic organic detergent and of ampholytic synthetic organic detergent * possibly present in the carpcsitions of the invention are not particularly decisive and can be chosen according to the results which it is desired to obtain. In general, either or both of these classes of detergent ingredients can be used to replace.

placing all or part of the detergent anionic organic surfactant and / or the detergent nonionic organic surfactant within the above ranges.

As in the case of anionic and nonionic 3Q surfactants, those skilled in the art will readily be able to determine whether to include the zwitterionic and ampholytic surfactants as a component of the mixer mixture intended to form the beads or * * 4 4 t.

9 ”16 spray-dried granules or add these compounds afterwards to the spray-dried beads to form the final reinforced detergent composition for heavy laundry work. In short, when they are in the form of aqueous solutions, they are preferably added to the mixer mixture and when they are in organic solvents they are added afterwards to the spray-dried beads.

10 Softening Agents of the Clay Type The softening clay can be chosen from all the softening clays known in the art to impart flexibility to the fabrics washed in their presence. Preferred clays are smectite clays, and those with an ion exchange capacity of at least about 50 meq / 100 g of clay (50 milliequivalents per 100 grams of clay) are preferred. .

The smectite clays useful in the present invention are three-layer clays characterized by the ability of the layered structure to increase by several times its volume by swelling or expanding in the presence of water to form a thixotropic gelatinous substance . There are two distinct classes of smectite clays: in the first class, aluminum oxide is present in the crystal lattice of silicate; in the second class, magnesium oxide is present in the crystal lattice of silicate. Substitution of atoms by iron, magnesium, sodium, potassium, calcium, etc., may exist within the crystal lattice of smectite clays. It is customary to distinguish clays according to their predominant cation. For example, a sodium clay is a clay in which the predominant cation is sodium.

'· ‘R i ·’ j "* * 17

The cation exchange capacity of a clay mineral is related to factors such as the swelling properties of the clay / the charge of the clay, which in turn are determined at least in part by the structure of the clay. network etc. The ion exchange capacity of clays varies over a wide range from about 2 meq / 100 g for kaolinites to about 150 meq / 100 g and more for certain clays of the montmorillonite variety. The illite type 10 clays have an ion exchange capacity located in the lower part of the interval, that is to say around 26 meq / 100 g for a medium illite type clay.

It has been determined that illite and kaolinite clays, with their relatively weak ion exchange capacities, are not useful as softening clays, or are only used marginally. In fact, these illite and kaolinite clays are a main component of clay soils and, as mentioned above, they are removed from the surface of fabrics using 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 / 100 g , and montmorillonite which has an ion exchange capacity greater than 70 meq / 100: g, have proven to be very useful softening agents in that they are deposited on the tissues by exerting the desired softening effects. . Therefore, preferred clay minerals useful herein can be characterized as expandable, three-layer smectite-type clays having an ion exchange capacity of at least about 50 meq / 100 g. A smectite-type clay 30, known as a "fooler clay", T *, ", * *

* 'V

18 discovered in a relatively thin vein above Black Hills, (USA), also exhibits the required ion exchange properties characteristic of the clays useful here and this clay is also globally by the expression "clay of smectite type ", as used here.

The smectite clays used in the compositions of the invention are all commercially available. These clays include, for example, montmorillonite, volchonskoïte, nontronite, hectorite, saponite, sauconite and vermiculite. These clays are available under various commercial brands, for example Thoxogel No. 1 (also "Thixo-Jel") and Gelwhite GP of Georgia Kaolin Company, 15 Elizabeth, New Jersey; Volclay BC and Volclay No. 325 from American Colloid Company, Skokie, Illinois; Black Hills Bentonite BH450 from International Minerais and Chemicals, · and Veegum Pro and Veegum F from R. T. Vanderbilt. It should be noted that these smectite type minerals obtained under the above trade marks may include mixtures of the various discrete mineral entities. These smectite mineral mixtures are suitable for use in the invention.

Although any of the smectite clays having a cation exchange capacity of at least about 50 meq / 100g is particularly useful here, certain clays are preferable. For example, Gelwhite GP clay is a very white form of smectite-type clay and is therefore preferable if one wishes to prepare white granular detergent compositions. Volclay BC, which is a smectite-type clay mineral with a crystal lattice containing at least 3 percent iron (expressed as Fe2C> 3) and which has a very high ion exchange capacity, is one of the most effective clays for use in laundry washing compositions and preferred for product performance.

Appropriate clay minerals can be chosen due to the fact that smectites have a true X-ray diffraction spectrum 14A. This characteristic spectrum, taken in association with the exchange capacity measurements carried out in the manner mentioned above, constitutes a basis for selection of the particular minerals of the smectite type to be used in the granular detergent compositions described here.

In the compositions of the present invention, the most preferred softening clays. are aluminum silicates in which sodium is the predominant cation, such as, for example, clays of the bentonite type. Among the bentonite clays, particular preference is given to those from Wyoming (generally called 20 bentonites from the western United States of America or from Wyoming).

Preferred swelling bentonites are sold under the trademark Minerai Colloid, as industrial bentonites, by Benton Clay Company, a subsidiary of Georgia Kaolin Company. These materials, which are the same as those previously sold under the trademark THIXO-JEL, are selectively extracted and enriched bentonites, and those which are considered to be the most useful are available under the designations Ore Colloid No. 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 from 8 to 9.4, maximum free moisture contents about 8% and densities of about 2.6, and with respect to, tr ψ *

" AT

In pulverized quality, at least about 85% (and preferably 100%) pass through a 74 micron mesh screen. Preferably, the bentonite is in a form such that almost all of its particles 5 (that is to say at least 90% of the particles, preferably more than 95%), pass through a 44 micron mesh screen. and, better still, all of the particles pass through such a sieve. The bulking power of bentonites generally corresponds to a water absorption capacity of 3 to 15 ml / gram and their viscosity, at a concentration of 6% in water, is generally around 8 to 30 mPa.s .

Instead of using THIXO-JEL or Colloid Ore bentonites, products such as that sold by the American Colloid Company, Industrial Division, under the name "General Purpose Bentonite Powder, 325 mesh" can be used, including a fraction of A minimum of 95% has a particle diameter less than 44 microns (size of the wet particles) and a minimum 96% fraction has a particle diameter less than 74 microns (the size of the dry particles). Such hydrated aluminum silicate consists mainly of montmorillonite (90% minimum), with lower proportions of feldspar, biotite and selenite. A typical analysis, on an "anhydrous" basis, is 63.05% silica, 21.5% alumina, 3.3% ferric ion (expressed as Fe O), 0.4% ferrous ion (expressed in FeO), 2.7% magnesium (expressed in MgO), 2.6% sodium and potassium (expressed in Na O) and 0.7% calcium (expressed in CaO), 5.6 % of water of crystallization (expressed as HO) and 0.7% of elements present in trace amounts.

Although bentonites from the western United States of America are preferred, it is also possible at 21 h to use other bentonites, such as those which can be manufactured by processing Italian bentonites or the like containing relatively low proportions of exchanged monovalent metals (sodium and potassium) with alkaline substances such as sodium carbonate, to increase the cation exchange capacities of these products. " It is considered that the Na20 content of the bentonite should be at least about 0.5%, preferably at least 10 - at least 1% and more preferably at least 2%, so that the clay swells well and has good softening and dispersing properties in aqueous suspension. Preferred swelling bentonites of the types described above are sold under the trademarks Laviosa and Winkelmann, for example Laviosa AGB and Winkelmann G-13.

Obviously, any other clay minerals which are substantive to textiles and are capable of imparting "softness" to them can be used in the present invention.

The preferred clays used here are "intangible", that is to say that they have a particle size which cannot be perceived by touch. Impalpable clays have particle sizes -25 less than about 50 micrometers; the clays used here have a particle size ranging from about 5 micrometers to about 50 micrometers.

Fabric softeners of the clay type are present in detergent compositions in proportions of about 1 to about 50 percent, preferably about 2 to 30%, more preferably about 4 to 20% by weight, relative to the entire composition.

* ίΛ 22

In the present invention, it is preferable that the softening clay and the softening diammonic compound be added afterwards to the spray-dried beads or granules. The softener diammoni-5 compound is preferably dissolved in an organic solvent or dispersed in an aqueous liquid and mixed with the particles of the clay mineral. The softening diammonic compound and the softening clay mineral are then intimately and uniformly mixed with the spray-dried beads or granules.

The softening ammonium compound and the softening clay are present in the detergent compositions of the invention in a proportion sufficient to give the desired softening effect when the composition is used in usual doses for a detergent washing composition. , for example from about 1/8 to 1/2 cup of detergent per wash load.

2o Detergency builders

The detergent compositions of the invention optionally, and preferably, contain at least one detergency builder of the type commonly used in detergent compositions. Useful detergency builders include any conventional mineral water soluble builders, such as water soluble silicates, carbonates, bicarbonates, borates, sulfates, etc. Organic detergency builders include oolyhydroxy sulfonates, polyacetates, aminopolyaceous tates, carboxylates, polycarboxylates, succinates, phytates, etc., which are water soluble.

Particular examples of non-phosphorus mineral deter-qence adjuvants include water-soluble mineral carbonates, bicarbonates and silicates. Carbonates, bicarbonates and silicates of 23 alkali metals, for example sodium and potassium are particularly useful here.

Zeolitic crystalline and amorphous aluminosilicates are particularly useful detergency builders. Generally, zeolites correspond to the general formula: (^ °) x. (A1203) y. (Si02) z.wH2 ° in which x is 1, y is 0.8 to 1.2 and preferably 10 to 1 , z is 1.5 to 3.5 or more and preferably 2 to 3, w is 0 to 9 and preferably 2.5 to 6, and M is preferably sodium. A typical zeolite is a zeolite of type A or of similar structure, type 4A being particularly preferred. Preferred aluminosiliates have calcium ion exchange capacities of about 200 milliequivalents per gram or more, for example 400 meq / g.

Various crystalline zeolites (i.e. aluminosilicates) which can be used are described in British Patent No. 1,504,168, United States Patent No. 4,409,136 and Canadian Patents N No. 1,072,835 and 1,087,477. An example of the amorphous zeolites useful here can be found in Belgian Patent No. 835,351.

Water soluble organic detergency builders are particularly useful. For example, the acetates, carboxylates, polycarboxylates and polyhydroxy sulfonates of alkali metals, ammonium and substituted ammonium are detergency builders useful in the compositions and methods of the present invention. Particular examples of detergency builders of the acetate and polycarboxy-late type include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diaminetetraacetic acid, nitrilotri-35 acid 24 * acetic, benzene-polycarboxylic acids (i.e. penta- and tetracarboxylic), carbo-xymethoxysuccinic acid and citric acid.

Other organic adjuvant salts useful in this context include the polycarboxylates described in US Patent No. 2,264,103, including the water-soluble alkali metal salts of mellitic acid. Water-soluble salts of polycarboxylic polymers and copolymers, such as those described in U.S. Patent No. 3,308,067, are also useful here.

Particular organic detergency builder salts which can be used include the alkali metal salts of hydro-xyacrylic acid polymers, preferably the sodium and potassium salts. A particularly preferred detergency builder is an alpha-hydroxy-acrylic acid polymer or its sodium salt; the hydroxyacrylic acid polymer or its salt which can be used as a detergency builder contains monomeric units of formula:

R, OH

I I

--c - c-- 1 2 3 4 5 6 7 8 9 10 11 il 2 L R9 coom 3 £ n 4 in which R ^ 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 6 propyl. The preferred substituents R 1 and R 2 are both hydrogen. M represents hydrogen or an alkali metal such as sodium or potassium, or an alkaline earth metal such as calcium, magnesium 10 or barium. The preferred substituent M is sodium.

11

The terminal or end groups of the polymer do not

• · »* V

25 are not very important and can be K, OH, CH- ^ or a carbon hydrocarbon chain. The degree of polymerization, i.e., the value of n, is generally determined by the limit compatible with the solubility of the polymer in water. The polymer of hydroxyacrylic acid or its salt can, for example, have a molecular weight of 2000 to 20,000. See for example the patents of the United States of America No. 3,920,570 and No. 4,107,411 which describe methods of making polymers.

Another class of useful organic detergency builder salts includes the alkali metal or ammonium salts of carboxy-methyloxy-succinic acid, preferably the trisodium salt. The salts of carboxy-methyloxy-succinic acid which can be used in the detergent compositions of the present invention correspond to the following general formula:

MOOC-CH-COOM

20 |

CH3O-CH-COOM

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

Another organic adjuvant detergent salt which can be used is an adjuvant organic detergent salt of alkali metal lower polycarboxylic acid. This class of organic detergency builder salts includes alkali metal salts of lower polycarboxylic acids, having for example two to four carboxyl groups "26 *, r 4

The preferred sodium and potassium salts of lower polycarboxylic acids are the citric acid and tartaric acid salts. The sodium salts of citric acid are the most preferred, especially 5-trisodium citrate.

Other organic detergency builders that can still be used are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, these detergency builder salts may consist of a copolymer which is the product of the reaction of an approximately equal number of moles of methacrylic acid and maleic anhydride, having been completely neutralized to form its sodium salt.

This detergency builder is commercially available under the trademark Sokalan CP5. This detergency builder is used, even when used in small amounts, to inhibit incrustation.

Examples of organic sequestering builder additives which can be used with alkali metal builder salts of lower polycarboxylic acids or in admixture with other organic and inorganic builder additives are alkali metal aminopolycarboxylates, ammonium and substituted ammonium, for example sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitriloacetates (NTA) and triethanolamine N- (2-hydroxyethyl) nitr -lodiacetates. Blends of these aminopolycarboxylates are also suitable.

Other suitable detergency builders of the organic type include polyacetal carboxylates. Polyacetal carboxylates and their use in detergent compositions are described, for example, in U.S. Patents 4,144,226, 4,315,092 and 4,146,495.

27 * l * t

Mixtures of organic and / or mineral detergency builders can be used. It should be understood that although it is preferred here to use, for economic reasons, varieties whose cations are alkali metals of the mineral and organic polyvalent anionic detergency builder salts described above, the water-soluble salts ammonium, alkanol-ammonium, for example triethanol-ammonium, diethanol-ammonium, etc., of all the anions of JQ detergency builders described above are useful here.

The detergency builder salts, including both the organic and inorganic detergency builder salts, are conveniently added to the mixer mixture to be incorporated with the anionic surfactant, etc., in the spray-dried beads or granules that these obtain approximately 15 to approximately 75%, preferably approximately 20 to 60%, better still approximately 22 to 55% by weight of detergency builder salts, based on the weight of the beads dried 20 'by atomization, and this proportion will generally be chosen so as to obtain, in the finished composition, after mixing with the ingredients added afterwards, approximately 2 to 80%, preferably 10 to 70% and better still 20 to 50%, of adjuvant salts. detergency based on the total composition.

Softening agent of the diammonic compound type

The softening agents used in the present invention are diammonic compounds which are characterized by their general insolubility in water. The diammonic compounds useful here for improving the softening performance of the composition are compounds corresponding to the general formula (1): '; ^ r i ’*. * * 28 R2, R4

I I

R - N + - R-- N + -. R ,. . 2X ~ (I) 5 wherein R-j is an aliphatic hydrocarbon group having ^ about 12 to about 30 carbon atoms; each of the symbols R2 / R3, R ^, R5 and Rg is .jq independently chosen from aliphatic hydrocarbon groups of 1 to 22 carbon atoms, with the condition that the total number of carbon atoms of all the aliphatic hydrocarbon groups, including R ^, is not more than about 75 and with the condi-.jç. further that no more than three of the groups R2 to Rg have more than 12 carbon atoms; R? is -CH2CH2 “or -CH2CH2CH2-; and X is an anion forming a water-soluble salt.

The preferred compounds of formula (I) are 2Q 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 R1 to Rg are: 22 Rj is an aliphatic hydrocarbon group, which may be straight chain or branched chain, and saturated or unsaturated (i.e. a linear or branched alkyl, alkenyl or alkynyl group) having 16 to 22 carbon atoms, for example 18 to 20 carbon atoms; R2 to Rg 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 22 all hydrocarbon groups aliphatic Rj ”Rg does not · ·» r τ *> * »29 be not greater than · approximately 50, preferably not greater than approximately 35, and with the additional condition that not more than 2, preferably not more than 1, and more preferably none of R2 to Rg has more than 12 carbon atoms; is -CH2CH2- or -CH2CH2CH2-, preferably -CH2CH2CH2-; and X is an anion forming a water-soluble salt such as, for example, halide, for example bromide, chloride or iodide, sulfate, methosulfate, ethosulfate, hydroxide, acetate, propionate, or other similar organic or inorganic monovalent anion solubilizer.

Examples of preferred R-j groups include stearyl, tallow, hydrogenated tallow, eicosyl, soy, etc.

Examples of preferred alkyl and alkenyl groups represented by R2 through Rg include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-butyl, octyl, 1-octenyl, etc. Particular preference is given to methyl, ethyl, propyl and isopropyl groups, and most preferably methyl and ethyl groups.

Particular examples of compounds of formula (I) which are commercially available or which can be readily manufactured by conventional techniques include: CH, CH, I 1 3 (1) Tallow „_N + _CH2CH2CH2- N + -GH3 . 2C1 30 CÏÏ3, (Adogen 477) “30 * f \ CH, CH, CH, CH, I 2 3! 2 3 (2) tallow N - CH, CH, CH, N- CHU. 2C1

v, | Z Z Z. O

CH, CH, 5 f 'i CH, CH, | 3 | 3 (3) stearyl-N - CH2CH2CH2-Kft-CH-j. 2CH3S04 10 CH, CH, k J -3) / CH, CH, I 3 | 3 (4) CH16H37_ N + __ CH2CH2 -N + -CH2CH2OH. 2C1 „r CH, C1 CH ,, 15 3 16 37} N.

S

CH, CH, i 3 I 3 (5) C16H37 - ν'1— CH2CH2CH2-N-CHj. 2CH3S04 "20 | C3H8 CH, L 3 etc. and ethosulfates, halides, acetates, etc.

corresponding water-soluble.

25

The compound (1) above, namely dimethyl-N- (tallow alkyl) -N'-trimethyl-propylene-diammonium dichloride is particularly preferred.

This compound is commercially available under the name Adogen 477 from Rewo Company. This compound can be prepared in the usual way, for example by reacting 1 mole of N-methyl-N-tallow-N1-methyl-propylene-diamine with 3 moles of methyl chloride and then quaternizing the resulting compound with methyl sulphate .

31

The beads or granules can be impregnated with the softener diammonic compound without using any solvent or carrier liquid. However, it is generally preferable to dissolve the diam-5 softening compound in an organic solvent or to disperse the diamonic softening compound in an aqueous liquid vehicle. The softener diammonic compound is preferably premixed with the softening clay mineral and the mixture is added to the spray-dried beads or granules.

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

The spray-dried beads are then intimately mixed with the softener diammonic compound and the softening clay, and the remaining ingredients, for example the nonionic surfactant, bleach, enzymes, fragrances and other ingredients sensitive to heat or at pH and / or insoluble in water, to prepare the final detergent-softener composition. The proportion of the spray-dried pearls and of the ingredients added afterwards is such that the final composition contains the following proportions of the essential ingredients: * * 32 _ _I Proportion (% by weight)

Ingredient__Large Tntermyti arrP .....- Pr-pfÔT-ήο Detergent 1.-95 5-50 5-30

Detergency builders2—80 10-70 20-50

Softening clay j.30 2-20 4-10 S'diamonic 0.25-10 0.5-5 1.0-2.5 "(Compound of Formula (I)) 5 Additives for detergents, Fillers, 0- 60 2-50 5-30 ", ___ uumite

Rgxort asmla a, ssaplissant / selcï: aTTrtrdpiæ - 10: 1 tO 1: 1 6: 1 to 3: 1

The rest, 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 sulfate, the latter being particularly preferred. The proportion of filler generally reaches approximately 5%, for example 0.1 to 2%, preferably 0.3 to 1% by weight of the composition.

Various additives can be incorporated into the laundry detergent compositions of the present invention. They generally include perfumes, coloring materials such as pigments and soluble dyes, bleaches such as sodium perborate, bleach activators, bleach stabilizers, anti-redeposition or soil suspending agents such as the alkali metal salts of carboxymethylcellulose, optical brighteners such as anionic, cationic or nonionic brighteners, foam stabilizers such as alkanolamides, foam enhancers, germicides, tarnishing agents, pH adjusting agents, enzymes, etc., which are all well known in the art of tissue washing for use in detergent compositions. Flow promoting agents commonly referred to as flow aids can also be used to maintain the particulate compositions in the form of beads or free flowing powder. Starch derivatives and special clays are commercially available as additives improving the flowability of otherwise tacky or tacky particulate compositions, two of these clay additives being currently marketed under the trade names "Satintone "and" Microsil ". Detergent compositions may also contain bound and free water in minor amounts which do not adversely affect the flowability of the granular or powder compositions. The humidity proportions are normally from 1 to 15%, preferably from 5 to 12% and better still from 8 to 12% of the entire composition. Within the limits of these proportions, a granular product, pulverulent or particulate, is obtained which flows satisfactorily and which can be prevented from being too dusty by acting on the particle size and the moisture content.

Suitable ranges of detergent additives are: enzymes - 0 to 2%, especially 0.2 to 1%? corrosion inhibitors about 0 to 15% and preferably 2 to 8%; defoaming agents and foam suppressants - 0 to 15%, preferably 0 to 8% 3Q for example 0.1 to 5%; soil suspending or anti-deposition agents and anti-aging agents - 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%, for example 0.2 to 0.8%; pH modifiers and pH buffers - 0 to 5%, preferably 0 to 2%; agent of .

f f 34 bleaching - 0% to about 40% and preferably 0% to about 25%; for example 2 to 20% ’; bleach stabilizers and bleach activators - 0 to about 15%, preferably 0 to 10%, for example 0.1 to 8%. The additives will be chosen so that they are compatible with the main constituents of the detergent composition.

Regardless of 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 an automatic washing machine so that its concentration in the wash water can be from about 0.05 to 1.5%, usually 0.1 at 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 softer waters can usefully be used. and harder.

The water temperature can be from 20 ° C to 100 ° C, and it is preferably from 60 ° C to 100 ° C in cases where the textile material or linen can withstand high temperatures without degradation or color fading. When it is desired to wash at a 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 wash water is generally about 1: 4 to 1:30, preferably 1:10 to 1:30.

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

J

35 ·

Example '1

The following composition is prepared by first forming the spray-dried beads (Δ) and then adding the components (B) afterwards.

<"T 36" A "(Spray dried pearls) Parts

Tap water 6.8

Tallow oil fatty acids or hydrogenated fish oil 2 8 5 ’

NaOH (35.7%) 1/3

Tap water 11.5

Sodium silicate (40%) (Nao0: Si09) 9.9 (1) 2

Anionic surfactant '' 16.0 (2) 10 Optical aviator '1 0.2

Carboxymethyl cellulose sodium 0.7 Zeolite (adjuvant mineral detergent salt) 33.9 Sodium sulfate (anhydrous) 0.7

Subtotal: 83.8 (4) 15

Ingredients added afterwards (B) Parts

Sodium perborate 15.0 20 Blue bentonite agglomerate 16.0

Adogen 477 ^ 2.5

Enzyme 0.5 Mixture 2 magnesium silicate / DTPA 0.2 Potassium methyl siliconate (50%) 0.6 (5) 25 Nonionic surfactant 3.0

Duet 787 (Perfume) 0.5

Subtotal 38.3 ^ Spray dried pearls (A) 61.7 100, - 30 1. (Linear dodecyl) benzene sulfonate-in the form of an aqueous solution.

2. Aviveur Stilbene N ° 4, highly concentrated granules.

3. Adogen 477 is N- (tallow alkyl) -N- (CH3) ~ (CH3) 3.2C1.

4. 61.7 parts after drying.

5. C-14-0-) 5 fatty alcohol ethoxylated with 11 moles of ethylene oxide per mole.

. * * "; * * * 37

The spray dried beads (A) are mixed with the after-added ingredients (B) to obtain product 1 (invention). The concentration of the mineral clay softener in the final composition is 16% and the concentration of the Adogen 477 softener in the final composition is "2.5%, in product 1 (invention).

For comparison, the same composition is prepared except that Adogen 477 is not used. The second composition, product 2 (comparison), has a clay mineral softener concentration of 16% and does not contain Adogen 477 .

Products 1 and 2 are used to wash test fabrics at 60 ° C using three cycles.

The evaluation of the softening, cleaning and bleaching carried out by the product 1 (invention) A + B shows that there is no negative effect on the performance parameters following the addition of Adogen 477 to, the composition, by comparison with parison, the product 2 A + B (without softening agent Adogen 477).

The effectiveness of product 1 (invention) for removing dirt is compared with that of product 2 (comparison) and it is found that products 1 and 2 are almost equivalent.

The qualities of flexibility communicated to the test fabrics by products 1 and 2 are compared, and product 1 (invention) is shown to be superior to product 2 (comparative).

The whiteness and the anti-deposition effect of the soils obtained with products 1 and 2 are compared on test fabrics in polyester-cotton blend, cotton and nylon, washed with these products, and product 1 ( invention) is superior to product 2 (comparative), in the three comparisons.

* 4 38

It is found that the washing liquor containing product 1 (invention) does not produce foam compared to product 2 (comparison) which produces foam.

5 Example 1 shows that the addition of Adogen 477 to the composition makes it possible to obtain a roughly equivalent removal of dirt, while ensuring superior properties of flexibility and whiteness / anti-deposition and low foaming.

10 Example 2

Following the same general procedure as in Example 1, the following composition is prepared: 15 "A" (Spray-dried pearls) Percent by weight

Sodium tridecylbenzenesulfonate 15.0 Zeolite (mineral detergency builder salt) 39.3

Sodium silicate (lNa20: 2.4 Si02) 7.0

Sodium sulfate 4.0

Optical aviator (Tinopal 5BM) 0.2

Carboxymethyl cellulose sodium 0.25 - _ 25 NaOH (40%). 1.75

Sub-total: € 67.5 * * »*; * <1 39

Ingredients added afterwards (B) Percent by weight

Thixogel clay N ° 1 10.0

Adogen 477 2.5 5 Sodium perborate 15.0

Enzyme 0.5 Potassium methylsiliconate 0.6

Non-ionic surfactant (1) 3.0 10 Magnesium silicate / DTPA (Mixture No. 2) 0.3

Duet 787 (perfume) 0.6

Subtotal: 32.5

Total: 100.0 15 1. Ci2 - Ci4 fatty alcohol condensed with 9 moles of ethylene oxide per mole.

In product 3 (invention) of Example 2, the concentration of softening clay in the final laaatpo-20 is 10 percent by weight and the concentration of Adogen 477 in the final composition is 2.5%. By way of comparison, a second composition (product 4) is prepared in which the softening clay concentration is 16 per cent by weight and no Adogen 477 is used.

The effectiveness of soil removal of product 3 (invention) and of product 4 (comparison) is compared and it is found that products 3 and 4 are almost equivalent.

The qualities of flexibility communicated to the fabrics by products 3 and 4 are compared, and product 3 (invention) is shown to be superior to product 4 (comparison).

The whiteness and the anti-deposition effect of the dirt obtained with the products 3 and 4 are compared on test fabrics in polyester / cotton blend I * 1 * * * "40 in cotton and Nylon, washed with these products, and product 3 (invention) is superior to product 4 (comparison) on 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 (comparison) which produces foam.

Example 2 shows that the addition of Adogen 477 10 to the composition allows a significant reduction in the amount of softening clay necessary to obtain the desired softening performance, while still ensuring an equivalent or greater efficiency with regard to elimination of dirty dirt, flexibility, whiteness / anti-redeposition and foaming.

v

Claims (14)

1 I 7 I 5 R3 R6 in the current 30 Rj is an aliphatic hydrocarbon group having approximately 12 to approximately 30 carbon atoms, each of the symbols R2f R- ^, R4, R5 and Rg is independently chosen from aliphatic hydrocarbon groups having 1 to 22 carbon atoms, with the proviso that the total number of carbon atoms "t 1 I 7 I 5 20 R3 r6 in which is an aliphatic hydrocarbon radical containing approximately 12 to approximately 30 carbon atoms, each of the symbols R2, R2, R ^, R ^, and Rg is independently chosen from aliphatic hydrocarbon groups having 1 to 22 atoms carbon, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups, including 30 Rj, is not greater than about 75, and with the additional condition that no more than two groups R2 to Rg are have more than 12 carbon atoms, R? is -CH2CH2- or -CH2CH2CH2-, and 42 *. . * τ <* X is an anion forming a water-soluble salt; and optionally one or more additives for detergents insensitive to heat and pH, fillers and humidity. 1. Detergent and softener composition without phosphate, in solid form, for washing clothes, comprising spray-dried beads consisting of a homogeneous mixture of: one or more detergent compounds insensitive to heat and to pH chosen from synthetic anionic detergents, synthetic nonionic detergents, synthetic ampholytic detergents, synthetic zwitterionic detergents and mixtures thereof; one or more mineral or organic detergency builder salts insensitive to heat and pH; a mineral softening agent of the clay type; A softening agent of the diammonium compound type chosen from the compounds corresponding to the formula; f2 f4 R - r - N - Rc. 2X (I) 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 detergent builder salt (s) include a mineral detergent adjuvant salt or an adjuvant salt organic detergency. 3. phosphate-free detergent and softener composition according to claim 1, characterized in that, in formula (I), 15 R- | is a linear or branched alkyl, alkenyl or alkynyl group having 16 to 22 carbon atoms, "R2 to Rg are each independently selected from alkyl and alkenyl groups having 1 to 16 carbon atoms, with the proviso that the total number of like carbon in all the aliphatic hydrocarbon groups R 1 to R 6 are not greater than about 50 and with the additional condition that not more than two of R 2 to R 6 have more than 12 carbon atoms. 4 to 45 in all the aliphatic hydrocarbon groups, including -R ^, is not greater than about 75, and with the additional condition that not more than three of the groups R2 to Rg have more than 12 carbon atoms, R? 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 materials selected from additives for detergents, fillers and moisture. 4. A phosphate-free detergent and softener composition according to claim 2, characterized in that R2 to Rg 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 R 1 to R 6 is not greater than about 35. 5. A phosphate-free detergent and softener composition according to claim 1, characterized in that it comprises approximately 10 to approximately 60% by weight of the detergent compound (s); ft 43 about 15 to about 90% by weight of the detergency builder salt (s); about 0.25 to about 10% by weight of the softening agent of the diammonic compound type; About 1 to 30% by weight of the mineral softening agent of the clay type; and about 0 to about 50% by weight of detergent additives, fillers and moisture. 6. A phosphate-free detergent and softener composition according to claim 4, characterized in that it comprises, on a weight basis, about 15 to about 40% of a synthetic anionic detergent of the (linear higher alkyl) benzene sulfonate type; About 25 to 65% of a zeolite mineral detergency builder; about 0.5 to 5% of said softening agent of the diammonic compound type: about 2 to 20% of said mineral softening agent of the clay type; and approximately 5 to 40% of one or more materials chosen from additives for detergents insensitive to pH and stable to heat, fillers, 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 mineral detergency builder is a zeolite, and the diammonium compound is the compound of formula: CH, CH, I 3 J 3 Suif - N + - CH2CH2CH2 - NÎ_CH3. 2C1 ~ 1 CH3 CH3 * * i "* Λ 44 8. phosphate-free detergent and softener composition, characterized in that it comprises a softening agent of the clay type and a softening agent of the diammonium compound type in mixture with the detergent composition in spray-dried beads for washing the laundry of claim 1. 9. A phosphate-free detergent and softener composition for washing clothes, in the form of 10 free-flowing granules or powders, comprising: (A) approximately 1 to approximately 95% by weight of one or more detergent compounds chosen from synthetic anionic detergents, synthetic nonionic detergents, synthetic amphoteric detergents, synthetic zwitterionic detergents and mixtures thereof; (B) about 2 to about 20% by weight of a mineral softening agent of the clay type: (C) about 2 to about 80% by weight of one or more detergency builders; (D) about 0.5 to 5% by weight of a softening agent of the diammonic compound type corresponding to the formula: 25 R2? 4 I I R, ._ Nt_ R -, - N + - Rc 2X (I) 10 CH3 L3 10. A phosphate-free composition according to claim 9, characterized in that it comprises spray-dried pearls consisting of an anionic surfactant, a detergency builder salt and one or more materials chosen from additives. for detergents insensitive to pH and stable to heat, the fillers and their mixtures, and in that the said ammonium compound is premixed with the softening clay and the premix is uniformly mixed with the spray-dried pearls. 11. A phosphate-free composition according to claim 9, characterized in that, in formula (I) R ^ is a linear or branched alkyl, alkenyl or alkynyl group having 16 to 22 carbon atoms; 25 and R2 to Rg are independently selected from alkyl and alkenyl groups having 1 to 16 carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups in Rg is not greater at about 50, and with the additional condition that no more than two of R2 to Rg have more than 12 carbon atoms. 12. A phosphate-free composition according to claim 11, characterized in that, in formula 35 (I), R2 to Rg are each independently an alkyl or alkenyl group of 1 to 6 carbon atoms, with 46 ΐ »β ~ · la provided that the total number of carbon atoms in all of the Rg hydrocarbon groups is not more than about 35. 13. A phosphate-free composition according to claim 9, characterized in that the softening agent of the diammonic compound type corresponds to the formula: CH-, CH- L 1 + tallow - N- CH2CH2CH2 -N-CH3. 2C1 14. A phosphate-free composition according to claim 13, characterized in that the mineral softening agent of the clay type constitutes approximately 10% of the composition and the softening agent of the diammonic compound type constitutes approximately 2.5% of the composition.