EP0784707B1 - Process for producing leather greasing agents - Google Patents

Description

The invention relates to processes for the production of leather greasing agents with high emulsion stability, containing cationic surfactants of the esterquat type, sulfated oils and nonionic surfactants.

State of the art

In addition to the tannins, the most important are fatty acids Tools to shape the character of leather. The effect the fatliquor comes through a fiber isolating Lubrication and by hydrophobization.

By covering the leather fibers with a grease film, the mutual friction is reduced and consequently the suppleness and stretchability of the fabric is improved. That has positive things Impact on the tear resistance of the leather, because In a stretchy material, many fibers are attached Tensile stress in the direction of tension and then expose it Tearing up a greater resistance than the same Fibers within a brittle material. Through the hydrophobization tanning effects are also achieved because it is associated with a displacement of water from the skin is.

• Die verseifbaren Fette und Öle sowie die natürlichen Wachse und Harze gehören zu den Estern. Unter Ölen und Fetten werden dabei vom Lederfachmann Ester aus Glycerin und Fettsäuren bezeichnet, die bei Raumtemperatur fest bzw. flüssig sind. Zur Lederfettung werden dabei aus der Gruppe der tierischen Fette insbesondere Trane, Fischöl, Rindertalg und Rinderklauenöl, aus der Gruppe der pflanzlichen Fette Rizinusöl, Rüböl und Leinöl herangezogen. In Wachsen und Harzen sind die Fettsäuren statt mit Glycerin mit höhermolekularen Alkoholen verestert. Beispiele für Wachse sind Bienenwachs, chinesisches Wachs, Caranubawachs, Montanwachs und Wollfett; zu den wichtigsten Harzen zählen Kolophonium, Juchtenöl und Schellack.
• Durch chemische Umwandlung pflanzlicher und tierischer Fette erhält man Produkte, die wasserlöslich sind und die darüber hinaus in unterschiedlichem Maße emulgierend auf wasserunlösliche Fettstoffe wirken. Bekannt sind etwa die sulfierten wasserlöslichen Öle verschiedenster Art, die durch Oxidation veränderten Trane, die als Dégras oder Moellon bezeichnet werden, ferner die Seifen, die bei der hydrolytischen Spaltung natürlicher Fette entstehen, gehärtete Fette sowie schließlich freie Fettsäuren wie Stearinsäure als Einbrennfette. Die meisten tierischen und pflanzlichen Fette weisen eine gewisse Affinität zur Ledersubstanz auf, die durch die Einführung oder Freilegung hydrophiler Gruppen noch beträchtlich gesteigert wird.
• Wichtig für die Lederherstellung sind weiter die mineralischen Fettungsmittel. Diese Kohlenwasserstoffe sind den natürlichen Fetten und Ölen in manchen Eigenschaften ähnlich, lassen sich jedoch nicht verseifen. Es handelt sich um Fraktionen der Erdöldestillation, die in flüssiger Form Mineralöl, in pastöser Form Vaseline und in fester Form Paraffin genannt werden.

Vegetable and animal oils, fats and waxes are generally used as leather greasing agents, furthermore the hydrolysis, sulfation, oxidation and hardening products obtained from these substances by chemical conversion and finally mineral greasing agents; in detail:

• The saponifiable fats and oils as well as the natural waxes and resins are among the esters. Oils and fats refer to esters of glycerin and fatty acids that are solid or liquid at room temperature. For leather greasing, from the group of animal fats in particular trane, fish oil, beef tallow and beef claw oil, from the group of vegetable fats castor oil, rape oil and linseed oil are used. In waxes and resins, the fatty acids are esterified with higher molecular weight alcohols instead of glycerin. Examples of waxes are beeswax, Chinese wax, caranuba wax, montan wax and wool fat; The most important resins include rosin, yeast oil and shellac.
• The chemical conversion of vegetable and animal fats gives products that are water-soluble and, in addition, have different emulsifying effects on water-insoluble fats. For example, the sulfated water-soluble oils of various types are known, the tears modified by oxidation, which are referred to as dégras or moellon, the soaps which are formed during the hydrolytic splitting of natural fats, hardened fats and finally free fatty acids such as stearic acid as stoving fats. Most animal and vegetable fats have a certain affinity for the leather substance, which is considerably increased by the introduction or exposure of hydrophilic groups.
• Mineral greasing agents are also important for leather production. These hydrocarbons are similar to natural fats and oils in some properties, but cannot be saponified. These are fractions from petroleum distillation, which are called mineral oil in liquid form, petroleum jelly in pasty form and paraffin in solid form.

In many cases, however, the surface of the Tanned and greased leather undesirable over time Stains known as "fatty spew" become. Fat rashes occur primarily on chrome-tanned Leather after shorter or longer storage than white, often veil-like covering, which only single places or also covered the entire leather surface. The rash is on Leakage of solid fatty substances from the leather. It can through the natural fat present in the leather or caused by fatty substances that only come in the course of The leather has been greased.

Fat mixtures used for greasing leather tend to have a particular tendency then to form a rash when they have a lot of free Contain fatty acids. Free fatty acids generally have a higher melting point than their glycerides. The hydrolytic Splitting of fatty substances during storage of the Leather accordingly increases the risk of occurrence of Fat rashes.

Soaps and licker greases are split in chrome leather, especially in insufficiently deacidified chrome leather, with the release of fatty acids. Sulphated oils and fats show a different tendency to form fat rashes, the tendency to rash generally decreases with a longer lifespan [cf. J.Int.Soc.Leath.Trad.Chem. 47 , 379 (1952) ].

Greasy rashes occur the easier the leather contains fatty substances that tend to develop rashes. For the The scope and composition of the rash are quantity, Composition and location of the fat mixture present in the leather decisive from natural fat and lickerfat. Loosely structured Leather is less prone to rash than leather with dense fiber structure. Fat rashes are low Temperatures observed more often than at warmer outside temperatures.

The crystalline fat rashes develop in the hair holes and gland canals, whereby small crystals are initially formed in the depth, which gradually fill the entire hair hole as larger fat crystals, swell out over the leather surface and matted into a dense crystal film. All fats that contain stearin or palmitin derivatives can cause crystalline fat rashes, with increasing concentration the risk of rashes increases [Ledertechn.Rundsch. 1 (1949) ].

In particular, the so-called neutral fats, i.e. such substances suitable for leather greasing which are not ionic Contain groups in the molecule, e.g. Fats, waxes and hydrocarbons, for the formation of fat rashes. Especially the neutral fats, the stearin and / or palmitin derivatives, such as corresponding ones Triglycerides or the free fatty acids.

Because in the course of leather processing, but after tanning anyway greasing is required as an almost obligatory operation is to the desired product properties achieve, it has become common in practice with special synthetic fatliquors work, their tendency is low for the formation of fat rash.

A class of. Commonly used in this regard Greasing agents are halogenated compounds such as chlorinated hydrocarbons. The increasing ecological and toxicological Requirements for resources that get into the environment or with which the consumer comes into contact however, this class of substances is increasingly unattractive.

In addition to anionic surfactants such as, for example, sulfated fats and oils or sulfosuccinates, cationic compounds of the quaternary ammonium compound (QAV) type, such as, for example, dimethyldistearylammonium chloride, are also important as fatliquoring agents. An overview of this topic by S.Gupta can be found in J.Am.Leath.Chem.Ass. 83: 239 (1988) . However, QAV are under discussion for ecological reasons and therefore also in leather auxiliaries. An alternative are cationic surfactants of the esterquat type, which, however, cannot readily be processed into stable emulsions together with anionic surfactants, in particular those of the sulfated oil type.

The object of the invention was therefore a method for the production of stable emulsions for the lubrication of To provide leathers that act as cationic surfactants Ester quats and sulfated oils as anionic components contain.

Description of the invention

(A) eine Lösung eines Esterquats (Komponente a) vorlegt und mit einer Mischung aus einem sulfatierten Öl (Komponente b) und einem nichtionischen Tensid (Komponente c) emulgiert oder

(B) ein sulfatiertes Öl (Komponente b) vorlegt und mit einer Mischung aus einer Lösung eines Esterquats (Komponente a) und einem nichtionischen Tensid (Komponente c) emulgiert.

The invention relates to a method for producing leather greasing agents, in which

(A) a solution of an ester quat (component a) and emulsified with a mixture of a sulfated oil (component b) and a nonionic surfactant (component c) or

(B) a sulfated oil (component b) is initially charged and emulsified with a mixture of a solution of an ester quat (component a) and a nonionic surfactant (component c).

Surprisingly, it was found that esterquats and allow sulfated oils to be processed into a stable emulsion, if you use nonionic surfactants as emulsifiers and these either the esterquats or the sulfated oils adds to form a premix.

Esterquats

The term ester quats is generally understood to mean quaternized fatty acid triethanolamine ester salts. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this connection, reference is made to international patent application WO 91/01295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. As representative of the extensive state of the art, reference is made to the publications US 3915867, US 4370272, EP-A2 0239910, EP-A2 0293955, EP-A2 0295739 and EP-A2 0309052 .

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.The quaternized fatty acid triethanolamine ester salts follow the formula (I)

in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.

Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut _fatty acids and in particular partially hardened C _16/18 tallow or palm fatty acids as well as C _16/18 fatty acid _cuts rich in elaidic acid are preferably used.

The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40).

From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R ¹ CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m , n and p is 0 and X is methyl sulfate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (III) should be mentioned as a further group of suitable ester quats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and optimal degree of esterification apply to those mentioned for (I) Examples also for the ester quats of the formulas (II) and (III). The ester quats are usually in the form of 50 to 90% by weight alcoholic solutions in the trade, if necessary can be easily diluted with water.

Sulphated oils

Sulfated oils are reaction products of predominantly unsaturated fats and oils of natural or synthetic origin with sulfuric acid or oleum. This reaction leads to the addition of sulfuric acid to the double bonds and - if available - hydroxyl groups of the triglycerides with the formation of sulfate groups. A saponification of the ester bond can also occur as a side reaction. However, the resulting partial glycerides in turn have free OH groups and are sulfated particularly quickly. Typical examples are sulfation products from olive oil, cottonseed oil, peanut oil, linseed oil, rapeseed oil from old and new breeds, sunflower oil from old and new breeds, castor oil, beef tallow and fish oil. The use of sulfated triolein, olive oil or fish oil is preferred. Overviews on this topic can be found, for example, in J.Am. Oil.Chem.Soc. 48, 314 (1970) and Soap Oils Fette Wwachs, 112 , 9 (1986).

Nonionic surfactants

Typical examples of nonionic surfactants which are suitable as emulsifying component (c) in the context of the process according to the invention are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polygylcol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, fatty acid (alk) enol glycole alkyl glucamides, protein hydrolyzates (especially vegetable products based on soy), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.

Fatty alcohol polyglycol ether

in der R⁸ für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, x für Zahlen von 1 bis 25 und y für 0 oder Zahlen von 1 bis 5 steht.In a preferred embodiment of the invention, fatty alcohol polyglycol ethers of the formula (IV) are used as nonionic surfactants,

in which R ^{8 represents} an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, x for numbers from 1 to 25 and y for 0 or numbers from 1 to 5.

These are preferably addition products from an average of 1 to 25, preferably 15 to 20 moles Ethylene oxide and 0 or 1 to 2 moles of propylene oxide in capron alcohol, Caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, Lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, Palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, Oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, Linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, Gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well their technical mixtures, e.g. in high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerization of unsaturated Fatty alcohols occur.

Addition products of an average of 15 to 20 moles of ethylene oxide onto technical C ₁₂ -C ₁₈ coconut or. C ₁₆ -C ₁₈ tallow alcohol cuts are used.

Alkyl and / or alkenyl oligoglycosides

In a further preferred embodiment of the invention, the nonionic surfactants of component (c) used are alkyl and alkenyl oligoglycosides which follow the formula (V) R ⁹ O- [G] _p (V) in which R ^{9 represents} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. Alkyl and / or alkenyl oligoglycosides can be obtained by the relevant methods of preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0301298 and WO 90/03977 .

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides .

The index number p in the general formula (V) indicates the degree of oligomerization (DP degree), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer and here can assume the values p = 1 to 6 in particular, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.

The alkyl or alkenyl radical R ⁹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C ₈ -C ₁₈ coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C ₁₂ - Alcohol can be contaminated and alkyl oligoglucosides based on technical C _9/11 oxo alcohols (DP = 1 to 3).

The alkyl or alkenyl radical R ⁹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C _12/14 coconut alcohol with a DP of 1 to 3 are preferred.

Fatty acid N-alkyl polyhydroxyalkylamides

in der R¹⁰CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.Finally, preferred nonionic surfactants which make up component (c) are also fatty acid N-alkylpolyhydroxyalkylamides of the formula (VI) ,

in which R ¹⁰ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.

The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their production, reference is made to US Pat. Nos. US 1985424, US 2016962 and US 2703798 and international patent application WO 92/06984 . An overview of this topic by H. Kelkenberg can be found in Tens. Surf.Det. 25 , 8 (1988) .

The fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The preferred fatty acid N-alkyl polyhydroxyalkylamides are therefore fatty acid N-alkylglucamides , as represented by the formula (VII):

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (VII) in which R ^{11 represents} hydrogen or an amine group and R ¹⁰ CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Fatty acid N-alkylglucamides of the formula (VII) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C _12/14 coconut fatty acid or a corresponding derivative are particularly preferred. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

Production of funds

To prepare the emulsions, a preferably aqueous premix is first prepared from the sulfated oil and the nonionic surfactant. This premix is then processed with a preferably aqueous solution of the ester quat with stirring, optionally at an elevated temperature of 30 to 40 ° C., to form a smooth emulsion which is distinguished by a high degree of stability. This is a purely mechanical process, there is no chemical reaction.

In the context of the method according to the invention, it has proven to be proven to be advantageous, components (a) and (b) and (a) and (c) or (b) and (c) each in a weight ratio of 1: 9 up to 9: 1, preferably 1: 2 to 2: 1.

Industrial applicability

The emulsions according to the invention are notable for good hydrophobic properties and are also increased Temperature stable without phase separation.

The following examples are intended to be the subject of the invention explain in more detail without restricting it.

Examples I. Surfactants used

A1) Methyl quaternized ditallow fatty acid triethanolamine ester methyl sulfate salt DEHYQUART ^(R) AU-46, Pulcra SA, Barcelona / ES

B1) Sulphated triolein, ammonium salt, anhydrous

C1) Tallow alcohol 20EO adduct, anhydrous

C2) C ₈ -C ₁₆ alkyl oligoglucoside, 30% by weight aqueous paste

C3) Coconut fatty acid-N-methylglucamide, 30% by weight aqueous paste

II. Stability studies

+++ glatte Emulsion, keine Phasentrennung

++ leichte Trübungen

+ leichtes Auf rahmen

- vollständige Phasentrennung

Method I (according to the invention) . 90 g of sulfated triolein (B1) were placed in a 500 ml beaker and 10 g - based on the solids content - of nonionic surfactant (C1-C3) were added at 20 ° C. while stirring. A 10% by weight solution of the ester quat (A1) was also placed in a second beaker with a capacity of approx. 1500 ml at 20 ° C. and stirred with the premix to form a smooth emulsion with a solids content of approx. 20% by weight .-% processed. The emulsion was stored at 40 ° C. and the stability was assessed after 1, 2 and 24 hours. The following applies:

+++ smooth emulsion, no phase separation

++ slight cloudiness

+ light frame

- complete phase separation

The details of the experiments are summarized in Table 1.

Method II (according to the invention) . Procedure I was repeated, but the nonionic surfactant was added to the ester quat solution. The details of the experiments are summarized in Table 1.

Procedure III (for comparison) . Process I was repeated, but the addition of the nonionic surfactant was dispensed with. The details of the experiments are summarized in Table 1.

Procedure IV (for comparison) . Procedure I was repeated, but the nonionic surfactant was added to the solution of sulfated fish oil and ester quat. The details of the experiments are summarized in Table 1.

Claims (11)

1. A process for the production of leather oiling formulations, in which either

   (A) a solution of an esterquat (component a) is initially introduced and emulsified with a mixture of a sulfated oil (component b) and a nonionic surfactant (component c) or

   (B) a sulfated oil (component b) is initially introduced and emulsified with a mixture of a solution of an esterquat (component a) and a nonionic surfactant (component c).
2. A process as claimed in claim 1, characterized in that esterquats corresponding to formula (I):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² and R³ independently of one another represent hydrogen or have the same meaning as R¹CO, R⁴ is an alkyl group containing 1 to 4 carbon atoms or a (CH₂CH₂O)_qH group, m, n and p together stand for 0 or numbers of 1 to 12, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate, are used.
3. A process as claimed in claim 1, characterized in that esterquats corresponding to formula (II):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² is hydrogen or has the same meaning as R¹CO, R⁴ and R⁵ independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate,
   are used.
4. A process as claimed in claim 3, characterized in that esterquats corresponding to formula (III):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² is hydrogen or has the same meaning as R¹CO, R⁴, R⁶ and R⁷ independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate,
   are used.
5. A process as claimed in claims 1 to 4, characterized in that sulfated triolein, sulfated olive oil or sulfated fish oil is used as component (b).
6. A process as claimed in claims 1 to 5, characterized in that nonionic surfactants selected from the group consisting of fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers, alk(en)yl oligoglycosides, fatty acid N-alkyl glucamides, protein hydrolyzates, polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates are used as component (c).
7. A process as claimed in claim 6, characterized in that fatty alcohol polyglycol ethers corresponding to formula (IV):

   

   in which R⁸ is an alkyl and/or alkenyl group containing 6 to 22 carbon atoms, x is a number of 1 to 25 and y is 0 or a number of 1 to 5,
   are used as the nonionic surfactants.
8. A process as claimed in claim 6, characterized in that alkyl and/or alkenyl oligoglycosides corresponding to formula (V): R⁹O-[G]_p    (V) where R⁹ is an alkyl and/or alkenyl radical containing 4 to 22 carbon atoms, G is a sugar unit containing 5 or 6 carbon atoms and p is a number of 1 to 10, are used as the nonionic surfactants.
9. A process as claimed in claim 6, characterized in that fatty acid N-alkyl polyhydroxyalkylamides corresponding to formula (VI):

   

   where R¹⁰CO is an aliphatic acyl radical containing 6 to 22 carbon atoms, R¹¹ is hydrogen, an alkyl or hydroxyalkyl radical containing 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical containing 3 to 12 carbon atoms and 3 to 10 hydroxyl groups,
   are used as the nonionic surfactants.
10. A process as claimed in claims 1 to 9, characterized in that components (a) and (b) are used in a ratio by weight of 1:9 to 9:1.
11. A process as claimed in claims 1 to 10, characterized in that components (a) and (c) and components (b) and (c) are used in a ratio by weight of 1:9 to 9:1.