CH670650A5 - - Google Patents

Description

DESCRIPTION

The invention relates to a detergent and softening agent composition which is suitable for cleaning and softening textiles in the wash cycle of a washing program at an elevated temperature of the wash water of at least 60 ° C. up to the boiling point thereof. The composition according to the invention contains a nonionic surfactant, a cationic quaternary ammonium compound as a softening agent and a polyfunctional additive to increase the substance of the softening agent and optionally an amphoteric surfactant.

Treatment mixtures to improve the softness and tactility of textiles are known.

Textile softening agents are usually added to the rinse water when washing in the household during the rinse cycle, which only lasts about 2 to 5 minutes, which is why the consumer is forced to monitor the washing program or take other measures to add the fabric softener at the right time. This makes it necessary for the consumer to go to the washing machine either shortly before or at the start of the washing program, which is of course annoying. In addition, special care must be taken to use a suitable amount of fabric softener to avoid overdosing, which can make the fabrics water-repellent by depositing a greasy film on the fabric surface or causes them to yellow to a certain extent.

To solve these problems, the use of fabric softening agents has already been proposed which are compatible with conventional detergents and can therefore be combined with these in a single package and used during the washing program. Examples of such fabric softening compositions to be added in the wash cycle are given in US Pat. Nos. 3,351,438, 3,660,286 and 3,703,480. These textile softening compositions to be added in the washing cycle contain a cationic quaternary ammonium compound as textile softening agent and additional constituents which make the softening compounds compatible with the usual detergents.

However, it is also known that the softening compounds added either as part of a surfactant softening composition or as softening agents in the washing cycle impair the lightening as well as the cleaning action of the detergent. This has led to attempts to compensate to some extent for this impairment in softening detergent compositions by using nonionic surfactants, higher concentrations of brighteners, carboxymethyl cellulose, yellowing preventing compounds, bluing agents, etc. However, only minor improvements have been made to laundry detergent softeners using several ten-sides, most of which are anionic.

However, there are also numerous publications on detergent compositions containing cationic softening agents including quaternary ammonium compounds as softening agents and nonionic as well as anionic, zwitterionic and amphoteric surfactants. Representative of this are US Pat. Nos. 4,264,457.4,239,659, 4,259,217, 4,222,905, 3,537,993, 3,583,912.3,983,079.4 203,872.

4 264 479, 3 951 879.3 360 470.3 351 483, 3 644 203 etc.

The following patents describe detergents and / or shampoos based on nonionic surfactants which contain a polyfunctional additive: US Pat. No. 3,313,734 (shampoo quaternary ammonium compound polymers); U.S. Patent 3,351,557 (ethylene / maleic anhydride copolymers - emulsion stabilizers); U.S. Patent 3,509,959 (acid group-containing polymer, e.g., polyacrylic acid, formed in situ, e.g., in the presence of nonionic surfactant); U.S. Patent 3,703,480 (aminopolyureylene resins to make cationic fabric softening agents compatible with anionic surfactant); U.S. Patent 3,723,322 (carboxylated polysaccharide detergent builder); U.S. Patent 3,962,418 (cationic cellulose ether thickener and hair conditioning substance); U.S. Patent 4,213,960 (hair treatment compositions with polyaminoamides and quaternary ammonium homopolymers and copolymers); U.S. Patent 4,371,517 (cationic polymers and anionic polymers). The use of polycationic compounds, polyamines and polyamides to improve the softening of classic quaternary textile softeners in the rinse cycle is e.g. known from US-PS 4 237 016, GB-PS 1 576 326 and 2 041 025A, the Belgian patent specification 844 122, the European patent specification 13780 and DE-PS 2 925 859A1.

Although many of these known formulations ensure satisfactory cleaning and / or softening under many different conditions, they have the disadvantages that they have to be added in the rinse cycle; insufficient softening, e.g. comparable to the softening agents added in the rinse cycle, especially in hot wash water, i.e. ensure at temperatures of 60 ° C and higher; require the formation of complexes of the cationic compound; less softening, water-soluble, e.g. use cationic mono higher alkyl quaternary ammonium compounds; are limited to liquid compositions, etc.

It is not uncommon nowadays that detergents and conventional automatic household washing machines, particularly in the United States, enable effective washing / cleaning of soiled textiles using cold or warm wash water, especially for delicate fabrics, wash-wear fabrics, permanent press fabrics and the like. Nevertheless, it is assumed that more effective cleaning (dirt removal) requires higher washing temperatures. In addition, in Europe and in other countries, household washing machines are operated at high temperatures of 60 ° C or more up to the boiling point of the washing water. Even though these high temperatures are beneficial for dirt removal, they are not equally beneficial for softening.

It has now been found that the softening of a detergent based on a mixture of nonionic surfactant and a softening cationic quaternary ammonium compound is significantly improved if a certain class of polyfunctional compounds is used which increases the substantivity of the water-insoluble cationic textile softener towards the substance to be treated increase and thus the softening effect. It has also been found that the softening effect is further improved by using the nonionic surfactant alone or in combination with an amphoteric surfactant, preferably one with a cloud point which is at least about 5 ° C. higher than the washing temperature, which is at least about Is 60 ° C. In addition, this improved softening is achieved without any or at least without any significant impairment of the wash. Cleaning performance achieved.

A relationship between the cleaning action and the cloud point of a nonionic / cationic surfactant mixture is known from U.S. Patents 4,222,905 and 4,259,217. In particular, column 5, lines 40 to 61 of the latter:

«There are procedures for washing textiles with the

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Compositions of the invention that provide superior greasy or oily soil removal and the benefits of gentle textile treatment have been proposed. In these processes, the detergent compositions are used under such temperature conditions that the aqueous wash solution either at or near (ie, within about 20 ° C) the cloud point (ie the temperature at which a phase rich in nonionic surfactants separates in the wash solution) of the nonionic / cationic surfactant mixture. This is preferably done by formulating these nonionic / cationic surfactant mixtures in such a way that

that its cloud point falls between about 0 and 95 ° C, especially about 10 to 70 ° C, especially between about 20 and 70 0 C, especially between about 30 and about 50 ° C. During washing, the temperature of the wash solution is kept within this temperature range and within 20 ° C from the temperature of the cloud point. The result is further improved if the temperature of the aqueous wash solution is within approximately 15 ° C., preferably within approximately 10 ° C., of the cloud point temperature of the nonionic / cationic surfactant mixture.

Obviously, the requirement to work at wash temperatures at or below the cloud point temperature is based on the premise that the cloud point of the surfactant mixture in the wash water corresponds to the temperature at which the micelle formation of the surfactant occurs to such an extent that these aggregations are so large and concentrated so that they emerge from the solution and thereby cause the observed turbidity. A further increase in temperature will lead to the complete phase separation of water and nonionic surfactant, and as a result the cleaning effect for soiled textiles and the overall cleaning ability will be lost.

However, although it is stated in US Pat. No. 4,259,217 that the nonionic / cationic mixtures “depending on the identity and concentration of the cationic component ... ensure the advantages known from the prior art for such cationic surfactants, such as, for example Nonetheless, the softening effect of textiles », there is no doubt that it does not say or suggest that the softening effects of cationic surfactants can be significantly improved by using certain nonionic surfactants which have high cloud point temperatures per se. Compared to the teaching of these US patents, which describe a relationship between the cloud point of the nonionic / cationic mixture, the washing temperature and the cleaning performance, it was found according to the invention that it was the relationship between the cloud point of the nonionic surfactant alone (or the nonionic and amphoteric surfactant as well electrolytes present in the wash water) and the wash temperature, which effects the softening of the water-insoluble cationic quaternary ammonium softening agents. In contrast to the condition according to the invention to use high cloud point temperatures (for example above about 60 ° C., preferably above about 90 ° C., especially above 100 ° C.), according to the above US Pat. Nos. 4,259,217 and 4,222,905, nonionic surfactants are used and combinations of nonionic and cationic substances with relatively low cloud points are preferred.

It was therefore completely surprising that the softening by the cationic softener could be dramatically improved, especially under hot water washing conditions, without the cleaning power or action of the nonionic surfactant being reduced when formulating a detergent-softening composition whose cloud point is higher than the washing temperature.

The use of nonionic surfactants, the cloud points of which are at least 60 ° C. and higher than the wash water temperature, is described in the applicant's patent application in accordance with US Serial No. 646,594. The use of amphoteric surfactants to increase the cloud point of the nonionic surfactants above the wash water temperature is also described in the application mentioned and in more detail in the applicant's application in accordance with US Serial No. 646 604. The teaching of these applications is hereby incorporated by reference.

According to the present invention, it was found that the softening effect of the fabric softening cationic quaternary ammonium compounds can be further improved by incorporating a polyfunctional additive into the composition of nonionic surfactant and cationic fabric softening agent, which increases the substantivity of the cationic fabric softening agent compared to the textiles to be treated. In addition, the cleaning effect of the nonionic surfactant can also be improved at the same time.

It is an object of the invention to improve the softening effect of detergents which contain water-insoluble cationic quaternary ammonium compounds as textile softening agents and nonionic surfactants, and not only not to adversely affect the overall cleaning effect but in some cases even to improve it.

To solve these and other tasks apparent from the following description, a detergent and softener composition is proposed which is suitable for cleaning and softening textiles in the wash cycle of a washing program at an elevated temperature of the wash water of at least 60 ° C. up to the boiling point of the same, and which is characterized by a) 1 to 20 parts by weight of a nonionic surfactant;

b) 2 to 20 parts by weight of a fabric softening water-insoluble cationic quaternary ammonium compound;

c) 0.5 to 10 parts by weight of a polyfunctional additive of the group which improves the substantivity towards textiles

(i) diquaternary ammonium compounds,

(ii) polymers of dimethyldiallylammonium chloride,

(iii) cationic guar gum and

(iv) poly (methyl vinyl ether / maleic acid); and

(v) diimidazolinium compounds;

d) zero to 10 parts by weight of an amphoteric surfactant.

In a preferred embodiment of the invention, the nonionic surfactant has a cloud point temperature above the elevated temperature of the wash water. In a particularly preferred embodiment of the invention, the compositions contain both the nonionic surfactant with the high cloud point temperature and an aphoteric surfactant. In each preferred embodiment, the detergent composition contains at least one additional detergent additive such as builders, thickeners, substances to prevent re-precipitation, corrosion inhibitors, bleaches, enzymes, dyes, bluing agents, optical brighteners, fragrances and the like.

Thus, the invention provides a preferred detergent composition for cleaning and softening textiles in an aqueous medium, especially at an elevated washing temperature of at least 60 ° C., which contains 1 to 20% by weight of a nonionic surfactant,

b) 2 to 20% of a textile-softening, water-insoluble, cationic quaternary ammonium compound,

c) 0.5 to 10% of a polyfunctional additive from the group

(i) diquaternary ammonium compounds,

(ii) polymers of dimethyldiallylammonium chloride,

(iii) cationic guar gum and

(iv) poly (methyl vinyl ether / maleic acid), the amount

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b) plus c) can be in the range from about 5 to 22% and the ratio of b) to c) can preferably be in the range from about 10: 1 to about 1: 3,

d) 0 to about 10% of an amphoteric surfactant,

e) about 25 to 80% of at least one builder,

f) 0 to about 40% of a bleaching agent,

g) 0 to about 7% of a bleach activator,

h) 0 to about 4% of dirt-carrying substances, substances which prevent re-precipitation and thickeners,

i) 0 to about 5% anti-corrosion agent,

j) 0 to about 1% organic chelating agents,

k) 0 to about 2% of coloring substances, pigments, bluing agents and optical brighteners,

1) 0 to about 2% enzymes,

m) 0 to about 0.5% perfume,

n) 0 to about 10% pH modifier and buffer,

o) 0 to about 50% inert fillers, the flowability-demanding substances and carriers, and p) contains about 2 to about 20% water.

According to a further more preferred embodiment of the invention, a detergent composition containing powdered or granulated free-flowing plasticizers for cleaning and softening soiled textiles is made available in an aqueous washing medium at an elevated temperature of at least 60 ° C to about 100 ° C, which contains, on a weight basis, the following components :

a) about 3 to 15% of a nonionic surfactant which has a hydrophobic group condensed with sufficient alkylene oxide to raise the cloud point thereof to above the elevated temperature;

b) about 2 to 20% of a textile-softening, water-insoluble, cationic quaternary ammonium compound which is distinguished by at least two long-chain aliphatic groups with 16 to 22 carbon atoms;

c) about 1 to 10% of a polyfunctional or polyfunctional additive from the group consisting of diquaternary ammonium compounds of the formula

R4-N + -Rj-R2

-N + -R3

r2

• 2X "

where R! represents a divalent, optionally a hydroxyl-substituted alkyl radical having 2 to 4 carbon atoms; each of the R2 groups, which may be the same or different, is lower, optionally hydroxyl-substituted alkyl having 1 to 4 carbon atoms;

R3 is a straight-chain or branched, saturated or unsaturated aliphatic hydrocarbon group having 1 to 22 carbon atoms, which may be interrupted by an oxygen or a -CONH group;

R4 is a radical from the group consisting of aliphatic, optionally interrupted by an oxygen atom or the -CONH radical, aliphatic hydrocarbon radicals with a total of 8 to 22 carbon atoms, alkylyl radicals with 8 to 16 carbon atoms in the alkyl moiety, and aryl radicals, X is a salt-forming anion;

and polymers of dimethyldiallylammonium chloride;

d) 0.1 to 10% of an amphoteric surfactant and e) builders, detergent additives, fillers and moisture as the rest.

In the above preferred embodiment, there is a content of about 25 to 50% builders, 0 to 5% corrosion inhibitors, 0 to 1% organic chelating agent, 0 to 40% oxygen bleach, 0 to 7% bleach activator, 0 to 4% thickeners and preventive agents the re-precipitation, 0.2 to 0.5% optical brightener, 0.7 to 1.3% enzyme, 0 to 0.5% fragrance and the remainder up to about 20% moisture are particularly preferred.

Without being able to provide a complete explanation 5, it was found that the softening effect of the cationic textile softening agents is best if the softening agents are present in the wash water in a very fine-particle form (diameter in the order of a few micrometers to the sub-micrometer range) and are insoluble in water. The finely divided 10 particles must of course be uniformly, even statistically, dispersed in the entire washing solution in order to be uniform with the objects to be washed, such as clothes, towels, white goods and laundry, etc. to come into contact. It appears that the softening particles are effectively captured by the Tex-15 fibers and adhere to them through a combination of electrical, chemical and physical forces.

With the composition according to the invention, the substantivity of the treated textiles is further improved and the softening effect of the cationic textile softener 20 is correspondingly increased if a polyfunctional additive, preferably a diquaternary compound, polyquaternary compound or a cationic polymer, is added to the composition of surfactant and softener . These polyfunctional additives, as is known from the state of the art mentioned above, can soften even the treated fabrics due to their own affinity for textiles, the manner in which they act in the “wash cycle compositions”, i.e. the detergent-softening compositions according to the invention to be added in the wash cycle, but obviously does not primarily involve a direct softening effect, but apparently is based primarily on one or both of the following factors: (1) their ability to stabilize the dispersion of the fabric-softening quaternary compound ; and (2) their ability to improve contact 35 between the quaternary compound and the fabric. Whichever way the polyfunctional additives improve the softness, it is a feature of the invention that the softness of the fabrics treated in the wash cycle is essentially equivalent to that of fabrics 40 treated with conventional fabric softeners added in the rinse cycle. In addition, it is possible to achieve significantly improved cleaning using the preferred compositions of the invention. The essential components in the softening detergents are therefore the nonionic surfactant, the textile softening water-insoluble cationic compound and the polyfunctional additive. The use of an amphoteric surfactant in addition to these essential components is particularly preferred, especially if the cloud point of the nonionic surfactant is at or 50 below the wash water temperature.

Although the compositions of the invention are found in cold wash water, e.g. at about 20 to 30 ° C, or in warm wash water, e.g. ensure good softening and cleaning at about 30 to 40 0 C or above, the best 55 results are obtained when used in wash water at elevated temperatures of at least 60 ° C to 100 ° C (boiling temperature).

Suitable nonionic surfactants are commercially available and are condensation products of an alkylene oxide or equivalent reactant and a hydrophobic compound with 60 reactive hydrogen. The hydrophobic organic compounds can be aliphatic, aromatic or heterocyclic, the first two classes being preferred. The preferred types of hydrophobic compounds are higher aliphatic alcohols and alkylphenols, although others can be used such as e.g. Carboxylic acids, carboxamides, mercaptans, sulfonamides, etc. The ethylene oxide condensation products with higher alkylphenols or higher fatty alcohols are preferred classes of nonionic compounds. In general

the hydrophobic portion should have at least 6 carbon atoms, preferably at least 8 carbon atoms and may even contain 50 carbon atoms or more, a preferred range being 8 to 22 carbon atoms, in particular 10 to 18 carbon atoms in the case of the aliphatic alcohols and 12 to 20 carbon atoms in the case of the higher alkylphenols. The amount of alkylene oxide varies considerably depending on the hydrophobic content. As a general guideline and rule, at least about 15 to about 30 moles of alkylene oxide per mole of hydrophobic compound should be used to achieve cloud point temperatures of at least 60 ° C or higher.

So the preferred nonionic surfactants can by the formulas

R0 (CH2CH20) nH (I)

wherein R is a primary or secondary alkyl chain of 8 to 22 carbon atoms and n is an average of 3 to 30; or

Rl ~ ^ 3K} "(CH2CH2 °) mH (II)

wherein R1 is a primary or secondary alkyl chain having 7 to 12 carbon atoms and m is an average value of 3 to 30.

The preferred alcohols from which the compounds of formula I can be prepared include the lauiyl, myristyl, cetyl, stearyl and oleyl alcohols and mixtures thereof. Particularly preferred meanings of R are Cio to C18, the Cl2 to C15 alkyls and mixtures thereof being particularly preferred.

The preferred meanings for R 'are C6 to Ci2, C8 and Cg including octyl, isooctyl and nonyl being particularly preferred.

A typical example of a nonionic compound of formula I is lauryl alcohol fused with 15 moles of ethylene oxide. A typical example of a nonionic compound of formula II is isooctyl phenol condensed with 30 moles of ethylene oxide.

Other nonionic compounds that can be used include the polyoxyalkylene esters of organic acids such as the higher fatty acids, resin acids, tall oil acids, acids of crude oil oxidation products, etc. These esters mostly contain 10 to 22 carbon atoms in the acid portion and about 15 to about 30 moles of ethylene oxide or equivalent the same.

Other nonionic surfactants are the alkylene oxide condensation products with higher fatty acid amides. The fatty acid group generally contains 8 to 22 carbon atoms and is condensed with about 15 to about 50 moles of ethylene oxide as the preferred compound. The corresponding carboxamides and sulfonamides can also serve as equivalent compounds.

According to the invention, the nonionic surfactants with a high cloud point described above can also be replaced in whole or in part by the corresponding nonionic surfactants with a low cloud point, i.e. the same hydrophobic group is present, but is only condensed with about 3 to 14 moles of ethylene oxide. However, when using the non-ionic surfactants with a low cloud point, it is essential to also incorporate one of the amphoteric surfactants, as will be explained in more detail below, in order to ensure a sufficiently high cloud point in the composition. Preferably no more than 50%, especially no more than 30% and especially no more than about 20% of the total nonionic surfactants present are those with a low cloud point. The amount of nonionic surfactant is generally the minimum amount that ensures an adequate cleaning effect when added to the wash water with or without amphoteric surfactant. Generally amounts in the range

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from about 2 to about 20%, preferably from about 3 to about 10%, and most preferably from about 4 to 9%, by weight of the composition, good cleaning.

The term “cloud point” here means the temperature at which a curve, in which the dependence of the light scattering intensity of the composition on the temperature of the washing solution is shown, begins to rise sharply to its maximum value, the experimental conditions being as follows:

The light scattering intensity is measured using a model VM-12397 photogoniodiffu-someter manufactured by the Société Française d'instruments de contrôle et d'analyses, France (hereinafter referred to as Sofica). The Sofica cell for the sample and its lid are washed with hot acetone and then left to dry. The surfactant mixture is prepared and brought into solution with distilled water at a concentration of 1000 ppm. A sample of the approximately 15 ml solution is added to the sample cell using a syringe with a 0.2 (x nucleopore filter). The syringe needle passes through the sample cell lid so that the interior of the cell is not exposed to atmospheric dust. The sample becomes Leave in a variable temperature bath and both the bath and the sample are constantly stirred The bath is heated using the Sofica heater (heating rate 1 ° C / minute) and cooled by adding ice, the temperature of the sample is increased The light scatter intensity (90 ° angle) of the sample is then determined at different temperatures, using a green filter and without a polarizer in the Sofica.

Cloud point determinations were made both for the solutions of the nonionic surfactant (with 1% by weight) in distilled water and in water containing 10% NaCl, although in the latter in general the amount of salt and electrolyte far exceeds the actual amount in normal use . Therefore, if the cloud point of the nonionic surfactant measured in a 10% NaCl solution meets the cloud point requirements, there is no problem in formulating compositions containing very high concentrations of builder salts and other electrolytes, e.g. up to about 85% of the composition as well as the polyfunctional additive.

The cloud point temperature of a given composition in the wash solution depends, as is known, on the physical and chemical properties (such as CMC and solubility) of the cationic, nonionic and additional components contained in this composition and can be reduced by lengthening the alkyl chain of the nonionic and amphoteric surfactant 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 from about 1 to about 15% of a given composition).

Since, according to the invention, water-insoluble cationic softening compounds are contained in the composition according to the invention, these have essentially no effect of any kind on the cloud point of the overall composition. In fact, since the plasticizing cationic compounds used here are water-insoluble, the cloud point temperature of the overall formulation is very difficult to measure because the mixtures are inherently somewhat cloudy. For this reason, the cloud point of the nonionic surfactant, with or without the addition of electrolytes, is determined in the absence of the cationic compound, which gives a sufficiently accurate measurement of the cloud point of the overall composition including the cationic compound.

Ensure at washing temperatures of around 60 to 70 ° C

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all the above-mentioned nonionic surfactants with 15 to 30 moles of ethylene oxide, in particular those of the formulas I and II, even with the polyfunctional additional component of the composition, cloud points above the washing temperature.

However, at higher wash temperatures from 71 ° C to 100 ° C, especially 80 ° C to 100 ° C, the more ethoxylated surfactants should be used with, for example, 25 to 30 moles of ethylene oxide per mole of hydrophobic portion. At these higher wash temperatures, the most preferred nonionic surfactants are the Cg_9 alkylphenols, which are ethoxylated with 25 to 30 moles, preferably with 28 to 30 moles, and especially with about 30 moles of ethylene oxide.

Alternatively, and as detailed in the aforementioned parallel applications corresponding to U.S. Serial Numbers 646,594 and 646,604, it has now been found that the cloud point of each nonionic surfactant is significant, i.e. by about 40 ° C, generally about 5 to 20 ° C, by adding an amphoteric surfactant, for example an amphoteric carboxyethylated higher fatty alkyl (eg coco) imidazoline compound, generally in an amount of 0.5 to 10%, preferably 1 to 4%, particularly preferably about 1 to 3%, based on the weight of the composition.

Therefore, the detergent according to a preferred embodiment of the invention, which is particularly suitable for washing soiled textiles in wash water at an elevated temperature in the range from 80 to 100 ° C., in addition to a) the nonionic surfactant of the formula I or II, b) water-insoluble quaternary ammonium compound of formula III or IV below, and c) the polyfunctional additive, an amphoteric surfactant d) in an amount sufficient to raise the cloud point of the composition to a temperature above the elevated temperature of 80 to 100 ° C.

The second essential component in the formulations according to the invention is the cationic fabric softener. In general, the cationic fabric softeners contain at least one hydrophilic functional group that carries a negative charge and one hydrophobic group that has a quaternary ammonium atom that is positively charged.

In order to give the treated fabrics a satisfactory softness, it is essential that the cationic compound is water-insoluble. Here, a compound is considered water-insoluble if its solubility in water at the washing temperature is less than about 1%, preferably less than about Vi%.

In general, it is desirable that the cationic plasticizer compound of the composition be incorporated in a form which ensures the greatest possible dispersibility in the washing liquid and thus maximum adhesion to the treated substance. To achieve this effect, dispersed particles can be used in the washing liquid, the sizes of which are in the range from about <10 to about 50 micrometers, preferably from about <10 to about 20 micrometers.

Suitable textile softening agents which are known in the trade are, above all, water-insoluble quaternary ammonium compounds of the following formulas in which R], R2, R5 and R $ are each, independently of one another, a long-chain aliphatic radical having 16 to 22 carbon atoms, R3, R4 and R7 , independently of one another, denote lower alkyl radicals, or R $ the group

-RgNHCR8

Ö

where Rg is a long chain aliphatic radical having 16 to 22 carbon atoms and where Rg is a divalent alkyl group having 1 to 3 carbon atoms and X is a water-soluble salt-forming anion such as a halide, e.g. Chloride, bro-mid, iodide; a sulfate, acetate, hydroxide, methosulfate, ethosulfate, or a similar inorganic or organic solubilizing - the mono- or divalent radical. The carbon chain of the aliphatic radical having 16 to 22, in particular 16 to 20, carbon atoms can be straight-chain or branched, saturated or unsaturated. The lower alkyl radicals preferably contain 1 to 4 carbon atoms and can have a hydroxyl radical. The carbon chains are preferably obtained from long-chain fatty acids, such as those derived from tallow and soybean oil. The terms "Disoja" and "Ditalg" etc. refer to the starting substance from which the long-chain fatty alkyl chains are derived. Mixtures of the above and other water-insoluble quaternary ammonium surfactants can optionally also be used. The preferred ammonium salt is a dialkyldimethylammonium chloride in which the alkyl group is derived from hydrogenated tallow or stearic acid, or a di-higher alkylimidazolinium chloride. Specific examples of quaternary Ammoniumweichmachungsmittel according to formula III, which are suitable for use in the detergents of the invention include the following: hydrogenated Ditalgdimethylammoni-monium chloride, Dimethyldisteaiylammoniiimchlorid, Dimethylstearyl-cetylammonium bromide, Dimethyldicetylammoniumchlorid, Disojadimethylammoniumchlorid, the corresponding sulfates, methosulfates, ethosulfates, bromides and hydroxides etc.

Examples of softening quaternary ammonium compounds of formula IV include l-methyl-l, 2-diheptadecylimidazolinium chloride (bromide, methosulfate), 1,2-dieicosylalkylamido-ethyl-l-methylimidazolinium chloride (bromide, methosulfate, etc.), 2-hexadecyl-1 -methyl- l [(2-dodecoylamido) ethyl] imidazolinium methyl sulfate, 2-heptadecyl-l-methyl-l [(2-stearoylamido) ethyl] imidazolinium methyl sulfate, 2-nonadecyl / heneicosyl-1-methyl-1 - [ (2-eicosoyl / docosoylimido) ethyl] imidazolinium methyl chloride.

Dimethyldisteaiylammonium chloride is particularly preferred because of its superior softening effect, biodegradability, low water solubility, availability and cost.

The amount of cationic fabric softener ranges from 2 to about 20%, preferably from about 3 to about 16%, and most preferably from about 6 to 15%, by weight of the composition. The weight ratio of the nonionic surfactant to the cationic plasticizer should be in the range from about 1:10 to 5: 1, preferably from about 1: 5 to 4: 1 and particularly preferably from 1.2 to 3.5: 1.

The polyfunctional additives used to increase the substantivity of the textile-softening water-insoluble cationic quaternary ammonium compound include

(i) diquaternary ammonium compounds,

(ii) polymers of dimethyldiallylammonium chloride,

(iii) cationic guar gum,

(iv) poly (methyl vinyl ether / maleic acid) and

(v) Diimidazolinium compounds.

The diquaternary ammonium compounds are particularly preferred and can be used as compounds of the general formula r2 r2

X - R4-N + -RI-N + -R3-X-

R2 R2

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are reproduced in which

Ri represents a divalent alkyl group with 2 to 4 carbon atoms and optionally a hydroxyl substituent;

R2 represents identical or different lower alkyl groups with 1 to 4 carbon atoms, which may have a hydroxyl substituent;

R3 represents an aliphatic hydrocarbon radical having 1 to 22 carbon atoms, which is optionally interrupted by an oxygen or the -CONH group and which can be straight-chain or branched, saturated or unsaturated;

R4 is a radical from the group consisting of aliphatic hydrocarbon radicals which are optionally interrupted by an oxygen atom or the -CONH group and have a total of 8 to 22 carbon atoms, alkylyl radicals having 8 to 16 carbon atoms in the alkyl moiety, and aliyl;

and X is a salt-forming anion, especially Cl ", Br, CH2 S03 ~, CH2CH2S03", etc.

A preferred class of diquaternary compounds that can also be used according to the invention are the compounds according to the formula

R6 * 6

X-R5-CH-CH2-N + -CH2-CH-CH2 "N + -CH2-CH-R5X-

OH R7 OH R7 OH

wherein r5 is an alkyl radical having 6 to 20, preferably 10 to 14 carbon atoms, Rfi and R7 are methyl, ethyl or hydroxyethyl, and X is chloride or bromide. Specific examples include tetramethyldi (octoxy-β-hydroxypropyl) -ß-hydroxypropylene-diammonium chloride, tetramethyl-di- (β-hydroxydodecyl) -ß-hydroxypropylene-diammonium dibromide, tetramethyl-di- (ß-hydroxytetradecyl) -ß-hydroxypropylene- diammonium dichloride, tetraethyl-di (dodecyloxy-ß-hydroxypropyl) -ß-hydroxypropylene-diammonium dichloride. These compounds are described in columns 3 and 4 in U.S. Patent 3,983,079.

A particularly preferred class of diquaternary compounds are the N-mono-higher-alkyl-penta-lower-alkyl-lower-alkanediammonium salts such as the compounds of the following formula

Rio Rio x-r8-n + -r9-n + -r12x-

rll rll wherein Rg is a long-chain aliphatic radical having 12 to 22, preferably 14 to 20 carbon atoms, R9 is a divalent alkyl radical having 2 to 4 carbon atoms, R10, Rn and RI2 each represent lower alkyl having 1 to 4 carbon atoms and X- is one salt-forming anion such as chloride, bromide, iodide, sulfate, methyl sulfate, ethyl sulfate, nitrate, etc. A special example is the Sherex compound sold under the name Adogen 477, which is an N-tallow pentamethyl propane diammonium chloride.

The polymers of dimethyldiallylammonium dichloride typically include both homopolymers and copolymers. The comonomers in the copolymers include, for example, acrylic acid, methacrylic acid, styrene, vinyl acetate, vinyl propionate, aciylamide, methacrylamide and similar copolymerizable monomers. Acrylamide and methacrylamide are preferred, acrylamide is particularly preferred.

Compounds of the formula are examples of the diimidazolinium compounds

Ä2

H2C N:

1 1 r3

N = -C-R

ch2

1 + 7 V

-R! + N CH2

R3 ^ | I.

r-C = N

■ X "

mentioned, in which R3 is a straight-chain or branched, saturated or unsaturated aliphatic group having 12 to 18 carbon atoms, R1 is a divalent aliphatic hydrocarbon group having 2 to 5 carbon atoms, R3 is a never-5 whose alkyl radical having 1 to 4 carbon atoms and X is a salt-forming anion.

As a specific example, 1-ethylene-bis (2-tallow-1-methyl-imidazolinium methyl sulfate) is mentioned.

The polymerization can be carried out in a manner known per se. The degree of polymerization is not particularly critical, and satisfactory results are obtained with polymers having molecular weights from about 500 to about 107. These polymers, like the cationic guar gums and poly (methyl vinyl ether / maleic acid), are commercially available.

The amount of polyfunctional additive is in the range of 0.5 to 10%, generally in the range of about 1 or 2 to about 10%, preferably 2 to about 8% of the total composition. It is also preferred that, within the amounts given above, the cationic fabric softener 20 (b) and the polyfunctional additive (c) in a (b) :( c) weight ratio of about 10: 1 to 1: 3, preferably about 6: 1 to 1: 2, especially from about 4: 1 to 1: 1.

As mentioned above, the composition according to the preferred embodiment of the invention also (d) contains a 25 amphoteric surfactant.

A special class of amphoteric surfactants are the complex fatty amido surfactants of the general formula (V)

30th

^ CH2

N CH2

R — C N + - R1 - OM

OH "R2 - COOM

(V)

35 wherein R is a straight-chain or branched, saturated or unsaturated aliphatic group having 12 to 18 carbon atoms (such as lauiyl, tridecyl, tetradecyl, pentadecyl, palmityl, heptadecyl, steaiyl, tallow, coco, soybean, oleyl, linoleyl), R1 and R2 each independently a divalent aliphatic hydrocarbon radical with 2 to 5 carbon atoms (e.g.

Are 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 that are commercially available include

45

50

/ CH ^

CiiH23

CH2

- CH2CH2-0Na

0H ~ N ^ COONa which is available as Miranol CM (liquid) and Miranol DM (paste) from Mira-nol Chemical Co.; Soromine AL and Soromine AT from GAF Corporation and the deriphat compounds from 55 General Mills.

The compounds indicated in columns 3 and 4 in U.S. Patent 4,203,872 can also be used. These include the following seven compound groups betaine surfactants of formula (1)

60 r2 °

RÌ-N + -R4-C-0-

■ R3

65 A suitable example is

(Cio-Ci ^) n-alkyl

CH3 0 n + ch2co "

CH3

670 650

10th

Betaine surfactants with an alkyl bridge of formula (2)

H

* 2

Ri - CH2 - C - N - CH2CH2CH2 - N + - R4 - CO "

R3

A suitable example is n

ch3

(c10 "clA) n-alkyl-CH2 - C - N - CH2CH2CH2 - N + - CH2CO"

xCH3

Imidazoline surfactants of formula (3)

CH2COOH

Rl-C-N

-NH

r4-0-CH2C0 "

CH2

A suitable example is

(CioCi4) n-alkyl — CN

Alkyliminopropionate surfactants of formula (4)

Rx - N - CH2CH2COOH alkyliminodipropionate surfactants of formula (5)

CH2COOH 0

N + - CH2CH20CH2C0 "CH2

CH2CH2COOH

y

R1-0CH2CH2CH2-N

^ CH2CH2COOH alkyliminodipropionate surfactants with ether bridge of the formula (6)

RI-OCH2CH2CH2-N

, CH2CH2C00H

CH2CH2COOH

Lmidazoline-based amphoteric surfactants of the formula (7)

H 0

Rj-C N + -CH20CH2CH2C0 ~

ï> 2

^ CH2

Mixtures of the amphoteric surfactants with one another and with the amine oxide surfactants indicated above can also be used.

In the formulas (1) to (7) above, R.! a straight-chain or branched, saturated or unsaturated aliphatic radical having 7 to 20, preferably 8 to 18, particularly preferably 10 to 14 carbon atoms; R2 and R3 each have lower alkyl with Q to C4, preferably methyl or ethyl, especially ethyl; R4 is a divalent Cr to C4 alkyl, preferably methylene or ethylene, particularly preferably ethylene.

A particularly preferred group of amphoteric compounds are the carboxyethoxyethylated higher fatty alkylimidazoline compounds of the formula (8)

CH?

^ ^ *

H2C HN -CH2CH2COO

R2 N-C-Ri

OH

wherein Rt is a straight-chain or branched, saturated or unsaturated aliphatic group having 7 to 20, preferably 8 to 18, particularly preferably 10 to 14 carbon atoms and R2 is a lower alkyl group having 1 to 4, preferably 1 or 2 carbon atoms. Preferred groups Rj include coco, tallow, heptadecyl, oleyl, decyl and dodecyl, especially coco (e.g. coconut fatty acid). The compound carboxyethylated cocoimidazoline is available as Rexoteric CSF, a product from Rexolin, 3o with 100% active ingredients or as a solution containing 45% active ingredients.

The open chain carboxyethylated alkyl amine derivatives of higher fatty alkyls are another preferred class of amphoteric compounds. These include the above groups (4), (5) and (6), 35 e.g. the alkyliminopropionate and ether-bridged alkyliminopropionate surfactants. A particularly preferred representative of this group is carboxyethylated octylamine, which is available as Rexoteric OASF from Rexolin.

Other classes of amphoteric surfactants such as the sarcosine, tau-4o rine, isethionate and the like can also be used.

Although there are no rigid guidelines for choosing combinations of nonionic and amphoteric surfactants or suitable amounts thereof to achieve the necessary cloud point temperature above the washing temperature to increase the softening effect of the cationic fabric softener, it is generally sufficient to use the amphoteric surfactant with the above specified amount of nonionic surfactant in an amount of about 0.1 to about 10%, preferably from about 0.5 to 50 4%, particularly preferably from about 1 to 3%, based on the total weight of the composition. In general, ratios of nonionic to amphoteric surfactant in the range of about 1: 5 to 10: 1, preferably 1: 3 to 6: 1, particularly 1: 2 to 4: 1 provide the desired high cloud point 55 and the improved softening effect, in particular in combination with the polyfunctional connection.

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

The detergent compositions according to the invention can also, as is generally the case, contain water-soluble builder salts. Water soluble inorganic alkaline builder salts that can be used with the surfactant alone or in admixture with other builders are e.g. Alkali-65 metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Ammonium or substituted ammonium salts can also be used. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium te-

11

670 650

traborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and diorthophosphate and potassium bicarbonate. The alkali metal silicates are valuable builder salts, which also have the function of rendering the composition anticorrosive to washing machine parts. Sodium silicates with Na2 0 / Si02 ratios of 1.6 / 1 to 1 / 3.2, in particular of about 1/2 to 1 / 2.8, are preferred. Potassium silicates with the same proportions can also be used.

Another class of preferred builders are the water-insoluble crystalline and / or amorphous aluminosilicates. Various crystalline zeolites (i.e., aluminosilicates) are described in British Patent 1,504,168, U.S. Patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, all of which are incorporated herein by reference. An example of amorphous zeolites which can be used according to the invention can be found in Belgian patent specification 835 351. The zeolites have the general formula

(M20) x • (Al203) y • (Si02) z • wH20

wherein x is 1, y is 0.8 to 1.2 and preferably 1, z is 1.5 to 3.5 or more and preferably 2 to 3, w is 0 to 9, preferably 2.5 to 6 and M preferably represents sodium. A typical zeolite is of type A or a similar structure, with type 4A being particularly preferred. The preferred aluminum silicates have calcium ion exchange capacities of about 200 milligram equivalents per gram or more, e.g.

400.

Other materials such as clays, especially the water-insoluble ones, can be valuable additives in the compositions according to the invention, especially bentonite. This material consists mainly of montmorillonite, a hydrated aluminum silicate in which, for example, Ys of the aluminum atoms can be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium etc. can be easily combined. In its purer form (e.g. without gravel, sand, etc.), the bentonite suitable for detergents invariably contains at least 50% montmorillonite, so that its cation exchange capacity is at least about 50 to 75 milligram equivalents (meq) per 100 g bentonite. Particularly preferred bentonites are the Wyoming or Western US bentonites, which are sold as Thixo-jels 1,2, 3 and 4 by Georgia Kaolin Co. These bentonites are described as fabric softening agents in GB-PS 401 413 and 461 221.

Examples of organic alkaline sequestering builder salts that can be used alone with the detergent or together with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g. Sodium and potassium ethylenediaminetetraacetate, sodium and potassium nitrilotriacetates and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetate. Mixed salts of these polycarboxylates are also suitable.

Other suitable organic builders include carboxymethyl succinates, tartronates and glycolates. The polyacetal carboxylates are of particular value. The polyacetal carboxylates and their. Detergent applications are described in U.S. Patent No. 4,144,226; 4,315,092 and 4,146,495. Other patents on similar builders include U.S. Patent 4,141,676; 4,169,934; 4,201,858; 4,204,852; 4,224,420; 4,225,685; 4,226,960; 4,233,422; 4,233,423;

4,302,564 and 4,303,777. European patent applications 0015024 are also relevant; 0021491 and 0063399.

Various other detergent additives or auxiliaries can be present in the product to achieve additional desired properties of a functional or aesthetic nature. For example, small amounts of dirt-bearing or reprecipitation substances can be incorporated into the formulation, e.g. Polyvinyl alcohol, fatty amides, sodium carboxyme

ethyl cellulose, hydroxypropyl methyl cellulose; optical brighteners such as cotton, amine and polyester brighteners, e.g. Stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidine sulfone, etc., with stilbene and triazole combinations being most preferred.

Bluing agents such as ultramarine blue can also be used; Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, tiypsin and pepsin and amylaseen enzymes; Bactericides, e.g. Tetrachlorosalicylanilide, hexachlorophene; Fungicides; Dyes; Pigments (water dispersible); Protective substances; Ultraviolet absorbers; anti-yellowing agents such as sodium carboxymethyl cellulose, a complex of Ci2-C22 alkyl alcohol with C] 2 to Qg alkyl sulfate; pH modifiers and pH buffers; color-preserving bleaching agents, fragrances as well as anti-foaming and anti-foaming agents, e.g. Silicone compounds.

The bleaching agents are appropriately roughly divided into chlorine bleaching agents and oxygen bleaching agents. Chlorine bleaches are, for example, sodium hypochlorite (NaOCl), potassium dichloro-socyanarat (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). Oxygen bleaches are, for example, sodium and potassium perborates and potassium monopersulfate. Oxygen bleaches are preferred. Bleach stabilizers and / or activators such as tetraacetylethylene diamine can also be incorporated.

The proportions of the components that may be present in the preferred total care compositions are in weight percent of active ingredients based on the total weight of the final product as follows: a) Nonionic surfactant - about 2 to about 20%, preferably about 3 to about 10%, especially 4 to 9%; b) quaternary ammonium textile softener - 2 to 20%, preferably about 3 to about 16%, especially about 6 to 15%; c) polyfunctional additive - 0.5 to 10%, preferably about 3 to 8%; d) amphoteric surfactant - 0 to 10%, preferably 0.1 to 5%, particularly 0.5 to 4% and especially about 1 to 3%; e) Alkali metal builder salts - about 25 to about 80%, preferably about 25 to about 70%, and most preferably about 25 to 50%, the balance being detergent additives, fillers and moisture. Suitable ranges for the detergent additives are: Enzymes - 0 to 2%, especially 0.7 to 1.3%; Corrosion inhibitors - about 0 to about 5%, preferably 0.1 to 2%; Anti-foaming agent and foam suppressor 0 to 4%, preferably 0 to 3%, e.g. 0.1 to 3%; dirt-bearing or re-precipitation-preventing substances and yellowing-preventing substances - 0 to 4%, preferably 0.5 to 3%; coloring substances, fragrances, brighteners and bluing agents in total 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 to 20%; Bleach stabilizers or bleach activators - 0 to about 15%, preferably 0 to 10%, for example 0.1 to 8%. The additives to be selected should be compatible with the main components of the detergent.

Although it is preferred that the high cloud point nonionic surfactants are the only surfactants in the detergents according to the invention, small amounts of other surfactants can also be used, including, for example, anionic and zwitterionic surfactants, preferably in amounts up to 20% by weight, preferably up to up to 10% by weight and above all up to 5% by weight.

Examples of suitable anionic surfactants include the water-soluble salts such as the sodium, potassium, ammonium, alkylolammonium salts of higher fatty acids having 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, e.g. Tallow, fat, coconut oil,

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

670 650

12

Tall oils and mixtures thereof can be obtained. The sodium and potassium salts of fatty acid mixtures from coconut oil and tallow, e.g. Sodium coconut soap and potassium tallow soap.

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

Examples of sulfonated anionic surfactants are the higher alkyl-substituted mononuclear aromatic sulfonates such as the higher alkylbenzenesulfonates with 10 to 16 carbon atoms in the higher, straight-chain or branched alkyl group, for example the sodium, potassium and ammonium salts of higher alkylbenzenesulfonates, higher alkyltoluenesulfonates, higher alkylphenolsulfonates and higher naphthalenesulfonate or higher alkylnaphthalenesulfonate. A preferred sulfonate is linear alkyl benzene sulfonate with a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, i.e. the benzene ring is preferably mainly linked to the 3- or higher (such as 4, 5, 6 or 7) position of the alkyl group, and the content of isomers in which the benzene ring is bonded to the 2- or 1-position is accordingly low . Particularly preferred substances are given in US Pat. No. 3,320,174.

Other suitable anionic surfactants are the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefin sulfonate surfactants can be prepared in a manner known per se by reacting SO3 with long-chain C8_25, preferably C12_2i olefins of the formula RCH = CHR ^ where R is a higher alkyl radical having 6 to 23 carbon atoms and Ri is an alkyl radical having 1 to 17 Is carbon atoms or hydrogen, whereby a mixture of sultones and alkenesulfonic acids is formed, which is then treated to convert the sultones into sulfonates. Other examples of sulfate or sulfonate surfactants are paraffin sulfonates having about 10 to 20, preferably about 15 to 20 carbon atoms, e.g. the primary paraffin sulfonates obtained by reacting long chain alpha olefins and bisulfites, and paraffin sulfonates in which the sulfonate groups are along the paraffin chain, as described in U.S. Patents 2,503,280; 2,507,088; 3,260,741; 3,372,188 and DE-PS 735 096 are distributed; Sodium and potassium sulfates of higher alcohols with 8 to 18 carbon atoms such as sodium laulyl sulfate and sodium tallow alcohol sulfate; Sodium and potassium salts of alpha-sulfofatty acid esters with about 10 to 20 carbon atoms in the acyl radical such as methyl-alpha-sulfomyristate and methyl-alpha-sulfonalgate, ammonium sulfates of mono- or diglycerides of higher (C10-Cis -) fatty acids, e.g. Stearin monoglyceride monosulfate; Sodium and alkylolammonium salts of alkylpolyethenoxy ether sulfates prepared by condensing 1 to 5 moles of ethylene oxide with 1 mole of higher (C8-cig) alcohol; Sodium higher alkyl (Cio-Ci8-) glyceiyl ether sulfonates; and sodium or potassium alkylphenol polyethenoxy ether sulfates having from about 1 to 6 oxyethylene groups per molecule, wherein the alkyl radicals have from about 8 to about 12 carbon atoms.

Suitable anionic surfactants also include the Q - cig acyl sarcosinates (eg sodium lauroyl sarcosinate), sodium and potassium salts of the reaction products of higher fatty acids with 8 to 18 carbon atoms which are esterified with isethionic acid, and sodium and potassium salts of Cg-Qg-acyl N-methyltaurides, e.g. Sodium cocoyl methyl taurate and potassium stearoyl methyl taurate.

Examples of zwitterionic surfactants include the derivatives of quaternary ammonium compounds with an aliphatic straight-chain C 1-6 group and a solubilizing anionic sulfate or sulfonate group. Specific examples are 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane

1-sulfonate, 3- (N, N-dimethyl-N-talloylammonio) -2-hydroxypropane-1-sulfonate and 6-N, N- (dimethyl-N-hexadecylammonio) hexanoate.

Whatever form the detergent is in, its use in the washing process is essentially the same. The particulate mixture is generally added to the washing water in an automatic washing machine so that the concentration thereof in the washing water is in the range of 0.05 to 1.5%, usually 0.1 to 1.2%. The wash water to which it is added is preferably of medium or low hardness, e.g. 30 to 120 ppm hardness than calcium carbonate, but both softer and harder water can be used successfully. The water temperature can be 20 to 100 ° C and, according to the invention, is at least 60 to 100 ° C, 15 if the textiles tolerate high temperatures without the colors running out or being damaged. If you want to wash at a lower temperature, the temperature can be kept at 20 to 40 ° C, achieving good cleaning and softening, although the fabrics may not be as clean as if they were washed at higher temperatures . At the above-mentioned detergent concentrations, the pH of the wash water is generally 7 to 11, preferably 8 to 10. At such pH values, the detergent is an effective detergent, not too acidic to the material to be washed or to human skin, and gives one effective cleaning and softening. The weight ratio of laundry: wash water is usually 1: 4 to 1:30 or 1:10 to 1:30.

The detergents according to the invention ensure a significantly improved softening at washing temperatures of at least 60 ° C. in comparison, for example, with formulations which are identical, with the exception that the nonionic surfactant has a cloud point below 60 ° C., e.g. a straight chain higher (Ci2_i5-) fatty alcohol with 7 to 13 ethylene-35 oxide units. This effect could not be expected based on the prior art, since the relationship between the cloud point of the nonionic surfactant and the softening effect was not known.

The methods for producing the compositions according to the invention are known per se. In particular, reference is made to US Pat. No. 4,269,722, which describes the production of relatively high density builder-containing nonionic powders from spray-dried base beads which are sprayed with nonionic surfactant (the other usual additives 45 in a small amount such as dye, fragrance, brightener, bleach, etc.).

The following are the cloud points (° C.) of various nonionic surfactants and of mixtures of nonionic / amphoteric surfactants, which were determined in concentrations of 50% by weight in distilled water and 10% NaCl.

Nonionic surfactant Distilled 10% NaCl

water

55

43 ± 2

<25

85 ± 2

59 ± 2

100

> 60

100

> 60

100

72

91

70

45

<30

75 + 2

50 ± 2

58 ± 2

28 ± 2

55 ± 2

42 ± 2

100

90 ± 2

95 ± 2

85 ± 2

100

80 ± 2

A. Ci2-Ci5 fatty alcohol EO 7: 1

B. Ci2-Ci5 fatty alcohol EO 11: 1 C12-Ci5 fatty alcohol EO 15: 1> isooctylphenol EO 30: 1> nonylphenol EO 20: 1> nonylphenol EO 15: 1 nonylphenol EO 8: 1

A. + Rexoteric OASF (1: 2)

A. + Rexoteric OASF (4: 1)

A. + Rexoteric CSF (4: 1)

B. + Rexoteric OASF (1: 2)> B. + Rexoteric OASF (4: 1)

B. + Rexoteric CSF (4: 1)>

13

670 650

The following examples are intended to illustrate the invention, all "parts" and "%" being by weight.

example 1

The following compositions were made:

C (%)

A (%)

B (%)

Nonylphenol EO 20: 1

15.0

C12-C15 fatty alcohol EO 11: 1

10.0

7.5

Rexoteric CSF (100%

Active substance)

2.5

Sodium tripolyphosphate

42.0

42.0

42.0

Dimethyldistearylammonium

chloride) (93% active substance)

6.45

6.45

6.45

N-tallow pentamethylpropane diammo-

nium dichloride (Adogen 477 (50%

Active substance)

3.0

3.0

3.0

Small amounts of mixed

Substances (e.g. optical brighteners,

Fragrance, moisture, etc.)

rest

rest

rest

Bath towels and hardened cotton terry towels were washed in about 20 liters of water at 60 ° C using 100 g of compositions A, B and C, respectively.

The softness of the washed textiles was assessed by a panel of 4 experts after cumulative washing after repeated repetitions. Each composition was rated on a 1 to 10 scale, with "10" being the highest rating and corresponding to the degree of softness obtained with a rinse aid softener (dimethyldistearylammonium chloride). On this scale, composition A and composition B were rated 8-10. Composition C achieved a rating of 4-5.

In addition, the total dirt removal and the stain removal on 10 different types of soiled textiles were determined, which was achieved with composition A and with composition B. The values obtained showed a comparatively excellent cleaning effect.

Example 2

The softening effect of the following compositions was compared under the same conditions as described in Example 1:

D (%)

E (%) F (%)

G (%)

Nonylphenol EO 20: 1

15.0

Sodium metasilicate

8.0

Sodium tripolyphosphate

28.0

Sodium pyrophosphate • 1020

23.0

Sodium orthophosphate

0.5

Nitrilotriacetate, sodium salt

8.0

Dimethyldisteaiylammoniumchlo-

rid (93% active substance) 8.0

8.0 6.45

8.0

Copolymer

(Dimethyldiallylammonium chloride /

Acrylamide) (40% active substance)

7.6

Adogen 477 (50% active ingredient)

3.0

6.0

Small amounts mixed

Substances

rest

The softening effect achieved with bath towels and hardened cotton terry cloth was as follows:

E was significantly better than C G was significantly better than D F was trending better than D E was trending better than G G was trending better than F F was trending better than D

Example 3

In the following, a preferred formulation of a powder-containing or granulated “complete composition” (full performance) according to the invention, including the range, is given:

Area %

Particularly preferred%

Ci2-C] 5-fatty alcohol EO 11.1

3-15

6.0

Rexoteric CSF (100% active substance)

0-3

1.5

Sodium tripolyphosphate

25-50

42.0

Sodium silicate (1: 2)

(40% active substance)

0-5

3.0

Ethylenediaminetetraacetic acid

0-1

0.45

Sodium perborate monohydrate

(NaB03H20)

0-15

13.0

Perborate Activator (TAED)

0-7

2.8

Sodium carboxymethyl cellulose

0-4

2.6

Optical brighteners (Tinopal)

0.2-0.5

0.33

Enzyme (Alcalase 2T, from Nova)

0.7-1.3

1.0

Dimethyldisteaiylammonium dichloride

5-15

8.6

N-tallow pentametiiylpropandiammoni-

umchloride1

1-5

3.4

Inert carriers and fluidity

demanding substance

0-5

3.0

Perfume

0-1

0.4

water

rest

rest

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

Claims (4)

670 650 1) 0 to about 2% enzymes, m) 0 to about 0.5% fragrance, n) 0 to about 10% pH modifier and buffer, o) 0 to about 50% inert fillers, the flow promoting substances and carriers and p) contains about 2 to about 20% water. 1. washing and softening agent composition which is suitable for cleaning and softening textiles in the wash cycle of a washing program at an elevated temperature of the washing water of at least 60 ° C. up to the boiling point thereof, characterized by a) 1 to 20 parts by weight of a nonionic surfactant ; b) 2 to 20 parts by weight of a fabric softening water-insoluble cationic quaternary ammonium compound; c) 0.5 to 10 parts by weight of a polyfunctional additive of the group which improves the substantivity towards textiles (i) diquaternary ammonium compounds, (ii) polymers of dimethyldiallylammonium chloride, (iii) cationic guar gum and (iv) poly (methyl vinyl ether / maleic acid); and (v) diimidazolinium compounds; d) zero to 10 parts by weight of an amphoteric surfactant. * 2 R1-CH2-C-N-CH2CH2CH2-N + -RA-C0 r3 Imidazoline surfactants of the formula (3) CH2COOH 0 Rl-C N + -R4-0-CH2C0 " Ns CH2 ch2 Alkyliminopropionate surfactants of formula (4) H Rl-N-CH2CH2COOH alkyliminodipropionate surfactants of formula (5) // CH2CH2COOH Rl-N CH2CH2COOH Alkylimino dipropionate surfactants with an ether bridge of the formula (6) ^ CH2CH2COOH Rl-OCH2CH2CH2-N ^ • ch2ch2cooh amphoteric imidazoline-based surfactants of the formula (7) H 0 R] _- C N + -CH20CH2CH2C0 ~ N CH2 \ / ch2 amphoteric surfactants based on carboxyethylated higher-fatty alkylimidazoline of the formula (8) CH2 H2C HNS "-CH2CH2COO r2 N + = C-R! OH and mixtures thereof, wherein Ri is an aliphatic radical having 7 to 20 carbon atoms, R2 and R3 are each a lower alkyl radical having 1 to 4 carbon atoms and R4 is a divalent alkyl radical having 1 to 4 carbon atoms. 11. Detergent composition for washing and softening textiles in washing water at an elevated temperature in the range from 60 to 100 ° C., characterized by a content of 15 a) 0.1 to 20% of at least one water-soluble nonionic surfactant of the formula I or II R0 (CH2CH20) nH (I) 20th Rl ~ © "° ~ (CH2CH20) mH (II) wherein R is a primary or secondary alkyl chain of 8 to 22 carbon atoms, R1 is a primary or secondary 25 alkyl chain of 7 to 12 carbon atoms, and n and m each represent an average of 3 to 30%; b) 2 to 20% of at least one water-insoluble cationic, quaternary ammonium compound of the formulas III or IV Rl. * 2 N * r4 R5 - / N Ré R7 (iii) (IV) wherein Rb R2, R5 and R <; are each independently long-chain aliphatic C16-22 radicals, R3, R4 and R7 each independently represent lower alkyl radicals, or R 'is the 45 group -RqNHCR " y «o O where Rg is a long chain aliphatic radical having 16 50 to 22 carbon atoms and R9 is a divalent alkyl radical having 1 to 3 carbon atoms and X is a salt-forming anion; c) 0.5 to 10% of a polyfunctional additive from the group consisting of diquaternary ammonium compounds of the formula 55 R10 R10 X "-Rg-N" 1 "-R9-N + -R12 • X" R11 Rn 60 65 wherein Rg is a straight chain or branched, saturated or unsaturated aliphatic hydrocarbon group having 12 to 22 carbon atoms; R9 represents a divalent alkyl group having 2 to 4 carbon atoms; each of the groups Ri0, Rn and Ri2 is the same or different and is lower alkyl of 1 to 4 carbon atoms and X is a salt-forming anion; 670 650 2. Composition according to claim 1, characterized in that it contains on a weight basis a) about 1 to 15% nonionic surfactant b) about 2 to 20% of the water-insoluble cationic quaternary ammonium compound as a fabric softening agent, c) about 0.5 to 10% of the polyfunctional additive, the amount of b) plus c) in the range of about 5 to 22% and the ratio of b) to c) in the range of about 10: 1 to about 1: 3, d) 0 to about 10% amphoteric surfactant, e) about 25 to 80% of at least one builder, f) 0 to about 40% of a bleaching agent, g) 0 to about 7% of a bleach activator, h) 0 to about 4% of dirt-carrying substances, substances which prevent re-precipitation and thickeners, i) 0 to about 5% corrosion-preventing substances, j) 0 to about 1% organic chelating substances, k) 0 to about 2% of coloring substances, pigments, bluing agents and optical brighteners, 2nd PATENT CLAIMS 3rd 670 650 7. The composition according to claim 6, characterized in that R is an alkyl having 12 to 15 carbon atoms, R1 is an alkyl having 8 to 9 carbon atoms and m and n each have an average value of about 15 to 30. 8. The composition according to claim 1, characterized in that the cationic compound (b) is dimethyldistearylammonium chloride. 9. The composition according to claim 1, characterized in that it also contains at least one additive from the group consisting of inorganic and organic builder salts, dirt-carrying substances, substances that prevent re-precipitation, fatty amides, foam depressants, foam-preventing substances, optical brighteners, dyes, pigments, bluing agents, contains the yellowing-preventing substances, enzymes, corrosion inhibitors, pH modifiers, pH buffers, bactericides, fungicides, protective substances, bleaches, bleach stabilizers, bleach activators, fragrances and water. 10. The composition according to claim 1, characterized in that it contains at least 0.1 part of the amphoteric surfactant (d) and that the amphoteric surfactant from the group Betaine surfactants of formula (1) R2 0 Rl-N + -R4-C-0- * 3 Betaine surfactants with an alkyl bridge of the formula (2) H 3. The composition of claim 1 in the form of a free-flowing powder or granules containing, on a weight basis, from a) about 3 to 15% of a nonionic surfactant having a hydrophobic group condensed with alkylene oxide, and b) about 2 to 20 % of a textile-softening, water-insoluble, cationic quaternary ammonium compound containing at least two long-chain aliphatic groups with 16 to 22 carbon atoms, c) about 1 to 10% of a polyfunctional additive from the group consisting of diquaternary ammonium compounds of the formula R2 R2 X "• R4-N + -RI-N + -R3-X" R2 R2. wherein Ri represents a divalent alkyl group, optionally having a hydroxyl substituent, with 2 to 4 carbon atoms; each of the R2 grapples can be the same or different and is lower, optionally hydroxyl-substituted alkyl having 1 to 4 carbon atoms; R3 is a straight-chain or branched, saturated or unsaturated aliphatic, optionally by oxygen or a - CONH group is interrupted hydrocarbon group with 1 to 22 carbon atoms; R4 is a group from optionally aliphatic-interrupted by an oxygen atom or the -CONH group see hydrocarbon radicals with a total of 8 to 22 carbon atoms, alkylaryl radicals with 8 to 16 carbon atoms in the alkyl part, and aliyl; X is a salt-forming anion; and polymers of dimethyldiallylammonium chloride; 10 d) 0.1 to 10% by weight of an amphoteric surfactant; e) Builders, auxiliaries, fillers and moisture as the rest. 4. Composition according to claim 3, characterized in that (e) about 25 to 50% builder, 0 to 5% corrosion inhibitor, 0 to 1% organic chelating agent, 0 to 40% acid 15 fabric bleach, 0 to 7% bleach activator, 0 to 4% thickener and anti-rejection agent, 0.2 to 0.5% optical brightener, 0.7 to 1.3% enzyme, 0 to 0.5% fragrance and the balance comprises up to about 20% moisture. 5. Composition according to claim 1, characterized in that the textile softening water-insoluble, cationic quaternary ammonium compound from the group of compounds of the following formulas 25th and or Rl> r2 " r5 - ■ / -r3 [ ^ R4 _ ^ N1 / \ Re R7 (in) (IV) is selected, wherein R 1, R 2, R 5 and in each case independently of one another are long-chain aliphatic C 6 to C 22 radicals, R 3, R 4 40 and R 7 each independently represent lower, optionally hydroxyl-substituted alkyl radicals; or R6 the group -RqNHCRQ y «0 O 45 where Rg is a long chain aliphatic radical having 16 to 22 carbon atoms, Rg is a divalent alkyl radical having 1 to 3 carbon atoms and X is a salt-forming anion; and that the weight ratio of nonionic surfactant to cationic compound b) is in the range from 1:10 to 5: 1. 6. The composition according to claim 1, characterized in that the nonionic surfactant (a) at least one compound from the group of compounds of the following formulas 55 RO (CH2CH2) nH (I) wherein R is a primary or secondary alkyl group of 8 to 22 carbon atoms and n has an average value of 3 to 30 60; and (CH2CH20) mH (II) wherein R1 is a primary or secondary alkyl chain of 7 to 12 carbon atoms and m is an average of about 3 to 30. 4th and polymers of dimethyldiallylammonium chloride; d) at least one amphoteric surfactant in an amount of 0.1 to 10% and e) builders, auxiliaries, inert substances and water as the rest.