EP0874802A1

EP0874802A1 - Fatty acid derivatives and the use thereof as surface active agents in washing and cleaning agents

Info

Publication number: EP0874802A1
Application number: EP96937203A
Authority: EP
Inventors: Alfred Oftring; Martin Aus Dem Kahmen; Christian Ott; Günter OETTER; Richard Baur
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1995-10-27
Filing date: 1996-10-21
Publication date: 1998-11-04
Also published as: US6320064B1; WO1997016408A1; US6004923A; US6057283A; US6380410B1; US6204238B1

Abstract

The fatty acid derivatives described are based on epoxidized unsaturated fatty acid esters or triglycerides and are reacted with amines such as hydroxy- and/or amino-substituted hydrophilic amines or amino acids and/or with alkanoles or with water on the epoxy group and/or the carboxylic ester group. These fatty acid amides can be used as surface active agents in washing and cleaning agents.

Description

Fatty acid derivatives and their use as surfactants in washing and cleaning agents

description

The present invention relates to the use of fatty acid derivatives of the general formula I

-co- R ^l

as surfactants for cleaning agent systems for cleaning grease-soiled non-textile material, where the substituents have the following meaning:

A ^{1 is} an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain, which contains one or more groups of the formula II in the chain

CH CH

I I II

N OH

^Λ contains;

R ^{1 is} a radical -N (R ² ) R ³ , a hydroxyl radical and its alkali or ammonium salts, a C ₁ -C ₄ alkoxy radical or a radical of a mono-, di- or triglyceride, the latter two radicals being more natural saturated or unsaturated fatty acids or the same or different radicals A ¹ ;

R ^{2 is} a hydrophilic radical with 2-40 C atoms;

R3 is hydrogen, a C 1 -C ₄ -alkyl radical or one of the radicals R ² .

The invention also relates to the new fatty acids of the formula I a

A ⁱ -COOR ⁴ la O 97/16408 „, - ,, -

PCT / EP96 / 04560

2 in which R ^{4 is} hydrogen or an alkali metal or ammonium cation of the corresponding fatty acid salt and A ^{1 has} the meaning given above and its use as surfactants. The invention also relates to surfactant formulations which contain the compounds I and Ia.

DE-A 27 34 596 discloses fatty acid derivatives of type I as active washing substances for washing textiles.

In order to clean non-textile surfaces, surfactants must have additional properties such as good fat-removing properties. Such cleaning processes are mainly found in the metal industry, in the food industry, in GabtsLütter. commercial and household. For example, metal objects often have to be freed of drawing and rolling greases after they have been processed. In the other areas mentioned as well, the primary task is to free equipment and containers from greases of different origins, since greases prevent the wetting of other dirt particles.

The invention was based on the use of surfactants for aqueous cleaning agent systems for cleaning non-textile material with a better fat-removing ability as an object.

Accordingly, the use of the amino hydroxy fatty acid derivatives I defined at the outset for the cleaning of non-textile fat-soiled materials, the compounds Ia as new substances and formulations comprising I have been found.

The compounds I are known per se by epoxidation of fatty acid esters III

^ ^K

A ² C III

^' B ^l

and further reaction of the epoxidized products IV with an amine V

^ R ²

H N V

^ "R3 accessible by opening the epoxy ring. A ² here stands for an unsaturated residue which corresponds to the saturated or partially saturated residue A ¹ in I, and B ¹ means the residue of a 1- to 3-valent aliphatic Ci-C _ß alcohol. If it is a polyhydric alcohol, its remaining hydroxyl groups can also be esterified, preferably with fatty acids.

Depending on the selected ratio III to V, the epoxy groups mainly react with the amine V. In the case of an excess of amine, B ^{1 is} replaced by the radical -N (R ² ) R ³ .

The new fatty acids or their alkali metal salts can be prepared, for example, from known reactions such as alkaline hydrolysis and, if desired, acidification, from the reaction obtained from the reaction.

The likewise new ammonium salts are preferably obtainable directly from the epoxidized fatty acids by reaction with V. In this case, the preferred ammonium salts are obtained with ®NH ₂ ^R2 R ³ as the cation, in which R ² and R ^{3 have the} same meanings as in the amino group of the fatty acid ester. Any ammonium salts can be prepared by subsequent reaction of a fatty acid Ia 'with an amine.

As unsaturated, unbranched aliphatic fatty acids from which the esters III are derived, ricinoleic acid can be considered as unsaturated hydroxy fatty acid, but preferably:

- monounsaturated C ₉ -C ₂₅ fatty acids such as Petroselin acid, undecenoic acid, Δ ⁹ -Decylensäure, Δ ⁹ -Dodecylensäure, vaccenic, palmitoleic acid, erucic acid and especially oleic acid

- Di-unsaturated C ₉ -C ₂₅ fatty acids such as stilingic acid prefer linoleic acid

triple unsaturated fatty acids such as elaeostearic and preferably linolenic acid.

Unsaturated Ciβ fatty acids are particularly suitable because of their good availability. The acids obtainable by isomerization of the double bond are also suitable. 4

Fatty acid or fatty acid ester mixtures, such as are obtainable, for example, by transesterification or saponification of natural fats with C ₁ -C ₄ alcohols, can also be used.

The preparation of the compounds I is preferably based on natural fats, that is to say the glycerol esters which contain at least one unsaturated radical A ² . Such natural fats are, for example, olive oil, cottonseed oil, linseed oil, tallow, fish oils, tall oils, castor oil, coconut oil, camelina oil, sunflower oil, peanut oil, palm oil, euphorbia oil and above all soybean oil and turnip oil.

The epoxidation is carried out in a manner known per se by reacting compound III with peracids such as performic acid and peracetic acid. However, some epoxidized fatty acid esters IV are also commercially available.

The amines V are primary or secondary amines with at least one hydrophilic aliphatic C ₂ -C ₄ n radical. The amines can be branched and carry several hydroxyl or amino groups, such as (trishydroxymethylene) methylamine, but preferably have at least one unbranched ω-hydroxyalkyl radical or an ω-aminoalkyl radical with 2 to 6 carbon atoms, the alkyl radical being formed by non-adjacent oxygen atoms, -NH groups, NC ₁ -C ₄ alkyl groups or NC ₁ -C ₄ hydroxyalkyl groups can be interrupted. Furthermore, the N -CC ₄ -alkyl-substituted derivatives are suitable if they still contain at least one reactive amino or imino group. The following are preferred:

- Hydroxyalkylamines such as mono- and diethanoiamine, mono- and diisopropanolamine, 2- (2-aminoethoxy) ethanol, 2- [(2-aminoethyl) amino] ethanol, 3-aminopropanol and N-alkyl-substituted hydroxyalkylamines such as methylethanolamine, n-propylethanolamine , Butylethanolamine, 2-aminobutanol-1 and particularly preferably aminopropyldiethanolamine.

Aminoalkylamines such as ethylenediamine, trimethylenediamine, 1,2-propylenediamine, 3-amino-1-methylaminopropane, diethylenetriamine, dipropylenetriamine, N, N'-bis (3-aminopropyl) ethylenediamine, 3- (2-aminoethoxy) propylamine , 2- (2-aminoethoxy) ethylamine, 3- (3-aminopropoxy) propylamine and their symmetrical and unsymmetrical N-substituted mono- and dialkyl derivatives such as N, N-dimethylaminopropylamine, diethylaminoethylamine, diethylaminopropylamine, 1-diethylamino 4-aminopentane, neopentane diamine, hexamethylene diamine 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-l, 13-diamine, 3- (2-aminoethyl) aminopropylamine.

Also preferred amines that lead to products with favorable properties are polyalkylene glycol amines of the general formula VI,

R4 (OC _n H _2n ) y (OC ₂ H ₄ ) χ (0 C _n H _2n ) _z NH ₂ VI

in the

ii a Zaύxl 2,3 or 4 x a number from 1 to 10 y and z a number from 0 to 10

R ^{4 is} hydrogen or a C1-C4 alkyl radical

with a total of 3 to 40, especially 3 to 20 carbon atoms. These known amines are usually obtained by alkoxylation of aliphatic C ₁ -C ₄ alcohols or ethylene glycol and subsequent amination. The alkoxylation can take place both with ethylene, propylene and / or butylene oxide and also with their mixtures.

Suitable amines are, for example, methylglycolamine and methyltetraglycolamine.

The reaction of the epoxidized fatty acid esters, acids or their salts with the amines is generally carried out at 30 to 170 ° C., preferably in the presence of an alkaline catalyst such as alkali metal hydroxides, carbonates or alcoholates, for example sodium methylate. The reaction is complete when no more epoxy groups can be detected. At 100 ° C the reaction is complete after about 2 to 4 hours.

The reaction can be carried out in the presence of a solvent, but this is usually not necessary, so that one preferably works without a solvent.

The amine is generally used in a stoichiometric to 10 molar amount, preferably a stoichiometric to 2.5 molar amount per epoxy unit. If epoxidized fatty acids are reacted, the reaction with at least 2 equivalents of amine is recommended, since part of the amine reacts to form the ammonium salt. 6

By reaction of the fatty acid esters with the amines, stoichiometric conversion gives, above all, fatty acid esters as reaction products, while reaction with 1.4 to 10 equivalents of the amine predominantly gives the fatty acid amides. A larger excess of amine is possible, but may require subsequent removal of the unreacted amine. Both the esters and the amides, as non-ionic surfactants, have an excellent fat-dissolving power, with the fatty acid amides being somewhat more water-soluble. Furthermore, the acids and salts have very good fat-dissolving power and very good water solubility, so that they are well suited as anionic surfactants.

When the epoxidized compound IV is reacted with the amines V, isomer mixtures are generally obtained since the oxirane rings can open at both C — O bonds.

Assuming natural fats, a reaction mixture is obtained which, in addition to the compounds I, may also contain glycerol and possibly the amides of saturated fatty acids. This

However, substances do not have to be separated off for the use according to the invention, since they do not interfere.

In application tests, the aminohydroxyfatty acid derivatives I show good fat-dissolving properties, such as are necessary for surfactants in aqueous cleaning systems on non-textile surfaces. The surfactants I also show good foam damping behavior. The cleaning processes described at the outset are predominantly mechanical processes in which the use of foam-suppressing surfactants is important. Since there is a strong circulation of water during machine cleaning, a lot of foam is otherwise generated, which weakens the mechanical cleaning power. Because of this extremely good foam damping behavior, the surfactants I are also suitable for use in

Agents, such as rinse aids for the dishwasher, in which the fat-removing ability is of little importance.

In addition to cleaning dishes, the surfactants are also suitable for cleaning all non-textile surfaces such as metal, lacquered wood, plastic or ceramic products, for example porcelain, tiles, tiles, which occur in the household and in trade. The agents can be applied manually, for example, with a damp cloth or sponge, or by spray cleaning. 7

The agents are usually marketed in the form of aqueous concentrates and can be used diluted or undiluted. Common cleaners for non-textile surfaces are, for example, car window cleaners, car shampoos, oven cleaners, window / synthetic leather cleaners, plastic cleaners, sanitary cleaners, abrasives and tub cleaners.

The fatty acid derivatives I according to the invention are therefore particularly suitable for aqueous cleaning systems for grease-soiled non-textile surfaces, since, in addition to their good ability to remove grease, they also have good foam damping properties. The nonionic surfactants, in particular from the group of fatty acid amines, are particularly preferred for the use according to the invention. Since ..-- Lei, they are easily accessible and readily biodegradable.

According to the invention, the aqueous-based cleaning agent systems for cleaning non-textile materials contain Tenide I, their mixtures and, if appropriate, builders, solvents or solubilizers and other additives customary for such agents in the amounts customary for the agents. It is possible to use surfactants I in combination with anionic or non-ionic surfactants such as mentioned in DE-A 27 34 597 to use.

Well-suited rinse aids for dishwashers contain e.g.

10 to 40, preferably 15 to 30% by weight of I

5 to 30% by weight of a solution mediator such as alcohol or cumene sulfonate and

1 to 20% by weight of other customary additives such as acids, for example citric acid or dicarboxylic acids.

A hand dishwashing detergent consists, for example, of 5 to 50, preferably 5 to 30,% by weight of I

5 to 30% by weight of a solubilizer such as cumene sulfonate or alcohol and

0.5 to 5% by weight of skin protection agents, fragrances and dyes.

A composition according to the invention of a dip degreasing agent for metal objects consists, for example, of 1 to 10, preferably 1 to 5% by weight of I and 10 to 70% by weight of alkaline builders. Examples

A. Preparation of the fatty acid derivatives I (Examples 1 to 5)

A mixture of n mol of an amine V and 29 g of a 30% strength methanolic sodium methoxide solution was mixed with 1 mol of an epoxidized fatty acid ester with stirring at 80 ° C. The mixture was then stirred at 90-95 ° C for 4 hours. The reaction products were obtained as viscous liquids.

B. Application properties of the aminohydroxy fatty acid derivatives

The fat-removing ability, the cloud point, the foaming power, the surface tension and the foam attenuation in the dishwasher of aqueous preparations were investigated as the application properties of the aminohydroxyfatty acid derivatives I.

To determine the fat-dissolving capacity, solid platelets wetted with motor oil or olive oil were immersed horizontally in the surfactant solution to be investigated (c = 1 g / l). The time until the first oil drop was removed from the respective plate was measured. The shorter this time, the better the fat loss capacity.

The measurement results of the fat dissolving power of the substances in Examples 1 to 5 can be found in Tables 1 and 2.

The cloud point was determined in accordance with DIN 53917. The temperature above which the solution becomes cloudy and is therefore a mixture of two liquid phases was determined. The lower the cloud temperature, the lower the foaming power.

The foaming power was determined in accordance with DIN 53902 by measuring the foam volume in ml one minute after the end of foam generation.

The surface tension was determined according to DIN 53924 by measuring the force in mN / m which is necessary to pull a plate or a horizontally suspended ring out of the liquid surface.

The foam damping behavior in the dishwasher was checked by the so-called "egg test". Foam was produced in a commercial household dishwasher by adding an egg and the average number of revolutions of the spray arm per minute was reached during a twelve-minute heating-up phase. averages. The formation of foam reduces the number of revolutions due to the reduced recoil force and thus represents a measure of the suitability of surfactants in cleaning machines.

The measurement results of the substances in Examples 1 to 3 below are shown in Table 3.

Table 2

Table 3

BDG = butyl diglycol

H n

9 \

The present invention further relates to alkoxylated fatty acid derivatives VII, obtainable by reacting the compounds VIII

A ² CO R ⁵ VIII, where the substituents have the following meanings:

A ^{2 is} an aliphatic Cβ-C ₂₄ radical with unbranched carbon chain, which contains one or more groupings of the formula IX in the chain

CH CH

N OH IX

/ \

R6 R ⁷

contains;

R ^{5 is} a radical -N (R ⁶ ) R ⁷ , a hydroxyl radical and its alkali metal or ammonium salts, a C ₁ -C ₄ alkoxy radical or a radical of a mono-, di- or triglyceride, the di- or triglyceride radicals Residues of natural saturated or unsaturated fatty acids or identical or different radicals A ² are and

R ⁶ and R ⁷ independently of one another are hydrogen, an unsubstituted C ₁ -C ₆ -alkyl radical or a C ₁ -C ₁₄ -alkyl radical which is hydroxyl-, amino-substituted and / or aminocarbonyl-substituted and / or by non-adjacent oxygen atoms, -NH groups and / or NC ₁ -C ₄ alkyl groups can be interrupted and / or the radicals -COOH or -SO ₃ H and their alkali metal salts or ammonium salts,

with 3 to 15 equivalents of ethylene oxide, propylene oxide and / or butylene oxide per equivalent IX.

In addition, the invention relates to novel fatty acid derivatives villa, the production of these fatty acid derivatives VII and villa, their use as surfactants in detergents and cleaning agents and formulations with these surfactants. 13

DE-A 16 19 081 discloses alkoxylation products of quaternary ammonium hydroxy fatty acid derivatives in softening agents for textiles.

Furthermore, DE-A 27 34 596 and DE-A 27 34 597 describe the uses of aminohydroxystearic acid amides or esters as detergent active substances in detergents or cold detergents.

EP-A-0 633 243 describes a production process for β-hydroxylated secondary and tertiary amines. The products obtained by reacting epoxidized olefins such as epoxydodecane with amino acids are surface-active substances and are therefore suitable for numerous uses.

The aim of the present invention was to provide surfactants with advantageous properties.

Accordingly, the alkoxylated fatty acid derivatives VII defined at the outset, the fatty acid derivatives serving as starting compounds, a process for the preparation of VII and Villa, their use as surfactants in detergents and cleaning agents and formulations comprising VII or Villa were found.

The alkoxylated fatty acid derivatives VII are obtained by reacting VIII with 3 to 15 equivalents of ethylene oxide, propylene oxide and / or butylene oxide per equivalent IX. The compounds VIII generally contain several reactive groups, but at least one hydroxyl group, which can be alkoxylated. The optionally present hydroxyl, -NH-, -NH ₂ and carboxylic acid residues of R ⁵ , R ⁶ and R ⁷ are also alkoxylated. Insertion by alkylene oxide can also be observed in the case of ester groups. Since the compounds VIII are reacted with at least the three-molar amount of alkylene oxide per mole VIII, product mixtures are obtained. As a rule, one would like to obtain water-soluble compounds with good lipophilic properties and vice versa. Mixtures with already good hydrophilic properties are obtained by the reaction with at least 3 equivalents, those with already good lipophilic properties are obtained by the reaction with at most 12 equivalents of alkylene oxide per equivalent IX.

The compounds are preferably reacted with ethylene oxide and / or propylene oxide, particularly preferably with ethylene oxide, since these products are particularly readily biodegradable. The reaction with several alkylene oxides can be carried out in succession or directly with a mixture. 14

The reaction takes place under known alkoxylation conditions, preferably in the presence of an alkaline catalyst such as potassium hydroxide, sodium hydroxide, sodium methoxide or potassium tert-butoxide. It is possible to carry out the reaction both under pressure and under pressure, preferably at a pressure of 1-20 bar, particularly preferably at 1.5-10 bar. In an advantageous embodiment, the alkylene oxide is added in portions.

The reaction takes place at room temperature, but is preferably carried out in a temperature range of 80-120 ° C. and results in mixtures above 150 ° C. in which the proportion of alkoxylated amino groups is increased. The ReaKtionsαauex beL -.--. YL Je-Lei depending on the selected temperatures between 0.5 and 10 hours, 5 whereby low temperatures require a longer reaction time and vice versa.

The use of inert solvents such as toluene or xylene is possible, but it is more advantageous not to use an additional solvent, since there is no need to separate off the solvent.

Compounds of the general formula VIII 5 are used as fatty acid derivatives VIII

A ² CO R ⁵ VIII

used with the radicals defined above. The compounds VIII 0 are in a manner known per se by epoxidizing fatty acids or their salts or esters

. ^ XI 5 R ^H and further implementation of the epoxidized products X with an amine XII

0 R6

HN ^XI1

"^ R ⁷ accessible by opening the epoxy ring. D stands for 5 an unsaturated radical which corresponds to the saturated or partially saturated radical A ² in VIII, and R ¹¹ denotes a hydroxyl radical and its alkali metal or ammonium salts or the 15

Remainder of a 1- to 3-valent aliphatic C -C -C alcohol. If it is a polyhydric alcohol, its remaining hydroxyl groups can also be esterified, preferably with fatty acids.

R ¹¹ can also be replaced by the radical -N (R ⁶ ) R ⁷ .

The fatty acids or their alkali metal salts can be prepared from the esters or amides optionally obtained by the reaction, for example by known reactions, such as alkaline hydrolysis and, if desired, acidification.

The ammonium salts are preferably αire-ct from the epoxidite-rLer. Fatty acids obtainable by reaction with XII. In this case, the preferred ammonium salts are obtained with ®NHR ⁶ R ⁷ as the cation, in which R ⁶ and R ^{7 have the} same meanings as in the amino group of the fatty acid ester. Any ammonium salts can be prepared by subsequent reaction of a fatty acid VIII with an amine.

As unsaturated, unbranched aliphatic fatty acids, from which the epoxidized fatty acid derivatives X are derived, ricinoleic acid can be considered as unsaturated hydroxy fatty acid, but preferably

monounsaturated C ₉ -C ₂₅ fatty acids such as petroselinic acid, undecenoic acid, Δ ⁹ -Decylensäure, Δ ⁹ -Dodecylsäure, vaccenic acid, palmitoleic acid, erucic acid, and especially oleic acid

- C ₉ -C ₂₅ di-unsaturated fatty acids such as stilingic acid, preferably linoleic acid

Unsaturated Ciβ fatty acids are particularly suitable because of their good availability.

The acids obtainable by isomerization of the double bond are also suitable.

Fatty acid or fatty acid ester mixtures, such as those obtainable, for example, by transesterification or saponification of natural fats with C ₁ -C ₄ alcohols, preferably methanol, can also be used. 16

The preparation of the compounds VII is preferably based on natural fats, that is to say the glycerol esters, which contain at least one unsaturated radical D. Such natural fats are, for example, olive oil, cottonseed oil, linseed oil, tallow, fish oils, tall oils, castor oil, coconut oil, hemp oil, sperm oil, lard, tallow, goose fat, beef tallow, claw oil, tallow fatty acid, camelot oil, sunflower oil, peanut oil, palm oil and Euphor all soybean oil and rapeseed oil.

The epoxidation is carried out in a manner known per se by reacting the compound XI with peracids such as performic acid and peracetic acid. However, some epoxidized fatty acid derivatives X are also commercially available.

The amines XII are ammonia, primary or secondary amines with an unsubstituted Ci-Cε-alkyl radical or a substituted C ₁ -C ₁₄ -alkyl radical.

The amines can be branched and carry several hydroxyl or amino groups, such as (trishydroxymethylene) methylamine, but preferably have at least one unbranched ω-hydroxyalkyl radical or an ω-aminoalkyl radical with 2 to 6 C atoms, the alkyl radical being formed by non-adjacent oxygen atoms, NH groups or NC _3. -C ₄ alkyl groups can be interrupted. Furthermore, the N-C 1 -C ₄ -alkyl-substituted derivatives are suitable if they still contain at least one reactive amino or imino group.

Suitable aliphatic amines are short-chain secondary amines, for example C ₁ -C ₆ -alkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, the corresponding mixed-substituted amines, for example methylethylamine, and primary amines, for example C ₁ -C ₆ -alkylamines such as methylamine, ethylamine, propylamine, Butylamine, pentylamine and hexylamine and branched amines, for example isopropylamine. Of these, the reaction products VIII of the primary amines are preferred since they contain an alkoxylatable imino group.

Preferred substituted amines are the reaction products VIII of the following amines:

Hydroxyalkylamines such as mono- and diethanoiamine, mono- and diisopropanolamine, 2- (2-aminoethoxy) ethanol, 2 - [(2-aminoethyl) amino] ethanol, 3-aminopropanol, aminopropyldiethanol-εutiine, aminosorbitol, glucamine and N-alkyl-substituted Hydroxyalkylamines such as methylethanolamine, n-propylethanolamine, butylethanolamine, N-methylglucamine and 2-aminobutanol-l, 17

Aminoalkylamines such as ethylenediamine, trimethylenediamine, 1,2-propylenediamine, 3-amino-1-methylaminopropane, diethylenetriamine, dipropylenetriamine, N, N'-bis (3-aminopropyl) ethylenediamine, 3- (2-aminoethoxy) propylamine, 2- (2-aminoethoxy) ethylamine, 3- (3-aminopropoxy) propylamine and their symmetrically and asymmetrically substituted mono- and dialkyl derivatives such as N, N-dimethylaminopropylamine, diethylaminoethylamine, diethylaminopropylamine, 1-diethylamino-4-aminopentane, Neopentan¬ diamine, hexamethylene diamine, 4,9-dioxadodecane-l, 12-diamine, 4,7,10-trioxatridecane-l, 13-diamine, 3- (2-aminoethyl) aminopro¬ pylamine.

Furthermore, the nurses can be amino acids l-cu.κlei_.ι.

The reaction of the epoxidized fatty acid derivatives with the amino acids leads to the new fatty acid derivatives Villa of the general formula

A ³ - CO R ⁸ villa

where the substituents have the following meaning:

A ^{3 is} an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain which contains one or more groupings of the formula IXa in the chain

CH CH

N OH IXa

/ \

R ⁹ R ^IO

contains

R ^{8 is} a radical -N (R ⁶ ) R ⁷ , a hydroxyl radical and its alkali metal or ammonium salts, a C ₁ -C ₄ alkoxy radical or a radical of a mono-, di- or triglyceride, the latter two radicals being more natural saturated or unsaturated fatty acids or the same or different radicals A ³ and

R ^{9 is} a Cχ-C ₆ -alkyl radical which can be hydroxy-, amino-substituted and / or aminocarbonyl-substituted and / or can be interrupted by non-neighboring NH groups and a radical 18th

-SO ₃ H or at least one residue -COOH and their alkali metal salts or ammonium salts and

R ^{10 is} hydrogen or one of the radicals R ⁹ .

Amino acids NHR ⁹ R ^{10 are} to be understood as aliphatic carboxylic acids or sulfonic acids with amino and / or imino groups. The carboxylic or sulfonic acids are preferably unbranched. They can also carry further acid or acid amide groups and can optionally be substituted with hydroxyl radicals. It is irrelevant for the effect of VII and Villa whether D or L forms or mixtures are used. The known amino acids are generally readily accessible, for example, by means of the Strecker reaction. A large part is also still commercially available. Examples of suitable amino acids are:

Monocarboxylic acids such as valine, leucine, isoleucine, ornithine, citrulline, serine, threonine, preferably alanine, arginine, lysine, particularly preferably glycine and sarcosine

Dicarboxylic acids such as asparagine, aspartic acid, glutamine, glutamic acid, particularly preferably iminodiacetic acid and ethylenediaminediacetic acid

Tricarboxylic acid such as aspartic acid monoacetic acid and

Sulfonic acids such as N-methyl taurine and taurine.

The reaction of the epoxidized fatty acid esters, acids or their salts with the amines is generally carried out at 30 to 280 ° C., preferably 80 to 140 ° C., preferably in the presence of an alkaline catalyst such as alkali metal hydroxides, carbonates or alcoholates for example sodium methylate. The reaction is complete when no more epoxy groups can be detected. For example, the reaction at 120 ° C. is complete after 2 to 4 hours.

The reaction can be carried out in the presence of a solvent, but this is usually not necessary, so that the process is preferably carried out without a solvent.

If the amines are not liquids, but solids such as amino acids, their implementation as a suspension in water-soluble or partially water-soluble solvents is preferred. For example, polyhydric alcohols and especially glycerin, ethylene glycol and

Propylene glycol, as they can then remain in the product. As a rule, the amino acid partly as a solution and partly undissolved 19 is present, in a preferred embodiment the Na salt of the amino acid is introduced in, for example, propylene glycol with the alkali catalyst and the epoxidized compound XI is added. Reaction temperatures of 60 to 200 ° C., in particular 100 to 180 ° C., are advantageous here.

Another advantageous process starting from solid amines is the reaction in the melt. For this purpose, temperatures are required at which the mixture is in the form of a melt, which may well be below the fixed point of the amino acid itself, generally above 200 ° C. Depending on the beginning decomposition of the amino acids, the preferred upper temperature range is 220 to 2bU ° C. In a voxLeiilial-.eu embodiment, the amino acid is dissolved in a little water and heated together with the base and the epoxidized fatty acid or its ester. The high temperatures cause the water to evaporate directly, so that the reaction mixture is in the form of a melt.

The amine is generally used in a stoichiometric to 5 molar amount, preferably 2.5 molar amount, per epoxy unit. If epoxidized fatty acids are reacted, then it is advisable to react with at least 2 equivalents of amine, since part of the amine reacts to form the ammonium salt.

By reaction of the fatty acid esters with the amines, reaction with 1.4 to 5 equivalents of the amine, especially the fatty acid amides, are obtained as reaction products. A larger excess of amine is possible, but may require subsequent removal of the unreacted amine.

When the epoxidized compound X is reacted with the amines XII, isomer mixtures are generally obtained since the oxirane rings can open on both C — O bonds.

If natural fats are used as the starting point, a reaction mixture is obtained which, in addition to the compounds VIII, can also contain glycerol and possibly the amides of saturated fatty acids. However, these substances do not need to be separated off for the subsequent alkoxylation since they do not interfere.

According to the invention, it has been found that the reaction products villa of epoxidized fatty acid derivatives with amino acids lead to compounds with good surface-active properties, which are therefore outstandingly suitable for use as anionic surfactants in washing and cleaning agents. Low surface and interfacial tension are found in the test. Dar- In addition, they show good fat dissolving power and good primary washing power.

Furthermore, synergistic effects can be observed in combination with nonionic surfactants such as Ci ₃ / i ₅ oxo alcohol with 7 moles of ethylene oxide in the primary washing ability, which outperform previously known effects with mixtures of anionic and nonionic surfactants.

Good properties of the compounds villa can already be observed in the fatty acid esters. The acids and their salts have a better effect. However, due to their better solubility, they are surpassed by the fectic acid amides.

The alkoxylated aminohydroxy fatty acid derivatives VII show good fat-dissolving properties in application tests. These grease-dissolving properties are a very important requirement in the field of cleaning agents for hard surfaces, since greases generally prevent the wetting of other dirt particles. The fat-dissolving power of a surfactant is just as important for washing textiles. Surfactants with such properties are often poorly water-soluble, which is evident in the low cloud points.

In addition to the good fat-dissolving power, the compounds VII according to the invention also have higher cloud points, so that they are suitable, for example, as a surfactant in a heavy-duty detergent.

The alkoxylated aminohydroxyfatty acid derivatives described above are used in detergents alone or in combination with at least one anionic and / or nonionic surfactant, usually in an amount of 2 to 50, preferably 8 to 30,% by weight, based on the total weight of the particular formulation.

The detergents can be in powder form or can also be in liquid form. The composition of the detergents and cleaners can be very different. Detergent and cleaning agent formulations usually contain 2 to 50% by weight of surfactants and optionally builders. This information applies to both liquid and powder detergents. Detergent and cleaning agent formulations that are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, volume 67, 35 (1989). Further information about the composition of detergents and cleaning agents can be found in Ullmann's encyclopedia of industrial chemistry, 21

Verlag Chemie, Weinheim 1983, 4th edition, pages 63 to 160.

Phosphate-reduced detergents are to be understood as meaning formulations which contain at most 25% by weight of phosphate, calculated as pentasodium triphosphate. The detergents can be full detergents or special detergents. Both anionic and nonionic or mixtures of anionic and nonionic surfactants are suitable as surfactants. The surfactant content of the detergents is preferably 8 to 30% by weight.

Suitable anionic surfactants are, for example, FcLLalkühol sulfates of fatty alcohols having 8 to 22, preferably 10 to 15, 18 carbon atoms, for example Cg to Cn alcohol sulfates, C ₂ to C ₁₃ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol.

Other suitable anionic surfactants are sulfated, ethoxylated Cβ to C ₂₂ alcohols or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a Cβ to C ₂₂ "# preferably a Cχo to Ciβ alcohol and then sulfating the alkoxylation product. Preferably 5 ethylene oxide are used for the alkoxylation, with one per mole of fatty alcohol 2 to 50, preferably 3 to 20, moles of ethylene oxide are used, but the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide, and alkoxylated C 6 -C ₂₂ -alcohols containing ethylene oxide and propylene 0 are also suitable The alkoxylated C 6 -C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.

5 Other suitable anionic surfactants are alkyl sulfonates such as Cβ- to C ₂₄ -, preferably Cio-Ciβ-alkanesulfonates and soaps such as the salts of Cβ- to C ₂₄ -carboxylic acids.

Other suitable anionic surfactants are C ₉ to C ₂ o-linear 0 alkylbenzenesulfonates (LAS). The fatty acid derivatives according to the invention are preferably used in LAS-poor detergent formulations with less than 4%, particularly preferably in LAS-free formulations.

5 The anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal salts such as sodium, potassium, lithium and 22

Ammonium salts such as Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Suitable nonionic surfactants are, for example, alkoxylated Cβ to C ₂₂ alcohols. The alkoxylation can be carried out with ethylene oxide,

Propylene oxide and / or butylene oxide can be carried out. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkyl .. oxide are used per mole of alcohol. Ethylene oxide is preferably used as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds contain 1 to 20, preferably 1.1 to 5, glucoside units.

Another class of nonionic surfactants are N-alkylglucamides of the general structure XIII or XIV

_γ - _c - _N - _z Y— N — C— Z

where Y is a Cβ to C ₂₂ alkyl, X is an H or C ₃ to C ₄ alkyl and Z is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxyl groups. Y is preferably C ₁₀ - to Ciβ-alkyl, X is CH ₃ - and Z is a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ -C ₃ . ₈ carboxylic acids. The detergent formulations preferably contain C ₁₀ -C ₁₆ alcohols ethoxylated with 3-12 mol ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.

Further preferred surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A-95/11225

L ¹ CO NH (CH ₂ ) _n 0 (AO) _: L ² 23 in the

L ¹ denotes a C ₅ to C ₂₁ alkyl or alkenyl radical,

L ^{2 is} a 0χ - to C ₄ -alkyl group, A is C ₂ - to C ₄ -alkylene, n denotes the number 2 or 3 and x has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyltetraglycolamine of the formula H ₂ N- ( CH ₂ -CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated Cβ- to Ciβ-Fettauremec-.ylesLexj ...

The powdered or granular detergents and, if appropriate, structured liquid detergents also contain one or more inorganic builders. All conventional inorganic builders such as aluminosilicates, silicates, carbonates and phosphates are suitable as inorganic builder substances.

Suitable inorganic builders are e.g. Aluminum silicates with ion-exchanging properties such as Zeolites. Different types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US-A-4 604 224, GB-A-2 013 259, EP-A- 0 522 726, EP-A-0 384 070A and WO-A-94/24251.

Other suitable inorganic builders are e.g. amorphous or crystalline silicates such as e.g. amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst AG). The silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg silicates are preferably used.

Other suitable inorganic builder substances are carbonates and hydrogen carbonates. These can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferably used.

The inorganic builders can be present in the detergents in amounts of 0 to 60% by weight together with organic cobuilders which may be used. The inorganic builders can either be used alone or in any combination. 24 be worked into the detergent. In powdered or granular detergents, they are added in amounts of 10 to 60% by weight, preferably in amounts of 20 to 50% by weight. In structured (multi-phase) liquid detergents, inorganic builders are added in amounts of up to 40% by weight, preferably up to 20% by weight. They are suspended in the liquid formulation components.

Organic cobuilders are present in powder or granular as well as in liquid detergent formulations in amounts of 0.1 to 20% by weight, preferably in amounts of 1 to 15% by weight, together with inorganic builders. The powdery or granular heavy-duty detergents can also contain, as other usual constituents, a bleaching system consisting of at least one bleaching agent, optionally in combination with a lead activator and / or a bleaching catalyst.

Suitable bleaches are perborates and percarbonate in the form of their alkali metal salts, in particular their Na salts. They are present in quantities of 5 to 30% by weight, preferably 10 to 25% by weight

Formulations included. Other suitable bleaching agents are inorganic and organic peracids in the form of their alkali or magnesium salts or in some cases also in the form of the free acids. Examples of suitable organic percarboxylic acids or salts are e.g. Mg monoterephthalate, phthalimidopercaproic acid and

Dodecane-1,10-diper acid. An example of an inorganic peracid salt is potassium peroxomonosulfate (oxone).

Suitable bleach activators are e.g.

Acylamines such as tetraacetylethylene diamine, tetraacetyl glycol uril, N, N '-diacetyl-N, N' -dimethylurea and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine

acylated lactams such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam

substituted phenol esters of carboxylic acids such as e.g. Na acetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Na nonanoyloxybenzenesulfonate

acylated sugars such as Pentaacetyl glucose

Anthranil derivatives such as 2-methylanthranil or 2-phenylanthrani1 25th

Enol esters such as Isopropenyl acetate

Oxime esters such as O-acetylacetone oxime

Carboxylic anhydrides, e.g. Phthalic anhydride or acetic anhydride.

Tetraacetylethylenediamine and Na nonanoyloxybenzenesulfonates are preferably used as bleach activators. The bleach activators are heavy-duty detergents in amounts of 0.1 to 15% by weight, preferably in amounts of 1.0 to 8.0% by weight, particularly preferably in amounts of 1.5 to 6.0% by weight. % added.

Suitable bleaching catalysts are quaternized imines and sulfonimines as described in US-A-5 360 568, US-A-5 360 569 and EP-A-0 453 003 and Mn complexes, cf. e.g. WO-A-94/21777. If bleach catalysts are used in the detergent formulations, they are in amounts of up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active manganese complexes in amounts of up to 0.1% by weight .% contain.

The detergents preferably contain an enzyme system. These are proteases, lipases, amylases and cellulases commonly used in detergents. The enzyme system can be limited to a single one of the enzymes or contain a combination of different enzymes. Of the commercially available enzymes, amounts of 0.1 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of the finished enzyme are generally added to the detergents. Suitable proteases are Savinase ^® and Esperase (manufactured by Novo Nordisk). A suitable lipase is, for example, Lipolase ^® (manufacturer Novo Nordisk). A suitable Cellu¬ lase is Celluzym ^® (manufactured by Novo Nordisk).

The detergents preferably contain soil release polymers and / or graying inhibitors as other common constituents. This is e.g. around

Polyesters from polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids. Polyesters from polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acids. Such polyesters are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US -A-5 142 020. Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, cf. US-A-4 746 456, US-A-4 846 995, DE-A-3 711 299, US-A-4 904 408, US-A-4 846 994 and US-A-4 849 126 or modi Treated celluloses such as methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

Graying inhibitors and soil release polymers are present in the detergent formulations in an amount of 0 to 2.5% by weight, preferably 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight. Soil release polymers are preferably used are the A-4 746 456 US-known graft polymers of vinyl acetate on polyethylene oxide of molecular 2büü from the - ^■ öύOü in weight ratio 1,2: / polyoxyethylene terephthalates terephthalate 1, as well as commercially available polyethylene: 1 to 3.0 the molecular weight 3000 to 25000 from polyethylene oxides of the molecular weight 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-4 403 866, the blocks from (a) contain ester units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units from aromatic dicarboxylic acids and polyhydric alcohols. These amphiphilic block copolymers have molecular weights from 1500 to 25000.

A typical powder or granular heavy-duty detergent can have the following composition, for example:

2 to 50, preferably 8 to 30% by weight of at least one of the anionic and / or nonionic surfactants described above,

5 to 50, preferably 15 to 42.5% by weight of at least one inorganic builder,

5 to 30, preferably 10 to 25% by weight of an inorganic bleaching agent,

0.1 to 15, preferably 1 to 8% by weight of a bleach activator,

0 to 1, preferably up to at most 0.5% by weight of a bleaching catalyst, 0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor based on water-soluble homopolymers of N-vinylpyrrolidone or N-vinylimidazole, water-soluble copolymers of N-vinylimidazole and N-vinylpyrrolidone Copolymers of N-vinyl imidazole and N-vinyl pyrrolidone with a particle size of 0.1 to 500, preferably up to 250 μm, these copolymers being 0.01 to 5, preferably 0.1 to 2% by weight of N, N ' -Divinylethyleneurea contain as crosslinker. Further color transfer inhibitors are water-soluble and also crosslinked polymers of 4-vinylpyridine-N-oxide, which can be obtained by polymerizing 4-vinylpyridine and subsequent oxidation of the polymers.

0.1 to 20, preferably 1 to 15% by weight of at least one organic cobuilder,

0.2 to 1.0% by weight of protease,

- 0.2 to 1.0% by weight of lipase,

0.3 to 1.5% by weight of a soil release polymer.

A bleaching system is often completely or partially dispensed with in color-gentle special detergents (for example in so-called color detergents). A typical powder or granular color detergent can have the following composition, for example:

10 to 60, preferably 20 to 55% by weight of at least one inorganic builder,

0 to 15, preferably 0 to 5% by weight of an inorganic bleaching agent,

0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor, cf. above,

0.1 to 20, preferably 1 to 15% by weight of at least one organic cobuilder,

0.2 to 1.0% by weight of protease, 0.2 to 1.0% by weight of cellulase,

0.2 to 1.5% by weight of a soil release polymer, e.g. a graft polymer of vinyl acetate on polyethylene glycol.

The powdery or granular detergents can contain up to 60% by weight of inorganic adjusting agents as other common constituents. Sodium sulfate is usually used for this. However, the detergents according to the invention are preferably low in adjusting agents and contain up to 20% by weight, particularly preferably up to 8% by weight of adjusting agents.

The invented Wa.1chϊύitte.1 l.önr.cr. have different densities in the range from 300 to 950 g / l. Modern compact detergents generally have high bulk densities, for example 550 to 950 g / l, and show a granular structure.

The liquid detergents according to the invention contain, for example

5 to 60, preferably 10 to 40% by weight of at least one of the anionic and / or nonionic surfactants described above,

0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor (cf. above),

0.1 to 20, preferably 1 to 15% by weight of at least one co-builder,

0 to 1.0% by weight of protease,

0 to 1.0% by weight cellulase,

0 to 1.5% by weight of a soil release polymer and / or graying inhibitor,

0 to 60% by weight of water,

- 0 to 10% by weight of alcohols, glycols such as ethylene glycol, diethylene glycol or propylene glycol or glycerin.

The detergents can optionally contain other customary additives. Other additives which may be used include, for example, complexing agents, phosphonates, optical brighteners, dyes, perfume oils, foam dampers and corrosion inhibitors. Cleaners for hard surfaces include, for example, cleaners for cleaning metal, plastics, glass and ceramics, floor cleaners, sanitary cleaners, all-purpose cleaners in the household and in commercial applications, technical cleaners (for use in car washes or high-pressure cleaners), cold cleaners, dishwashers , Hand dishwashing detergents, rinse aids, disinfectant cleaners, cleaners for the food and beverage industry, in particular as bottle cleaners, as CIP cleaners (cleaning-in-place) in dairies, breweries and other companies operated by food manufacturers. Cleaners that contain the surfactants according to the invention are particularly suitable for cleaning hard surfaces such as glass, plastic and plastic. The cleaners can be alkaline, acidic or τ> neutral. They usually contain surfactants in amounts of about 5 to 90, preferably 10 to 75,% by weight, based on the active substance content. These can be anionic, nonionic or cationic surfactants and mixtures of surfactants which are compatible with one another, for example mixtures of anionic and nonionic or of cationic and nonionic surfactants. Alkaline cleaners may contain soda, potash, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodium hydroxide, potassium hydroxide, amine bases such as monoethanolamine, diethanoiamine, triethanolamine, ammonia or silicate in amounts of up to 60% by weight, in some cases even up to 80% by weight. %. The cleaners can also contain citrates, gluconates or tatrates in amounts of up to 80% by weight. They can be in solid or liquid form.

The surfactants VII and Villa mentioned are also suitable as dyeing aids in leather dyeing.

The percentages in the examples mean% by weight, unless stated otherwise.

Examples

Preparation of the aminohydroxy fatty acid derivatives VIII (general specification)

A mixture of n mol of an amine and 29 g of a 30% strength methanolic sodium methoxide solution was admixed with 1 mol of an epoxidized fatty acid ester with stirring at 80.degree. The molecular weight was determined by titration of the epoxide and / or from the saponification number. If both amide formation and epoxide opening are desired, an average molar mass from the epoxy / soaping number has been used. This was followed by 4 hours 30 stirred at 90-95 ° C. The reaction products were obtained as viscous liquids.

Example 6

A mixture of 111 g (1 mol) of sarcosine sodium salt and 14.4 g of a 30% solution of sodium methoxide (0.08 mol) in methanol was suspended in 123 g of propylene glycol. At temperatures of 160 ° C, 152.8 g (0.5 mol) of epoxidized beet oil methyl ester were added. The mixture was then stirred at temperatures from 160 to 170 ° C for 7 hours.

Example 7

3.6 g (0.09 mol) of sodium hydroxide dissolved in 3.6 g of water and 152.8 g (0.5 mol) of epoxidized beet oil methyl ester were added to a solution of 111 g (1 mol) of sarcosine sodium salt in 150 ml of water ¬ ben. The mixture was heated to 240 ° C. for 5 hours with stirring. The reaction product was obtained as a beige dye.

Example 8

18.0 g (0.23 mol, 50% by weight) of sodium hydroxide solution were added to a solution of 22.5 g (0.3 mol) of glycine in 33 ml of water, so that a pH of 9 -10 set. 47.3 g (0.15 mol) of epoxidized beet oil methyl ester were added dropwise. With stirring, the solution was heated to 107-115 ° C, the water within 80 min. distilled off. The pH was kept at 9-10 with 2 g (0.025 mol, 50% by weight) of sodium hydroxide solution. The mixture was then stirred at 230 ° C. for 6 h. The reaction product was obtained as a light beige solid.

Example 9

15.6 g (0.2 mol, 50% by weight) of sodium hydroxide solution were added to a solution of 26.6 g (0.2 mol) of iminodiacetic acid in 30 ml of water, so that a pH of 9-10 set. 31.5 g (0.1 mol) of epoxidized beet oil methyl ester were added dropwise. The solution was heated to 102-115 ° C. with stirring, the water distilling off within 1 h. The pH was adjusted to 2.5 g (0.03 mol,

50% by weight) sodium hydroxide solution kept at pH 9-10. The mixture was then stirred at 230 ° C. for 8 h. The reaction product was obtained as a gray-beige solid.

B. Preparation of the Alkoxylated Fatty Acid Derivatives VII (Examples 10 to 14) 31

The derivatives VIII obtained in accordance with the general instructions or special embodiment of Example 7 were mixed with m mol of ethylene oxide (this corresponds to k mol per epoxy unit originally present) in the presence of 1% by weight of potassium hydroxide (based on VIII) at 100-110 ° C. implemented in a pressure vessel at 1.4 to 5.9 bar. The addition time was 5 hours and stirring was continued for a further 4 hours. The compounds according to the invention were obtained in the form of yellow pastes. (The number of epoxy units was determined by titration.)

Application properties

The fat-removing ability, the cloud point, the foaming power and the surface tension of aqueous preparations were investigated as application-technical kigenschafLeu Jti Aiuirichydrci-yfettcüurc derivatives VIII and the alkoxylation products VII.

To determine the fat-dissolving capacity, solid platelets wetted with motor oil or olive oil are dipped horizontally into the surfactant solution to be investigated (c = 1 g / l). The time until the first oil drop is removed from the respective plate is measured. The shorter this time, the better the fat-removing ability.

The measurement results of the fat dissolving power of the substances of Examples 6, 7 and 10 to 14 can be found in Table 4.

The cloud point was determined in accordance with DIN 53917. The temperature is determined above which the solution becomes cloudy and thus exists as a mixture of two liquid phases. In general, the lower the cloud temperature, the lower the foaming power.

The foam capacity was determined in accordance with DIN 53902 by measuring the foam volume in ml one minute after the end of foam generation.

The surface tension was determined in accordance with DIN 53914 by measuring the force in mN / m which is necessary to pull a plate or a horizontally suspended ring out of the liquid surface.

The measurement results of the substances in the examples are shown in Table 5. -4

Table 4

OJ to

n

3 ä

©

Table 5

The surfactants Villa according to the invention were tested under standard conditions (60 ° C., 5 g / l, 19% addition Villa) in model detergent formulation A without other surfactants.

Furthermore, the surfactants according to the invention from Examples 8 and 9 were used in combination with a nonionic surfactant in a model detergent formulation A without further surfactants under standard conditions (60 ° C., 5 g / l, 19% additive, thereof 38.6% Villa and 61.4% Ci ₃ / ιs-oxo alcohol with 7 mol ethylene oxide) checked.

The washing tests were carried out under the following conditions:

Launder-O-meter washing machine from Atlas

Washing cycles 1

Rinse cycles 1

Wash temperature 60 ° C

Washing time 30 min.

Water hardness 3 mmol / 1

Approx 4: 1

Amount of liquor 250 ml

Detergent concentration 5 g / l

Dirty fabric WFK 10 D, WFK 20 D

Test fabric from WfK-Testgewebe GmbH EMPA 101, EMPA 104 Test fabric from the Federal Material Testing Institute St. Gallen

Detergent formulation A:

Zeolite A 30%

Sodium carbonate 12%

Sodium silicate 3%

Tylose CR 1500 p 1.2%

Sodium perborate monohydrate 14.4%

Tetraacetylethylenediamine 4% Acrylic acid / maleic acid - 5% copolymer MW 70000

Soap 0 5%

Sodium sulfate 4%

Water 6 9 surfactant 19% (or 19% of a mixture of

61.4% according to the invention surfactant and 38.6% C ₁₃ / ι ₅ oxo alcohol with 7 moles of ethylene oxide & 7 EO)

After rinsing, the fabrics were spun and the fabrics hung up individually to dry. The fabric was measured with an Elrepho 2COO from Data Color. Heidenheim, namely 6 measuring points per piece of tissue. The reflectance value was determined at 480 nm.

Table 6 summarizes the total remission value R and the mean values of the primary washing power.

Table 6

The surfactants according to the invention can be used in the following example detergent formulations. O 3 tons

Table 7

Detergent compositions A-P

υi

π

9

Ut

Oev

0

(Continuation of table 7) Ό β \ s

ω o.

r.

H

13

©

3

O

(Continuation of table 7) o o ϊe

OJ

Cobuilder 1 = AS / MS (acrylic acid / maleic acid) copolymer MW 70000

O

Ut

The present invention further relates to fatty acid amide derivatives with nonionically hydrophilically substituted amide groups and anionically substituted amine groups in the fatty acid chain or with anionically substituted amide groups and nonionically hydrophilic substituted amine groups in the fatty acid chain. The invention further relates to a process for the preparation of these fatty acid amide derivatives via corresponding epoxidized fatty acid amides and such epoxidized fatty acid amides themselves as intermediates in the production of surfactants. The invention further relates to mixtures of fatty acid amide derivatives with amine groups in the fatty acid chain and those with alkoxy groups in the fatty acidececte. Contrary to the present invention are also detergents and cleaning agents which contain the fatty acid amide derivatives or the mixtures of fatty acid amide derivatives mentioned as surfactants.

DE-A 27 34 596 and DE-A 27 34 597 disclose the uses of aminohydroxystearic acid amides or esters as detergent substances in detergents or cold detergents.

US Pat. No. 3,155,658 discloses the reaction of epoxycarboxylic acid amides with amines. The products obtained are suitable as corrosion inhibitors, mineral oil additives and ore flotation aids.

The object of the present invention was to provide surfactants with an even more advantageous range of properties than with the surfactants known in the prior art.

Accordingly, fatty acid amide derivatives of the general formula XV

found in which the substituents have the following meaning:

A ^{4 is} an aliphatic C ₈ -C ₂₄ radical with an unbranched carbon chain, which contains one or more in the chain

Groupings of Formula XVI CH - - CH

N OH (xvi)

/ \

R * ⁴ R15

contains

R ^{12 is} a hydroxyl- and / or amino-substituted hydrophilic radical with 2 to 40 C atoms,

Ri3 is hydrogen, an unsubstituted Ci C _b alkyl radical or a radical R ¹² ,

Ri ^{4 is} a C 1 -C ₄ -alkyl radical which carries carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali metal or ammonium salts and which has non-adjacent oxygen atoms, -NH groups and / or NC ₁ -C ₄ alkyl groups can be interrupted,

R ^{15 is} hydrogen, an unsubstituted Ci-Cβ-alkyl radical or a radical R ¹⁴ ,

the meaning of the two pairs of substituents R ¹² / R ¹³ and R ¹⁴ / R ^{15 can} also be interchanged.

As unsaturated, unbranched aliphatic fatty acids, from which the fatty acid amide derivatives XV are derived, ricinoleic acid can be considered as unsaturated hydroxy fatty acid, but preferably

monounsaturated C ₉ -C ₂₅ fatty acids such as petroselinic acid, undecenoic acid, Δ9-decylenic acid, Δ9-dodecylic acid, vaccenic acid, palmitoleic acid, erucic acid, elaidic acid and especially oleic acid,

C ₉ -C 25 polyunsaturated fatty acids such as stilingic acid and in particular linoleic acid as well

triple unsaturated C ₉ -C ₂₅ fatty acids such as elaeostearic and in particular linolenic acid.

Unsaturated Ciβ fatty acids are particularly suitable due to their good availability. The fatty acids obtainable by isomerization of the double bond are also suitable.

The fatty acid amide derivatives XV according to the invention can also be based on mixtures, in particular naturally occurring mixtures of such fatty acids.

The amines HN (R ¹² ) R ¹³ on which the amide groups in XV are based, with one or two nonionic hydrophilic substituents, can be branched and carry several hydroxyl or amino groups, such as (trishydroxymethylene) methylamine, but preferably have at least one unbranched ω-hydroxyalkyl group or one unbranched ω-amino-alkyl group βαil in each case 2 to 6 C-Λ.toπιer, whereby the underlying alkyl group by non-adjacent oxygen atoms, NH groups, N-Cι-C ₄ alkyl groups, N-Cι-C ₄ -hydroxy - Alkyl groups or N -CC ₄ aminoalkyl groups can be interrupted. Furthermore, the N-C 1 -C ₄ -alkyl-substituted derivatives are suitable if they still contain at least one reactive amino or imino group.

The following are particularly suitable as such amines:

Hydroxyalkylamines such as mono- and diethanoiamine, mono- and diisopropanolamine, 2- (2-aminoethoxy) ethanol, 2- [(2-aminoethyl) amino] ethanol, 3-aminopropanol, aminopropyldiethanolamine, aminosorbitol, glucamine and N-alkyl-substituted Hydroxyalkylamines such as methylethanolamine, n-propylethanolamine, butylethanolamine, N-methylglucamine and 2-aminobutanol-1,

Aminoalkylamines such as ethylenediamine, trimethylene diamine,

1,2-propylenediamine, 3-amino-1-methylaminopropane, diethylenetriamine, dipropylenetriamine, N, N'-bis (3-aminopropyl) ethylenediamine, 3- (2-aminoethoxy) propylamine, 2- (2-aminoethoxy ) ethylamine, 3- (3-aminopropoxy) propylamine and their symmetrically and asymmetrically substituted mono- and dialkyl derivatives such as

N, N-dimethylaminopropylamine, diethylaminoethylamine, diethylamino propylamine, l-diethylamino-4-aminopentane, neopentanediamine, hexamethylene diamine, 4,9-dioxadodecane-1, 12-diamine, 4,7, 10-trioxatridecane-1, 13- diamine and 3- (2-Aπ.inoethyl) aminopropylamine.

The amines HN (R ¹⁴ ) R ¹⁵ ) on which the amine groups in the fatty acid chain in XV are based with one or two anionic substituents are amino or iminocarboxylic acids (“amino acids”) or amino or iminosulfonic acids, amino acids being particularly preferred. These carboxylic or sulfonic acids are preferably unbranched. You can also further acid or acid wear amide groups and optionally substituted with hydroxyl radicals. It is irrelevant for the effect whether D or L forms or mixtures thereof, for example racemates, are used. The known amino acids are generally easily accessible, for example, by the Strecker reaction. A large part of the amino acids is commercially available. Examples of amino acids which can be considered are:

Monocarboxylic acids such as valine, leucine, isoleucine, ornithine, citrulline, serine, threonine, in particular alanine, arginine, lysine, especially glycine and sarcosine,

Dicarboxylic acids such as ATP, aspartic acid, glutamine, glutamic acid, especially iminodiacetic acid and ethylenediaminodiacetic acid,

Tricarboxylic acid such as aspartic acid monoacetic acid and

Sulfonic acids such as N-methyl taurine and taurine.

If the radicals R ¹³ and / or R ^{15 are} Cχ-C ₆ -alkyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, see. -Pentyl, tert. -Pentyl, neo-pentyl, hexyl or in particular methyl or ethyl.

The fatty acid amide derivatives XV according to the invention are advantageously prepared by an epoxidized fatty acid amide of the general formula XVII

_B 3__ _C0 - _N ^ ^{Rl2 (} XVID

^ R "in which B ³ denotes an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain, which contains one or more epoxy groups in the chain, with at least one equivalent of amine of the general formula HN (R ¹⁴ ) R ¹⁵ per epoxy unit , wherein the substituents R ¹² to R ^{15 have} the meaning given above.

The reaction of the epoxidized fatty acid amides XVII with the amines HN (R ¹⁴ ) R ¹⁵ is usually carried out at 20 to 280 ° C, in particular 50 to 200 ° C, especially 80 to 180 ° C, usually at normal pressure and preferably in Presence of a basic catalyst, for example an alkali metal hydroxide, alkali metal carbonate or alkali metal alcoholate such as sodium methylate, sodium ethylate or potassium tert. -butylate. The reaction is complete when no more epoxy groups can be detected.

When the epoxidized fatty acid amides XVII are reacted with the amines mentioned, isomer mixtures are generally obtained, since the oxirane rings can open on both C — O bonds.

The epoxidized fatty acid amides XVII themselves can be obtained by reacting corresponding epoxidized fatty acid esters, fatty acids or their salts with the amines HN (R ¹² ) R ¹³ . In principle, the same conditions with regard to temperature, pressure, catalysts used or other reaction parameters as Dei der UmseLzuny are epoxidized. Fatty acid amides XVII with the amines HN (R ¹⁴ ) R ¹⁵ applied.

The epoxidized fatty acid esters, fatty acids or their salts used as starting materials can be prepared by epoxidation of corresponding unsaturated fatty acid esters, fatty acids or their salts by customary methods. The epoxidation is usually carried out in a manner known per se by reaction with peracids such as performic acid and peracetic acid. However, some epoxidized fatty acid esters or fatty acids are also commercially available.

The production of the epoxidized fatty acid esters or fatty acids is preferably based on natural fats, that is to say the glycerol esters, in particular triglycerides, which contain at least one unsaturated fatty acid residue. Such natural fats are, for example, olive oil, cottonseed oil, linseed oil, tallow, fish oils, tall oil, castor oil, coconut oil, hemp oil, sperm oil, lard, tallow, goose fat, beef tallow, claw oil, tallow fatty acid, camelina oil, sunflower oil, peanut oil, palm oil and Euphor all soybean oil, rapeseed oil and turnip oil. However, fatty acid or fatty acid ester mixtures can also be used, such as those obtainable, for example, by transesterification or saponification of natural fats with C ₁ -C ₄ alcohols, preferably methanol.

The reaction of the epoxidized fatty acid esters or fatty acids with the amines HN (R ¹² ) R ¹³ and the reaction of the epoxidized fatty acid amides XVII with the amines HN (R ¹⁴ ) R ¹⁵ can be carried out in the presence of a solvent, but this is often not the case is necessary, so that one often gets by without a solvent.

If the amines HN (R ¹² ) R ¹³ or HN (R ¹⁴ ) R ^{15 are} not liquids, but solids such as, for example, the amino acids, their implementation as a suspension in water-soluble or partially water-soluble solvents possible. For example, polyhydric alcohols and, in particular, glycerin, ethylene glycol and propylene glycol are suitable, since they can subsequently remain in the product. Since, as a rule, some of the amino acid 5 is present as a solution, some undissolved, in a preferred embodiment the Na salt of the amino acid is introduced in, for example, propylene glycol with the basic catalyst and the reactant is metered in; Reaction temperatures of 60 to 200 ° C., in particular 100 to 180 ° C., are advantageous here. It is also possible to use the amines mentioned, in particular the amino acids, as purely aqueous solutions in the reaction. In another preferred embodiment, the Na salt of the amino acid ars besx.a i.oLZ de-u reaction gich is added.

15 Another advantageous process based on solid amines such as amino acids is the reaction in the melt. For this purpose, temperatures are required at which the mixture is in the form of a melt, which may well be below the fixed point of the amino acid itself, usually above

20 200 ° C. Depending on the start of the decomposition of the amino acids, the preferred upper temperature range is 220 to 260 ° C. In an advantageous embodiment, the amino acid is dissolved in a little water and heated together with the base and the epoxidized fatty acid or its ester. The high temperatures cause the water to evaporate directly, so that the reaction mixture is in the form of a melt.

The epoxidized fatty acid esters, epoxidized fatty acids or their salts are generally reacted with one or approximately one equivalent of amine HN (R ¹² ) R ¹⁵ per carboxylic acid unit. Such a production process for the epoxidized fatty acid amides XVII is also the subject of the present invention. The amine reacts alone or to a large extent with the ester or. Carboxylic acid function with amide formation, the epoxy grouping remains 5 completely or almost completely. If epoxidized fatty acids are used in the acid form, the reaction with up to two equivalents of amine is recommended, since part of the amine reacts to form the ammonium salt.

The epoxidized fatty acid amides XVII are reacted with at least one equivalent of amine HN (R ¹⁴ ) R ¹⁵ per epoxy unit, 1 to 2.5, in particular 1 to 1.3 equivalents of amine per epoxy unit being preferred.

A mode of operation is very particularly preferred in which the reaction of the epoxidized fatty acid esters or fatty acids with the amines HN (R ¹² ) R ¹³ and the subsequent reaction of the obtained ones epoxidized fatty acid amides XVII with the amines HN (R ¹⁴ ) R ¹⁵ in a two-stage "one-pot" synthesis, ie in the same reaction vessel without intermediate isolation. For example, epoxidized fatty acid lower alkyl esters or epoxidized triglycerides with hydroxyalkylamines or aminoalkylamines can be reacted with alcohol to the corresponding epoxidized fatty acid amides XVII and then the fatty acid amide derivative with the solid Na salt of an amino acid or with the aqueous solution of such a salt Make XV. For example, epoxidized fatty acid lower alkyl esters or epoxidized triglycerides with the Na salt of an amino acid in solution or suspension to the corresponding epoxidized fatty acid amides XVII uinaetüeij u.iJ then by further reaction with hy ^β -hydroxyal.kylamines or aminoalkylamines derived therefrom the fatty acid amide derivative Make XV.

The epoxidized fatty acid amides XVII described thus represent a central intermediate on the way to the fatty acid amide derivatives XV. However, starting from the compounds XVII, it is not only possible to prepare the end products XV suitable as surfactants but also surfactants of a different structure which are produced by conversion tion of the compounds XVII with all possible types of N, S, 0 or C nucleophiles are available by opening the oxirane ring. Examples of such N, S, 0 or C nucleophiles and other nucleophiles which can be used are the following:

N-nucleophiles: amines (e.g. NH ₃ , urotropin), amino acids,

Aminoacetonitriles (e.g. RNH-CHR '-CN), amides, ureas, thioureas, imides, hydroxylamines (e.g. H ₂ N0H), hydrazines (e.g. H ₂ NNH ₂ ),

Hydrazides (e.g. RC0NHNH ₂ ), cyanamides (e.g. RNH-CN), nitrocyanamides (e.g. NaN (N0 ₂ ) CN), isocyanide ("N = C), nitrate, nitrite (N0 ₂ -), azide (N ₃ -), Nitrones, N-oxides, cyanates, isocyanates (NCO "), isothiocyanate,

Guanidines, cyanguanidine, formamidine;

0-nucleophiles: alcohols (e.g. Ci-Cβ-alkanols, also polyhydric alcohols such as ethylene glycol, glycerin), sugar (e.g. glucose, sucrose),

Carboxylates (eg acetates, formates, oxalates, lactates, salts of malic acid) and the corresponding free acids, water, hydroxide (OH-), hydroperoxide (OOH-), phenolates; S nucleophiles: bisulfite (HSO ₃ -), sulfite (S0 ₃ ² "), thiocyanate (SCN"), isothiocyanate, S ₂ ² ', mercaptans (HS ", RS"), S ₂ 0 ₃ ² ";

C-nucleophiles: cyanide, carbanions or enolates, for example of ketones, esters, acids, also of nitriles and nitro compounds, 1,3-dicarbonyl compounds (for example malonic esters, ß-ketoesters) and their analogues such as malodonitrile (NC-CH ₂ -CN), enamines, imines and their iminium salts (such as H ₂ C = NH ₂ ⁺ ), cyanohydrins, acetylides (RC-≡C), 1,3-dithiane;

other nucleophiles: phosphonates, borates and the corresponding free acids, LiAIH ₄ and other H'-donors, halides.

In the compounds mentioned, R and R 'are organic radicals.

Accordingly, the present invention also relates to epoxidized fatty acid amides of the general formula XVII

.R ¹²

B ³ - CO- N (XVII) ^' Rl ³ in which the substituents have the following meaning:

B ^{3 is} an aliphatic C ₈ -C ₂₄ radical with an unbranched carbon chain which contains one or more epoxide groups in the chain,

R "is a hydroxyl- and / or amino-substituted hydrophilic radical having 2 to 40 C atoms or a C ₁ -C ₁₄ alkyl radical which carries carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali metal or ammonium salts and which can be interrupted by non-adjacent oxygen atoms, -NH groups and / or N-C 1 -C ₄ -alkyl groups, and

R 1 is hydrogen, an unsubstituted C 1 -C 6 -alkyl radical or a radical R ¹² ,

as intermediates in the manufacture of surfactants. According to the invention, it was found that the fatty acid amide derivatives XV are compounds with excellent surface-active properties, which are therefore outstandingly suitable for use as anionic surfactants in detergents and cleaning agents. Low surface and interfacial tension are found in the test. In addition, they show good fat-dissolving power and good primary washing power. The extremely advantageous property profile of these surfactants is mainly explained by the balanced balance between non-ionically hydrophilic and anionic substituents in XV.

The present invention therefore also relates to detergents and cleaning agents which contain the er-.iiidur.gsgemc-l.cr- fatty acid amide derivatives XV as surfactants in amounts customary for this purpose and other additives customary for such agents.

Furthermore, in combination with nonionic surfactants such as alkoxylated long-chain alcohols, for example C ₃ / i ₅ oxo alcohol with 7 moles of ethylene oxide, synergistic effects can be observed in the primary washing power which exceed previously known effects with mixtures of anionic and nonionic surfactants. In some cases, synergistic effects also occur with anionic surfactants, for example with fatty alcohol sulfonates or fatty alcohol ester sulfates.

The fatty acid amide derivatives XV show good fat-dissolving properties in application tests. These grease-dissolving properties are a very important requirement in the field of cleaning agents for hard surfaces, since greases generally prevent the wetting of other dirt particles. The fat-dissolving power of a surfactant is just as important for washing textiles. Surfactants with such properties are often poorly water-soluble, which is reflected in low cloud points.

In addition to the good fat-dissolving power, the compounds XV according to the invention also have higher cloud points so that they are suitable, for example, as a surfactant in a heavy-duty detergent.

The compounds XV are used in detergents alone or in combination with at least one anionic and / or nonionic surfactant, usually in an amount of 2 to 50, preferably

8 to 30 wt .-%, based on the total weight of the respective formulation used.

The detergents can be in powder form or can also be in liquid form. The composition of the detergents and cleaners can be very different. Detergent and cleaning agent formulations usually contain 2 to 50% by weight Surfactants and optionally builders. This information applies to both liquid and powder detergents. Detergent and cleaning agent formulations that are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, volume 67, 35 (1989). Further information on the composition of detergents and cleaners can be found in Ulimann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63 to 160.

Phosphate-reduced detergents are understood to mean those formulations which contain at most 25% by weight of phosphate, calculated as pexite-αxiaLrit-i -triphosphet. In the. Detergent can be a full detergent or a special detergent. Both anionic and nonionic or mixtures of anionic and nonionic surfactants are suitable as surfactants. The surfactant content of the detergents is preferably 8 to 30% by weight.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ to Cn alcohol sulfates, Cχ ₂ to C ₃ . _3- alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated, ethoxylated Cβ to C ₂₂ alcohols or their soluble salts. Compounds of this type are prepared, for example characterized in that firstly a C _Θ - to C ₂₂ -, preferably a C ₁₀ - to Ciβ alcohol alkoxylated and subsequently sulfating the alkoxylation. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Also suitable are those alkoxylated Cβ to C ₂₂ alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide. The alkoxylated Cs * to C ₂₂ "alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in a statistical distribution.

Other suitable anionic surfactants are alkyl sulfonates such as Cβ- to C ₂₄ -, preferably Cio-Ciβ-alkanesulfonates and soaps such as the salts of Cβ- to C ₂₄ -carboxylic acids. Other suitable anionic surfactants are Cg to C ₂₀ linear alkylbenzenesulfonates (LAS). The fatty acid derivatives according to the invention are preferably used in low-LAS detergent formulations with less than 4% by weight, particularly preferably in LAS-free formulations.

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal salts such as sodium, potassium or lithium salts and ammonium salts such as e.g. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Suitable nonionic yensides are, for example, alkoxylated Cβ to C ₂₂ "alcohols. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide added can be used as surfactants. Also block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or adducts which contain the alkylene oxides mentioned in a statistical distribution, 2 to 50, preferably 3 to 20, mol of at least one alkylene oxide being used per mole of alcohol ethylene oxide as the alkylene oxide The alcohols preferably have 10 to 18 carbon atoms.

y c N Z Y N C Z II I (XIII) I II (XIV)

where Y is a Cζ to C ₂₂ 'alkyl, X is an H or Cj to C ₄ alkyl and Z is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. Y is preferably C ₁₀ - bis

Ciβ-alkyl, X for CH ₃ - and Z for a C ₅ or Cβ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of Cio-Ciβ-carboxylic acids. The detergent formulations preferably contain C ₁₀ -C ₁₆ alcohols ethoxylated with 3-12 mol ethylene oxide, O 97/16408 PO7EP96 / 04560

49 particularly preferred ethoxylated fatty alcohols as nonionic surfactants.

L ¹ CO NH (CH ₂ ) _n 0 (C _m H ₂ 0) _x L ²

in the

L ^x is a C ₅ -. ₂ to C ι-alkyl or alkenyl bese- ⁵ ^ hr) »= ι-.

L ^{2 represents} a C 1 to C ₄ alkyl group, m denotes the number 2, 3 or 4, n denotes the number 2 or 3 and x has a value from 1 to 6.

Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ O) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyl tetraglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated Cβ- to Ciβ-fatty acid methyl esters.

Suitable inorganic builders are e.g. Aluminum silicates with ion-exchanging properties such as Zeolites. Different types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US-A-4 604 224, GB-A-2 013 259, EP-A- 0 522 726, EP-A-0 384 070 and WO-A-94/24251.

Other suitable inorganic builders are, for example, amorphous or crystalline silicates such as, for example, amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst AG). The silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg silicates are preferably used. Other suitable inorganic builder substances are carbonates and hydrogen carbonates. These can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferably used.

The inorganic builders can be present in the detergents in amounts of 0 to 60% by weight together with organic cobuilders which may be used. The inorganic builders can be incorporated into the detergent either alone or in any combination with one another. In powdered or granular detergents, they are added in amounts of 10 to 60% by weight, preferably in amounts before _* 20 to 50% by weight. In structured (multi-phase) liquid detergents, inorganic builders are added in amounts of up to 40% by weight. %, preferably up to 20% by weight. They are suspended in the liquid formulation components.

Organic cobuilders are present in powder or granule form and in liquid detergent formulations in amounts of 0.1 to 20% by weight, preferably in amounts of 1 to 15% by weight, together with inorganic builders. The powdery or granular heavy-duty detergents can also contain, as other usual constituents, a bleaching system consisting of at least one bleaching agent, optionally in combination with a bleaching activator and / or a bleaching catalyst.

Suitable bleach activators are e.g.

Acylamines such as tetraacetylethylenediamine (TAED), tetraacetylglycoluril, N, N'-diacetyl-N, N'-dimethylurea and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine,

acylated lactams such as, for example, acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam, substituted phenol esters of carboxylic acids such as, for example, Na acetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Na nonanoyloxybenzenesulfonate,

5 - acylated sugars such as Pentaacetyl glucose,

Anthranil derivatives such as 2-methylanthranil or 2-phenylanthranil,

10 - enol esters such as Isopropenyl acetate,

Oxime esters such as O-acetylacetone oxime,

Carboxylic anhydrides, e.g. Phthalic anhydride or 15 acetic anhydride.

Tetraacetylethylene diamine and Na nonanoyloxybenzenesulfonates are preferably used as bleach activators. The bleach activators are heavy-duty detergents in amounts of 0.1 to 20 15% by weight, preferably in amounts of 1.0 to 8.0% by weight, particularly preferably in amounts of 1.5 to 6.0% by weight. -% added.

Suitable bleaching catalysts are quaternized imines and sulfonimines as described in US Pat. Nos. 5,360,568, 5,360,569 and 5 EP-A-0 453 003 and Mn complexes, cf. e.g. WO-A-94/21777. If bleaching catalysts are used in the detergent formulations, they are up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active manganese complexes up to 0.1% by weight .% contain. 0

The detergents preferably contain an enzyme system. These are proteases, lipases, amylases and cellulases commonly used in detergents. The enzyme system can be limited to a single one of the enzymes or contain a combination of different enzymes. Of the commercially available enzymes, amounts of 0.1 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of the finished enzyme are generally added to the detergents. Suitable proteases are Savinase ^® and Esperase (manufactured by Novo Nordisk). A suitable lipase is 0 eg Lipolase ^® (manufactured by Novo Nordisk). A suitable Cellu¬ loosely Celluzym ^® (manufactured by Novo Nordisk).

The detergents preferably contain soil release polymers and / or graying inhibitors as other common constituents. 5 These are, for example, polyesters made of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids or Polyesters from polyethylene oxides end-capped with di- and / or polyhydric alcohols and dicarboxylic acids. Such polyesters are known, cf. for example US-A-3 557 039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US -A-5 142 020.

Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US Pat. No. 4,746,456, US Pat. No. 4,846,995, DE-A-3,711,299, US) -A-4 904 408, US-A-4 846 994 and US-A-4 849 126) or modified celluloses such as, for example Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

Graying inhibitors and soil release polymers are contained in the detergent formulations in an amount of 0 to 2.5% by weight, preferably 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight. Soil release polymers used with preference are the graft polymers of vinyl acetate on polyethylene oxide of molecular weight 2500-8000 in a weight ratio of 1.2: 1 to 3.0: 1, known from US Pat. No. 4,746,456, and commercially available polyethylene terephthalate / polyoxyethylene terephthalates the molecular weight 3000 to 25000 from polyethylene oxides of the molecular weight 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-4 403 866, the blocks from (a) contain ester units from polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units from aromatic dicarboxylic acids and polyhydric alcohols. These amphiphilic block copolymers have molecular weights from 1500 to 25000.

A typical powder or granular heavy-duty detergent can, for example, have the following composition:

5 to 50, preferably 15 to 42.5% by weight of at least one inorganic builder,

5 to 30, preferably 10 to 25% by weight of an inorganic bleaching agent, 0.1 to 15, preferably 1 to 8% by weight of a bleach activator,

0 to 1, preferably up to at most 0.5% by weight of a bleaching catalyst,

0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor based on water-soluble homopolymers of N-vinylpyrrolidone or N-vinylimidazole, water-soluble copolymers of N-vinylimidazole and

N-vinylpyrrolidone, crosslinked copolymers of N-vinylimidazole and N-vinylpyrrolidone with a particle size of 0.1 to 5CC, preferably up to and including 250 μn>, the copolymers being 0.01 to 5, preferably 0.1 to Contain 2% by weight of NN'-divinylethylene urea as crosslinking agent; further color transfer inhibitors are water-soluble and also crosslinked polymers of 4-vinylpyridine-N-oxide, which can be obtained by polymerizing 4-vinylpyridine and subsequent oxidation of the polymers;

0.1 to 20, preferably 1 to 15% by weight of at least one organic cobuilder,

0.2 to 1.0% by weight of protease,

0.2 to 1.0% by weight of lipase,

0.3 to 1.5% by weight of a soil release polymer.

10 to 60, preferably 20 to 55% by weight of at least one inorganic builder,

0 to 15, preferably 0 to 5% by weight of an inorganic bleaching agent, 0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor (cf. above),

0.1 to 20, preferably 1 to 15% by weight of at least one organic cobuilder,

0.2 to 1.0% by weight of protease,

0.2 to 1.0% by weight of cellulase,

The powdery or granular detergents can contain up to 60% by weight of inorganic stabilizers as other common constituents. Sodium sulfate is usually used for this. However, the detergents according to the invention are preferably low in adjusting agents and contain up to 20% by weight, particularly preferably up to 8% by weight of adjusting agents.

The detergents according to the invention can have different bulk densities in the range from 300 to 950 g / l. Modern compact detergents generally have high bulk densities, e.g. 550 to 950 g / l, and show a granular structure.

Typical liquid detergents contain, for example:

0.1 to 20, preferably 1 to 15% by weight of at least one co-builder,

0 to 1.0% by weight of protease,

0 to 1.0% by weight of cellulase,

0 to 1.5% by weight of a soil release polymer and / or graying inhibitor,

0 to 60% by weight of water, 0 to 10 wt .-% alcohols, glycols such as ethylene glycol, diethylene glycol or propylene glycol or glycerin.

The detergents can optionally contain other customary additives. As further additives, e.g. Complexing agents, phosphonates, optical brighteners, dyes, perfume oils, foam dampers and corrosion inhibitors can be included.

Among cleaning agents, in particular those for hard surfaces, for example cleaners for cleaning metal, plastics, glass and ceramics, floor cleaners, sanitary cleaners, all-purpose cleaners in the household and in commercial applications, are intended to be more technical (for use in car washes) or high-pressure cleaners), cold cleaners, dishwashers, hand dishwashing detergents, rinse aids, disinfectant cleaners, cleaners for the food and beverage industry, in particular as bottle cleaners, as CIP cleaners (cleaning-in-place) in dairies, breweries and other food businesses - manufacturers are understood.

In addition to the applications mentioned in the field of textile detergents and as a cleaner for hard surfaces, there are also applications in cosmetics, in the photo industry, in crop protection formulations and in chain lubricants.

Further possible fields of application for the fatty acid amide derivatives XV according to the invention are the following:

Surfactants for household products:

In addition to the detergents mentioned, they are also used in detergents, such as Detergent booster for strong, localized grease soiling as well as soaking agent for generally heavily soiled laundry can be used. Detergent boosters are products rich in surfactants, the focus of which is on easy-care textiles, in which certain washing temperatures should not be exceeded. Soaking agents are usually strongly alkaline washing aids based on mixtures of anionic and nonionic surfactants that loosen stubborn and firmly adhering dirt.

Post-treatment agents (after the actual washing process) such as softening agents, tumble aids, form washers, spray starches, ironing aids and other stiffeners. Carpet cleaning agents, including detaching agents, which are offered as aerosols for removing water-soluble stains based on surfactant and alcohol, and foam cleaners (spray and liquid products with aqueous solutions of surfactants, to which water-soluble organic solvents can be added) and powder cleaners and spray extraction cleaner. The powdery cleaners suitable for intermediate cleaning consist of a combination of active cleaning solutions and carrier materials with a large surface area. The active substances contain mixtures of surfactants, solvents and water. Spray extraction cleaners are aqueous concentrated Löö-u-yer. or powders containing surfactants, water softeners and optionally defoamers.

In addition to the dishwashing detergents (manual and machine), cleaning agents such as all-purpose cleaners, abrasives, special cleaners (e.g. for limestone and urine scale) can also be used.

Surfactants for industrial cleaners:

Here are solvent-based cleaning agents and aqueous cleaning agents (alkaline, neutral, acidic), surfactants for washing cars, trucks, railroad cars (automatic washing lines, systems and engine washing as well as for manual car cleaning), passivating cleaning agents (passivating cleaning agents) the iron surfaces, if they dry on them) and combined cleaning and disinfectants (food processing industry).

Other surfactants in the food industry:

Favoring and / or stabilizing oil-in-water emulsions (mayonnaise, sauces, etc.) and water-in-oil emulsions (margarine and the like), also in the production and processing of (soft) ice cream , Biscuits, chewing gum, liquorice, caramels, chocolate, baked goods, dry products (such as powdered beverages, milk powder, pudding powder, etc.), sausage and cheese.

Agricultural surfactants:

In addition to the plant protection product formulations, they are also suitable for fertilizers, synthetic fertilizers and salts (powders, granules, prills) which tend to form agglomerates ("baking"). Surfactants show anti-caking properties if they have a hy Form a hydrophobic film on the surface of the crystals and displace the water.

Surfactants in the pharmaceutical industry (also in disinfectants):

For example, the active ingredient in a preparation can be specifically activated by surfactants, so that absorption and compatibility can be controlled.

Surfactants in the production of synthetic fibers and in the textile industry:

Pretreatment agents for fibers, production of rayon fibers, spin finishes and textile lubricants, dyeing aids, finishing agents, water repellents, auxiliaries for printing, antistatic agents and flocking and coating agents are mentioned here.

Surfactants in the plastics industry:

Here the production of plastic dispersions, bead polymers, foams, microcapsules and the use in surface-active mold release agents for coloring plastics and for antistatic finishing of plastics come into consideration.

Surfactants for biotechnology and for paints, pigments and printing inks

Surfactants for cosmetic care products and cosmetic cleaning agents

Surfactants in the pulp and paper industry:

They are suitable for resin removal in pulp and paper production, pigment dispersion and foam control in the production of paper and paper coating, paper sizing agents and their dispersion or emulsion in paper finishing, for cleaning the machines, for

Sieving and felting, for the regeneration / deinking of waste paper, for fiber recovery and wet strengthening.

Surfactants in adhesives Surfactants in the leather industry:

Here they are used for the pretreatment of the leather, tanning of the leather, post-treatment of the wet (e.g. greasing) and dry leather (e.g. dressing) and care of the leather. The surfactants XV mentioned are also suitable as dyeing aids in leather dyeing.

Surfactants in the photo industry:

Here are watering aids, antistatic agents, lubricants, emulsifiers and dispersants for the preparation of active ingredient emulsions, -disper't> iυ .- <- i- and Lc-tice-. and to name additions to inheritance baths.

Surfactants in the metalworking industry:

They are suitable in and for the production of cooling lubricants, hardness oils, hydraulic oil emulsions, polishing pastes, mold release agents, drawing oils, pickling agents, metal cleaners and metal dryers.

Surfactants in electroplating

- surfactants for corrosion inhibition

Surfactants in the manufacture of polishes and protective layers and in their removal, in particular in the case of care products for floors, shoe polish, furniture, car paints and other household and industrial items.

Surfactants as additives in the mineral oil industry:

Additives for fuels (petrol and diesel engines), aircraft turbines, heating oils and lubricants are of interest here.

Surfactants for road construction, building materials and soil restoration

- Surfactants in mining and flotation Surfactants for the extraction and processing of petroleum:

Here they are used for the extraction of petroleum, for emulsion splitting, as wetting agents, in drilling fluids, as anti-corrosion agents, for removing oil spills, for improving the injectivity during water flooding, as paraffin inhibitors.

Surfactants as biocides, for fire fighting (foam extinguishers, quick wetting of parts of buildings); Treatment of glass devices and glass fibers in order to maintain their strength and the desired properties; for dust control (e.g. in grinding processes, tensides are added to the spray water used), - Teijsidt, to pump feir.gc-r.ah.lcne coal or non-flowing heavy oils through pipelines with the help of aqueous dispersions (slurries) (increase in price).

Cleaners containing the surfactants XV according to the invention are particularly suitable for cleaning hard surfaces such as glass, ceramic, plastic and metal, e.g. of floors, tiles and tiles. The cleaners can be alkaline, acidic or neutral. They usually contain surfactants in amounts of about 5 to 90, preferably 10 to 75,% by weight, based on the active substance content. These can be anionic, non-ionic or cationic surfactants as well as mixtures of surfactants that are compatible with one another, e.g. Mixtures of anionic and non-ionic or of cationic and non-ionic surfactants. Alkaline cleaners can contain soda, potash, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodium hydroxide, potassium hydroxide, amine bases such as monoethanolamine, diethanoiamine,

Triethanolamine, ammonia or silicate in amounts up to 60% by weight, in some cases even up to 80% by weight. The cleaners can also contain citrates, gluconates or tartrates in amounts of up to 80% by weight. They can be in solid or liquid form.

The fatty acid amide derivatives XV according to the invention are particularly advantageous in that they

- have an excellent application-related property profile as surfactants in detergents and cleaning agents, in particular the universal fat-dissolving power, the good primary washing power and the good wetting power should be mentioned here;

- are low-foaming and readily biodegradable; have low surface tension and very low interfacial tension;

show synergistic effects in combination with nonionic surfactants and partially with anionic surfactants;

have good solubility even in hard water and water hardness insensitivity;

can be produced in many cases without solvents or dispersants;

in simple apparatus inexpensive in high A'jsbeπtfn. can be produced with short reaction times;

by reactions whose reaction sequence can be followed quickly and easily, for example by infrared spectroscopy (IR), gas chromatography (GC) or by common titration methods.

In many cases it has been found that mixtures of

Fatty acid amide derivatives of the general formula (XVIII)

(XVIII)

in which the substituents have the following meaning:

A ^{4 is} an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain which contains one or more groupings of the formula XVI in the chain

CH CH-

N OH (XVI)

/ \

Rl ⁴ Rl5

contains

R ¹⁴ and R ^{16 and,} independently of one another, a hydroxy- and / or amino-substituted hydrophilic radical with 2 to 40 carbon atoms.

Atoms or a C ₁ -C ₁₄ alkyl radical, the carboxyl and / or sulfonic acid groups in the form of the free 97/16408 PO7EP96 / 04560

61

Carries acids and / or their alkali metal or ammonium salts and which can be interrupted by non-adjacent oxygen atoms, -NH groups and / or N-C 1 -C ₄ -alkyl groups, and

R ¹⁵ and R ^{17 are} hydrogen, an unsubstituted Ci-C _ß- alkyl radical or a radical R ¹⁴ or R ¹⁶ , and

(ii) Fatty acid amide derivatives of the general formula XIX

E CO ^N _\ ^(χιχ)

E is an aliphatic Cβ-C ₂₄ residue with unbranched

Carbon chain means which one or more groupings of the formula XX in the chain

CH CH

OR ¹⁸ OH ^(XX) contains, wherein

R ^{18 represents} C ₁ -C ₄ alkyl, and

Ri6 and R ^{17 have} the meaning given above,

the components (i) and (ii) being in a weight ratio of 99: 1 to 1:99, in particular 90:10 to 30:70, especially 80:20 to 45:55,

lead to improvements in physicochemical and application data when used as surfactants in detergents and cleaning agents. These mixtures are therefore also the subject of the present invention.

Of particular interest here are mixtures in which the above-mentioned fatty acid amide derivatives XV occur as component (i) (ie R ^iβ / R ¹⁷ = R ¹² / R ¹³ ).

As radical R ¹⁸ , in particular ethyl, propyl, isopropyl, butyl, tert-butyl and especially methyl are possible.

Mixtures of components (i) and (ii) according to the invention can be, for example: Mixtures of fatty acid amide derivatives XVIII in which the groupings -N (R ¹⁴ ) R ¹⁵ and -N (R ¹⁶ ) R ^{17 are} each derived from hydroxyalkylamines or aminoalkylamines (preferably -N (R ¹⁴ ) R ¹⁵ and -N ( R ¹⁶ ) R ¹⁷ identical), and fatty acid amide derivatives XIX, which are also based on hydroxyalkylamines or aminoalkylamines in the amide group (preferably the identical amines to the amines in XVIII);

Mixtures of fatty acid amide derivatives XVIII, in which the groups -N (R ¹⁴ ) R ¹⁵ and -N (R ¹⁶ ) R ^{17 are} each derived from amino acids (preferably -N (R ¹⁴ ) R ¹⁵ and -N (R ¹⁶ ) R ¹⁷ identical), and fatty acid amide derivatives XIX, which are also based on Mi.-io-.aurei. ixi the A-rάdgruppierung {delay * .. 'ise the identical amino acids to the amino acids in XVIII);

Mixtures of fatty acid amide derivatives XVIII, in which the groupings -N (R ¹⁴ ) R ^{15 are derived} from amino acids and the grouping -N (R ¹⁶ ) R ^{17 is derived} from hydroxyalkylamines or aminoalkylamines, and fatty acid amide derivatives XIX, which are likewise derived from hydroxyalkylamines or aminoalkylamines the amide group (preferably the identical amines to the amines in the amide group -N (R ¹⁶ ) R ¹⁷ of XVIII);

Mixtures of fatty acid amide derivatives XVIII, in which the groupings -N (R ¹⁴ ) R ^{15 are derived} from hydroxyalkylamines or aminoalkylamines and the grouping -N (R ¹⁶ ) R ^{17 is} derived from amino acids, and fatty acid amide derivatives XIX, which are also based on amino acids in the amide grouping (preferably the identical amino acids to the amino acids in the amide group -N (R ¹⁶ ) R ¹⁷ of XVIII).

The mixtures according to the invention can be prepared by corresponding epoxidized fatty acid amides, in particular the above-mentioned epoxidized fatty acid amides XVII, or corresponding epoxidized fatty acid esters, fatty acids or their salts with corresponding amines in the presence of alkanols of the formula R ¹⁸ -0H or their Salting. Some of the epoxy groups then react with the amine, the other with the alkanol. With regard to the fatty acid amide derivatives XIX, as with the fatty acid amide derivatives XVIII, isomer mixtures are generally obtained, since the oxirane rings can open at both C-O bonds.

Since the reaction of the said epoxidized fatty acid derivatives with the amines in some cases takes place under alkali metal alcoholate catalysis - for example, 1 to 60 mol%, in particular 5 to 30 mol%, based on the amount to be converted is preferably used. amine, an alkali metal alcoholate such as sodium methoxide or sodium ethanolate - the built-in residue -OR ¹⁸ comes from this alcoholate. If a fatty acid lower alkyl ester, for example a fatty acid methyl ester, is used as the starting material, the built-in radical -OR ¹⁸ comes from this alcohol released by exchanging the alcohol residue for the amine residue.

In addition to more favorable physicochemical and application properties, the mixtures according to the invention also have the advantage that no excess amine can be removed for their preparation if such free amine is not desired in the product, because without the reaction with alkanols κ ^ιε - üH become noiiuαlerweiae ÜLci≤chuß-.iei "iC," he. to Arr.ir_ is required to fully open the oxirane ring, since amines are somewhat less reactive than alcohols or alcohol ions under the reaction conditions towards oxiranes. Furthermore, the mixtures according to the invention are readily biodegradable.

The present invention furthermore relates to detergents and cleaning agents which contain the mixture according to the invention of components (i) and (ii) as surfactants in the amounts customary for this purpose and other additives customary for such agents. The surfactant mixture mentioned comprises (i ) and (ii) is also suitable as a dyeing aid for leather dyeing.

The present invention is illustrated by the following examples.

The percentages in the examples mean% by weight, unless stated otherwise.

Example 15

Reaction product of diethanoiamine and sarcosine with epoxidized. Rape oil methyl ester

152.8 g (0.5 mol) of epoxidized beet oil methyl ester and 14.4 g NaOCH ₃

(30% in methanol, 0.08 mol) were at 100 ° C with 52.5 g

(0.5 mol) diethanoiamine added. After the additions were complete, stirring was continued for 15 minutes. , checked for complete amidation by means of IR and GC, then mixed with 56.0 g (0.5 mol) of sarcosine sodium salt and heated at 160 ° C. for a further 6 h. The conversion was checked by means of GC, amine-epoxy double titration and Preussmann test and the product mixture was released after the reaction was complete. The product was a tan solid and clearly water soluble. Example 16

Reaction product of diethanoiamine and glycine with epoxidized rape oil methyl ester

152.8 g (0.5 mol) of epoxidized beet oil methyl ester and 14.4 g of NaOCH ₃ (30% in methanol, 0.08 mol) were mixed with 52.5 g (0.5 mol) of diethanoiamine at 100 ° C. After the addition had ended, the mixture was stirred for a further 15 min. after, checked for complete amidation by means of IR and GC, then added 49.1 g (0.5 mol) of glycine sodium salt and heated at 150 ° C. for a further 6 h. The conversion was checked by means of GC, amine-epoxy double titration and a Prussian test, and Je-o was left after complete reaction eb. The product was a light yellow solid and clearly soluble in water.

Example 17

Reaction product of aminopropyldiethanolamine and glycine with epoxidized beet oil methyl ester

152.8 g (0.5 mol) of epoxidized beet oil methyl ester and 14.4 g of NaOCH ₃ (30% in methanol, 0.08 mol) were mixed with 81.2 g (0.5 mol) of aminopropyldiethanolamine at 100 ° C. After the addition had ended, the mixture was stirred for a further 20 min. after, checked for complete amidation by means of IR and GC, then added 49.1 g

(0.5 mol) glycine sodium salt and heated at 150 ° C. for a further 6 h. The conversion was checked by GC, amine-epoxy double titration and Prussian test and the product mixture was discharged after the reaction was complete. The product was a light yellow solid and clearly water soluble.

Example 18

Reaction product of aminopropyldiethanolamine and sarcosine with epoxidized rapeseed oil methyl ester

41.8 g (0.26 mol) of aminopropyldiethanolamine and 7.4 g (0.04 mol, 33% in methanol) of NaOCH ₃ were placed in a laboratory reactor under protective gas. 89.0 g (0.3 mol) of epoxidized rape oil methyl ester were then added dropwise. In the meantime, the temperature was raised to 120 ° C. After 20 min. Intermediate stage III had already formed, which was easily detectable by GC analysis. The methanol released from the methyl ester remained (as did the methanol from the 30% NaOCH ₃ solution) in the reaction vessel (reflux). 78.4 g were added to this mixture with stirring

(0.3 mol) sarcosine sodium salt solution (aqueous, 42.9%). 15 g of water were added for dilution. After finished Addition, the temperature was raised to 140 ° C. The mixture was then stirred for about 10 h until no more epoxide (intermediate XVII) was detectable by GC. The reaction product was filled out. The surfactant was obtained as a dark yellow oil.

Application properties

The interfacial tension, the contact angle, the surface tension, the solubility and the fat-removing ability were investigated as the application properties of the fatty acid amide derivatives XV. The measurement results of the substances of Examples 15 and 16 are summarized in Table 8.

The interfacial tension was determined as a function of the contact time between an aqueous surfactant solution and an oil phase.

The contact angle was measured as the wetting ability of a hard surface by the surfactant solution. Complete wetting (spreading) corresponds to zero contact angle.

To determine the fat-removing capacity, solid platelets wetted with motor oil or neutral oil are dipped horizontally into the surfactant solution to be investigated (c = 1 g / l). The time until the first oil drop is removed from the respective plate is measured. The shorter this time, the better the fat loss capacity.

Table 8

LAS: Na dodecylbenzenesulfonate

The fatty acid amide derivatives XV according to the invention show a typical property profile of anionic surfactants. They stand out from conventional anionic surfactants such as LAS due to their lower surface tension and lower interfacial tension, especially with a longer oil contact time. In particular, they show a very good fat-removing ability of olive oil and neutral oil from glass, they are usually soluble in clear water or only slightly cloudy in hard water.

The reaction products of aminopropyldiethanolamine with sarcosine or glycine and epoxidized beet oil methyl ester (examples 17 and 18) show similarly good performance properties as the reaction products of diethanoiamine with sarcosine or glycine and epoxidized beet oil methyl ester (examples 15 and 16). Example 19 and Comparative Example 20

The substances from Example 15 were further tested under standard conditions (60 ° C., 5 g / l) in a model detergent formulation together with a C ₃ / Is oxo alcohol reacted with 7 mol of ethylene oxide as nonionic surfactant (19% surfactant additive , 47% of which the substance from Example 15 and 53% of the non-ionic surfactant mentioned) (Example 19). The comparison used was an analog model detergent formulation with 19% of surfactant, of which 47% of a Cι ₂ / ιβ * alkyl sulfate as the anionic surfactant and 53% of the ge nonionic surfactant called (Example 20).

uie iiαsuiϊciouwu uL.ki.ws--.ir wj _* cnyc leads:

Launder-O-meter washing machine from Atlas

Washing cycles 1

Rinse cycles 1

Wash temperature 60 ° C

Washing time 30 min.

Water hardness 3 mmol / 1

Ca: Mg 4: 1

Amount of liquor 250 ml

Detergent concentration 5 g / l

Dirt fabric WFK 10 D, WFK 20 D test fabric from WfK-Testgewebe GmbH EMPA 101, EMPA 104 test fabric from the Swiss Federal Material Testing Institute St. Gallen

Detergent formulation A:

Zeolite A 30%

Sodium carbonate 12%

Sodium silicate 3%

Tylose CR 1500 p 1.2%

Sodium perborate monohydrate 14.4%

Tetraacetylethylenediamine 4%

Acrylic acid / maleic acid - 5% copolymer (MW 70000)

Soap 0.5%

Sodium sulfate 4%

Water 6.9%

Surfactant mixture (see above) 19% After rinsing, the fabrics were spun and the fabrics hung up individually to dry. The fabric was measured with an Elrepho 2000 from Data Color, Heidenheim, namely 6 measuring points per piece of fabric. The reflectance value was determined at 480 nm.

The sum of the reflectance values R gave the value 205.9 (8282.1 absolute effectiveness) for example 19 and the value 190.7 (75 75.9 absolute effectiveness) for the comparison example 20 (blank value without surfactant system: R = 140 , 6 = 41.6 absolute effectiveness). It is clear from this that the combination of the fatty acid amide derivatives XV according to the invention with nonionic surfactants produces synergistic effects in primary washing.

Examples 21 to 23

Reaction products of diethanoiamine with epoxidized rape oil methyl ester with the use of sodium methylate / methanol (example 21)

A mixture of 1575 g (15 mol) of diethanoiamine and 369 g of sodium methylate solution (2.0 mol, 30% in methanol) was heated to 90 ° C. under a protective gas atmosphere and under reflux and slowly at this temperature with 2291 g ( 7.5 mol) of epoxidized rape oil methyl ester. The mixture was then heated to 130 ° C. and stirred at this temperature for a further 5 h. The conversion was checked by means of GC, amine-epoxy double titration and Preussmann test and the product mixture was released after the reaction was complete. The reaction product was obtained as a highly viscous yellowish liquid. It contained the corresponding components (i) and (ii) in a weight ratio of 80:20.

Example 22

Example 21 was repeated with the difference that instead of 15 mol of diethanoiamine only 7.5 mol of diethanoiamine was used. The resulting product mixture contained the corresponding components (i) and (ii) in a weight ratio of 45:55.

Example 23

Analogously to Example 21, starting from 15 mol of diethanoiamine, 2.0 mol of NaOCH ₃ , 15 mol of methanol and 7.5 mol of epoxidized rape oil methyl ester, a product mixture was produced which contained the corresponding components (i) and (ii) in weight. Ratio of 61:39 included. Application properties

The interfacial tension, the contact angle, the surface tension, the cloud point, the wetting power on cotton, the solubility and the ability to remove grease were investigated as the application properties of the mixtures of components (i) and (ii). The measurement results of the product mixtures of Examples 21 to 23 are summarized in Table 9.

The wettability of a hard surface through the surfactant solution was measured via the rend angle. Complete wetting (spreading) corresponds to zero contact angle.

To determine the fat dissolving power, solid platelets wetted with neutral oil or olive oil are dipped horizontally into the surfactant solution to be investigated (c = 1 g / l). The time until the first oil drop is detached from the respective plate is measured. The shorter this time, the better the fat loss capacity.

Table 9

The interfacial tension values of the mixtures according to the invention of components (i) and (ii) against the various oils are significantly lower than those of conventional nonionic surfactants such as corresponding sugar surfactants or corresponding fatty alcohol ethoxylates. The wetting capacity on cotton of the mixtures according to the invention is at least as good as that of most conventional nonionic surfactants. Your fat-removing ability from various Sen surfaces, especially in olive oil, is significantly better than many common nonionic surfactants, such as fatty alcohol ethoxylates.

Biodegradability

The mixture of components (i) and (ii) according to the invention show degradation values of 40 to 60% in the modified storm test in the order of 40 to 60% DOC degradation after 28 days and degradation values in the order of 50 to 70% in the tooth-wave test. after 28 days or 80 to 90% after 56 days (DOC elimination level in each case). With an increasing proportion of component (ii) in the inventive mixtures, the biodegradability also increases noticeably.

However, it has also been found that not only the mixtures of fatty acid amide derivatives XVIII and fatty acid amide derivatives XIX referred to above are of interest, but also frequently the pure fatty acid amides substituted vicinally in the fatty acid chain or vicinally dihydroxy-substituted dihydroxy fatty acids as surface-active Substances have improved physicochemical and application data.

K.L. Johnson describes in J. Am. Oil Chem. Soc, 1966, 43, pp. 497-500 as nonionic detergents based on epoxidized oils, the compounds obtainable by reaction of methylpolyglycols with methyl epoxystearic acid and subsequent reaction with alkanolamines. The reaction of the methyl polyglycols with the epoxy ester takes place in the presence of a "Friedel-Crafts catalyst" such as tin tetrachloride, boron trifluoride or antimony pentachloride. The fatty acid amides obtained are recommended as surface-active agents in low-foam cleaners, in dishwashing detergents, in floor cleaning agents and in other cleaning formulations.

From WO-A 90/09366 vicinally C ₃ - to Cio-alkenoxy (or alkynoxy) -hydroxy-substituted fatty acid amides are known in the fatty acid chain. These are suitable as emulsifiers, textile auxiliaries or cosmetic additives.

Since corresponding vicinal Ci to C ₄ -alkoxy-hydroxy-substituted fatty acid amides have not been described in the prior art and have proven to be advantageous, also subject of the present invention are mel fatty acid amide of the general research XXI

in the

G is an aliphatic Cβ * C ₂₄ radical with an unbranched carbon chain which has one or more groupings of the formula XXII in the chain

- CH CH— OR ¹⁹ OH ⁽ XXII ⁾ contains, where

R ¹⁹ represents C 1 -C ₄ -alkyl or hydrogen,

R ^{16 is} a hydroxyl- and / or amino-substituted hydrophilic radical having 2 to 40 C atoms or a C ₁ -C ₁₄ alkyl radical which carries carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali metal or ammonium salts and which can be interrupted by non-adjacent oxygen atoms, -NH groups and / or NC ₁ -C ₄ alkyl groups means and

j> - ⁷ 'Messersteff denotes an unsubstituted Ci -Cr alkyl radical or an R ¹⁶ radical.

The unsaturated unbranched aliphatic fatty acids are those mentioned above. Unsaturated Ciβ fatty acids are preferred.

Methyl is particularly suitable as the C 1 -C ₄ -alkyl radical for R ¹⁹ .

The amines HN (R ¹⁶ ) R ¹⁷ on which the amide groups in XXI are based, with one or two nonionic hydrophilic substituents, can be branched and carry several hydroxyl or amino groups such as (trishydroxymethylene) methylamine, but preferably have at least one unbranched ω-hydroxyalkyl group or one unbranched ω-aminoalkyl group, each having 2 to 6 carbon atoms, the underlying alkyl group being formed by non-adjacent oxygen atoms, NH groups, NC ₁ -C ₄ alkyl groups, NC ₁ -C ₄ hydroxyalkyl groups or N-C ₁ -C ₄ -Aminoalkyl groups can be interrupted. Furthermore, the N-Ci-C ₄ -alkyl-substituted derivatives are suitable if they still contain at least one reactive amino or imino group.

Such amines include, in particular, those mentioned above.

The compounds containing the amide groupings -N (R ¹⁶ ) R ¹⁷ in XXI on which the carbon and / or sulfonic acid residues are based are, in particular, amino acids as mentioned above.

The present invention also relates to a process for the preparation of the fatty acid derivatives XXI according to the invention, which is characterized in that an epoxidized fatty acid derivative of the general formula XXIII B ³ -CO-R ²⁰ (XXIII)

in the

B ^{3 is} an aliphatic Cβ-C24 radical with unbranched carbon chain, which contains one or more epoxy groups in the chain, and

R ^{20 is} a hydroxyl radical and its alkali metal or ammonium salts, a C ₁ -C ₄ alkoxy radical or a radical of a mono-, di- or triglyceride, the di- or triglyceride radicals being residues of natural saturated or unsaturated fatty acids,

mean,

with a Ci to C ₄ alkanol or water catalyzed by protic acids or Lewis acids to the fatty acid derivative of the general formula XXIV

G-CO-R ²⁰ (XXIV)

in which G has the meaning given above, and then reacted with an amine of the general formula XXV

R "H -N tT (xxv)

^ R ⁱ⁷

to the fatty acid amide derivative XXI.

The reaction of the epoxidized fatty acid derivative with 2 equivalents of amine is base-catalyzed by the conventional method, as described above. One molar equivalent of the amine initially reacts with the ester to form amine, then the remaining amine reacts with the epoxide. The alkanol released from the alkyl ester, like the alkanol from the alcoholate catalyst solution, usually remains in the reaction system according to this process, as a result of which the alcohol competes with the amine when attacking the epoxy group and it also forms in the fatty acid chain alkoxy-substituted structures comes.

In the process according to the invention, the epoxidized fatty acid derivative XXIII, usually an ester or triglyceride, is first acid-catalyzed, preferably using Lewis acids such as BF ₃ . OEt ₂ , FeCl ₃ or TiCl ₄ or with protonic acids such as tetrafluoroboric acid, orthophosphoric acid or phosphorous acid or with acidic rem ion exchanger with which alcohol is reacted. The epoxide is opened very quickly to the vicinal alkoxy-hydroxy-fatty acid ester. There is no transesterification. This ester or triglyceride is then base-catalyzed with the hydrophilic amine or the amino acid to form the surface-active compound. The vicinal alkoxy-hydroxy fatty acid ester can be distilled for purification or can also be used directly in the subsequent amidation. These two reaction steps can also be easily combined to form a "one-pot reaction". In this case, slightly more basic catalyst must be used to neutralize the acidic catalyst.

EbST-f? ! ! * ⁵ f -'Ch Cλ?. <? eoτn f) <aιj .- «τι pnΛyi r "-j pτ-l- f = - Pot- I-. acid derivative, usually an ester or triglyceride, acid-catalyzed, preferably with protic acids such as H ₃ P0 ₄ , H ₃ P0 ₃ or HBF ₄ or with an acidic ion exchanger, with water The epoxide is opened to the vicinal dihydroxy fatty acid ester, and under the chosen reaction conditions there is practically no saponification to give the carboxylic acid, and this ester is then reacted with the hydrophilic amine or the amino acid, the vicinal dihydroxy Fatty acid ester can be distilled for purification or can also be used directly in the subsequent amidation.

The process according to the invention differs from the conventional base-catalyzed process in particular in that the total reaction time is significantly shortened, since the rate-determining epoxide opening is considerably faster in the present acid catalysis (generally <30 min compared to> 300 min).

Since the conventional method, as described above, uses two equivalents of amine per epoxidized fatty acid derivative, a residue of unreacted amine usually remains in the product due to by-product formation (depending on conditions, up to 20% by weight is possible). After the acid-catalyzed process, the amine is required exclusively for the amidation of the ester. There are no significant competitive reactions. The amine therefore reacts almost completely. It is thus possible with this process to achieve a residual amine content in the product of <1% by weight.

The uniform products produced by the acid-catalyzed process are highly viscous, sufficiently pure and clearly water-soluble. The amidation can be carried out without a solvent. However, opening the epoxy with the alcohol usually requires a certain excess of alcohol (usually 5 to 10 equivalents of alcohol) as a solvent. The excess alcohol can then be removed from the product without problems, for example by distillation. The alcohol can be used again for the epoxy opening. In the synthesis of the vicinal dihydroxy fatty acid esters, toluene or cyclohexane is preferably added. In both cases, the solvent can then simply be separated from the higher-boiling product of value in a vacuum. The direct conversion of the epoxidized oil into water is also possible (without additional organic solvent). An added phase transfer catalyst shortens the reaction time.

The fatty acid amide derivatives XXI according to the invention are compounds with excellent surface-active properties, which are therefore outstandingly suitable for use as nonionic or anionic surfactants in detergents and cleaning agents, as described above. Low surface and interfacial tension are found in the test. In addition, they show good fat dissolving power and good primary washing power. In addition, they also have good solubility in hard water and are generally insensitive to water hardness.

The present invention therefore also relates to detergents and cleaning agents which contain the fatty acid amide derivatives XXI according to the invention as surfactants in amounts customary for this purpose and other additives customary for such agents. The surfactants XXI mentioned are also suitable as dyeing aids in leather dyeing.

The fatty acid amide derivatives XXI according to the invention are simple and inexpensive to produce by means of the process described. When carrying out the reaction by means of the "one-pot reaction" mentioned, only a simple apparatus (for example a conventional stirred kettle) is required, in which the reaction can be carried out in short yields in high yields. Here, the course of the reaction can be tracked quickly and easily using infrared spectroscopy, gas chromatography (GC) or titrations.

The fatty acid amide derivatives XXI according to the invention are based on renewable raw materials and are therefore particularly ecologically advantageous. As a rule, they are readily biodegradable. The present invention is illustrated by the following examples.

The percentages in the examples mean% by weight, unless stated otherwise.

Example 24

Synthesis of 9,10-hydroxy-methoxy-stearic acid methyl ester by reacting epoxidized rape oil methyl ester with methanol

3000 g (93.75 mol) of methanol were introduced and vprsetrl- with 4461 g (15.04 mol) of epoxidized rape oil methyl ester, slowly and dropwise, a total of 12.4 g (0.087 mol) of BF ₃ -OEt ₂ were then added, the The reaction mixture started to boil. Without further heating, stirring was continued for 30 minutes. further, checked the complete conversion by GC analysis and then added 4.7 g (0.26 mol) of H ₂ O for the hydrolysis of the BF ₃ -OEt ₂ . The mixture was then concentrated in vacuo (45 ° C.). The ester obtained could be used directly for further reactions.

Example 25

Synthesis of 9,10-hydroxy-isopropoxy-stearic acid methyl ester by reaction of epoxidized beet oil methyl ester with isopropanol

56.3 g (0.94 mol) of methanol were introduced and 44.7 g (0.15 mol) of epoxidized rape oil methyl ester were added. A total of 0.13 g (0.9 mmol) of BF ₃ -OEt _{2 was then} added slowly and dropwise at room temperature, the reaction mixture being heated to 50.degree. Without further heating, stirring was continued for 30 minutes. further, checked the complete conversion by GC analysis and then added 2 drops of H ₂ O for the hydrolysis of the BF ₃ -OEt ₂ - the mixture was then concentrated in vacuo (45 ° C.). The ester obtained could be used directly for further reactions.

Example 26

Reaction of epoxidized beet oil methyl ester with water under acidic catalysis

916.5 g (3.0 mol) of epoxidized beet oil methyl ester were dissolved in 1200 ml of toluene, and 108 g (6.0 mol) of water and 45.0 g (0.48 mol) of orthophosphoric acid (85% strength) were added. 13.0 g (20 mmol) of tetrabutylammonium hydroxide solution (40%) were added as the phase transfer catalyst. This mixture was kept under for 4 h Reflux heated. The complete conversion was checked by epoxy titration and then concentrated in vacuo (50 ° C.). The ester obtained could be used directly for further reactions.

Example 27

Reaction of epoxidized soybean oil with water under acidic catalysis

124.5 g (0.5 mol) of epoxidized soybean oil were dissolved in 200 ml of toluene and mixed with 18 g (1.0 mol) of water and 9.3 g (0.08 mol) of ortho-pVioβpi-ior-säii ro ( ^p ς% ig) presupposes, As PhaRr-nt'r? "-> ^e ! f ^ rV -» * - »iy? f» tor 3.1 g (5 mmol) of tetre-butylammonium hydroxide This solution was heated under reflux for 5 hours, the complete conversion was checked by epoxy titration and then concentrated in vacuo (45 ° C.) The triglyceride obtained could be used directly for further reactions.

Example 28

Reaction of methyl dihydroxystearate with aminopropyldiethanolamine

A mixture of 64.8 g (0.4 mol) of aminopropyldiethanolamine and 41.0 g of sodium methylate solution (0.228 mol, 30% strength in methanol) was heated to 80 ° C. under an inert gas atmosphere and under reflux and slowly at this temperature 154.8 g (0.4 mol) of methyl di-hydroxystearate from Example No. 26 were added. The mixture was then heated to 100 ° C and at this for 1 h

Temperature stirred. The conversion was checked by GC and the product mixture was discharged after the reaction was complete. The reaction product was obtained as a highly viscous yellowish liquid.

Example 29

Reaction of 9, 10-hydroxy-methoxy-stearic acid methyl ester with aminopropyldiethanolamine

Analogously to Example No. 28, 9, 10-hydroxy-methoxy-stearic acid methyl ester from Example 24 was reacted with aminopropyldiethanolamine in the presence of sodium methylate solution. Application properties

The interfacial tension, the contact angle, the surface tension, the wetting power on cotton, the solubility and the fat-removing ability were investigated as the application properties of the fatty acid amide derivatives XXI. The measurement results of the substances of Examples 29 and 28 are summarized in Table 10.

The contact angle was measured as the wettability of a hard surface by the surfactant solution. Complete wetting (spreading) corresponds to zero contact angle.

To determine the fat-removing capacity, solid platelets wetted with motor oil or neutral oil are immersed horizontally in the surfactant solution to be investigated (c = 1 g / l). The time until the first oil drop is removed from the respective plate is measured. The shorter this time, the better the fat loss capacity.

Table 10

The interfacial tension values of Umsetzung¬ invention sprodukte against the various oils are sometimes significantly niedri¬ ger than the corresponding market sugar surfactants and ^■ "corresponding fatty alcohol ethoxylates All syntheti¬ terraced products, the fat-removal capacity is surfaces of various Ober¬ -. Especially in olive oil - at least comparable to or significantly better than that of conventional surfactants, especially the reactions with aminopropyldiethanolamine lead to products

40 with better colloid chemical properties, in particular with regard to the interfacial tension and the stability to water hardness.

45 In the Zahn-Wellens test, the reaction product from Example No. 29 shows good biodegradability or eliminability: the DOC elimination degree is <10% after 3 h and 60-70% after 28 d.

Claims

claims

1. Use of fatty acid derivatives of the general formula I

Al - CO - R ¹ _τ

as surfactants for cleaning agent systems for cleaning grease-soiled non-textile material, the substituents having the following meanings:

A ^{1 is} an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain, which contains one or more groupings of the formula II in the chain

CH- CH-

II

N OH

R Λ ² contains R ³ ;

R ^{1 is} a radical -N (R ² ) R ³ , a hydroxyl radical and its

Alkali or ammonium salts, a C 1 -C ₄ alkoxy residue or a residue of a mono-, di- or triglyceride, where the latter two residues can be natural saturated or unsaturated fatty acids or the same or different residues A;

R ^{2 is} a hydrophilic radical with 2-40 C atoms;

R ^{3 is} hydrogen, a C ₁ -C ₄ alkyl radical or one of the radicals R ² .

2. Use of fatty acid derivatives of the formula I according to claim 1, in which the substituents have the following meanings:

A ^{1 is} an aliphatic Cβ-C ₂₄ * radical with an unbranched carbon chain which contains one or more groups of the formula II in the chain

contains

R ^{1 is} a radical -N (R ² ) R ³ ;

R ^{2 is} a hydrophilic radical with 2-40 C atoms;

^ ³ hydrogen, a "Cι-C ₄ -Alky.lrept or a ήor- Re" 5 * -p R ² .

3. Use of fatty acid derivatives of the formula I according to claims 1 and 2, in which the radical A ^{1 is derived} from an unsaturated Ciβ fatty acid.

4. Use of fatty acid derivatives of the formula I according to claims 1 to 3, in which R ² denotes an unbranched ω-hydroxyalkyl group or an unbranched ω-aminoalkyl group with 2 to 6 C atoms, the alkyl radical not being adjacent beard oxygen atoms, -NH groups, N-Cχ-C ₄ alkyl groups or N-Cι-C ₄ hydroxyalkyl groups can be interrupted.

5. Use of fatty acid derivatives of the formula I according to claims 1 to 3, in which R ^{2 can be} a polyalkylene glycol group having 3 to 40 carbon atoms.

6. Use of fatty acid derivatives of the formula I as claimed in claims 1 to 5 as surfactants for machine cleaning processes.

7. Use of fatty acid derivatives of the formula I as claimed in claims 1 to 5 as surfactants in a mixture with other surfactants.

8. Fatty acid derivatives of the general formula Ia

A ⁱ -COOR ⁴ Ia in which R ^{4 is} hydrogen or an alkali metal or ammonium cation of the corresponding fatty acid salt and A ^{1 has} the meaning given in claim 1.

9. Agents suitable for cleaning non-textile materials on an aqueous basis, containing fatty acid derivatives of the formula I according to Claims 1 to 5 and other additives customary for such agents.

10. Alkoxylated fatty acid derivatives VII, obtainable by reaction of the compounds VIII

A ² CO R ⁵ VIII, where the substituents have the following meanings:

Λ ² an aliphatic Co-r " _2ä -P ° Pt" mi * - πr <ver''v ^τ, - _' igt'; r carbon chain, which contains one or more groups of the formula IX in the chain

- CH CH -

N OH IX

/ \

R6 R ⁷

contains;

R ^{5 is} a radical -N (R ⁶ ) R ⁷ , a hydroxyl radical and its alkali or ammonium salts, a C ₁ -C ₄ alkoxy radical or a radical of a mono-, di- or triglyceride, the di- or triglyceride radicals being more natural are saturated or unsaturated fatty acids or identical or different radicals A ² and

R ⁶ and R ⁷ independently of one another are hydrogen, an unsubstituted C 1 -C 6 -alkyl radical or a C 1 -C ₁₄ -alkyl radical which is hydroxyl-, amino-substituted and / or aminocarbonyl-substituted and / or by non-adjacent oxygen atoms, NH groups and / or NC ₁ -C ₄ -alkyl groups can be interrupted and / or carry the radicals -COOH or -S0 ₃ H and their alkali metal salts or ammonium salts,

11. Alkoxylated fatty acid derivatives VII according to claim 10, obtained by converting the compounds VIII A ² CO R ⁵ VIII, where R ^{5 is} a radical -N (R ⁶ ) R ⁷ .

5 12. Alkoxylated fatty acid derivatives VII according to claims 10 or 11, in which the radical A ^{2 is derived} from an unsaturated Ciβ fatty acid.

13. Alkoxylated fatty acid derivatives VII according to claims 10 to 10 12, in which R ⁶ and R ⁷ independently of one another are hydrogen, an unbranched ω-hydroxyalkyl group or an unbranched ω-aminoalkyl group having 2 to 6 carbon atoms, the

Alkyl radical can be interrupted by non-adjacent oxygen atoms, ϊHi groups or NC ₁ -C ₄ alkyl groups. 15

14. Alkoxylated fatty acid derivatives VII according to claims 10 to 12, in which the grouping

R ^ß 20 N <^

R ⁷

means the rest of an amino acid.

25 15. Alkoxylated fatty acid derivatives VII according to claims 10 to 14, obtainable by reacting the compounds VIII with a total of 3 to 12 equivalents of ethylene oxide per equivalent IX.

16. A process for the preparation of the compounds VII according to claims 30 to 14, characterized in that the compounds VIII are reacted with a total of 3 to 15 equivalents of ethylene oxide, propylene oxide and / or butylene oxide per equivalent IX.

5 17. The method according to claim 16, characterized in that the reaction takes place in the absence of an additional solvent.

18. Use of the fatty acid derivatives VII according to claims 10 0 to 15 as surfactants in detergents and cleaning agents.

19. Detergents and cleaning agents containing surfactants VII according to claims 10 to 15 and other additives customary for such agents. 5

20. Fatty acid derivatives villa of the general formula A ³ CO R ⁸ Villa where the substituents have the following meaning:

A ^{3 is} an aliphatic Cβ * C24 * radical with an unbranched carbon chain which has one or more groups of the formula IXa in the chain

CH CH

N OH IXa / \ R ⁹ R ^IO

contains;

R ^{8 is} a radical -N (R ⁶ ) R ⁷ , a hydroxyl radical and its alkali metal or ammonium salts, a C ₁ -C ₄ alkoxy radical or a radical of a mono-, di- or triglyceride, the di- and

Triglyceride residues of natural saturated or unsaturated fatty acids or identical or different residues A ³ can be and

R ^{9 is} a C 1 -C 6 -alkyl radical which may be hydroxyl-, amino-substituted and / or aminocarbonyl-substituted and / or may be interrupted by non-adjacent NH groups and carries a radical -S0 ₃ H or at least one radical -COOH and their alkali metal salts or Ammonium salts and

Rio hydrogen, or one of the residues R ⁹ ,

21. A process for the preparation of the fatty acid derivatives Villa according to claim 20, characterized in that an epoxidized fatty acid derivative of the general formula X

B ² - CO - R ^U X in the

B ^{2 is} an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain, which contains one or more epoxide groups in the chain and

R ^{Ü is} a hydroxyl radical and its alkali metal or ammonium salts, a C 1 -C ₄ -alkoxy radical or a radical of a mono-, di- or triglyceride, the di- or triglyceride cerid residues of natural saturated or unsaturated fatty acids or identical or different residues A ³ ,

mean,

with at least one equivalent of amino acid HN (R ⁹ ) R ⁱ ° per epoxy unit and then, if appropriate, derivatized in the usual way.

22. Use of the fatty acid derivatives villa according to claim 20 as surfactants in detergents and cleaning agents.

23. Detergents and cleaning agents containing surfactants Villa according to claim 20 and other usual for such agents

Additives.

24. Fatty acid amide derivatives of the general formula XV

in which the substituents have the following meaning:

CH CH-

N OH (XVI)

/ \

Rl ⁴ Rl5

contains

R ^{12 is} a hydroxy- and / or amino-substituted hydrophilic radical with 2 to 40 C atoms,

R ¹³ is hydrogen, an unsubstituted Ci-C _ß alkyl radical or a radical R ^12,

R ^{14 is} a C ₁ -C ₁₄ alkyl radical which carries carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali metal or ammonium salts and which is not neighboring oxygen atoms, -NH groups and / or NC ₁ -C ₄ alkyl groups can be interrupted,

R ^{i5 is} hydrogen, an unsubstituted Ci-C _ß- alkyl radical or 5 a radical R ⁱ⁴ ,

where the meaning of the two pairs of substituents Ri ² / Ri ³ and Ri ⁴ / R ^{15 can} also be interchanged.

10. 25. Fatty acid amide derivative XV according to claim 24, in which the radical A ^{4 is derived} from an unsaturated Ciβ fatty acid.

26. Fatty acid amide derivatives XV according to claim 24 or? 5, with dpτ> en R ⁱ² an unbranched ω-hydroxyalkyl group or an un-

15 indicates chain ω-aminoalkyl group each having 2 to 6 carbon atoms be¬, wherein the underlying alkyl group to be interrupted by nonadjacent oxygen atoms, NH groups, N-Cι-C ₄ alkyl, NC ₁ -C ₄ hydroxyalkyl or N-Cι -C ₄ aminoalkyl groups can be interrupted.

20th

27. Fatty acid amide derivative XV according to claims 24 to 26, in which the grouping

means the rest of an amino acid.

30 28. A process for the preparation of fatty acid amide derivatives XV according to claims 24 to 27, characterized in that an epoxidized fatty acid amide of the general formula XVII

35 _B 3__ _C0 _ _N ^ ^Rl2 (XVII)

^ Rl ³ in B ^{3 is} an aliphatic Cβ-C ₂₄ radical with unbranched carbon chain, which contains one or 40 more epoxy groups in the chain, with at least one

Equivalent amine of the general formula HN (Ri ⁴ ) R ⁱ⁵ per epoxy unit, where the substituents R ¹² to R ^{15 have} the meaning given above.

45 29. Epoxidized fatty acid amides of the general formula XVII _B 3 _ _C0 _ _NC ^ ^{Rl2 (} XVII)

^ R ^l3

in which the substituents have the following meaning:

B ^{3 is} an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain which contains one or more epoxy groups in the chain,

R ^{i2 is} a hydroxy and / or amino substituted hydrophilic

Residue with 2 to 40 carbon atoms or a C 1 -C ₄ alkyl residue, the carboxyl and / or Sαllonaäuryiuppen in Foiiu of free acids and / or their alkali metal or ammonium salts and by non-adjacent oxygen atoms, -NH groups and / or NC ₁ -C ₄ alkyl groups can be interrupted, and

R ^{i3 is} hydrogen, an unsubstituted Ci-Cβ-alkyl radical or a radical R ⁱ² ,

as intermediates in the manufacture of surfactants.

30. A process for the preparation of epoxidized fatty acid amides XVII according to claim 29, characterized in that corresponding epoxidized fatty acid esters, epoxidized fatty acids or salts thereof with one or approximately one equivalent amine of the general formula HN (R ⁱ² ) R ⁱ³ per carboxylic acid unit.

31. Use of epoxidized fatty acid amides XVII according to claim 29 as intermediates in the preparation of tensides.

32. Use of fatty acid amide derivatives XV according to claims 24 to 27 as surfactants in detergents and cleaning agents.

33. Washing and cleaning agents containing fatty acid amide derivatives XV according to claims 24 to 27 as surfactants and other additives customary for such agents.

34. Mixtures of

(i) Fatty acid amide derivatives of the general formula XVIII _A 4_ _C0 _ _{N c;} ^/ (XVIII)

^ R ^l7

in which the substituents have the following meaning:

CH CH-

N OH VAW∑y

R "R15

contains

R ⁱ⁴ and R ⁱ⁶ independently of one another are a hydroxy- and / or amino-substituted hydrophilic radical having 2 to 40 carbon atoms or a C ₁ -C ₁₄ -alkyl radical, the carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali - carries metal or ammonium salts and which can be interrupted by non-adjacent oxygen atoms, -NH groups and / or NC ₁ -C ₄ alkyl groups, and

R ⁱ⁵ and R ^i? Hydrogen, an unsubstituted Ci-Cβ-alkyl radical or a radical R ⁱ⁴ or R ¹⁶ , and

(ii) Fatty acid amide derivatives of the general formula XIX

in the

E is an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain which contains one or more groupings of the formula XX in the chain CH CH

OR ¹⁸ OH ^(XX)

contains, where

R ^{i8 represents} C ₁ -C ₄ alkyl, and

Ri6 _U and Ri ^{7 have} the meaning given above,

wherein the components (i) and (ii) are in a weight ratio of 99: 1 to 1:99.

35. Use of mixtures of fatty acid amide derivatives XVIII and XIX according to claim 34 as surfactants in detergents and cleaners.

36. Fatty acid amide derivatives of the general formula XXI

in the

G is an aliphatic Cβ * C ₂₄ * radical with an unbranched carbon chain which has one or more groups of the formula XXII in the chain

CH CH

_0R 19 _0H (XXII)

contains, where

Ri9 represents C ₁ -C ₄ alkyl or hydrogen,

Salts R ⁱ⁶ a hydroxy- and / or amino-substituted hydrophilic radical having 2 to 40 carbon atoms or a C ₁ -C ₁₄ alkyl radical, of the carboxyl and / or sulfonic acid groups in the form of the free acids and / or their alkali metal or ammonium and which can be interrupted by non-adjacent oxygen atoms, -NH groups and / or NC ₁ -C ₄ alkyl groups, means and R ¹⁷ denotes hydrogen, an unsubstituted Ci-Cε-alkyl radical or a radical R ¹⁶ .

37. Fatty acid amide derivatives XXI according to claim 36, in which 5 the radical G is derived from an unsaturated Ciβ fatty acid.

38. Fatty acid amide derivatives XXI according to claim 36 or 37, in which R ^{16 is} an unbranched ω-hydroxyalkyl group or an unbranched ω-aminoalkyl group each having 2 to 6 carbon atoms.

10 indicates, the underlying alkyl group to be interrupted by nonadjacent oxygen atoms, NH groups, NC ₁ -C ₄ alkyl, NC ₁ -C ₄ hydroxyalkyl or N-Cι-C ₄ aminoalkyl groups un- } ^r ** nn

15 39. Fatty acid amide derivatives XXI according to claims 36 to 38, in which the grouping

.R16

N

20 ^• Rl ⁷

means the rest of an amino acid.

5 40. A process for the preparation of fatty acid amide derivatives XXI ge according to claims 36 to 39, characterized in that an epoxidized fatty acid derivative of the general formula XXIII

0 B ³ -CO-R ²⁰ (XXIII)

in the

B ^{3 is} an aliphatic Cβ-C ₂₄ radical with an unbranched carbon chain, which contains one or more epoxy groups in the chain, and

R ^{20 is} a hydroxyl radical and its alkali or ammonium salts, a C ₁ -C ₄ alkoxy radical or a radical of a mono-, di- or triglyceride, the di- or triglyceride radicals being residues of naturally saturated or unsaturated fatty acids are,

mean 5 with a Ci to C ₄ alkanol or water catalyzed by protic acids or Lewis acids to the fatty acid derivative of the general formula XXIV

G-CO-R ²⁰ (XXIV)

in which G has the meaning given in claim 36, and then reacted with an amine of the general formula XXV

to the fatty acid amide derivative XXI.

41. A process for the preparation of fatty acid amide derivatives XXI according to claim 40, characterized in that boron trifluoride etherate, tetrafluoroboric acid, iron (III) chloride, titanium tetrachloride, orthophosphoric acid, phosphorous acid or acid are used as protonic acid or Lewis acid catalysts Ion exchanger uses.

42. Use of fatty acid amide derivatives XXI according to claims 36 to 39 as surfactants in detergents and cleaning agents.

43. Washing and cleaning agents containing fatty acid amide derivatives XXI as claimed in claims 36 to 39 as surfactants and other additives customary for such agents.