GB1565808A

GB1565808A - Fabric softeners and detergent compositions containing imidazolines derivatives

Info

Publication number: GB1565808A
Application number: GB36625/76A
Authority: GB
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1975-09-04
Filing date: 1976-09-03
Publication date: 1980-04-23
Also published as: SE426600B; SE7609755L; CH606594A5; FR2322963A1; NL7609621A; JPS5234098A; SE8006264L; DK398576A; FR2322963B1; LU75717A1; IT1074422B

Description

(54) FABRIC SOFTENERS AND DETERGENT COMPOSITIONS CONTAINING IMIDAZOLINE DERIVATIVES (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 8003 20, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to fabric softeners and detergent compositions.

It is known that washed textile materials, especially those made of cellulose fibers, show an unpleasant hard feel after drying. This is particularly the case, if the washing was performed in a washing machine.

It has already been shown that this undesired hard feel can be avoided, if the textile materials are treated after washing in a rinsing bath with cationic substances which contain at least 2 long-chain aliphatic radicals in the molecule. The commercial fabric softeners which contain as active components in most cases quaternary dialkyl-dimethyl-ammonium salts having two longer alkyl radicals in the form of an aqueous dispersion show the drawback that there is a thickening of the dispersion due to a gel formation during transport and storage, above all at a fairly low temperature, especially below freezing point, which cannot be eliminated by reheating these substances to room temperature, nor by vigorously shaking the same.

It is in fact known that certain imidazolinium compounds may be used as fabric softeners, which are capable of flowing in the form of concentrated alcoholic solutions and which can be diluted with cold water. These imidazolium compounds include, for example, the methosulfate of l-alkylamido-ethyl-2-alkyl-3methyl-imidazoline, whose softening effect, however, is by far inferior to that of the dialkyl-dimethyl-ammmonium salts.

Another drawback is to be seen in the fact that these softening substances must be introduced into the household washing machine separate from the main washing cycle, since the textile fabric softeners based or cationic surfactants are not compatible with the anionic detergents of the washing agent. When used together, the cationic products are eliminated from the washing system in the form of electroneutral salts and thus cannot be adsorbed by the fibre.

If washing agents based on non-ionic detergents which are compatible with cationic softeners are used, a redeposition of the dirt onto the fibre is observed, so that although the washing goods do have a pleasant soft feel, the dirt particles are not removed by the washing.

The invention provides a textile fabric softener composition consisting of an aqueous solution or dispersion of an imidazoline of the general formula I or a salt thereof, or a mixture of such imdiazolines or salts thereof

in which R is an aliphatic radical having from 13 to 21 carbon atoms, n is 2 or 3, and X represents a hydrogen atom or an acyl group of the general formula II R.CO- (II) in which R has the above-mentioned meaning. Preferably the fabric softener contains from 1 to 15% or 20 to 35% by weight of the compound or compounds of the general formula I. Preferably R is alkyl of 15-17 carbon atoms and n is 2.

Preferably the group R and R' are alkyl groups. However, the compounds of the general formula I are suitably prepared from natural fatty acid mixtures, and therefore mixtures of compounds of the general formula I in which, for example, a small proportion of these compounds contain alkenyl groups represented by R may be used.

An imidazoline of the general formula I may be prepared by the condensation of from about 1 to 2 moles, preferably from 1.2 to 1.9 moles, of a fatty acid of the formula RCOOH where R has the meaning given above or one of its esters with I mole of p-hydroxy-ethyl-ethylene-diamine or p-hydroxypropyl-ethylene-diamine. If the fatty acid is reacted with the amine in a molar ratio of about 1:1, an imidazoline of the formula I is predominantly obtained, in which X represents hydrogen, and if a molar ratio of about 2:1 is used, imidazoline derivatives are obtained in which X in the formula I predominantly represents an acyl group. Suitable fatty acids are, for example, saturated fatty acids or fatty acid mixtures which contain only minor proportions of olefinicially unsaturated acids. Especially suitable are fatty acids based on entirely or partially hardened fats.Suitable fatty acids are, for example, palmitic acid, stearic acid, and tallow fatty acid. Suitable esters of these fatty acids are especially the esters with lower alcohols, especially the ethyl and methyl esters.

The condensation is effected in known manner by heating the components for several hours at a temperature in the range of from about 180 to 3000 C, preferably from 160 to 2500 C. Depending on the temperature and the fatty acid component used, up to 10 hours, in most cases from about 2 to 8 hours, are required in order to reach equilibrium. In the case of a condensation in vacuo, the reaction may be effected at a lower temperature, for example, in the range of from 150 to 1900C.

After the condensation has been completed, the melt of the reaction product is cooled and is brought in known manner into the form of flakes, for example by means of a cooling roll, or into the form of granules, by means of an extruder, or may be pulverized by way of comminution. Prior to this shaping, the melt of the reaction product may be adjusted, if necessary, to a slightly alkaline to slightly acid range (pH 4 to 8) by adding water-soluble organic acids or mineral acids.

As a modification of this operational method, it is also possible to disperse the melt of the reaction product in water, in which process the melt - after having been adjusted to a slightly alkaline to slightly acid range with a pH of from about 4 to 8 - is either stirred into water, together with a water-soluble strong organic or inorganic acid, or wherein the melt is stirred into water, while the organic or Inorganic acid is being added at the same time or subsequently. As organic and/or inorganic acids there may be mentioned, above all, mineral acids, such as hydrochloric acid, phosphoric acid, sulphuric acid, acetic acid or oxalic acid. In this manner, an aqueous dispersion is obtained which can be diluted with cold water and which has a content of up to about 35,Ó by weight of the active substance of the formula I. In order to incorporate this dispersion into a detergent, it may be added to the detergent paste to be comminuted or may be sprayed onto the detergent. It is also possible, however, to further dilute this dispersion with water and to use it directly as fabric softener, optionally while adding a cationic disinfecting agent or further quaternary ammonium compounds showing a softening effect.

The invention also provides a detergent composition for textile materials which comprises one or more surfactants in admixture with an imidazoline of the general formula I. The detergent may be for example a heavy-duty detergent for easy-care textiles, or an ordinary-duty detergent, and may contain, for example, anionic and/or hybrid-ionic and/or non-ionic surfactants. Other known additions used in the preparation of detergents may also be present.

Preferably, a detergent composition of the invention comprises: (a) from about 4 to 70% by weight, preferably from 6 to 60% by weight of a surfactant component having at least one surfactant of the above-mentioned types, with the non-ionic surfactants optionally present being in the range of up to about 70% by weight, however, preferably not exceeding 10% by weight of this surfactant component, and (b) from about 3 to 20% by weight, preferably from 5 to 15% by weight of one or more imidazolines of the general formula I as fabric softening agents, and (c) known detergent additive which make up the balance to 100% by weight.

Known detergent additives are, for example, builders having a neutral to alkaline reaction, complexing agents, bleaching components, foam stabilizers, foam inhibitors, anti-redeposition agents and enzymes, optical brighteners, perfumes, dyestuffs, water.

The incorporation of the imdiazoline of the general formula I in order to prepare a detergent composition of the invention having a fabric-softening effect may be effected according to various known methods.

In order to arrive at an optimum use of the fabric-softening effect it is recommended that the imidazoline derivatives of the formula I should be present in a very fine division in the detergents of the invention.

This desired very fine division can be obtained by evenly mixing the finely pulverized imidazoline of the formula I with the other detergent particles, or by spraying the imidazoline of the formula I in a melted form or dissolved or dispersed in appropriate liquid carriers, especially water, onto the other solid detergent particles, so as to coat the latter entirely or partially, or by incorporating the imidazoline of the formula I into the detergent pastes to be pulverized, in which case aqueous dispersions of the imidazoline of the formula I are especially suitable.

The composition of particularly interesting detergent compositions of the invention in practice is generally in the range of the following formulation: From about 6 to 60% by weight of a surfactant component consisting essentially of anionic surfactants of the sulfonate and/or sulfate type having preferably from 8 to 18 carbon atoms in the hydrophobic radical, soaps and optionally non-ionic surfactants, with the non-ionic surfactants optionally present being in the range of up to about 70% by weight, however, preferably not exceeding 10% by weight of this surfactant component, from about 5 to 15% by weight of the above described imidazolines corresponding to the formula I, and a proportion of other detergent additive making up the balance of 100% by weight, particularly builders having an alkaline to neutral reaction and other auxiliary agents, such as, for example, bleaching agents, anti-redeposition agents, enzymes, optical brighteners, perfumes, dyestuffs, water.

In the detergent compositions containing soap, the ratio between the anionic surfactants of the sulfonate and/or sulfate type and the soap is in the range of from about 10:1 to 1:5, preferably 7:1 to 1:2.

The detergent compositions may also contain a bleaching component, which is considered in the above formulation as a part of the other detergent additive. If a bleaching component is present, it is preferably perborate, optionally in combination with activators, or active chlorine compounds. The fabric softeners used according to the invention are, however, preferably incorporated into highduty detergents suitable for washing machines which do not need to contain a bleaching component.

The detergent compositions of the invention are preferably suitable for the washing of delicate articles and easy-care textiles, in particular those made of cotton, polyester, polyacrylonitrile and polyamide, in particularly woven and knitted fabrics. As washing temperature, a temperature in the range of from 30 to 60"C is advantageously chosen. However, it is also possible to wash at a temperature of up to boiling point.

The components of the high-duty, easy-care and heavy-duty detergents are the components already known, as they have been described before in detail in literature (cf., for example, Schwartz, Perry, Berch, "Surface Active Agents and Detergents, Vol. II (1958), pages 25-93, 120-138 and 288-317); Lindner, "Tenside Textilhilfsmittel, Waschrohstoffe" Vol. I, 1964), pages 561-921 and 1025-1041; P. Bert. "Chemie und Technologie moderner Waschmittel", Chemikerzeitung 94, 1970 No. 23/24, pages 974 et seq.

As anionic, hybrid-ionic and non-ionic washing active substances of the detergents of the invention there may be mentioned, above all, the following products: The anionic, hybrid-ionic or non-ionic surfactants contain in the molecule at least one hydrophobic radical having, in most cases, from 8 to 26, especially from 10 to 18 carbon atoms, and at least one anionic, non-ionic or hybrid-ionic watersolubilizing group. The preferably saturated hydrophobic radical is mostly of an aliphatic, optionally also of an alicyclic nature; it may be bound to the watersolubilizing groups directly or via intermediate members. As intermediate members there may be mentioned, for example, benzene rings, carboxylic acid ester or carbonamide groups.

The hydrophobic radical is preferably an aliphatic hydrocarbon radical having from about 10 to 18, preferably from 12 to 18 carbon atoms, with possible deviations from this preferred range, depending on the nature of the respective surfactant.

As anionic washing active substance there may be used soaps on the basis of natural or synthetic fatty acids, optionally also on the basis of resin acid or naphthene acids, especially if these acids show iodine numbers of 30 at the most and preferably of less than 10.

Of the synthetic anionic surfactants, the sulfonates and sulfates are of particular importance in practice.

To the sulfonates belong, for example, the alkylarylsulfonates, especially the alkylbenzene sulfonates which are obtained, inter alia, from preferably straightchain aliphatic hydrocarbons having from 9 to 15, especially from 10 to 14 carbon atoms, by the chlorination and alkylation of benzene, or from corresponding terminal or non-terminal olefins by the alkylation of benzene and the sulfonation of the alkylbenzenes obtained. Furthermore, aliphatic sulfonates are interesting, as they may be obtained, for example, from preferably saturated hydrocarbons containing from about 8 to 18 and preferably from 12 to 18 carbon atoms in a straight chain in the molecule, by a sulfochlorination with sulfur dioxide and chlorine, or by a sulfoxidation with sulfur dioxide and oxygen, and conversion of the products thus obtained into the sulfonates.As aliphatic sulfonates there may also be used mixtures containing alkene sulfonates, hydroxyalkane sulfonates and disulfonates, which mixtures are obtained, for example, from terminal or non terminal olefins having from about 8 to 18 carbon atoms by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonation products. In the aliphatic sulfonates thus prepared the sulfonate group is in many cases present at a secondary carbon atom; however, it is also possible to use sulfonates obtained by reacting terminal olefins with bisulfite, said sulfonates having a terminal sulfonate group.

The sulfonates to be used may include additionally salts, preferably dialkali metal salts of a-sulfo fatty acids, as well as salts of esters of these acids with mono or polyvalent alcohols containing from 1 to 4, preferably from 1 to 2 carbon atoms.

Further suitable sulfonates are salts of fatty acid esters of hydroxy-ethane sulfonic acid or of dioxypropane-sulfonic acid, the salts of the fat alcohol esters of lower aliphatic or aromatic sulfomono- or -dicarboxylic acids containing from 1 to 8 carbon atoms, the alkylglycerylether sulfonates, as well as the salts of the amide like condensation products of fatty acids and/or sulfonic acids with amino-ethane sulfonic acid.

As surfactants of the sulfate type there are to be mentioned fat alcohol sulfates, especially those prepared from coconut oil alcohols, tallow fat alcohols or oleyl alcohol. Suitable sulfonation products of the sulfate type may also be obtained from terminal or non-terminal olefins having from about 8 to 16 carbon atoms. This group of surfactants includes furthermore sulfated fatty acidalkylolamides or fatty acid-monoglycerides, as well as sulfated alkoxylation products of alkylphenols (C815-alkyl), fat alcohols, fatty acid amides or fatty acid alkylolamides which may contain in the molecule from about 1 to 20, especially from 2 to 4 ethylene- and/or propyleneglycol radicals.

As anionic surfactants of the type of carboxylates there are suitable, for example, the fatty acid esters or fat alcohol ethers of hydroxycarboxylic acids, as well as the amide-like condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, for example, with glycocoll, sarcosine and the like.

The non-ionic surfactants include products which owe their water-solubility to the presence of polyether chains, aminoxide, sulfoxide or phosphinoxide groups, alkylolamide groups, and generally to an accumulation of hydroxyl groups.

Particularly interesting in practice are those products which may be obtained by the addition of ethylene oxide and/or propylene glycol to fat alcohols, alkylphenols, fatty acids, fatty amines, fatty acid- or sulfonic acid amides, which products may contain from about 4 to 60, especially from 8 to 20 ether radicals, in particular ethylene-glycol-ether radicals per molecule.

Furthermore, the non-ionic surfactants include those which are obtained by an ethoxylation of polypropylene-glycols which are in fact water-insoluble, or of water-insoluble propoxylated lower aliphatic alcohols containing from 1 to 8, preferably from 3 to 6 carbon atoms and/or of water-insoluble propoxylated alkylene diamines.

The non-ionic surfactants also include fatty acid- or sulfonic acidalkylolamides which are derived, for example, from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, for example, the glycamines. They may be replaced by amides obtained from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

As appropriate surfactants there are also suitable capillary active aminoxides; to this group belong, for example, the products derived from higher tertiary amines showing a hydrophobic alkyl radical and two shorter alkyl and/or alkylol radicals containing up to 4 carbon atoms each.

Hybrid-ionic surfactants contain in the molecule acid as well as basic hydrophilic groups. To the acid groups belong carboxyl-, sulfonic acid-, sulfuric acid-semiester-, phosphonic acid- and phosphoric acid-partial ester groups. As basic groups there may be mentioned primary, secondary, tertiary amine and quaternary ammonium groups. Hybrid-ionic compounds with quaternary ammonium groups belong to the type of the betaines.

The foaming capacity of the surfactants may be increased or reduced by the.

combination of suitable types of surfactants, just as it may be modified by the addition of non-surfactant-like organic substance. As foam stabilizers there are suitable, above all for surfactants of the sulfonate or sulfate type, capillary active carboxy-or sulfobetaines, as well as the above-mentioned non-ionics of the alkylolamide type; besides, fat alcohols or higher terminal diols have been proposed for this purpose.

Products having a reduced foaming capacity are suitable above all for the use in washing and dishwashing machines, in which case a limited defoaming is sometimes sufficient, whereas in other cases a stronger defoaming may be desired.

Of particular importance in practice are those products which still foam in the medium temperature range, up to about 65"C, however, which show a decreasing foaming capacity with rising temperatures, up to 100"C.

A reduced foaming capacity is often obtained by the combination of different types of surfactants, especially by the combination of synthetic anionic surfactants, in particular of sulfates and/or sulfonates, or of non-ionic surfactants on the one hand, and of soaps on the other hand.

However, the foaming capacity of the surfactants may also be reduced by the addition of known non-surfactant-like foam inhibitors.

As builders for the detergents of the invention there are suitable inorganic or organic salts showing a slightly acid, neutral and alkaline reaction, especially inorganic or organic complexing agents.

Suitable salts showing a slightly acid, neutral or alkaline reaction are, for example, the bicarbonates, carbonates or silicates of the alkalis, furthermore mono-, di- or trialkali metal-orthpphosphates, di- or tetraalkali metalpyrophosphates, meta-phosphates known as complexing agents, alkali metal sulfates, as well as the alkali metal salts or organic, non-capillary active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing from 1 to 8 carbon atoms. This group includes, for example, water-soluble salts of benzene-, tolueneor xylene-sulfonic acid, water-soluble salts of sulfo-acetic acid, sulfobenzoic acid, or salts of sulfo-dicarboxylic acids, as well as the salts of acetic acid, lactic acid, citric acid, and tertaric acid.

As complexing builders there are also suitable for meta-phosphates showing a slightly acid reaction, as well as the poly-phosphates showing an alkaline reaction, especially tripolyphosphate. They may be replaced entirely or partially by organic complexing agents. The organic complexing agents include, for example, nitrilotriacetic acid, ethylene-diamine-tetraacetic acid, N-hydroxy-ethyl-ethylenediamine-triacetic acid, polvalkvlene-polyamine-N-polycarboxylic acids, and other known organic complexing agents with combinations of different complexing agents also optionally being used.

The imidazolines of the formula I are soluble or dispersible in water. Therefore they may also be used as softening agents for textile materials in a way that the goods to be treated are soaked with aqueous baths of these imidazolines by dipping or spraying. In this process, an amount in the range of from about 0.01 to 0.7%, calculated on the weight of the textile material, of compounds of the formula I is applied onto the goods. The aqueous solutions or dispersions of the fabric softener of the invention, which show a content of from about 1 to 15% by weight, in most cases from 4 to 10% by weight, or 2 to 6% by weight, of the imidazoline compounds of the formula I, may also contain disinfecting agents as well as further known quaternary ammonium compounds as fabric softeners.

As disinfecting agents there may mentioned the known quaternary ammonium compounds, as they have been described, for example, in "Soap and Chemistry Specialities", March 1969, pages 47/48, as well as, preferably, the compounds characterized by the general formulae V and VI, as shown below:

In these formulae, R5 and R6 represent alkyl or alkenyl radicals having from 8 to 12 carbon atoms, preferably from 8 to 10 carbon atoms, R7 stands for an alkyl or alkenyl radical having from 8 to 18 carbon atoms, preferably from 12 to 16 carbon atoms R8 and R9 represent hydrogen, chlorine or bromine, and A is chlorine or bromine, preferably chlorine. These disinfecting agents are used in an amount of from 1 to 6% by weight.

As cationic softening components of the fabric softeners according to the invention which may optionally be used at the same time, there are to be mentioned quaternary ammonium compounds which contain lipophilic radicals and which are already known for this purpose, as they have been described, for example, in "Chemistry and Industry", June 1969, pages 893 to 894. They are used in an amount of up to 15% by weight, preferably from 1 to 9% by weight.

As fabric softeners of this nature there are used above all the compounds characterized by the general formulae II to IV.

In these formulae, R, and R2 represent an alkyl or alkenyl radical having from 12 to 20 carbon atoms, as is present in stearic acid, tallow fatty acid, oleic acid and/or sperm oil-fatty acid. R3 stands for hydrogen or a methyl group R4 represents a preferably saturated aliphatic radical having from 13 to 21 carbon atoms, preferably an alkyl radical having from 15 to 17 carbon atoms, and x is an integer of from 1 to 5, preferably 1; A may be Cl or Br or CM3SO4, preferably Cl or CH3SO4.

In order to prepare the fabric softener according to the invention, the components may be introduced in any order into an aqueous phase and may be dispersed by stirring. In order to accelerate the dispersion, the aqueous phase may be heated.

The preparation of the fabric softener compositions may also be effected by melting the active substances together with the emulsifying agent at about 70"C and mixing the melt with hot water. If fabric softener compositions are used that may be processed in the cold state, a mixing of the imidazoline derivatives corresponding to the formula I in the form of aqueous dispersions, with the known textile fabric softening agents III and/or IV and/or the mixtures thereof, together with the disinfecting quaternary ammonium compounds, optionally while adding the non-ionic emulsifying agents, is sufficient.

The simultaneous use of non-ionic emulsifying agents may also be advantageous or necessary in order to emulsify in a satisfactory manner the optical brighteners, perfumes which may be added to the fabric softener composition. The non-ionic emulsifying agents are in most cases used in an amount of up to about 1% by weight, preferably from 0.2 to 1.0% by weight, calculated on the aqueous dispersion of the fabric softener.

As non-ionic dispersing or emulsifying agents there are suitable the surfactants known for this purpose. They include products which owe their hydrophilic properties to the presence of polyether chains, aminoxide, sulfoxide or phospinoxide groups, alkylolamide groups, as well as, generally, to an accumulation of hydroxyl groups.

The non-ionic surfactants contain in the molecule at least one hydrophobic radical having from 8 to 20, preferably from 10 to 18 carbon atoms, and at least one non-ionic water-solubilizing group. The preferably saturated hydrophobic radical is in most cases of an aliphatic or alicyclic nature; it may be bound to the watersolubilizing groups directly or via intermediate members. As intermediate members there are suitable, for example, benzene rings, carboxylic acid ester or carbonamide groups, radicals of polyvalent alcohols showing an ether- or ester-like bond, for example those of ethylene-glycol, of propylene glycol, of glycerol, or corresponding polyether radicals.

Particularly interesting in practice are the products which can be obtained by the addition of from about 3 to 40, especially from 5 to 20 moles of ethylene oxide to 1 mole of fat alcohols, alkylphenols, fatty acids, fatty amines, fatty acid- or sulfonic acid amides. In these polyethylene-glycol-ether radicals and/or at their ends, propylene- or butylene-glycol-ether radicals and/or -polyether chains may also be present.

Furthermore, the suitable non-ionic emulsifying agents include the known commercial water-soluble addition products of ethylene oxide to water-insoluble polypropylene-glycols as well as addition products of propylene oxide to alkylene diamines or to lower aliphatic alcohols containing from I to 8, preferably from 3 to 6 carbon atoms. In these products, the water-insoluble propylene oxide derivatives represent the hydrophobic radical.

The addition of disinfecting agents prevents microorganisms from multiplication on the textile material by their absorption on this material. This germ-inhibiting effect of the fabric softeners is especially desirable, since even in the case of cotton fabrics, boiling is more and more avoided and the goods are washed more frequently at 60"C.

The amount used of the fabric softening compositions according to the invention may be in the range of from about 80 to 120 g per 4 kg of fabric. This corresponds as to the softening effect to an amount of from 80 to 121 ml of a commercial fabric softener having about 6% of active substance on the basis of distearyldimethylammoniumchloride.

In case the fabric softener composition of the invention contain mixtures of imidazolines of type I together with quaternary ammonium compounds of the type III and/or IV which may be processed in the cold state, the amount used in the last rinsing bath needs to be somewhat increased, in order to obtain softening effects which are comparable to those obtained by means of a commercial fabric softener on the basis of distearyl-dimethylammoniumchloride.

These fabric softener compositions are used by introducing the abovedescribed solutions or dispersions into the last rinsing bath, following the washing of the textile goods.

In the course of this process, the textile materials thus treated. particularly those made of natural or regenerated cellulose, wool, cellulose acetate and triacetate, polyamide, polyacrylonitrile, polyester and polypropylene, obtain a pleasant soft feel. The use of the compositions of the invention is particularly advantageous as fabric softener composition for terry fabrics and underwear.

The following Examples serve to illustrate the invention. In these Examples, the percentages are per cent by weight.

EXAMPLE 1.

52 Grams (0.5 mole) of aminoethylethanolamine and 238 g (0.9 mole) of stearic acid were condensed for 5 hours at 1900 C, while nitrogen was passed through the mixture, and for another 3 hours at 1650C in vacuo and 25 Torr. 265 Grams of a colorless product were obtained (content of nitrogen showing alkaline reaction 1.6%, acid number = 1.0), which was stirred, after cooling to about 100"C, with 795 g of water of 90"C. The solution was adjusted to a pH of 4.7 (measured in a 1% aqueous solution) by adding 34.5 g of acetic acid. A colorless dispersion was obtained, which could be dispersed in cold water and which contained 28% by weight of solid material.

EXAMPLE 2.

156 Grams (1.5 moles) of aminoethylethanolamine and 528 g (2.1 moles) of stearic acid were condensed for 4 hours at 1600C and for 2 hours at 1800C and 50 Torr, while nitrogen was passed through the mixture. 624 Grams of a yellowish product were obtained (content of nitrogen showing alkaline reaction 2.7%, acid number 1.0) which was stirred, after having been cooled to 100%, with 1840 g of water of 90"C, and which was adjusted to a pH of 4.6 (measured in a 1% aqueous solution) by means of 75 g of acetic acid. A colorless dispersion was obtained, which contained 29% by weight of solid material and which was dispersible in cold water.

EXAMPLE 3.

104 Grams (1 mole) of aminoethylethanolamine and 324 g (1.2 moles) of stearic acid were reacted in an manner analogous to that of Example 1, and the mixture was diluted to a 29, ó dispersion.

EXAMPLE 4.

104 Grams (1 mole) of aminoethylethanolamine and 432 g (1.6 moles) of stearic acid were reacted in a manner analogous to that of Example 2, and the mixture was diluted to a 29% dispersion.

Test of the softening effect of fabric softening compositions As other testing methods were unfeasible, the softening effect of the compounds specified in Examples 1 through 4 was determined by judging the feel of terry cloths treated accordingly.

In order to precisely determine the softening effect of a softening raw material, as compared against a standard product, the cotton terry cloths treated with the product to be tested were ranged, according to their degree of softnees, into a series of cloths treated with various concentrations of a standard product, and on this basis the effectiveness of the respective softener was determined with a precision of about +10%.

Test performance The marked terry cloths (weight about 20 g) were washed at 80"C at a goodsto-liquor ratio of 1:10 with 6 g/l of a commercial normal-duty detergent and were rinsed five times with cold drinking water. After a short centrifuging (about 3 seconds) the cloths which now showed a given hard feel were ready for the aftertreatment.

A 1% aqueous dispersion (calculated on the active substance) was prepared from the softening agent to be tested and/or the ready-made softening composition.

2 Millilitres and 4 ml each of this dispersion were diluted with drinking water to 200 ml (corresponding to 0.1 and/or 0.2 g/l of softening active substance). The prepared terry cloths which were still moist were placed into these diluted solutions and were subsequently treated for 5 minutes at 200C in the launderometer. The goods-toliquor ratio was 1:10. Subsequently the test cloths were removed from the containers, were centrifuged for 5 seconds, then dried at a temperature of from 70 to 800C in the drying closet and subsequently stored for 24 hours in the climatic chamber at 200C and a relatively air humidity of 60%. Thereafter the feel was judged independently by 7 experts each time.

Evaluation As has already been mentioned above, the terry cloths treated with varying amounts of the test product were ranged, depending on their degree of softness, into a series of cloths treated with varying concentrations of a standard product (1 tallow fat-alkyl-amidoethyl-2-tallow fat-alkyl-3-methylimidazolinium-metho sulfate). The concentration sequence must naturally be adjusted to the corresponding effectiveness of the test product and needs to be modified accordingly, if necessary. In order to increase the reliability of the rest results, the test was repeated at least once. In this way a relatively precise value of the softening effect of a test substance was obtained as a mean value of all tests, as compared against a standard product.

According to this test method, the results specified in the following Table were obtained for the products of Examples 1 through 4. It became evident that the imidazolines of the formula I showed a markedly improved softening effect as compared against the comparable commercial fabric softening composition.

TABLE

Softening effect as compared against the standard Softening agent according to product 0.1 g Example 1 =0.12 g of standard product** 120% 0.2 g Example I = 0.24 g of standard product* * 120% 0.1 g Example 2=0.125 g of standard product** 125% 0.2 g Example 2 p 0.24 g of standard product** 120% 0.1 g Example 3 n 0.128 g of standard product** 128% 0.2 g Example 3 =0.25 g of standard product** 125% 0.1 g Example 4=0.125 g of standard product** 125% 0.2 g Example 4=0.26 g of standard product** 130% ** commercial softener on the basis of 1-tallow fat-alkyl-amido-ethyl-2-tallow fat alkyl-3-methyl-imidazolinium-methosulfate A fabric softening agent was prepared, which had the following composition:: 4% of distearyl-dimethyl-ammoniumchloride as softener 2% of imidazoline derivative of the formula I prepared by reacting 1.4 moles of stearic acid with 1 mole of D-hydroxyethyl-ethylene-diamine 4% of di-C8C,;-alkyl-dimethylammoniumchloride as disinfectant 0.5% of an addition compound of 12 moles of ethylene oxide to 1 mole of an oleyl alcohol having 14 to 16 carbon atoms as emulsifying agent.

balance to 100%: perfumes, dyestuff, optical brighteners and water.

The softening agent of the invention is prepared by melting the softening active substances with the emulsifying agent at a temperature of from 70 to 80"C.

Subsequently the quaternary ammonium compound having an antimicrobial effect was added by mixing. Afterwards the amount of water of the same temperature which was required for the adjustment of the desired concentration was added.

It is recommended to stir the reaction mixture until it has been cooled to about 50"C.

The perfuming should be effected at a temperature in the range of from 40 to 50"C. Only those products are suitable for the perfuming which are compatible with the cationic surfactants.

The product was a stable emulsion and did not show any signs of separation, neither after the quick test on the one hand -- examination of the emulsion stability at 3500 revolutions per minute within 2 hours in the centrifuge -- nor in the test at changing temperatures - examination of the emulsion stability in determined cycles at +50 C, room temperature and 40"C during 14 days - on the other hand.

After the temperature of the product had been adjusted to room temperature, there was no gel formation. As to the softening effect obtained, 100 g of the softening composition thus obtained were comparable with about 100 g of a commercial liquid fabric softener on the basis of distearyl-dimethyl-ammoniumchloride having a content of active substance of about 6%.

The softening effect of the fabric softener was tested by judging the feel of terry cloths.

In the examination of the disinfecting effect of the fabric softener according to Example 1 on the fabric sample treated therewith, in a washing process effected at 60"C, an inhibition zone of more than 2 mm diameter was observed for Staphylococcus aureus and E-coli; no colonies of microorganisms were to be observed on the treated fabric sample in the case of Pseudomonas aeruginosa.

A fabric sample washed at 950C and then treated with a commercial liquid fabric softener did not shown any growth inhibition of microorganisms, whereas the sample treated with the liquid fabric softening composition according to Example 1 showed germ-reducing properties. The use of the liquid fabric softening composition according to the invention also acted favorably on the rinsing bath with which the fabric was washed at 600 C, which fabric did not show any increase of microorganisms. The bacteriostatic examinations were carried out according to the inhibition zone test (cf. "Die antimikrobielle Ausrüstung von Textilien", Textilveredlung, 1970, 1, pages 3 through 14).

In a manner analogous to the method described above, the following softening dispersions were prepared: a) 60o/ of an imidazoline derivative of the formula I prepared by reacting 1.5 moles of stearic acid with 1 mole of p-hydroxyethyl-ethylene-diamine 4% of di-C8-C10-alkyl-dimethyl-ammoniumchloride 0.5% of an addition compound of 12 moles of ethylene oxide to 1 mole of an oleyl alcohol having from 14 to 18 carbon atoms; balance to 100 Ó: perfume, dyestuff, optical brighteners and drinking water.

b) 4 Ó of a disallow fat-alkyl-dimethyl-ammoniumchloride 2% of an imidazoline derivative of the formula I prepared by the condensation of 1.4 moles of stearic acid with 1 mole of p-hydroxyethyl-ethylene-diamine.

4% of di-C-C10-alkyl-dimethyl-ammoniumchloride 0.5 of an addition compound of 12 moles of ethylene oxide to I mole of an oleyl alcohol having from 14 to 18 carbon atoms; balance to 100, io: perfume, dyestuff, optical brighteners and drinking water.

c) 4 Ó of di-tallow-alkyl-monomethyl-monooxypropyl-ammoniumchloride 2% of an imidazoline derivative of the formula I prepared by the condensation of 1.6 moles of of stearic acid with 1 mole of 23-hydroxyethyl-ethylene-diamine.

4% of di-C8-C10-alkyl-dimethyl-ammoniumchloride 0.5% of an addition compound of 12 moles of ethylene oxide to 1 mole of an oleyl alcohol having from 14 to 18 carbon atoms; balance to 100%: perfume, dyestuff, optical brighteners and drinking water.

d) 4% of I tallow-alkyl-amido-ethyl-2-tallow-alkyl-3-methyl-imidazolinium- chloride 2% of an imidazoline derivative of the formula I prepared by the condensation of 1.8 moles of stearic acid with 1 mole of p-hydroxyethyl-ethylene-diamine 4% of di-CaC10-alkyl-dimethyl-ammoniumchloride 0.5% of an addition compound of 12 moles of ethylene oxide to 1 mole of an oleyl alcohol having from 14 to 18 carbon atoms; balance to 100%: perfume, dyestuff, optical brighteners and drinking water.

The properties of the products with regard to their application and in view of the stability of the fabric softener formulation, the judgment of the feel and the disinfecting effect on textile materials treated therewith are comparable to those of the liquid fabric softeners described before.

In the following Examples, three types of detergent have been chosen to represent the various possible variations of detergent formulations.

The composition of the detergents described in the Examples may be seen from the following Tables. The salt-like components contained in the detergents salt-like surfactants, other organic salts, as well as inorganic salts - are present as sodium salts, unless expressly stated otherwise; the percentages are per cent by weight, unless otherwise stated.

The expressions and/or abbreviations used have the following meanings: SAS alkane sulfonate, a sulfonate obtained from paraffin having from 13 to 18 carbon atoms via a sulfoxidation, ABS alkylbenzene-sulfonate, the salt of an alkylbenzene-sulfonate, the salt of an alkylbenzene-sulfonic acid having from 12 to 14 carbon atoms in the alkyl chain, which acid has been obtained by the condensation of straight-chain olefins with benzene and by sulfonating the alkylbenzene thus obtained, AOS olefin sulfonate, a sulfonate obtained from olefin mixtures having from 12 to 18 carbon atoms by sulfonating with SO3 and hydrolyzing the sulfonation product with lye, which sulfonate consists mainly of alkene sulfonate and oxyalkane sulfonate, but contains also a small amount of disulfonates, FAAS fat alcohol-ethersulfate prepared by the addition of 3 moles of ethylene oxide to 1 mole of a C,2C,4-alcohol and by the subsequent sulfonation with SO3 and neutralization with NaOH, N non-ionic surfactant prepared from 1 mole of a fat alcohol with a number of carbon atoms indicated each time, by reacting it with the number of moles indicated each time of alkylene oxide (EO = ethylene oxide).

soap: from a fatty acid mixture having from 16 to 22 carbon atoms, CMS carboxymethyl-cellulose, sodium salt.

The surfactant combinations T, to T7 used in the Examples contain as fabric softener an imidazoline derivative corresponding to the formula I from the series (a) through (d) described below: Preparation of the imidazoline derivatives (a) through (d): a) 52 g (0.5 mole) of aminoethyl-ethanolamine and 238 g (0.9 mole) of stearic acid were condensed for 5 hours at 1900C, while nitrogen was passed through the mixture, and for 3 hours at 1750C in vacuo at 25 Torr. 265 Grams of a colorless product were obtained (content of nitrogen showing an alkaline effect 1.6%, acid number 1.0), which was adjusted at 1000C to a pH of 4.7 (measured in a 1% solution) by means of 34.5 g of acetic acid. The product was brought into the form of a powder by way of comminution.

b) 156 g (1.5 moles) of aminoethyl-ethanolamine and 528 g (2.1 moles) of stearic acid were condensed for 4 hours at 1600C and for 2 hours at 180"C and 50 Torr., while nitrogen was passed through the mixture. 624 Grams of a yellowish product were obtained (content of nitrogen showing an alkaline effect 2.7%, acid number I .0) which was adjusted at 100% to a pH of 4.6 (measured in a 1 Ó solution) by means of 75 g of acetic acid. The product was brought into the form of a powder by way of comminution.

c) 104 g (I mole) of aminoethyl-ethanolamine and 324 g (1.2 moles) of stearic acid were reacted in a manner analogous to that of Example a).

d) 104 g (1 mole) of aminoethyl-ethanolamine and 432 g (1.6 moles) of stearic acid were reacted in a manner analogous to that of Example a).

In the reaction products a through d, the content of imidazoline is in the range of from 80 to 90% by weight.

Composition of the surfactant combinations containing softening agents T1 T2 T Components (% by wt.) (% by wt.) (% by wt.) T4 SAS 36 - - - ABS - 36 - - AOS - - 36 - N C18-C20-alcohol + 11 EO 12 12 12 N C9-C15-alcohol + 9 EO 30 N C9-C13-alcohol + 5 EO 30 Soap 12 12 12 Fabric softener a 40 - - b - 40 - c - - 40 - d - - - 40 Composition of the surfactant combinations containing softening agents T5 T, T7 Components (% by wt.) (%by wt.) (% by wt.) SAS 55 - - ABS 55 - AOS - - 55 FAAS 10 10 10 N C9-C15-alcohol + 5EO 5 5 5 Fabric softener a 30 - b 30 - c - - 30 Composition of the detergents W,/T1 W2/T2 W3/T3 Components (% by wt.) (% by wt.) (% by wt.) Surfactant combination 20 25 30 NasP3O,0 38 38 38 Na-perborate 20 20 20 Na-metasilicate 5 5 5 Na-magnesium-silicate 3 3 3 Carboxymethyl-cellulose 2 2 2 Optical brightener 0.3 0.3 0.3 Balance to 100% = water Composition of the detergents W4/T4 W5/T4 We/T4 W,/T4 Components (% by wt.) (% by wt.) (% by wt.) (% by wt.) Surfactant combination 15 20 25 30 NaP30,0 32 32 32 32 Na-pyrophosphate 14 14 14 14 Metasilicate with 4 H2O 9 9 9 9 CMC 3 3 3 3 Optical brightener 0.3 0.3 0.3 0.3 Balance to 100% = sodium sulfate and water Composition of the detergents W8/T5 Wg/Te Wlo/T7 Components (% by wt.) (% by wt.) (% by wt.) Surfactant combination 30 35 40 Sodium sulfate 45 40 35 Na2P3O,o 12 12 12 Na2O SiO2 4 4 4 CMC 3 3 3 Balance to 100% = water As optical brighteners there were used cotton brighteners, polyamide brighteners, polyester brighteners, or combinations thereof, depending on the purpose of application of the detergents.

The fabric-softening effect of the imidazoline derivatives used according to the invention in the detergent compositions of the invention was shown by means of a washing test as follows: EXAMPLE W".

The washing test was carried out with detergents of the invention having the following composition: 10% of an imidazoline derivative from the series (a) through (d) 12% of SAS 4% of N(tallow fat-alcohol + 11 EO) 4% of soap 40% of sodiumtripolyphosphate 5% of sodium-metasilicate 3% of magnesium silicate 2% of CMC Balance to 100%: sodium sulfate and water.

The detergent used in the control test (e) contained another 10% by weight of sodium sulfate instead of the imidazoline derivatives.

Method Samples of new terry cloth, as well as samples of cotton terry fabric having a hard feel, were washed three times each at 60OC with ballast material (goods-toliquor ratio from 1:5 to 1:8) in a washing bath containing 4.3 g/l of the abovementioned detergent composition having a content of the imidazoline derivative to be tested in a cylinder washing machine (AEG Lavamat Regina de Luxe).

As a control, 4.3 g/l of the above-mentioned detergent which was free from fabric-softening agents were used.

After each washing the fabric was rinsed and dried while hanging and was subsequently left in the climatic chamber for 24 hours at 200C and a relative air humidity of 60%. As other testing methods were unfeasible, the softening effect obtained in the washing tests was determined by having the feel judged independently by 7 experts each time.

The judgment of the feel was expressed in feel marks in the range of from 0 to 100, with 100 standing for a full and very soft feel, and 0 representing a very hard feel.

The limiting values of 0 and 100 have been established as follows: Samples of new cotton terry cloth were treated 10 times in the washing machine by being washed in the boiling state in water with a commercial normalduty detergent. After drying, the fabric now has a hard feel and it was given the feel mark of 0.

Samples of a new cotton terry fabric were freed from their finishing and treated with a solution of di-stearyl-dimethyl-ammoniumchloride (1 g of active substance of the softener per kg of material). The fabric thus softened was given the feel mark of 100.

Detergent Wtl with fabric softener Feel mark (imidazoline derivative a) through d) 1st test 2nd test 3rd test a 80 80 80 b 70 70 70 c 80 80 80 d 60 60 60 e (control without softener) 0 0 0 Result If a detergent according to the invention was used, which had a content of imidazolines as fabric softeners (Examples W,1 a through d), a fabric with a hard feel was softened in a distinctive manner, as compared against the control test e).

The improvement of the feel of the pre-hardened fabric was in Examples W a) through d) in the range of from 60 to 80%.

In contradistinction thereto, the pre-hardened fabric was still judged by the feel mark of 0 after the washing with detergents that were free from softening agents according to the control test e).

The detergent compositions of the invention showed their fabric-softening effect particularly in delicate articles and easy-care materials made of cotton, polyester, polyacrylonitrile and polyamide, especially in the processing as woven and knitted fabrics which are washed at a temperature of from 20 to 700 C, preferably from 30 to 600 C. The washing may also be performed, however, at higher temperatures. The textile materials thus washed showed after drying a remarkably pleasant and soft feel.

The feel of fabrics which had already been hardened was improved in an excellent way by washing with the detergents of the invention. This treatment imparted an antistatic effect to the textile materials.

WHAT WE CLAIM IS: 1. A textile fabric softener composition consisting of an aqueous solution or dispersion of an imidazoline of the general formula I or a salt thereof or a mixture of such imidazolines or salts thereof -

in which R is an aliphatic radical having from 13 to 21 carbon atoms, n is 2 or 3, and X is hydrogen or an acyl group of the formula RCO- II in which R has the above-mentioned meaning.

2. A textile fabric softener composition as claimed in claim 1 containing from 1 to 15% by weight of an imidazoline of the formula I or a mixture of imidazolines of the formula I.

3. A textile fabric softener composition as claimed in claim 1 containing from 20 to 35% by weight of an imidazoline of the formula I or a mixture of imidazolines of the formula I.

4. A textile fabric softener composition consisting of a textile fabric softener composition as claimed in claims 1 or 2 together with 1 to 6% by weight of a cationic disinfectant.

5. A textile fabric softener composition as claimed in claim 4 containing 2 to 6% by weight of an imidazoline of formula I.

6. A textile fabric softener composition as claimed in claims 4 and 5 containing as cationic disinfectant a compound of the formula V and/or VI

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. The improvement of the feel of the pre-hardened fabric was in Examples W a) through d) in the range of from 60 to 80%. In contradistinction thereto, the pre-hardened fabric was still judged by the feel mark of 0 after the washing with detergents that were free from softening agents according to the control test e). The detergent compositions of the invention showed their fabric-softening effect particularly in delicate articles and easy-care materials made of cotton, polyester, polyacrylonitrile and polyamide, especially in the processing as woven and knitted fabrics which are washed at a temperature of from 20 to 700 C, preferably from 30 to 600 C. The washing may also be performed, however, at higher temperatures. The textile materials thus washed showed after drying a remarkably pleasant and soft feel. The feel of fabrics which had already been hardened was improved in an excellent way by washing with the detergents of the invention. This treatment imparted an antistatic effect to the textile materials. WHAT WE CLAIM IS:

1. A textile fabric softener composition consisting of an aqueous solution or dispersion of an imidazoline of the general formula I or a salt thereof or a mixture of such imidazolines or salts thereof -

wherein R5 and R, are alkyl or alkenyl having from 8 to 12 carbon atoms, R7 is alkyl or alkenyl having from 8 to 18 carbon atoms, R8 and R9 are hydrogen, chlorine or bromine, and A is chlorine or bromine.

7. A textile fabric softener composition as claimed in claims 4 to 6 containing 2 to 4% by weight of the cationic disinfectant.

8. A textile fabric softener composition consisting of a textile fabric softener composition as claimed in claims 4 to 7 together with 0 to 15% by weight of a cationic fabric softener.

9. A textile fabric softener composition as claimed in claim 8 containing as a cationic fabric softener a compound of the formulae II, III and/or IV

in which R1 and R2 are alkyl or alkenyl radicals having from 12 to 20 carbon atoms, R3 is hydrogen or a methyl group, R4 is a preferably saturated aliphatic radical having from 13 to 21 carbon atoms, x is 1 to 5, A is chlorine or bromine or CH3SO4.

10. A textile fabric softener composition consisting of a textile fabric softener composition as claimed in claims 4 to 9 together with 0 to 1% by weight of a nonionic dispersing agent.

11. A textile fabric softener composition as claimed in claims 1 to 10 containing an imidazoline of the formula I or a mixture of imidazolines of the formula I wherein R is alkyl of 15 to 17 carbon atoms and n is 2.

12. A textile fabric softener composition consisting of a textile fabric softener composition as claimed in claims 4 to 11 together with one or more known textile fabric softener additives.

13. A detergent composition for textile materials which comprises a surfactant or mixture of surfactants in admixture with an imidazoline of the general formula I given in claim 1.

14. A detergent composition as claimed in claim 13, wherein the surfactant comprises anionic and/or hybrid-ionic and/or non-ionic surfactants.

15. A detergent composition as claimed in either claim 13 or claim 14, which has the following composition: (a) from 4 to 70% by weight of surfactant component containing at least one anionic or hybrid-ionic or non-ionic surfactant, and (b) from 3 to 20% by weight or one or more imidazolines of the general formula I, and (c) one or more known detergent additives which make up the balance of the 100% by weight.

16. A detergent composition as claimed in claim 15, wherein component (a) contains up to 70% of non-ionic surfactant.

17. A detergent composition as claimed in claim 16, wherein component (a) contains up to 10% of non-ionic surfactant.

18. A detergent composition as claimed in any one of claims 15 to 17, which contains from 6 to 60% by weight of component (a).

19. A detergent composition as claimed in any one of claims 15 to 18, which contains from 5 to 15% by weight of component (b).

20. A detergent composition as claimed in any one of claims 15 to 19, wherein component (c) comprises one or more additives selected from builders, complexing agents, bleaching components, foam stabilizers, foam inhibitors, anti-redeposition agents, enzymes, optical brighteners, perfumes, dyestuffs and water.

21. A detergent composition as claimed in claims 13 to 20 containing as an imidazoline compound of formula I the reaction product from hydroxyethylethylene-diamine and stearic acid.

22. A process for softening textile materials, which comprises treating the material with a fabric softener composition as claimed in any one of claims I to 12.

23. A process for washing textile materials, which comprises treating the material with a detergent composition as claimed in any one of claims 13 to 21.