EP0559636A1

EP0559636A1 - Novel thiodiglycol derivatives, process for producing them and their use as textile softeners

Info

Publication number: EP0559636A1
Application number: EP19900915771
Authority: EP
Inventors: Alfred Meffert; Ingo Wegener; Gerhard Stoll; Ditmar Kischkel; Peter Daute; Andreas Syldatk; Faize Berger
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1989-11-06
Filing date: 1990-10-29
Publication date: 1993-09-15
Also published as: DE3936862A1; WO1991006534A1; JPH05501406A

Abstract

L'invention concerne de nouveaux mono- et/ou bis-éthers, ainsi que mono-et/ou bis-esters d'oxydes sulfoniques et/ou de sulfones de thiodiglycol, ayant la formule générale (I), dans laquelle X1 et/ou X2 représentent notamment des résidus alkyle et/ou acyle substitués par un beta-hydroxyle d'acides alkyl-monocarboxyliques ayant chacun 8 à 30 atomes de carbone, et z est égal à 1 (oxydes sulfoniques) ou à 2 (sulfones). Il est également décrit un procédé de fabrication des composés thiodiglycoliques selon l'invention, ainsi que leur utilisation comme composants d'avivage optimisés dans des agents de lavage et/ou de rinçage de textiles, en particulier dans l'avivage en bain de rinçage, sous forme d'un mélange aqueux de matières actives.The invention relates to new mono- and / or bis-ethers, as well as mono-and / or bis-esters of sulfonic oxides and / or thiodiglycol sulfones, having the general formula (I), in which X1 and / or X2 represent in particular alkyl and / or acyl residues substituted by a beta-hydroxyl of alkyl-monocarboxylic acids each having 8 to 30 carbon atoms, and z is equal to 1 (sulfonic oxides) or 2 (sulfones). A method of manufacturing thiodiglycolic compounds according to the invention is also described, as well as their use as optimized brightening components in washing and / or rinsing agents for textiles, in particular in brightening in a rinsing bath, in the form of an aqueous mixture of active ingredients.

Description

New Thiodiσlvkol derivatives, processes for their preparation and their use as plasticizers for textiles "

In the field of fabric softeners for household and commercial use, the quaternary ammonium compounds, in particular dimethyldistearylammonium chloride, are of substantial practical importance to this day (see: P. Vogel and H. Krüßmann, Soaps, Oils, Fats, Waxes, Volume 111, page 567 to 574, 1985 as--. like L. Godefroy and H. Hein, Soaps, Oils, Fats, Waxes, Volume 115, pages 3 to 8, 1989).

As a result of the increasing consideration of storage stability and viscosity characteristics as well as the biodegradability of highly concentrated fabric softeners, numerous proposals for the replacement of these components by nitrogen-free exchange compounds or corresponding systems have been published. These proposals include both inorganic, in particular inorganic insoluble components such as layered silicate compounds (see, for example, in German Patent 23 34 899), as well as selected organic components, for example disalts of long-chain alpha sulfo fatty acids and combinations of such systems (see moreover in the German patent specification DE-3604039). The present invention now relates to a hitherto not described nitrogen-free class of organic compounds which are particularly suitable for the field of application of textile softening and not only fully replace the textile softeners based on quaternary ammonium compounds which are still common today, for example as part of the known rinse bath finishing can, but moreover, with suitable selection and application, tactile grip effects on the finished textile become accessible, which go beyond the technical possibilities that exist to date.

Accordingly, the invention relates in a first embodiment to new mono- and / or bis-ethers and mono- and / or bis-esters of thiodiglycolsulfoxides and / or sulfones of the general formula (I)

in the X \ and / or X2 ß-hydroxyl-substituted alkyl radicals with 8 to

30 carbon atoms and / or acyl residues of alkyl onocarboxylic acids with 8 to

30 mean carbon atoms in which Xj and X2 are identical or different, in the case of monoethers or monoesters Xj or X2 being the same

Is hydrogen and in which the number z represents 1 or 2.

The thiodiglycol compounds of the general formula (I) defined according to the invention are a class of substances not previously described. They are produced by reacting thiodiglycol with α-olefin epoxy compounds with 8 to 30 C atoms in the molecule or by the corresponding reaction of the thiodiglycol with alkyl monocarboxylic acids of comparable chain length.

Depending on the molar ratio set between thiodiglycol and α-olefin epoxide compound (1: 1 to 1: 2), ring opening results in the formation of the corresponding mono- and / or bis-ether of thiodiglycol of the general formula (I) in Xj and / or X2 B-hydroxylalkyl groupings. In contrast, the teaching of British patent publication BP 1 097 396 describes another route to the bisether derivatives of thiodiglycol. Divinyl sulfones and alcohols are used as starting compounds there, but they do not lead to the β-hydroxylalkyl grouping according to the invention in the corresponding bis- [2-alkoxyethyl] sulfones.

In a preferred embodiment of this invention, the thiodiglycol is reacted in the desired molar ratio (1: 1 to 1: 2) with the CQ to C3o ** α-01efin compound in such a way that a conventional basic catalyst, such as, for example, an alkali metal hydroxide and / or an alkali methoxylate, in an amount of at least 0.05% by weight to about 5% by weight, preferably from about 0.1 to 1% by weight, in each case based on the total weight.

The actual reaction takes place at temperatures of at least 120 ° C to about 200 ° C, preferably from about 160 to 170 ° C, within about 3 to 6 hours to an epoxy oxygen content of below 0.5%, preferably of below 0.2% instead. The epoxy oxygen content is used for constant reaction control and ultimately also for determining the quantitative course of the reaction. When thiodiglycol is reacted with the alkyl monocarboxylic acids or their reactive derivatives, depending on the molar ratio of thiodiglycol to alkyl monocarboxylic acid (1: 1 to 1: 2), the corresponding compounds of the general formula (I) of the mono- and / or bis-ester type are formed. A similar implementation is already described in Russian literature (VA Trofi ov, IN Gurshko and VI Isagulyants, Zh. Prikl. Khim., Volume 48, pages 626 to 628, 1975). In this reference thiodiglycol is converted in the presence of pyridine in benzene with acid chlorides to the corresponding bis-esters of thiodiglycol, the subsequent oxidation with cumyl hydroperoxide in n-heptane leading to the sulfoxides.

The reaction products obtained from the mono- and / or bis-ether or mono- and / or bis-ester type of thiodiglycol are then in a manner known per se, for. B. with a certain amount of 30 to 70%, preferably 70% hydrogen peroxide in glacial acetic acid to the sulfoxide - z in the general formula (I) is 1 - and / or with the comparatively at least twice as large amount of 70% hydrogen peroxide in glacial acetic acid to the sulfone - z in the general formula (I) is 2 - oxidized.

Within the comparatively broad framework of the new thiodiglycol derivatives according to the invention defined by the general formula (I), selected narrower subclasses are particularly notable for their suitability for the aim of softening textiles which is the aim of the invention. Accordingly, it is preferred according to the invention that the radicals Xj and X2 are derived from β-hydroxyl-substituted alkyl radicals or from acyl radicals having 12 to 24 carbon atoms and in particular having about 12 to 18 carbon atoms. The pre- residues of this type for Xj and X2 are corresponding straight-chain residues.

Compounds of the general formula (I) fall within the scope of the invention, which are characterized in that different radicals of the type indicated are present in X- = and X2, so that corresponding mixed radicals of the type defined according to the invention are therefore present in the respective molecule available. Structurally identical, but if desired also structurally different radicals can be present in Xj and X2. For reasons of easier accessibility, structurally identical radicals will be preferred, which, however, in the case of the compounds with mixed radicals Xi and X2 then contain, for example, corresponding radicals of different chain lengths.

For the purpose of textile softening according to the invention, thiodiglycol derivatives of the general formula (I) can be particularly preferred which have residues which are uniform in Xj and X2 and in particular have the same, ie identical residues of the type indicated. Both in this and in the aforementioned embodiment of the compounds with mixed radicals X _j and X2, however, the invention comprises mixtures of different compounds of the general formula (I). As will be described in detail below in connection with the use of these components for textile softening, it can be particularly expedient to use certain selected mixtures of compounds of the general formula (I) with comparatively longer radicals in X _j u ^ ^ with corresponding, in particular to use the same structural component Jer general formula (I) but shorter-chain radicals Xj and X2. The reason for this is that the particular properties of the radicals Xj and X2 influence certain material properties can be taken, which are of technological importance in connection with textile finishing. Accordingly, it is possible and within the scope of the invention to use mixtures of substances in which the individual components are optimized in a certain way with regard to a desirable performance profile, but are then combined in a mixture with other components, which in turn are different in terms of their performance profile are selected and structured.

What is said here about the radicals Xj and X2 from the compounds of the general formula (I) applies in the same way to the possibility of combining the parameter z, ie. H. for the selection of compounds of the sulfoxide type or of the sulfone type. The sulfones - z = 2 - can be of particular importance in practice if only because compounds of this type are not endangered by disproportionation reactions, as can occur in principle with sulfoxide compounds. As a result of this disproportionation reaction, in addition to the odor-neutral sulfones, the unpleasant-smelling sulfides can arise. In principle, however, both the sulfones according to the invention and the sulfoxides can be perfumed with common odoriferous substances without suffering a substantial loss of the softening properties. On the other hand, sulfoxide compounds of the type specified can have such an interesting performance profile that their sole use or joint use in combination with sulfones falls within the scope of the inventive action.

In its most important embodiment, the invention comprises mixtures of active ingredients which soften the textile and which contain the thiodiglycol compounds of the general formula (I) either as such or in admixture with solvent, emulsifier and / or dispersing auxiliaries or with Contain stabilizers, and these auxiliaries used in addition to the compounds of the general formula (I) can be equipped with or without self-washing power and / or cleaning-enhancing effect.

The various possibilities for acting according to the invention are evident from the examples below, which describe partial aspects from the inner core of the embodiment of the teaching according to the invention concerned here. Compounds of the general formula (I) of the bisether type which contain β-hydroxyl-substituted straight-chain alkyl radicals with a comparatively shorter chain length, for example with 12 carbon atoms, when applied via an aqueous auxiliary phase in the rinse bath finish both in the shape of the sulfone as well as in the shape of the sulfoxide compound have excellent softening effects, which go beyond the standard of today's household practice in the adjustable handle quality.

It initially looks different when analogous compounds with an increased carbon number in the chain length of Xj and X2 are used. If corresponding β-hydroxyl-substituted Ci6 ~ derivatives or even corresponding Cig derivatives are used without the use of auxiliaries, then there appears to be no pronounced softening of the treated textile. However, if the component of general formula (I) used as plasticizer is combined with dispersing or emulsifying aids, for example of the type of anionic and / or nonionic surfactants and / or together with emulsifiers, for example of the type of glycerol partial ether or glycerol partial ester , then the textile-softening effects not only fully occur again, for example as part of the rinse bath finish, they can reduce the effect of the corresponding short-chain derivatives of the general formula (I) also significantly exceed. The use of dispersing or emulsifying agents and / or stabilizers in the last-mentioned case therefore has a clearly increased effect. If, on the other hand, the same auxiliaries are used in connection with the previously mentioned short-chain thiodiglycol derivatives of the chain length C12 ^{in x} l ^uπt * ^x 2, then their level of performance with regard to the softening of the text can be significantly reduced. In this case, it is advisable to do without such additional aids in order to optimize the desired result. On the basis of this illustration, which can only be seen by way of example, the person skilled in the art can determine and compile the particular suitable or optimized substance mixtures by simple preliminary tests.

Due to this different behavior of systemically identical components, but different chain lengths in residues Xj and / or X2, optimization in the sense of the invention can also be carried out by selecting appropriately selected components with shorter C chain lengths in Xj and / or X2 can be combined with comparable components but with a longer C chain in Xj and / or X2. This is exemplified by the rewetting behavior of a suitably finished textile material: The aforementioned compounds of the general formula (I) with β-hydroxyl-substituted Ci2-alkyl radicals in Xj and X2 are characterized by exceptionally good values when used as textile softening agents the rewettability of the finished textiles. The transition to the longer-chain corresponding residues with 16 and / or 18 carbon atoms in Xj and / or X2 leads to a weakening of the rewettability, but can, in particular in combination with surfactant auxiliaries, lead to significant lead to better grip characteristics. The combination of both types in the textile finishing aid according to the invention can then lead to an optimization of the two qualities of effectiveness considered here - both improved rewettability and improved grip.

In the course of the work according to the invention, it has also been shown that the extent of the dispersion or emulsification of the compounds of the general formula (I) in the application state can have a decisive influence on the effectiveness of the proposed new substance class as textile softening agent. It is important both for the absolute action and for the maintenance of the action in particular aqueous washes over longer periods of time to ensure that the extent of the very fine emulsification or dispersion of the active ingredients is as high and stable as possible. Two measures are particularly suitable for this purpose, which can also be combined with one another: the use of dispersing or emulsifying aids in the production of the, in particular aqueous, active substance combinations, and a certain process technology in the production of the aqueous preparations. The following applies in detail:

The higher the chain length of the radicals X \ and / or X2 in the sulfone or sulfoxide used, the more pronounced is the need to use emulsifying and / or dispersing auxiliaries. Compounds with more than 14 carbon atoms in the respective radicals Xj or X2 and in particular those in the range of about 16 to 20 carbon atoms which is particularly effective for the purposes of textile softening according to the invention generally require the use of such additional components in the active substance mixture. In these cases, an important form of the invention, the thiodiglycol compounds of the general formula (I) are used in admixture with auxiliaries having a surfactant character. Surfactants in broad definition come into consideration as active auxiliaries. The invention therefore provides for blends with anionic surfactants as well as corresponding blends with nonionic surfactant compounds. Suitable anionic surfactants are, for example, fatty alcohol sulfate salts as well as alkyl sulfonate salts, preferably the alkali and alkaline earth metal salts and in particular the Na and Mg salts having proven successful. From the first group, tallow alcohol sulfate and related compounds are to be mentioned as a particularly suitable mixing component. The second group includes, for example, -sulfofatty acid methyl ester sulfonates, alkylbenzenesulfonates, alkanesulfonates, di-salts of α-sulfofatty acids and comparable compounds. From the field of non-ionic surfactant components, both the classic oligoethoxylates of oleophilic components with active hydrogen atoms and, in particular, the alkyl glycosides belonging to the class of nonionic surfactants can be mentioned. Understandably, the optimization in the sense of the invention will not only focus on the desired increase in effectiveness with regard to textile softening, in particular the general compatibility of the textile finishing auxiliaries will also be taken into account. Tallow alcohol sulfate, wetting or emulsifying alkyl glucoside compounds and / or disalts of α-sulfo fatty acids with wetting and emulsifying action can be of particular importance.

Another class of auxiliaries for the formulation of potent, in particular aqueous, preparations of the compounds of the general formula (I) are emulsifiers or stabilizers for maintaining the adjusted state of the very fine emulsions. gation or dispersion. Experts know numerous types of compounds of this type. In the sense of the invention, glycerol partial ethers and / or glycerin partial esters are particularly suitable which, in addition to one or two free hydroxyl groups, have longer-chain hydrocarbon radicals in the ether or ester-forming functional substituents.

In such active ingredient mixtures of thiodiglycol compounds of the general formula (I) and auxiliaries of the last-mentioned type, the thiodiglycol compounds described according to the invention can be present in amounts of 5 to 95% by weight, based on the total active ingredient mixture, amounts of about 20 to 70 wt .-% can be preferred. Mixing ratios of the sulfones and / or sulfoxides to pronounced emulsifying aids, in particular of a surfactant nature, can advantageously be used in mixing ranges from 1: 5 to 5: 1 and in particular in the range from about 1: 3.5 to 4: 1.

The previously mentioned second possibility for increasing the effectiveness lies in the choice of special working conditions in the production of the, in particular, aqueous active substance concentrates for their subsequent dilution with further water for practical use in textile softening. Two process parameters must be taken into account here in particular:

In order to ensure a particularly fine emulsification state, it has proven to be expedient to carry out the emulsification of the optionally melted active ingredients or active ingredient mixtures in the aqueous phase at at least room temperature to about 100 ° C. It may be appropriate to carry out the emulsification preferably in the temperature range from about 80 to about 95 ° C. What is important here is the highly intensive mixing of the aqueous phase with the active substance phase which may contain melted thiodiglycol compounds. It may also be expedient to maintain intensive mixing even while the aqueous concentrate is cooling to ambient temperature.

It has furthermore proven to be particularly expedient to use the combined use of thiodiglycol compounds of the general formula (I) and dispersing or emulsifying auxiliaries, for example of the type of tallow alcohol sulfates, first to intensively standardize the active substance mixture, in particular in the melt, and then emulsify this mixture of active substances in the aqueous phase under the conditions specified above. In this way, not only can a particularly reliable very fine emulsification and thus an increase in activity in the intended use be set, at the same time, storage-stable concentrates of the active ingredient mixture are obtained over long periods of time.

In the preparation of such aqueous dispersions and / or emulsions, active substance contents in the primarily prepared aqueous preparation form are advantageously maintained in the range from about 1 to 50% by weight and advantageously in the range from about 5 to 20% by weight. In the use concentration of such emulsions for textile softening and in particular in the context of a rinse bath finish, the concentrates can then be used in such an amount that the active compounds or active compound mixtures according to the invention ultimately in amounts of approximately 0.05 to 2% by weight and in particular in amounts of approximately 0.1 to 0.5% by weight, based in each case on the dry textile weight. The preparation of the aqueous auxiliary agents in the sense of the definition according to the invention permits the setting of a relatively broad pH range. The pH values of corresponding aqueous solutions can be approximately in the range from 4 to 11 and preferably in the range from approximately 5.5 to 10.

It has also been shown that the degree of hardness of the water that is used in the rinse bath finish has no effect-regulating role. However, it is advantageous if a certain minimum hardness is present. Degrees of hardness of at least 5 ° dH and especially those in the range of about 8 to 30 ° dH or above are particularly well suited to trigger the desired softening effects.

The use of the active substances or active substance mixtures according to the invention for the purpose of textile finishing is independent of the drying state of the textile material to be treated. The desired softening occurs both with the action on wet fabric and with the action on dry fabric. The active ingredient mixtures according to the invention are generally applied to the corresponding textile both from an aqueous liquor and by forced application. The quality of the handle is not directly comparable with the results achieved in practice to date. Textile materials that are equipped with fabrics in the sense of the invention are perceived as pleasantly dry with a high degree of softness. Example

Manufacturing process for bis- [2- (2-hydroxyalkoxy) ethyl] sulfoxides and su 1 hair dryer

example 1

654.8 g of 1,2-epoxy-hexadecane (α-Ci6-01efinepoxid) and 152.7 g of bis (2-hydroxyethyl) sulfide (thiodiglycol) were mixed with 3.3 g of a 45% potassium hydroxide solution in a reaction vessel submitted and the possibly existing traces of water removed with heating at 80 to 100 ° C in a vacuum. The weakly exothermic mixture was brought to about 160 ° C to 170 ° C with nitrogen. To monitor the reaction, the epoxy content was determined at regular intervals, the reaction generally being completed after 3 to 6 hours with an epoxy oxygen content of less than 0.2%. The resulting bis- [2- (2-hydroxyhexadecyloxy) ethyl] sulfide could be oxidized both to the sulfoxide and to the corresponding sulfone in the manner described below: a) Oxidation to the sulfoxide

Half of the bis- [2- (2-hydroxyhexadecyloxy) ethyl] sulfide was mixed with 100 ml of glacial acetic acid and heated. At about 60 ° C, 30.4 g of 70% hydrogen peroxide were added dropwise with an exothermic reaction, the reaction temperature should not be above -90 ° C. The reaction was complete after about 5 hours at 80.degree. The mixture was then washed with hot water until until the peroxide test in the wash water was negative. The yellow, solid sulfoxide was then dried in vacuo at 120 ° C. Analytical key figures of bis- [2- (2-hydroxyhexadecyloxy) ethyl] sulfoxide: OH number: 209.5; Acid number: 0.4 b) Oxidation to the sulfone

The other half of the bis- [2- (2-hydroxyhexadecyloxy) ethyl] sulfide was mixed with 100 ml of glacial acetic acid and heated. 60.8 g of 70% hydrogen peroxide were added dropwise at about 60 ° C. with an exothermic reaction. The oxidation and work-up conditions corresponded to those of the sulfoxide. In the case of separation problems, butyl acetate was recommended as a solvent and 5% aqueous sodium sulfate solution as a separation aid.

Analytical key figures of bis- [2- (2-hydroxyhexadecyloxy) ethyl] sulfone: OH number: 156.4; Acid number: 1.2

A selection of the mono- and bis-ethers of thiodiglycol sulfoxides or thiodiglycol sulfones according to the invention produced in this way is shown in Table 1 and Table 2.

Table 1: Mono and bis ethers of thiodiglycol sulfoxides

Table 2: Mono and bis ethers of thiodiglycol sulfones

Manufacturing process for bis- [2- (alkylcarbonyloxy) ethyl] sulfoxides and sulfones

Example 2

2 moles of a corresponding fatty acid and 1 mole of bis (2-hydroxyethyl) sulfide (thiodiglycol) were placed in a reaction vessel with a stirring apparatus, 5 g of tin grinding (per 1000 g of total weight) were added and the mixture was brought to a reaction temperature while introducing nitrogen heated from about 200 ° C. The course of the reaction could be controlled and the thiodiglycol added if necessary within 5 to 10 hours by means of the amount of water which had been split off and the acid number, which should be below 5. In order to separate off the tin cut, the batch was suctioned off hot over Celite after the reaction.

The oxidation to the sulfoxide or sulfone was carried out by the dropwise addition of 1 mol or 2.1 mol of hydrogen peroxide (70% strength) to the intermediate product, which was at about 60 ° C. As a result of the strongly exothermic reaction, cooling was necessary if necessary, the reaction time being between 4 and 6 hours at a reaction temperature of about 90 ° C. The mixture was then washed with hot water until the wash water was free of peroxide. In the event of separation problems, butyl acetate was used as the solvent. The corresponding bis-ester sulfoxides or bis-ester sulfones were dried at 120 ° C. in vacuo.

Table 3 shows a selection of the mono- and bis-esters of thiodiglycol sulfoxides and thiodiglycol sulfones produced in this way.

Table 3: Mono- and bis-esters of thiodiglycol sulfoxides (A) and sulfones (B)

Table 4: Properties of active ingredient mixtures based on sulfoxide

Softener effect on cotton according to DIN 10 954 (sensory test in pairs) with 0.5% active substance based on dry weight; Fleet 1:20; 16 ° dH water hardness; Blank value = 1 (water); Maximum value = 4 (connection D)

2 Absorbance of 2 x 2 cm cotton terry cloth laps via the height measurement [cm] according to DIN 53924 - 5% application solution

4 Odor classification into weak, clear and strong (example 1 to 9 after sulfoxide; example 10 after isopropanol)

A bis- [2- (2-hydroxydodecyloxy) ethyl] sulfoxide

B bis- [2- (2-hydroxyhexadecyloxy) ethyl] sulfoxide

C sulfopone T 55 (sodium salt of tallow alcohol sulfate)

D dimethyldistearylammonium chloride

From Table 4 it can be seen that a mixture of 10% of compound A, 30% of compound B and 60% of compound C (example 6) with regard to the grip behavior and the absorbency is at the same level in comparison to commercially available active ingredients (example 10) moved and also stands out from the known prior art by a significantly better odor behavior and by an environmentally friendly nitrogen-free consistency.

Table 5: Properties of aqueous active ingredient mixtures based on tallow alcohol sulfate / sulfone

A: bis [2- (2-hydroxyhexadecyloxy) ethyl] sulfone B: sulfopone T 55 (tallow alcohol sulfate, Na salt) C: process water (approx. 16 ° dH)

1 In order to evaluate the grip of this new N-free fabric softener, no "standard handles" could be specified. The handle could be described as "pleasant", "dry", "light" and "soft". According to the announcer's classic grip scale, the observed grip effect was defined as follows according to the modified DIN 10954:

0 = roughest handle (without fabric softener) t

4 = softest grip (mix 5) '

Because of their high consistency, the blends 8, 9 and 10 were not tested with regard to the handle. Between 4 and 8, the mixes were found to be equally good in terms of handling.

1.1 Wacker, liquor ratio 1:10, 0.3% fabric softener active substance (based on the test material) in a 10% aqueous fabric softener active ingredient mixture, 5 min. Treatment time, 16 ° dH water hardness

1.2 Washing machine (Miele-W 717), 60 "wash, 0.3% active fabric softener (based on the test material) in a 10% aqueous fabric softener mixture, 16 ° dH water hardness

² Viscosity determination (according to Höppler) on the Haake falling ball viscometer

Table 5 refers to the new handle evaluation of aqueous active substance mixtures based on tallow alcohol sulfate / sulfone, which cannot be compared with the handle evaluation from fabric softeners known from the prior art. Because of their favorable viscosity behavior, Examples 4 to 7 are particularly preferred for the field of application.

Table 6: Properties of aqueous active ingredient mixtures based on emulsifier / sulfone

t

A: Bis [2- (2-hydroxyhexadecyloxy) ethyl] sulfone

B: Sulfopon T 55 (tallow alcohol sulfate, Na salt)

C: 33% A + 67% B

D: Texin ES 68 (Ciö / iß fatty acid ethyl ester sulfonate)

E: APG 501 (Cχ2 / i4-alkyl polyglucoside)

F: Eumulgin SMS 20 (polyethylene glycol 20 sorbitan monostearate)

G: APG 225 (Cβ / io-alkyl polyglucoside)

H: service water (approx. 16 ° dH)

1 The test rags were equipped in the washing machine (see Table 6)

² Absorbency according to DIN 53924 (rise height measurement)

3 3.1: The pH was determined 24 hours after the emulsion had been prepared

3.2: The pH value was determined after a two-month storage test at room temperature

In Table 6, aqueous active ingredient mixtures which contain a thiodiglycol sulfone (compound A) according to the invention are optimized for their grip properties, absorbency and pH storage stability with the addition of an appropriate emulsifier. For the possible use of fabric softener in the washing machine, the white-blue emulsions from Examples 1 and 2 have proven particularly useful.

Claims

Patent claims

1. New mono- and / or bis-ethers and mono- and / or bis-esters of thiodiglycol sulfoxides or sulfones of the general formula (I)

in which Xj and / or X2 mean β-hydroxyl-substituted alkyl radicals with 8 to 30 C atoms and / or acyl radicals of alkyl monocarboxylic acids with 8 to 30 C atoms, in which Xi and X2 are identical or different, in the case of the monoethers or mono-ester Xj or X2 is hydrogen and in which the number z represents 1 or 2.

2. Thiodiglycol compounds according to claim 1, characterized in that the radicals Xj and X2 are derived from β-hydroxyl-substituted alkyl radicals and / or from acyl radicals having 12 to 24 carbon atoms, preferably having 12 to 18 carbon atoms, which are preferably straight-chain are.

3. Thiodiglycol compounds according to Claims 1 and 2, characterized in that they contain mixed radicals in Xi and X2 of the type indicated, in particular structurally identical radicals of different chain lengths, but with Thiodiglycolsulfones (z = 2) with uniform and identical radicals of the type indicated are preferred.

4. A process for the preparation of the thiodiglycol compounds of the general formula (I), characterized in that thio diglycol with Cg to C30-o-01efinepoxiden or with CQ to C30 alkyl monocarboxylic acids in a molar ratio of 1: 1 to 1: 2 and the obtained mono- and / or bis-ether or mono- and / or bis-ester are oxidized in a manner known per se to sulfoxide and / or sulfone.

5. The method according to claim 4, characterized in that in the reaction of the thiodiglycol with Cg- to C3o * -oc-01efinepoxi- in the presence of a basic catalyst at temperatures of at least 120 to about 200 ° C, preferably from about 160 to 170 ° C, works.

6. Process according to claims 4 and 5, characterized in that as basic catalysts alkaline bases, such as alkali hydroxides and / or alkali methoxylates, in an amount of at least 0.05 wt .-% to about 5 wt .-%, preferably of about 0.1 to 1 wt .-% - each based on the total weight - used.

7. The method according to claims 4 to 6, characterized in that one carries out this reaction within about 3 to 6 hours to an epoxy oxygen content of below 0.5%, preferably below 0.2%.

8. Textile softening active ingredient mixtures which, in addition to solvents, dispersing agents, emulsifiers and / or Stabilizers with or without detergency and / or cleaning-enhancing action contain thiodiglycol compounds of the general formula (I).

9. Active ingredient mixtures according to claim 8, characterized in that they contain the thiodiglycol compounds of the general formula (I) in their mixtures with dispersing aids, emulsifiers and / or stabilizers in amounts of 5 to 95% by weight, preferably in the range from 20 to 70% by weight -% by weight, based on the mixture of active ingredients - and preferably in an aqueous mixture.

10. Active substance mixtures according to claims 8 and 9, characterized gekenn¬ characterized in that they contain the thiodiglycol compounds together with surfactant components, emulsifiers and / or stabilizers such as glycerol partial esters and / or ethers.

11. Mixtures of active substances according to claim 10, characterized in that the thiodiglycol compounds in admixture with alkylglycosides, in admixture with anionic surfactants, e.g. B. based on fatty alcohol sulfates, in particular in a mixture with tallow alcohol sulfate and / or in a mixture with nonionic surfactants.

12. Active ingredient mixture according to claims 8 to 11, characterized gekenn¬ characterized in that it contains the thiodiglycol-containing active ingredient mixture in aqueous solution and / or aqueous dispersion or emulsion with active ingredient contents of 1 to 50 wt .-%, preferably about 5 to 20 wt. -%, contain.

13. Active ingredient mixture according to claims 8 to 12, characterized gekenn¬ characterized in that combinations of compounds of general formula (I) each with about 10 to 14 carbon atoms, preferably 12 carbon atoms in the β-hydroxyl-substituted alkyl radical (Xi and X2) on the one hand and those with 16 to 20 carbon atoms, preferably 16 to 18 carbon atoms, are present in corresponding radicals Xj and X2 on the other hand.

14. Use of thiodiglycol compounds of the general formula (I) or their mixtures with solvent-imparting, emulsifying and / or dispersing auxiliaries as textile finishing components in textile detergents and / or dishwashing agents, in particular as rinse bath additives, preferably in amounts of 0.05 to 2% by weight of active substance, in particular in amounts of approximately 0.1 to 0.5% by weight of active substance -% by weight, in each case based on the dry weight of Texti1.

15. Embodiment according to claim 14, characterized in that aqueous preparations with the usual degrees of hardness, preferably from about 5 to 30 ° dH, in a pH range from about 4 to 11, preferably from 5.5 to 10, are used come.

16. Embodiment according to claims 14 and 15, characterized gekenn¬ characterized in that aqueous active substance preparations are used which have been prepared as follows:

Intensive mixing of the compounds of the general formula (I) with the dispersing aids, emulsifiers and / or stabilizers in concentrate form, if appropriate in the melt phase, and subsequent processing with an aqueous phase at least from room temperature to about 100 ° C., preferably at about 80 ° C to about 95 ^C C, for the commercial and / or application form of the new active ingredient mixtures.