LU86067A1 - DETERGENT-SOFTENER COMPOSITIONS FOR WASHING CYCLE AND WHICH SOFTENER HAS A GREATER TISSUE AFFINITY - Google Patents

Description

LU 1907

8 “ft" "Π Π 7 GRAND-DUCHY OF LUXEMBOURG

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¥, j! of the JE ..... 3 ·. September 1985 Minister _, Rwra of the Economy and the Middle Classes

Tit.rp issued; ή, ί * BJr ........................................ cjæM Property Department Intellectual

ζ 'Sg? LUXEMBOURG

Invention Patent Application I. Request -... LcL..sQcié.të .dite.iÎ .. COLGATE-PALMOLIVE COMPANY ...................... .................................................. .................................. (1) ............. .....................................

______ represented by Mr. A. Zewen, P.Eng. Industrial Property Attorney ^ ...... ssis.SBn.t ..... en ... 4u.aIi.t.é .... de ... .roaadafcaii: e .............................................. .................................................. .................................................. .....

deposit) this________ three September 1900 eighty-five ........................................ ...... (3) at .......... 1.5 °° ........ hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. la present request for obtaining a patent of invention concerning: ....... "C.Qi" p.ôsi..tiQns ..... de ..... d.é.texg .eiit.-as.s.Qupl.iss.ant .... pour ..... cy.cl.e .... de .... la'yage .... et ... jdjoint_ ( 4) the softener has a greater affinity for fabrics "___ 2. the delegation of power, dated .......................... ........................................... the ...... ..............................................

3. the description in French ___________ language ............................... of the invention in two copies; 4 ................. / ............. drawing boards, in two copies; 5. the receipt of the taxes paid to the Luxembourg Registration Office on ...... â .... septfimb.ra .... LS85 .............. .................................................. .................................................. .......: .......................................... ................................................

declare (s) assuming responsibility for this declaration, that the inventor (s) is (are); ....... l) ..... Andr.e.as .... Jan .... S.QMERS., ..... 39 ..... Sacr.amen.ts. traat, ..... 3-700 .TONGEREN, -Belgium -, ------------------ (5) ...... 2.) ... ..Genevxev.a ... E01JNECHEREr. „. Ru & ... de-LQncin.-84,. 434-1 - ÂWANS ·, - Belgium -............................... — ......- ......- 3.) -. Leopold- -LA-ÏTEMs rue · • de-, Merdorp'-2-i --5960 -Grp le-Grand j ••••• Belgium ----- ---------------------— claims (nt) for the above patent application the priority of one (of) applications () of (6) .... ................................................. breY and ..................... filed in (7) ........... EUA ........ .................................................. ............................................

on ................. 4 S.ep, tejiibre. ,,. 1.9.g4 ..... s.QUS 64.7 ... Q.7.9. „.. to .... n.Qms ..... of ..inventors, .....................- (8) ....... .............. doat ~~ La ~ dejaaade-r-esee-es-fe-4rLayaafe ~ dreit “i ................ .................................................. .......................................------- on behalf of. .................................................. .. (9) elect (elect) for him / her and, if appointed, for their proxy, in Luxembourg --------------------_ .... ..4, place Winston-Churchill, BP ..... 4471 Luxembourg ................................. .................................................. . (10) 'request) the grant of a patent for the invention for the subject described and represented in the abovementioned appendices, - with postponement of this grant to ............ 6 .. ..............................................month. (11)

The Laandataire ./v ....................

dd deposit report • The above application for a patent for invention has been filed with the Ministry of the Economy and the Middle Classes, Intellectual Property Service in Luxembourg, on:

3 198S

> ^ ftbour0 PfrSv ......... Pr. the Minister at 3:00 p.m. / Economy and the Middle Classes, A 68007_-, * i \ \ - - * t i

Br. ^ 76 2t1> 7 Adjournment to 6 months LU 1907 DESCRIPTION MEMORY filed in support of a PATENT OF INVENTION request in the name of the company called: COLGATE-PALMOLIVE COMPANY for: ~ "Detergent-softener compositions for washing cycle and whose softener has a greater affinity for fabrics "CI Priority of American patent application No 647.079 filed September 4, 1984 in the names of Andreas Jan SOMERS, Geneviève BONNECHERE and Leopold LÀITEM, whose plaintiff is the 'have right. . () ~. - (5

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The present invention relates to a composition and method for cleaning and softening fabrics during the washing cycle of a bleaching operation. More particularly, the present invention relates to fabric softener compositions for use in the washing cycle of a laundering operation, in particular using hot water, the composition comprising a nonionic surfactant, a fabric softener of the cationic quaternary ammonium-10 re type, and a polyfunctional additive intended to increase the affinity of the softening agent.

The compositions useful for treating fabrics in order to improve their flexibility and touch characteristics are known in the art.

When used in domestic laundering, fabric softeners are generally added to the rinse water during the rinse cycle which lasts only about 2 to 5 minutes. Therefore, the consumer should monitor the laundering process or take other precautions so that the fabric softener is added at the correct time. This requires that the consumer returns to the washing machine either immediately before the start of the rinsing cycle of the washing operation, or at the start of this cycle, which of course is tedious for the user. In addition, special care should be taken to use the correct amount of fabric softener to avoid an overdose which could make the garments hydrophobic by depositing a greasy film on the surface of the fabrics, as well as imparting certain degree of yellowing.

As a solution to the above-mentioned problems, it is known to use fabric softeners which are compatible with common laundry detergents, so that the softeners can be combined with the detergents in a single package to be used during

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* λ '2, washing cycle of the laundering operation. Examples of such fabric softening compositions added during the wash cycle are described in U.S. patents. 3,351,438, 3,660,286 and 3,703,480. In general, these fabric softener compositions for washing cycles contain a cationic quaternary ammonium softener and other ingredients which make the softener compounds compatible with common laundry detergents .

It is known, however, that the cationic softening compounds added to the washing cycle, either as an ingredient of a detergent-softening composition or as a softener for the washing cycle, interfere with the brightening action thus only with the cleaning power of the detergent. Thus, attempts have been made to compensate to some extent for this interference from detergent-softener compositions by using non-ionic surfactants, higher levels of brightening compounds, carboxymethylcellulose, anti-yellowing compounds, whitening agents, etc. However, only a small improvement in the softening compositions for the wash cycle has been obtained using various detergents, most of which are anionic.

However, there are a large number of descriptions in the art relating to laundry detergent compositions containing cationic fabric softeners, including softeners of the quaternary ammonium compound type, and nonionic surfactants, as well as other surfactants, for example anionic, zwitterionic and amphoteric compounds. As a representative of this technique, we can mention the patents of the USA. 4,264,457, 4,239,659, 4,259,217, 4,222,905, 3,951,879, 3,360,470, 3,351,483, 3,644,203, etc.

* 35 the following patents describe detergents and / or shampoos containing nonionic surfactants, which i 'Γ Λ * _ · "k

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3 include a polyfunctional additive: No. 3,313,734 (shampoo - quaternary ammonium) - containing polymers; 3,351,557 (ethylene / maleic anhydride copolymers - emulsion stabilizers); 3,509,059 (polymer containing acid groups, for example polyacrylic acid, formed in situ, i.e. in the presence of nonionic surfactant); 3,703,480 (amino-polyuretylene resins - to make cationic fabric softener and anionic surfactant compatible); 3,723,322 (carboxylated polysaccharide - as a detergency builder); 3,962,418 (cationic cellulose ether - thickener and hair treatment agent); 4,213,960 (polyaminoamides and homopolymers and copolymers of quaternary ammonium - hair treatment agent); 4,371,517 (cationic-15 qUes polymers and anionic polymers). The use of poly-cationic compounds, polyamines and polyamides to enhance the softening effect of fabric softeners of the conventional quaternary compound type in fabric softeners for the rinsing cycle is known, for example from after the USA patent No. 4,237,016, the British patents No. 1,576,326 and No. 2,041,025A, the Belgian patent 844,122, the European patent 13780 and the German patent DE 2,925,859A1.

Although many of these prior art formulations provide satisfactory cleaning and / or softening under many different conditions, they still have the disadvantages of requiring addition to the rinse cycle; not to provide a suitable softening - comparable for example to the results obtained with softeners added to the rinsing cycle - in particular under washing conditions in hot water, that is to say at a temperature of 60 ° C. and more ; to require the formation of complexes of the cationic compound; to use water-soluble cationic compounds of lower softening power, for example of the mono (higher alkyl) quaternary ammonium 2 type, to be limited to liquid compositions 1, etc.

'i 4 •' * »Although it is common for current laundry detergent compositions and conventional household automatic washing machines, especially in the United States, to be capable of washing / cleaning fabrics soiled using cold or lukewarm wash water, especially for delicate fabrics, fabrics that do not require ironing, fabrics with permanent pleating, etc., it is nevertheless realized that more cleaning effective (dirt removal, requires higher washing temperatures. In Europe and other countries, domestic washing machines operate at high temperatures of 60 ° C or more, reaching temperatures While the boiling water is boiling, although these elevated temperatures are advantageous for removing soiling, an equal advantage is not derived therefrom as to the softening action.

: The present invention is based on the discovery that the softening power of a detergent system based on a mixture of a nonionic detergent compound and a cationic quaternary ammonium compound is markedly improved by using a limited class. of polyfunctional compounds, which increase the affinity of the water-insoluble cationic softener for the treated fabric, and therefore increase the softening power. It has further been discovered that the softening power is further improved by using , as a non-ionic surfactant, an over-factive having a cloud point, alone or in combination with an amphoteric surfactant, which is at least about 5 ° C higher than the washing temperature which is at least about 60 ° C. In addition, this improvement in softening power is obtained without degradation or at least without significant degradation of the washing power (that is to say cleaning).

A relationship between cleaning power and cloud point i of a mixture of nonionic / ionic detergents is known from U.S. patents. 4,222,905

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"5 and 4 259 217. More particularly, as established in column 5, lines 40-61 of the aforementioned patent 4 259 217:" Methods are described here for bleaching fabrics with the compositions of the present invention which provide greater removal of greasy and oily soils and fabric maintenance benefits. In these methods, laundry detergent compositions are used under temperature conditions such that the aqueous laundry solution is found. a temperature at or near (i.e., about 20 ° C) of the cloud point (i.e., the temperature at which a phase rich in non-ionic surfactant separates in the solution of bleaching) of the mixture of nonionic / cationic surfactants. This can preferably be obtained by formulating these mixtures of nonionic / cationic surfactants so that their cloud point falls between about 0 and 95 ° C., in particular between envy ron 10 and 70 ° C, in particular between about 20 ° and 70 ° C, better still between about 30 and about 50 ° C. During the washing operation, the temperature of the laundry solution is maintained in this temperature range + 25 and at -20 ° C from the cloud point temperature.

The yield is further improved when the temperature of the aqueous bleach solution is at -15 ° C, more particularly 1 to about -10 ° C from the cloud point of the mixture of nonionic / cationic surfactants.

Apparently, the need to operate at wash temperatures at or below the cloud point is based on the assumption that the cloud point of the mixture of surfactants in the wash water corresponds to the temperature at which micelles of the surfactant aggregate will agglomerate to such an extent that these large aggregates f

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% »2 Λ 6 so much that they separate from the solution and, as a result, a turbidity is observed. A further rise in temperature leads to complete separation of the phases from the water and the nonionic surfactant and, as a result, the detersive action exerted on the soiled fabrics and the overall cleaning ability are lost.

However, although it is established by the U.S. patent. 4 259 217 supra that nonionic / ca-ionic mixtures may "depending on the identity and concentration of the cationic component ... provide the advantages known in the prior art with respect to such cationic compounds, for example. fabric softening effects ", it is nevertheless obvious that it is not recognized or suggested that the softening effects of ca-15 cationic compounds can be greatly improved by the use of certain nonionic compounds having high temperatures trouble point, per se. This is tantamount to saying that, although the U.S. patents 4,222,905 and 4,259,217 mentioned above describe a relationship between the cloud point of the nonionic / cationic mixture, washing temperature and cleaning power, it has now been discovered that this is the relationship between the cloud point of the non-ionic compound flows (or the non-ionic, amphoteric compound and any electrolytes present in the wash water) and the wash temperature which determines the softening action of fabric softeners of the com- type. cationic quaternary ammonium insoluble in | 1! Water. Contrary to the need of the present invention to use non-ionic compounds; 30 high cloud point temperature (i.e. above about 60 ° C, especially above about 90 ° C, and more preferably above about 100 ° C), the aforementioned patents prefer surfactants not ionic and combinations of nonionic-cationic surfactants * 35 having relatively low cloud points.

Therefore, it was totally unexpected that '

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i »7 the softening power of the cationic softener, in particular under washing conditions in hot water, can be greatly improved without reducing the cleaning power of the nonionic surfactant by formulating the detergent-softener composition so that it has a cloud point higher than the washing temperature.

The use of non-ionic surfactants having cloud points of at least about 60 ° C and higher than the temperature of the wash water is described in the Applicant's patent application entitled "Detergent-Softener Composition for wash cycle "filed on the same day as this application. The use of amphoteric sur-facti.fs to raise the cloud point of the nonionic surfactants above the temperature of the washing water is also described in this application and is described in more detail. as regards i- non-ionic surfactants with a low cloud point in the application entitled "Detergent-as- composition, softener for washing cycle in hot water" filed on the same day by the same Applicant.

The present invention is based on the discovery that the softening power of tissue softeners of the cationic compound type insoluble in quaternary ammonium water can be further improved by in-corporation in the composition of the nonionic surfactant and the cationic fabric softener, a polyfunctional additive which increases the affinity of the cationic fabric softener with the treated fabrics. In addition, the cleaning power of the nonionic surfactant can also be improved simultaneously.

It is on the basis of this discovery that the present invention has been developed.

The object of the present invention, therefore, is to improve the softening power of detergent compositions containing softening agents of the cationic compound type insoluble in quaternary ammonium water and nonionic detergent compounds without affecting .

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8 badly, to a large extent, the overall cleaning power.

These and other objects according to the invention which will be apparent from the following description are achieved by preparing a laundry detergent composition capable of washing soiled fabrics in an aqueous washing liquid at an elevated temperature. '' at least about 60 ° C and capable of reaching the boiling point of about 100 ° C, which comprises, by weight, 1 to 20 parts of a water-soluble nonionic surfactant, 2 to 20 parts of fabric softener of the water insoluble quaternary ammonium compound type and 0.5 to 10 parts of a polyfunctional additive increasing affinity for fabrics and possibly up to about 10 parts of a surfactant amphoteric.

In a preferred embodiment of the invention, the nonionic surfactant has a cloud point above the elevated temperature of the wash water. In a particularly preferred embodiment of the invention,. the compositions include the high cloud point nonionic surfactant and an amphoteric surfactant.

In each of the preferred embodiments, the detergent composition contains at least one additional detergent additive comprising detergency builders, thickeners, anti-redeposition agents, corrosion inhibitors, bleaches, enzymes, dyes, brighteners, optical brighteners, perfumes etc.

In one aspect, therefore, the present invention provides a detergent composition for cleaning and softening textile materials in an aqueous medium, particularly at an elevated washing temperature of at least about 60 ° C, which comprises, on a weight basis (a) about 1 to 20% of a nonionic surfactant, (b) about 2 to 20% of a fabric softening agent of the type water-insoluble cationic quaternary ammonium compound.

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1 * * "* * (c) about 0.5 to 10% of a polyfunctional additive chosen from the group comprising (i) quaternary diammonium compounds, (ii) polymers of 5-dimethylldyl chloride 1yl-ammonium , (iii) cationic guar gum, and (iv) poly (vinyl and methyl ether / maleic ether), the amount of (b) plus (c) being between about 4 and 22%, the ratio of (b) to (c) being comprised between approximately 10: 1 and approximately 1: 3, (d) O to approximately 10% of an amphoteric surfactant, (e) approximately 25 to 80% minus a detergency builder, (f) 0 to about 40% of a bleach, 15 (g) 0 to about 7% of a bleach activator, (h) 0 to about 4% of each the following agents: soil suspending agents, anti-redeposition agents and thickening agents, (i) 0 to about 5% anti-corrosion agents, (j) 0 to about 1% organic chelating agents, (k) 0 to about 2% of dyes, pigments, brighteners and optical brighteners, (1) 0 at approximately 2% of enzymes, 25 (m) 0 to approximately 0.5% of perfume, (n) 0 to approximately 10% of pH modifiers and buffers, (o) 0 to approximately 50% of inert fillers, d 'flow promoting agents and carriers, and about 30 to about 20% water.

According to a still preferred embodiment of the invention, there is provided a softening powdered or granular detergent composition flowing freely for cleaning and softening textured materials in an aqueous washing medium at a low temperature. high temperature between about 60 ° C and about 100 ° C, the composition comprising, on a weight basis, ^ j 10 "* Λ (a) about 3 to 15% of a nonionic surfactant having a hydrophobic group condensed with a sufficient amount of alkylene oxide to increase the cloud point of the nonionic surfactant to a value greater than the elevated temperature, (b) about 2 to 20% of a fabric softener of the cationic compound type insoluble in quaternary ammonium water characterized by at least two long chain aliphatic groups of 16 to 22 carbon atoms, (c) about 1 to 10% of a polyfunctional additive chosen from quaternary diammonium compounds of formula: R2 R2 15 R4 - N + - R l — N + -R .2X '

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. R2 R2 J

wherein represents a divalent alkylene group of 2 to 4 carbon atoms, which may optionally contain a hydroxy substituent; the R2 groups are identical or different and are lower alkyl groups of 1 to 4 carbon atoms, which may optionally contain a hydroxy substituent;

9 R

3 Rg is a saturated or unsaturated, straight or branched chain aliphatic hydrocarbon group of 1 to about 22 "carbon atoms, which hydrocarbon group may be interrupted by an oxygen atom or a group - OHN-, R- represents a radical chosen from the 30 ** aliphatic hydrocarbon radicals optionally interrupted by an oxygen atom or a group -CONH, having in total approximately 8 to approximately 22 carbon atoms, the alkylaryl radicals having approximately 8 to 16 carbon atoms in the

• alkyl fragment, and the aryl radicals, and 3 R

X is a salt-forming anion; and polymers of dimethyl diallyl ammonium chloride, f

X

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* η (d) 0.1 to 10% by weight of an amphoteric surfactant; and (e) the remainder consisting of detergency builders, detergent additives, fillers and moisture.

® In the preferred embodiment above, it is particularly preferred to incorporate about 25 to 50% of detergency builders, 0 to 5% of corrosion inhibitor, 0 to 1% of organic chelating agent, 0 at 40% oxygen bleach, 0 to 7% activator ^ bleach, 0 to 4% thickener and anti-redeposition agent, 0.2 to 0.5% optical brightening, 0.7 to 1.3% of enzyme, 0 to 0.5% of perfume, the rest consisting of a maximum of 20% of humidity.

Although the reason is not entirely clear, the Applicant has discovered that the best softening power of cationic softeners * is reached when the softener is very finely divided in washing water with a diameter of l 'order of a few micrometers to a dimension less than a micrometer and insoluble in water. The finely divided particles must, of course, be uniformly, although randomly, dispersed in the wash bath in order to come into uniform contact with all the items of washing consisting of clothing, towels, shirts, and the like. It seems | That the softener particles are effectively trapped by the fibers of the tissues and adhere to them by a combination of electrical, chemical and physical attraction.

According to the present invention, the affinity for the treated tissues is further improved, and the ace-30 power of the proportional cationic softener 1e- | ment increased by adding a polyfunctional additive to the detergent-softener composition, preferably a diquaternary compound, a polyquaternary compound or a cationic polymer. Although these polyfunctional additives can by themselves impart flexibility to the treated fabrics due to their own affinity for the fabrics,! y ψ 12 t • · as is known from the aforementioned prior art, their mode of action in the detergent-softener compositions for washing cycle of the present invention does not seem to involve mainly a softening action 5 any direct, but rather is apparently based primarily on one or both of the following factors: (1) their ability to stabilize the dispersion of fabric softener of the quaternary compound type; and (2) their ability to improve contact between the quaternary compound and the tissue. Regardless of the mode of action by which polyfunctional additives improve flexibility, a feature of the present invention is that the flexibility of fabrics treated during the wash cycle is substantially equivalent to that of fabrics treated with a conventional fabric softener added in the rinse cycle. Furthermore, it is possible to obtain a significant improvement in cleaning power by using the preferred compositions of the present invention.

The essential ingredients of the detergent-softener compositions are therefore the nonionic surfactant, the fabric softener of the cationic compound type which is insoluble in water and the polyfunctional additive. The use of an amphoteric surfactant in addition to the above essential ingredients is very advantageous, in particular when the cloud point of the nonionic surfactant is equal to or less than the temperature of the wash water.

Although the compositions of the present invention may provide suitable softening and cleaning power in cold wash water, for example at about 20-30 ° C, or lukewarm wash water, for example at about 30 ° C-40 ° C or higher, the best results are obtained when the washing compositions are used in high temperature wash water from about 60 * 0 to about 100 ° C (boiling temperature).

Suitable nonionic surfactants, y »13« are commercially available and originate from the condensation of an alkylene oxide or equivalent reactant and a hydrophobic compound containing reactive hydrogen. Hydrophobic organic compounds can be aliphatic, aromatic or heterocyclic, although the first two classes are preferred. Preferred types of hydrophobes are higher aliphatic alcohols and alkyl phenols, although others may be used such as carboxylic acids, carboxamides, mercaptans, sulfonamides, etc. The condensation products of ethylene oxide and (higher alkyl) phenols or higher fatty alcohols represent the preferred classes of nonionic compounds. Usually the hydrophobic unit must contain at least about 6 carbon atoms, and preferably at least about 8 carbon atoms, and it can contain up to about 50 carbon atoms or more, a preferred range being about 8 to 22 carbon atoms, better still 10 to 18 carbon atoms for aliphatic alcohols and 12 20 to 20 carbon atoms for (higher alkyl) phenols.

The amount of alkylene oxide varies considerably depending on the hydrophobic compound, but as a rule, at least about 15 mol of alkylene oxide is used per mole of hydrophobic compound and up to about 30 moles of alkylene oxide per mole of hydrophobic compound, to obtain cloud points of at least 60 ° C or more.

The preferred nonionic surfactants can be represented by the formula: R0 (CH "CH90) H (I).

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wherein R is a primary or secondary alkyl chain of about 8 to 22 carbon atoms and n has an average value of 15 to 30; RO- (CH2CH20) mH (II) in which R 'is a primary or secondary alkyl chain of 4 to 12 carbon atoms and m has a.

- 35 y »14; »Average value from 15 to 30.

Preferred alcohols from which the compounds of formula I are prepared include laury, myristyl, cetyl, stearyl and oleyl alcohols and mixtures thereof. Particularly preferred values for R are C-jq to C-jg alkyls, C-j g to C-j g alkyls and mixtures thereof being particularly preferred.

Preferred values of R "are C6 to C12 alkyl groups, with Cg and Cg groups, including octyl, isooctyl and nonyl groups, being particularly preferred.

A representative example of a nonionic compound of formula (I) is lauryl alcohol condensed with 15 moles of ethylene oxide. A representative example of a nonionic compound of formula II is isooctylphenol condensed with 30 moles of ethylene oxide.

Other nonionic compounds which can be used include the polyoxyalkylene esters of organic acids such as higher fatty acids, rosin acids, tall oil acids, acids from petroleum oxidation products, etc. . These esters usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 3 to about 15 to about 30 moles of ethylene oxide or its equivalent.

Still other non-ionic surfactants are the condensation products of alkylene oxide with higher fatty acid friends. The fatty acid group generally contains about 8 to about 22 carbon atoms and is condensed with about 15 to about 50 moles of ethylene oxide as a preferred example. The corresponding carboxamides and sulfonamides can also be used as suitable equivalents.

The invention also contemplates replacing all or a portion of the high cloud point nonionic surfactants described above with non-ionic compounds.

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corresponding low cloud point ions, ie the same hydrophobic group but condensed with only about 3 to 14 moles of ethylene oxide. However, when using non-ionic compounds with a low hole point, it is essential to also include one of the amphoteric surfaces, as described in more detail below, to ensure a point sufficiently high composition disorder. Preferably, a proportion not exceeding 50%, in particular not exceeding 30%, and most advantageously not more than about 20% of the total nonionic compound, consists of a compound of low cloud point.

The amount of the nonionic compound is generally the minimum amount which, when added to the wash water with or without the amphoteric surfactant, provides a suitable cleaning agent. In general, amounts of between about 2 and about 20%, preferably between about 3 and about 10%, and more preferably between about 4 and 9% by weight of the composition, provide a suitable cleaning power.

As used herein, the term "cloud point" denotes the temperature at which a graph which plots the light scattering intensity of the composition as a function of the temperature of the solution begins to increase suddenly to its maximum value under the following experimental conditions: The light scattering intensity is measured using a photogoniodiffusometer Model VM-12397, manufactured by the French Society of Control and Analysis Instruments , France (the apparatus being designated below by (SOFICA). The SOFICA sample cell and its cover are washed with hot acetone and left to dry.

The mixture of surfactants is prepared and brought into solution with distilled water at a concentration of 1000 ppm. A . About 15 ml of the solution sample is placed in the sample cell using a syringe fitted with a 0.2 µm nucleopore filter. The syringe needle passes through the cover of the sample cell 1Ί u-h in a manner

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Λ 16 re that the interior of the cell is not exposed to atmospheric dust. The sample is left in a variable temperature bath and both the bath and the sample are subjected to constant stirring. Bath 5 is maintained at temperature by heating using the SOFICA heater and is cooled by the addition of ice (the heating rate = 1 ° C / minute); the temperature of the sample is determined by the temperature of the bath. The light scattering intensity (angle 10 of 90 °) of the sample is then determined at various temperatures, using a green filter and no polarity in SOFICA.

In the present invention, the cloud point measurements are made by the two solutions of nonionic surfactant (at 1% by weight) in distilled water and in water containing 10% NaCl, although the latter generally far exceeds the amount of salts and electrolytes. Therefore, if the cloud point of the non-ionic surfactant measured in a 10% NaCl solution satisfies the conditions of the cloud point of the present invention, then there is no problem for the formulation of compositions. containing very high concentrations of detergency builder salts and other electrolytes, for example up to about 85% of the composition.

In this regard, it is known that the cloud point temperature for a given composition in the washing solution depends on the physical and chemical properties (e.g. CMC and solubility) of the cationic, 30 'nonionic and other components included in this composition. composition, and can be lowered by increasing the length of the alkyl chains of the nonionic and amphoteric surfactant compound, by decreasing the degree of ethoxylation of the nonionic component, or by adding electrolytes such as phosphates, polyphosphates, perborates, carbonates, sulfates, etc., in particular in relatively / small amounts (for example between about 1 and about 15% of a given 17 * "λ composition.).

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Because in the present invention cationic water-insoluble softening compounds are used, the cationic compounds will have substantially no effect whatsoever on the cloud point of the total composition. In fact, since the cationic softening compounds used in the present invention are insoluble in water, the cloud point temperature of the total formulation is very difficult to measure since the mixtures are naturally quite cloudy. Consequently, the cloud point of the nonionic compound with or without the addition of electrolytes is determined in the absence of the cationic compound and this ensures a sufficiently precise measurement of the cloud point of the total composition comprising the cationic compound.

For washing temperatures of between approximately 60 and 70 ° C., even with the polyfunctional additive component of the composition, all of the nonionic surfactants at 15-30 E0 described above, in particular those of formulas I and II, must have cloud points higher than the washing temperature.

However, for washing temperatures higher than 71 ° C to 100 ° C, in particular 80 ° to 100 ° C, it is necessary to use the most highly ethoxylated surfactants, for example 25 to 30 moles of oxide. ethylene by hydrophobic compound mode. For these higher washing temperatures, the nbn ionic surfactants which are particularly preferred are the (C 1 -C 1 alkyl) phenols ethoxylated with 25 to 30 moles, in particular 28 to 30 moles, 30 and better still about 30 moles of ethylene oxide.

Alternatively, and as described in more detail in the aforementioned applications, it has now also been discovered that for all nonionic surfactants, the cloud point can be raised by as much as about 40 ° C, general about 5 to 20 ° C by the addition to the composition of an amphoteric surfactant compound, for example an amphoteric rest of the type (al ky 1 higher fat) "Λ 18% (for example copra) imidazoline carboxyethylated , generally in a proportion of about 0.5 to 10%, preferably 1 to 4%, more preferably about 1 to 3%, by weight of the composition.

Therefore, in a preferred embodiment of the invention which is particularly useful for washing soiled fabrics in washing water "at an elevated temperature between about 80 ° and 100 ° C, the detergent composition contains more than (a) the nonionic surfactant of formula I or formula II, (b) the water-insoluble quaternary ammonium compound of formula III or formula IV, given below, and (c) l poly-functional additive, (d) an amphoteric surfactant in a sufficient proportion to raise the cloud point of the composition to a value above the elevated temperature from 80 to 100 ° C.

The second essential ingredient of the formulations of the present invention is the cationic fabric softener. In general, cationic fabric softeners - from tis-20 consist of at least one hydrophilic functional group carrying a negative exchange and a hydrophobic group containing a quaternary ammonium atom which is positively charged.

In order to impart sufficient flexibility to the treated tissue, it is essential that the cationic compound be insoluble in water. As used herein, a compound is considered insoluble in water if its solubility in water at the washing temperature is less than about 1%, preferably less than about 0.5%.

It is generally desirable that the cationic softening compound be included in the composition in a form ensuring high dispersibility in the washing liquid and therefore maximum fixation to the treated tissue. This can be achieved by using particle sizes dispersed in the washing liquid of between about <10 and about 50 microns, preferably between about <10 and about 20 microns.

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19 * meters for the cationic softening compound.

Fabric softeners of the type water-insoluble quaternary ammonium compound type which are known in the trade can be represented by the following formula: R, R ~ + \ / 3.

NX (III) R / \ K2 ^ 4 10 1 Γ _ + ^ Νη R5 - £ 1 X '(IV) r / \ 15 [_ R6 * 7 where Rj and Rg and Rg and Rg each independently represent a radical long chain aliphatic of 16 to 22 atoms of: carbon, Rg and R ^ and Ry represent, independently, lower alkyl radicals, or else Rg can be the group -RgNHCRg where Rg is a long chain aliphatic radical 0 having 16 to 22 carbon atoms, and Rg is a divalent alkyl group of 1 to 3 carbon atoms, and X is an annion forming a water-soluble salt, for example a halide, that is to say chloride, bromide, iodide; a sulfate, acetate, hydroxide, methosulfate, ethosulfate or a mono- or dibasic mineral or organic radical similar to solubilization. The carbon chain of the aliphatic radical containing 16 to 22 carbon atoms, in particular 16 to 20 carbon atoms, can be straight or branched, saturated or unsaturated. Lower alkyl radicals have 1 to 4 carbon atoms and may contain a hydro-35 xy radical. Preferably, the carbon chains are obtained from long chain fatty acids such as those derived from 20 · tallow and soybean oil. The terms "di-soybean" and "continuous", etc., as used herein, refer to the source from which the long chain fatty alkyl chains originate. Mixtures of the above may also be used, if desired, as well as other water-insoluble quaternary ammonium surfactants. The preferred ammonium salt is a dial-kyl-dimethyl-ammonium chloride in which the alkyl group is derived from hydrogenated tallow or stearic acid, or a chloru-re je di (a1ky1 higher} imidazolini um. Examples particular softening agents of the quaternary ammonium type of formula III, suitable for use in the composition of the present invention include the following: hydrogenated di-tallow chloride-dimethyl.-ammonium, dimethyl-distearyl ammonium chloride, bromide dimê-thy1-stëaryl-cétyl-ammonium, dimethyl-dikétyl-ammonium chloride, di-soybean-dimethyl-ammonium chloride, the corresponding sulfates, methosulfates, ethosulfates, bromides and hydroxides; etc.

Examples of quaternary ammonium softeners of formula IV include 1-methyl-1,2-diheptadecyl-imidazolinium chloride (bromide, metho-sulfate), 1,2-dieicosylalkylamidoethyl-1-methyl chloride -imidazolinium (bromide, methosulfate, etc.), 2-hexadecyl-1-methyl-1 [-2-hexadecyl-1-methyl-2 [(2-dodecoylamino) ê-thyljimidazolinium, 2-heptadecyl-1 ^ methyl-1-thyl sulfate [2-stëaroyl ami do) -êthyl] i mi daz * ol i ni um, 2-nonadecyl chloride / heneicosyl-1 - [(2-eicosoyl / docosoyl imido) é-thyl] imidazoli ni um.

Dimethyldistearyl ammonium chloride is particularly preferred because of its superior softening power, its biodegradability, its low solubility in water, its availability and its cost.

The amount of cationic fabric softener can generally be between about 2 and about 20% and preferably between about 3 and about 16%, and more preferably between about 6 and 15% based on the weight of the composition.

The weight ratio of the nonionic surfactant to the cationic fabric softener can be between about 1:10 and 5: 1, preferably between about 1: 5 and 4: 1, more preferably between 1: 2 and 3.5: 1.

Polyfunctional additives which are used to increase the tissue affinity of water-insoluble cationic quaternary ammonium compound fabric softeners include (i) quaternary diammonium compounds, (ii) polymers dimethyldia11 yl-ammonium um chloride, (iii) cationic guar gum, (iv) poly (methyl vinyl ether / maleic acid), and (v) diimidazolinium type compounds.

The quaternary diammonium compounds are particularly preferred and can be represented generally by the compounds of formula I2 ^ 2 X - R4-N + -RrN + -R3-X- ..

R2 R2 25 wherein R-j represents a divalent alkyl group of 2 to 4 carbon atoms, which may optionally carry a hydroxy substituent; R2 represents the same or different lower alkyl groups of 1 to 4 carbon atoms, which may optionally carry a hydroxy substituent; R2 represents an aliphatic hydrocarbon group of 1 to approximately 22 carbon atoms, which carbon-containing hydro-2g group may optionally be interrupted by an oxygen atom or the group -CONH-;

R4 represents a radical chosen from the group J

2 2 »resisting alipbhatic hydrocarbon radicals, optionally interrupted by an oxygen atom or the group -CONH-, having in total approximately 8 to 22 carbon atoms, the alkyl-aryl radicals having approximately 8 to approximately 16 ato-5 mes carbon in the alkyl, and aryl moiety; and X is a salt-forming anion, in particular CT, Br “, CH2 $ 03 ~, CH2CH2S03“, etc.

A class of diquaternary compounds which can be used in the present invention are the re-18 compounds presented by the formula: r6 -¾ X-Rc-CH-CH, -N + -CH9-CH-CH, -N + -CfVCH -RcX "5 I 2 I 2 I 2 | 2 I 5

OH Ry OH R7 OH

In which Rg is an alkyl radical containing 6 to

about 20, preferably 10 to 14, carbon atoms, Rg and R ~ j are methyl, ethyl or hydroxyethyl, and X is chloride or bromide. Particular examples include tetramethyl-di- (octoxy-beta-hydroxypropyl) dichloride-beta-hydroxy-propylene-diammonium dichloride, tetramethyl-di- (beta-hydroxydodecyl) -beta-hydroxy-propylene-diammonium dibloride , tetramethyl-di- (beta-hydroxytetradecyl) -beta-hydroxypropylene-di ammonium dichloride, tetraethyl-di- (dodecyloxy-beta-hydroxypropyl) -25 beta-hydroxypropylene-diammonium dichloride. These compounds are described in the U.S. patent. 3,983,079, in columns 3 and 4C

A particularly preferred class of diquaternary compounds are the N-mono (upper alkyl) -pen-ta- (lower alkyl) - (lower cane) -diammonium salts such as the compounds represented by the following formula: * 1 ° fi Γ rq-n + -r0-n + -r1c, x “8 '9 P 12 35 d 11 K11 in which Rg represents a long chain aliphatic radical' 'chain of 12 to 22 carbon atoms, preferably 14 to

.J

23 20 carbon atoms, Rg represents a divalent alkylene group of 2 to 4 carbon atoms, and and R ^ and R12 each represent a lower alkyl group of 1 to 4 carbon atoms, and X ”is a salt-forming anion , for example chloride, bromide, iodide, sulfate, methyl sulfate, ethyl sulfate, nitrate, etc. As a particular example, there may be mentioned the compound sold under the trademark Adogen 477, a Sherex product which is N-tallow-pentamethylpropane-diammonium chloride.

Polymers of dimethyldiallylammonium dichloride include homopolymers and copolymers. Comonomers of the copolymers include, for example, acrylic acid, methacrylic acid, styrene, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, and the like copolymerizable monomers. Acrylamide and methacrylamide are preferred, and acrylamide in particular.

As an example of the diimidazolinium compound, mention may be made of the compounds of formula 20 CH2 CH2

X *. 'F VN-R1 - ^ N / <^ 2 -X

2 R3 r3 1 I

N = C-R3 R-C ~ N

25 3 in which R is a saturated or unsaturated, straight or branched chain aliphatic group having 12 to 18 carbon atoms, R1 is a divalent aliphatic hydrocarbon group 3 having 2 to 5 carbon atoms, R is an alkyl group 30 1 to 4 carbon atoms lower, and X is an anion forming a salt i: As a specific example, mention may be made of 1-ethylene-bis (2-tallow-1-methyl-imidazoli-nium methyl sulfate) .

The polymerization can be carried out by conventional techniques well known in the art. The degree of polymerization is not particularly critical and is 24

»V

»Obtains satisfactory results with polymers having molecular weights of about 500 to about 10%. These polymers, as well as cationic guar gums and poly (methyl vinyl ether / maleic acid) are commercially available.

The amount of polyfunctional additive generally represents approximately 0.5 or 2 to approximately 10%, preferably 2 to approximately 8% of the total composition. It is also preferable that, among the amounts described above, the cationic fabric softener (b) and the polyfunctional additive (c) be used at a weight ratio of (b) :( c) of about 10 : 1 to 1: 3, preferably from about 6: 1 to 1: 2, more preferably from about 4: 1 to 1: 1.

As mentioned above, in the preferred embodiment of the invention, the composition also contains (d) an amphoteric surfactant.

A particular class of amphoteric surfactants are the complex fatty amide surfactants of general formula (V) 20 CH, / \

Il L n 2 R _ C-; +. Rl_ OM - (V)

25 0H / NR2-COOM

wherein R is a saturated or unsaturated straight or branched chain aliphatic group having 12 to 18 carbon atoms (e.g. lauryl, tridecyl, tetradecyl, pen-30 tadecyl, palmityl, heptadecyl, stearyl, tallow, copra, soybeans , oleyl, linoleyl), R and R each independently represent a divalent aliphatic hydrocarbon group of 2 to 5 carbon atoms (for example methylene, ethylene, propylene, butylene, 2-methylbutylene, pentylene, etc.), and M is hydrogen or an alkali metal (e.g. sodium, potassium, cesium and lithium). Examples of compounds of formula V which are available in trade include ch2 N '\ CH9 i' "ά C -C -N + - ChLCHL-ONa

5. / \ L L

OH- CH ^ COONa available under the designation Miranol CM (liquid) and Miranol DM (paste) from the company Miranol Chemical Co.; Soro-mine AL and Soromine At from GAF Corporation and compounds 10 Deriphat from General Mills.

The amphoteric compounds described in columns 3 and 4 of the E.U.A. 4,203,872 can also be used. They include the following seven groups of compounds.

15 (1) Detergents of the betaine type of formula: R? 0 '+ 11 R, -N-R.-C-0- 1 I ^ 20 R3

A suitable example is CHo 0 I .. "(c10" c14) n-alky1 - N + CH2C0 "25 - C" 3 (2) Detergents of the betain type with an alkyl bridge of formula 30 0 R2 0

H H 1 H

R1-CH2-C-N-CH2CH2CH2-N + -R4-C0-! R3

A suitable example is 0 ch3 0 "H l +" /

(C10-C14) n-alkyl-CH2-C-N-CH2CH2CH2-N -CH2C0J

ch3 5 J

26 (3) Imidazoline detergents of the formula CH9C00H 0 1+ 11 5 RrÇ— N -R4-0-CH2C0 N .CH, \ / ch2

A suitable example is 10 CFLCOOH 0! ^

II

(c10C14) n-alky1-c - N + -CH2CH20CH2C0 'N \ / CH2 ch2 15 (4) Detergents of the alkyl iminopropionate type of formula

H

r1-n-ch2ch2cooh 20 (5) 'Detergents of the alkyl ijrinodipropionate type of formula ch2ch2cooh 25 r1-och2ch2ch2-n ^

CH2CH2C00H

(6) Ether-bridge alkyl iiaincidipropionate type detergents of formula 30

CH9CH9C00H

/

R-j -0CH2CH2C ^ -N

ch2ch2cooh 35 (7) Amphoteric detergents based on copra-imidazo- 1 i ne of formula r 3 i 27 Ö Ο

I U

R-j -C- N + -CH2OCH2CH2CO "

"I

V / CH2 CH, 5 2

Any mixtures of amphoteric detergents can also be used with each other and with the amine oxide detergents listed above.

In the formulas (1) to (7) above, 10 Rj is a straight or branched chain radical, its ture or unsaturated containing about 7 to about 20, preferably about 8 to 18, and better still about 10 to 14 carbon atoms, R, and R ~ each represent an lower alkyl group C 13 to C 4, preferably methyl or ethyl, better still ethyl, R 4 is a C 1 -C 4 alkylene group divalent, preferably methylene or ethylene, better still ethylene.

A particularly preferred group of amphoteric p n compounds are compounds of the (higher fatty alkyl) imidazolnme carboxyethoxylate type of formula (8) CH2 "/ \ H2 H \ \|| + -CH2CH2C00 · hor4- N c -R1.

j! in which R ^ is a saturated or unsaturated, straight or branched, aliphatic group of 7 to 20 carbon atoms, 30, preferably 8 to 18 carbon atoms, better still 10 to 14 carbon atoms, and R ^ is a divalent lower alkyl group of 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Preferred R-j groups include copra, tallow, heptadecyl, oleyl, decyl and dodecyl, in particular copra (ie derivative of coconut fatty acid) groups. The preferred group R is ethylene

. V

11 λ 28 ne (-CH2CH2-) · The copra-imidazoline carboxyëthy-lée compound is available under the designation Rexoteric CSF, which is a trademark for a Rexolin product, 100% active ingredient, or in the form of '' a 45% solution of active ingredient.

Another preferred class of amphoteric compound is carboxyethylated open chain (higher fatty alkyl) friend derivatives. They include the above groups (4), (5) and (6), that is to say detergents of the alkyl imino-propionate and alkyl iminopropionate type with an ether bridge. The carboxyethylated octylamine which is available under the designation Rexoteric OASF from Rexolin is a particularly preferred element from this group.

Other classes of amphoteric surfactants such as sarcosines, taurines, isethionates, etc. can also be used.

Although there is no strict rule regarding the choice of combinations of nonionic surfactants and amphoteric surfactants or the appropriate amounts of each to achieve the necessary cloud point temperature in excess of the wash temperature to promote the softening power of the cationic fabric softener of the T Φ tissues, it is generally sufficient to use the amphoteric surfactant with the amount of nonionic surfactant mentioned above - born in a proportion of approximately 0.1 to 10 %, preferably from about 0.5 to about 4%, more preferably from about 1 to about 3%, based on the total weight of the composition. In general, ratios of nonionic surfactant to amphoteric surfactant of from about 1: 5 to 10: 1, preferably from 1: 3 to 6: 1, more preferably from 1: 2 to 4: 1, give the cloud point high and improved softening power desired, especially in combination with the polyfunctional compound.

The detergent compositions of the present invention are preferably provided in the form of free flowing powders or granules, but may also be in liquid form.

The detergent composition of the invention can also comprise, and in general it comprises, hydrosoluble detergent adjuvant salts. Water-soluble inorganic alkaline detergency builder salts which can be used alone with the detergent compound or in admixture with other builders are the alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (The ammonium and substituted ammonium salts can also be used). Particular examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexameta-phosphate , sodium sesquicarbonate, sodium mono- and di-orthophosphates and potassium bicarbonate. The alkali metal silicates are useful detergency builder salts which also serve to make the composition anti-corrosive for parts of the washing machine. Sodium silicates having Na2O / SiO2 ratios of 1.6 / 1 to 1 / 3.2, in particular about 1/2 to 1 / 2.8, are preferred. It is also possible to use potassium silicates in the same ratios.

Another class of detergency builders useful here are the water-insoluble aluminosilicates, both crystalline and amorphous. Various crystalline zeolites (i.e., alumino-silicates) are described in British Patent No. 1,504,168, the U.S. Patent. No. 4,409,136 and Canadian Patents No. 1,072,835 30 and No. 1,087,477 which are all cited here for reference. An example of amorphous zeolites useful here can be found in Belgian Patent No. 835,351, this patent also being incorporated herein by reference.

Zeolites generally have the formula: (M20) x. (A1203) y. (Si02) z.wH20 / l · 35 30 in which x is equal to 1, y is between 0.8 and 1.2, and preferably is equal to 1, z is between 1.5 and 3.5 or more, and preferably between 2 and 3 and w is between 0 and 9, preferably between 2.5 and 6 and 5 M is preferably 'this sodium. A representative zeolite is of type A or of analogous structure, type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange powers of about 200 ml equivalent per gram or more, for example 400.

Other materials such as clays, particularly water-insoluble types, may be useful additives in the compositions of the present invention. Bentonite is particularly interesting. This material is mainly montmori11onite which is a hydrated aluminum silicate in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which various amounts of hydrogen, sodium, potassium, calcium, etc. can be weakly combined. Bentonite in its more pu-rified form (i.e. free of sandstone, sand, etc.) suitable for detergents invariably contains at least 50% montmori11onite and thus its cation exchange power is d '' at least about 50 to 75 miniequivalents per 100 g of bentonite. A particularly pre-fermented bentonite is constituted by bentonites from Wyoming or from the western United States of America sold under the designations Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known for soften the textile materials as described in the British patents N ° 401 413 30 and N ° 461 221.:

Examples of organic alkaline sequestering adjuvant salts which can be used alone with the detergent or in admixture with other organic or mineral detergency adjuvants are the aminopolycarbo-xylates of alkali metals, ammonium or ammonium substituted, for example, ethylene diaminetetraacetates of sodium and potassium, tri-otriacetates of sodium and potassium and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates. The mixed salts of these polycarboxy-lates are also suitable.

Other suitable detergency builders of the organic type include tartronate succinates and carboxymethyl glycolates ". Polyacetal carboxylates are of particular interest. Polyacetal carboxylates and their use in detergent compositions are discussed. described in US Patents No. 4,144,226; No. 4,315,092 and No. 4,146,495. Other patents relating to similar detergency builders include No. 4,141,676; No. 4,169,934; No. 4,201,858; N ° 4,204,852; N ° 4,224,420J N ° 4,225,685; N ° 4,226,960; N ° 4,233,422; 15 n ° 4,233,423; N ° 4,302,564 and N ° 4,303 777. European patent applications No. 0015024; No. 0021491 and No. 0063399 are also relevant.

Various other additives or adjuvants for detergent may be present in the detergent product to give it other desired properties, of a functional or aesthetic nature. Thus, minor amounts of suspending or anti-redepositive agents can be incorporated into the formulation of soiling, for example polyvinyl alcohol, fatty amides, the sodium salt of carboxymethyl ! 1ulose, hydroxypropylmethyl-1u-lose; optical brightening agents, for example cotton brightening agents, polyamides and * polyesters, for example: st i1bêne, triazole and benzidine-sulfone, in particular triazinyl-sti1bêne sulfonés substituted, naphtotriazole-30 stilbène sulfoné , benzidine sulfone, etc., with combinations of stilbene and triazole being preferred.

It is also possible to use whitening agents such as oversea blue; enzymes, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase-like enzymes; bactericides, for example tet.

- · J

* 32 "trachlorosalicylanilide, hexachlorophene; fungicides; soluble dyes; pigments (dispersible in water); preservatives; ultraviolet adsorbers; anti-yellowing agents such as the sodium salt of carboxymethylcellulose, a C 2 -C 22 alkyl alcohol complex with a C 1 -C 4 alkyl sulphate pH modifiers and pH buffers; bleaching agents preserving colors, perfumes, and anti-foaming agents or foam suppressants, for example pie the silicon compounds.

Bleaches are broadly classified for convenience by chlorinated bleaches and oxygenated bleaches. Chlorine bleaches are exemplified by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). Oxygenated bleaches are represented by sodium and potassium perborates and potassium monopersulfate. Oxygen bleaches are preferred. Stabilizers and / or activators of bleaching agents such as, for example, tetraacetylethylenediamine cannot also be included.

go

The proportions of the components which can be ready! In the preferred total compositions, percent by weight (of active substances) based on the total weight of the final product are as follows: i (a) non-ionic detergent - about 2 *% to about 20%, preferably about 3% to about 10%, especially 4 to 9%; (b) fabric softener of the quaternary ammonium type - about Z% to about 20%, preferably about 3% to about 16%, more particularly about 6 to 15%; (c) polyfunctional additive - about 0.5 to 10%, preferably about 3 to 8%; (d) amphoteric surfactant - 0 to en-7 approximately 10%, preferably 0.1 to 5%, in particular 0.5 to 35 4%, and better still approximately 1 to 3%; (e) alkali metal salts adjuvant detergents - about 25% to about 80%, and preferably about 25% to about 70%, and more preferably, about 25 to 50%, the remainder consisting of additives for detergents, fillers and moisture. Suitable ranges of detergent additives are: enzymes - 0 to 2%, in particular 0.7 to 1.3%; corrosion inhibitors 5 - about 0 to about 5%, and preferably 0.1 to 2%; defoaming agents and foam suppressants - 0 to 4%, preferably 0 to 3%, for example 0.1 to 3%; soil suspending or anti-redeposition agents and anti-yellowing agents - 0 to 4%, preferably 0.5 to 3%; co-10 lorants, perfumes, brighteners and brighteners - total by weight 0% to about 2%, and preferably 0% to about 1%; pH modifiers and pH buffers - 0 to 5%, preferably 0 to 2%; bleaching agent - 0% to about 40%, and preferably 0% to about 25%, for example 2 i _ _! '5 to 20%; bleach stabilizers and bleach activators - 0 to about 15%, preferably 0 to 10%, for example 0.1 to 8%. Among the adjuvants, those which are compatible with the main constituents of the detergent composition will be chosen.

Although the high cloud point nonionic compounds are preferably the only detergent surfactant compounds used in the compositions of the present invention, small amounts of other surfactant compounds, including for example anionic compounds and 25 zwitterionics can also be used, preferably in proportions up to 20% by weight, in particular 10% by weight, and better still 5% by weight.

Examples of suitable anionic detergents include water-soluble salts, for example the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing about 8 to 20 carbon atoms, 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, tall oil and mixtures thereof. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, for example coconut soap and potassium tallow soap.

The anionic class of detergents also includes water-soluble sulfated and sulfonated synthetic detergents having an alkyl radical of 8 to 26, and preferably about 12 to 22 carbon atoms, in their molecular structure. (The term alkyl includes the alkyl portion of the higher acyl radicals).

. Examples of sulfonated anionic detergents are monocyclic aromatic (higher alky1) sulfonates such as (higher alky1) benzene sulfonates containing 10 to 16 carbon atoms in the straight or branched chain alkyl group, for example sodium salts, potassium -sium and ammonium um of (higher alkyl) benzene-sul fonates, of (higher alkyl1) toluene-sulfonates, of (higher alkyl) phenol-sulfonates, and of naphthalene-sulfonate.

A preferred sulfonate is a (1-alkyl) benzene sulfonate having a high content of 3- (or more) phenyl isomers and a correspondingly low content (well below 50%) of 2-or less phenyl isomers , i.e. in which the benzene nucleus is preferably largely connected to position 3 or higher (e.g. 4, 5, 6 or 7) of the alkyl group and the content of isomers in which the benzene nucleus is connected to position 2 or 1 is correspondingly weak.

Particularly preferred materials are indicated in the U.S. Patent. N ° 3 320'174.

Other suitable anionic detergents are olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkyl cane sulfonates. These detergent olefin sulfonates can be prepared in known manner by the reaction of SOg with long chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula RCH = CHR ^,

J

Where R is a higher alkyl group of 6 to 23 carbon atoms and is an alkyl group of 1 to 17 carbon atoms or hydrogen to form a mixture of sultones and alkene acids- sulfonic acid which is subsequently treated to transform the sultones into sulfonates. Other examples of detergent sulfates or sulfonates are paraffin sulfonates containing about 10 to 20, preferably about 15 to 20 carbon atoms, for example primary paraffin sulfonates prepared by reacting long alpha-olefins and bisulfites chain and paraffin sulfonates in which the sulfonate groups are distributed along the paraffin chain as described in the US Patents 2,503,280; No. 2,507,088; No. 3,260,741; No. 3,372,188 and the German patent 735,096; sodium and potassium sulfates of higher alcohols containing 8 to 18 carbon atoms, for example sodium auryl sulfate and sodium tallow alcohol sulfate; sodium and potassium salts of esters of alpha-sulfonated fatty acids containing about 10 to 20 carbon atoms in the acyl group, for example methyl alpha-sulfomyristate and alpha-sulfo- (radical derivative of methyl tallow, ammonium sulfates of mono- or diglycerides of higher fatty acids in C10 "C18 'For example monosu.1 fate of stearic monoglyceride; sodium and alkylolammonium salts alkyl polyethenoxy ether sulfates produced by the condensation of 1 to 5 moles of ethylene oxide with one mole of higher alcohol (Cg-C-jg); des (higher alkyl Cj qC- | g) 9Ty ~ sodium ceryl-ether-sulfonates; and sodium or potassium alkyl-phenol -50 polyethenoxy-ether-sul fates with about 1 to 6 oxyethylene groups per molecule and where the alkyl radicals contain about 8 to about 12 atoms = of carbon.

? Suitable anionic detergents also include Cg-C-ac-jg sarcosinate acyls (e.g. sodium 1-amoyl-sarcosinate), sodium and /

’P

4 I * 3 6 a potassium of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule estë-7 rifiës with isethionic acid, and the sodium and potassium salts of (acyl in Cg- Cj 8) -N-methyl-taurides, for example sodium cocoyl-methyl-taurate and potassium stea-royl-methyl-taurate.

Examples of zwitterionic surfactants include derivatives of quaternary ammonium compounds containing an aliphatic straight chain group of 14 to 18 carbon atoms and an anionic solubilization group of the sulfate or sulfonate type. Particular examples include 1e 3- (Ν, Ν-dimethyl-N-hexadecyl-ammoni o) -2-hydroxypropane-1-sulfonate, 3- (Ν, Ν-dimethyl-N- (tallow) -ammonio) -2 -hydroxy-propane-1-sulfonate, and 6-N, N- (dimethyl-N-hexadecyl-15 ammonio) -hexanoate.

Regardless of the form of the laundry detergent, its use in the washing process is essentially the same. The particulate composition is normally added to the wash water in an automatic washing machine so that its concentration in the wash water can be between about 0.05 and 1.5%, generally between 0, 1 and 1.2%. The water to which it is added is preferably of medium or low hardness, for example of a hardness equivalent to 30 to 120 parts per million in the form of calcium carbonate, but it is also possible to use softer and more hard. The temperature of the water can be from 20 ° C to 100 ° C and is preferably from 60 ° to 100 ° C in case the textile material or the linen is capable of withstanding high temperatures without deterioration or attenuation colours. When it is desired to carry out laundering at low temperature, the temperature can be maintained at 20-40 ° C. and it is possible under these conditions to clean and soften it cor- rectly. rects, although the product may not be as clean as when washed at higher temperatures. At the concentrations of the detergent compositions mentioned, the pH of the wash water is usually 7 to 11,

C J

X

Preferably from 8 to 10. At such pH, the composition is effective as a detergent, is not too harsh for the material to be washed or for the skin of the human body, and effectively cleans and softens it. The weight ratio of the laundry to the wash water is generally about 1: 4 to 1:30 or 1:10 to 1:30.

The compositions of the present invention provide greatly improved softening power, at wash temperatures of at least 60 ° C, compared, for example, to identical formulations, except that the nonionic surfactant has a cloud point below 60 ° C, for example a higher fatty alcohol, for example in a straight chain with 7 to 13 units of ethylene oxide. This effect could not have been predicted from the prior art, since there was no known correlation between the cloud point of the nonionic surfactant and the softening power.

The methods of making the compositions described herein are generally well known in the art and reference is made in particular to the U.S. Patent. 4,269,722 in which non-ionic detergent powders reinforced with detergency builders, of relatively high density, are produced from spray dried base beads which have been sprayed with nonionic detergent (which may contain other minor conventional additives such as colorants, perfumes, brightening agents, bleaching agents, etc.). The description of this patent is cited here for reference.

The cloud points (° C) of various nonionic surfactants at weight concentrations of 1%, and mixtures of nonionic / amphoteric surfactants at concentrations of H by weight measured in distilled water and in NaCl at 10% are indicated below, v Non-ionic surfactant. Distilled water 10% NaCl 35 A. Fatty alcohol in Cig-C-jg / EO 7: 1 43 ± 2. <25 B. Fatty alcohol, C ^ -C ^ / EO 11: 1 85 ± 2 59 ± 2 days 3 8. * i

C ^ -C ^ / EO fatty alcohol 15: 1> 100> 60

Isooctylphenol / EO 30: 1> 100> 60

Nonylphenol / EO 20: 1> 100 72

Nonyl phenol / EO 15.:1 91 70 5 Nonylphenol / EO 8: 1 45 <30 A. + Rexoteric OASF (1: 2) 75 ± 2 50 ± 2 A. + Rexoteric OASF (4: 1) 58 ± 2 28 ± 2 A. + Rexoteric CSF (4: 1) 55 ± 2 42 ± 2 B. + Rexoteric OASF (1: 2)> 100 90 ± 2 10 B. + Rexoteric OASF (4: 1) 95 ± 2 85 ± 2 B. + Rexoteric CSF (4: 1)> 100 80 + 2% The invention will now be described by the following nonlimiting examples. Unless otherwise specified, all parts and percentages are expressed in 15 points.

Example 1

The following compositions are prepared: · C (%) A (%) BU) 3 20 Nonylphenol / Eo 20: 1 15.0

Fatty alcohol, C12 "C- | 5 / E0 11: 1 10.0 7, -5

Rexoteric CSF (100% 2.5 active substances)

Sodium tripolyphosphate 42.0 42.0 42.0 25 Dimethyldistearyl ammonium chloride (93% active substance) 6.45 6.45 6.45

N-tallow-pentamethyl-propane-diammonium dichloride (Adogen 477) (50% of active substances) 3.0 3.0 3.0

Minor and miscellaneous additives (for example, optical brightening agents, the rest resins fragrance, humidity, etc.) te te

Using 100 g of each of Compositions A, B and C, towels and cotton terry cloth are washed in about 20 liters of water at 60 ° C.

35 The flexibility of the fabrics washed is estimated by a jury of 4 specialists on multiple replicas after a cumulative wash. Each of the compositions is noted on / hr I · r 1 * 3 9 on a scale from 1 to 10, the note "10" being the best quality and representing the degree of flexibility obtained with a softener added to the rinsing cycle. (dimethyl-distearyl ammonium chloride). On this scale, Composition A and Composition B each receive a score of 8-10. Composition C receives a score of 4-5.

In addition, each of Compositions A and B is evaluated for the total removal of soiling and stains on 10 different types of soiled fabrics and it is found that they give an equally excellent cleaning power. Example 2

Each of the following compositions is compared with regard to the cleaning power under the same conditions as those described for Example 1:

15 D E F G

%%%%

Nonyl phenol / Eo 20: 1 -------- 15.0 ---------! Sodium metasilicate -------- 8.0 --------- | Sodium tripolyphosphate -------- 28.0 --------- I 20 Sodium pyrophosphate. 10:20 am -------- 23.0 ---------

Sodium orthophosphate -------- 0.5 ---------

Ni triotriacetate, Sodium salt -------- 8.0 ---------

Dimethyl-di stearyl-ammonium chloride (93% of active substances) 8.0 8.0 6.45 8.0 25 Copolymer (dime-thyldiallyl ammonium chloride / acrylamide) (40% of active substances) * 7> 6

Adogen 477 (50% of active substances) 3.0 6.0 2Q Minor and various additives ------------ the rest -------

The following results are indicated with regard to the softening power on the towels and the terry cotton fabric: r E significantly better than D

35 G significantly better than D, F tends to be better than D j.

40: (

E tends to be better than G w G tends to be better than F

- F tends to be better than D

Example 3 ^ A preferred formulation of a powder or granular composition reinforced with a detergency builder and. optimized according to the invention is indicated below as well as extended ranges:

Range% Individual% 10 ·

C12-C15 fatty alcohol E0 11: 1 3-15 6.0

Rexoteric CSF (100% of sub- 0-3 1.5 active substances)

Sodium tripolyphosphate; 25-50 42.0

Sodium silicate (1: 2) (40% 15 of active substances) 0-5 3.0

Ethylenediamine-tetraaceto acid as 0-1 0.45

Sodium perborate monohydrate (N a B 0 3.hTO) - 0-15 13.0 ^ Perborate activator (TAED) 0-7 2.8 20

Carboxymethylcelulose sodium 0-4 2.6

Optical brightening agent (Tinopal) 0.2-0.5 0.33

Enzyme (Alcalase 2T-from NOVA) 0.7-1.3 1.0

Dimethyl-distearyl ammonium dichloride 5-15 8.6 25 N-tallow-pentamethylpropane-diammonium chloride 1-5 3.4

Inert support and flow promoting agent * 0-5 3.0

Perfume 0-1 0.4

Water Ie rest the rest 30

Claims (5)

1. Laundry detergent-softener composition for cleaning and softening soiled fabrics during the washing cycle of a washing operation using washing water at a high temperature of at least 60 ° C and capable of reaching the boiling point of the washing water, said composition comprising: (a) 1 to about 20 parts by weight of a nonionic surfactant; (b) about 2 to 20 parts by weight of a fabric softener of the type water-insoluble cationic quaternary ammonium compound; (c) about 0.5 to 10 parts by weight of a polyfunctional additive increasing the affinity for tissues, chosen from (i) quaternary diammonium compounds (ii) polymers of dimethyl-Jm-diallyl chloride -ammonium, 2 ^ (iii) cationic guar gum, (iv) poly (methyl vinyl ether / maleic acid); and "· (v) diimidazolini um compounds; (d) up to 10 parts by weight of an am-25 photeric surfactant; provided that the nonionic surfactant (a) alone "or the combination of the nonionic surfactant (a) and the amphoteric surfactant (d) impart to the composition when added to the wash water at a concentration of 1 (1% by weight, a cloud point higher than the high temperature of the wash water. 2. Composition according to claim 1, characterized in that it comprises, on a weight basis, '* (a) approximately 1 to 15% of said nonionic surfactant, OC (b) approximately 2 to 20% of said tissue softening agent of the type composed of cationic quaternary ammonium. insoluble in water, * * »42 * (c) approximately 0.5 to 10% of said polyfunctional additive the quantity of (b) plus (c) being between approximately 5 and 22%, the ratio of (b) to (c) being between approximately 10: 1 and approximately 1: 3.5 (d) 0 to approximately 10% of an amphoteric surfactant, (e) approximately 25 to 80% d '' at least one detergency builder, (f) 0 to about 40% of a bleach, (g) 0 to about 7% of a bleach activator, (h) 0 to about 4 % of each of the adjuvants that are the agents for suspending soil, anti-redeposition agents and thickening agents, (i) 0 to approximately 5% of anti-corrosion agents, 15 (j) 0 to approximately 1% d '' organic chelating agents, (k) 0 to about 2% dyes, pigments, azuranti and optical brighteners, (l) 0 to about '2% enzymes, (m) 0 to about 0.5% fragrance, 20 (n) 0 to about 10 % of pH modifiers and pH buffers, (o) 0 to about 50% inert fillers, flow promoting agents and carriers, and (p) about 2 to about 20% water. 25 3 - Composition according to claim 1, in the form of a powder or free flowing granules, comprising, on a weight basis, (a) about 3 to 15% of a nonionic surfactant having a condensed hydrophobic group with alkylene oxide; (b) about 2 to 20% of a fabric softener of the type water-insoluble cationic quaternary ammonium compound, characterized by at least two long chain aliphatic groups of 16 to 22 carbon atoms, 35 (c) about 1 to 10% of a polyfunctional additive chosen from the quaternary diammonium compounds defor- / Y * 43 mul e: R2 R2 x'.r4-n + -r1-n + -r3.x "r2 r2 5 in which R- | represents a divalent alkylene group of 2 to 4 carbon atoms which may optionally bear a hydroxy substituent; the groups R2 are identical or different and each represent a lower alkyl group of 1 to 4 carbon atoms, which can optionally carrying a hydroxy substituent; R3 is a saturated or unsaturated, straight or branched chain aliphatic hydrocarbon group of 1 to about 22 carbon atoms, which hydrocarbon group may be interrupted by an oxygen atom or a group —COHN- ; R ^ represents a radical chosen from the radicals hy aliphatic drocarbons optionally interrupted by * an oxygen atom or a group -CONH, having a total of about 8 to about 22 carbon atoms, the alkylaryl radicals of about 8 to 16 carbon atoms in the alkyl moiety, and the aryl radicals; and X is an anion forming a salt; . -and polymers of dimethyldiallyl-ammonium chloride; (d) 0.1 to 10% by weight of an amphoteric surfactant; The quantity of said amphoteric surfactant being sufficient to increase the cloud point of the nonionic surfactant (a) above high temperatures, (e) the remainder consisting of detergency builders, additives for detergents, loads and moisture. 30 4 - Composition according to claim 3, characterized in that (e) contains about 25 to 50% of detergency builders, 0 to 5% of corrosion inhibitor, 0 to 1% of organic chelating agent. 0 to 40% oxygen bleach, 0 to 7% bleach activator, 0 to 4% thickener and anti-redeposition agent, 0.2 to 0.5 % of optical brightener, 0.7 to 1.3% of enzyme- / 'r # * 44 i Ί * me, 0 to 0.5% of perfume, the rest, up to approximately - - 20%, humidity. 5. Composition according to claim 4, characterized in that (b) is dimethyl distearyl ammonium chloride. 6. Composition according to claim 1, characterized in that the cationic compound insoluble in quaternary ammonium water capable of softening the washed fabrics is chosen from the compounds represented by the following formulas: R! R + '' yf K3 NN x- (III) 15 n / 'p K2 K4 and ". Ni + ^ 20 R5 -r X" / \ <IV> R6 r7_? »In which j R- | and R2, and R5 and Rg each independently represent a long chain aliphatic radical C-j g-C ^, R3 and R ^, and Ry each independently represent lower alkyl radicals; or Rg can be the group -RgNHCRg where Rg is a long chain aliphatic radical of 16 to 22 carbon atoms, and Rg is a divalent alkylene radical of 1 to 3 carbon atoms, and X is an anion forming a salt ; the ratio, by weight, of the nonionic surfactant to the cationic compound being from 1:10 to 5: 1. / 7. Composition according to claim 1, characterized / in that the nonionic surfactant (a) is at least ^ a compound chosen from the compounds represented by the following formula 45 ft * * H R0 (CHgCI ^ O) (I) O w in which R is a primary or secondary alkyl chain of approximately 8 to 22 carbon atoms and n is on average equal to approximately 3 to 30; and the following formula 10 R1 -fo) —0_ (CH2CH20) mH (III) wherein R1 is a primary or secondary alkyl chain of 7 to 12 carbon atoms, and m is on average about 3 to 30. 8. Composition according to claim 7, characterized in that R is: an alkyl group of 12 to 15 carbon-carbon atoms and R ^ is an alkyl group of 8 or 9 carbon atoms, and m and n are equal each at an average of about 15 to 30. 20 9 - A composition according to claim 8, characterized in that the cationic compound (b) is di-methyl-distearyl ammonium chloride. • * 10. Composition according to claim 1, characterized in that the cationic compound is dimethyl-distearyl ammonium chloride. 11. Composition according to Claim 1, characterized in that it additionally comprises at least one additive for detergents chosen from mineral salts with detergency builders, organic salts with detergency builders, soil suspending agents, anti-redeposition agents, fatty amides, foam suppressants, anti-foam agents, optical brightening agents, - dyes, pigments, brighteners, anti-yellowing agents, enzymes, corrosion inhibitors, 3. pH modifiers, pH buffers, bacteria, fungicides, preservatives, bleaches, whitening agent stabilizers, enhancers bleaches, perfumes and water. * 12 - Composition according to claim 1, characterized in that it contains at least 0.1 part of the amphoteric over-charge (d) and in that the amphoteric surfactant 5 is chosen from: (1) detergents of betaine type of formula: H ï R1-N + -R4-C-0 10 R R3 (2) detergents of the betaine type with an alkyl bridge of formula 15. S Ri-CH2-CN-CH.CH2CH2-N + -R4-C0 '* 3 L. · (3) detergents of the imidazoline type of formula ^ 20 CH, CÛ0H 0 i + 2 R] -C-N + -R4 -0-CH2C0 "I 25. CH, \ / 2 ch2 (4) detergents of the alkyl iminopropionate type of formula 30 H R1-N-CH2CH2C00H (5) detergents of the alkyl iminodipropionate type of formula 35 CH2CH2C00H f CH2CH2C00H / 47,. * Μ * (6) detergents of the alkyl iim'nodipropionate 4 type, with ether bridge of formula CH2CH2C00H r1-och2ch2ch2-n ^ 5 CH2CH2C00H (7) amphoteric detergents based on copra-imi-dazoline of formula * 10 'S Ri-C - N + -CH90CH9CH9C0 ~ Il I 2 2 2 N CH2 ch2 15 (8) amphoteric detergents based on d1 (alkyl higher fat) carboxyethylated imidazoline of formula î Λ2 *. h9c hn -ch9ch9coo - 2 i 22 20 W Γ D H0R2 - N - C - R1 and their mixtures, where Rj represents an aliphatic radical of 7 to 20 carbon atoms, ο c R2 and R ^ each represent a lower alkyl group of 1 to 4 carbon atoms and, * R4 represents a divalent lower alkylene radical of 1 to 4 carbon atoms. 13. Method of cleaning and softening. 30 fabrics soiled in washing water at a temperature of at least about 60 ° C, characterized in that it consists in washing the fabrics in an aqueous solution of the composition according to claim 1, said aqueous solution being heated at a temperature of at least 60 ° C. 35 14. Method according to claim 13, characterized in that the temperature of the washing water is approximately 100 ° C and in that the nonionic surfactant is 48 *. ’Ethylene oxide. 15. A detergent composition for washing and softening soiled fabrics in an aqueous washing liquid at an elevated temperature between 60 ° and 5 100 ° C, said composition comprising (a) 0.1 to 20% d '' at least one water-soluble nonionic surfactant compound of formula I or II R0 (CH2CH20) nH (I) 10 1 / - \ R 0 “\ O) ~ (CH2CH20) mH (II) in which R is a primary alkyl chain or a secondary of about 8 to 22 carbon atoms, is a primary or secondary alkyl chain of about 7 to 12 carbon atoms, and n and m are each on average 3-30; * (b) 2 to 20% of at least one cationic quaternary ammonium compound insoluble in water of formulas III or IV; "20 Γ 1 Rl \ / R3 X" (III) "" "25 r - + R5-X". (IV) NJ R6 \ 2q in which Ri and R ^, and Rg and Rg each independently represent radicals C 1 to C 22 long chain aliphatics, R3 and R ^ and R ^ each independently represent lower alkyl radicals, or Rg may be the group -RgNHCRg where Rg is a long chain aliphatic radical 35 0 16 to 22 carbon atoms, and Rg is a divalent alkylene radical of 1 to 3 carbon atoms, and, X is a salt-forming ion; ** j (c) about 0.5 to 10% of an additive polyfunctional, I 1 * "* 49 chosen from the quaternary diammonium compounds of formula R10 R10 X" .R8 - N + - Rg-N + -R12.X "1 i Rn RH in which Rg is a saturated or unsaturated, straight or branched chain aliphatic hydrocarbon group of about 12 to about 22 carbon atoms; Rg represents a divalent alkylene group of 2 to 4 carbon atoms; The groups R ^ q, and R ^ 2 are the same or different and represent lower alkyl groups of 1 to 4 carbon atoms; and X is a salt-forming anion; - and polymers of dimethyl dial 1-yl-ammonium chloride; 5 15. (d) at least one amphoteric surfactant in a proportion of 0.1 to 10%, so that the composition has a cloud point higher than the elevated temperature; and (e) the remainder consisting of detergency builders, detergent additives, inert fillers and water. 20 ^ r *