EP0000201B1 - A sulphonyl urea-containing softener and water-repellant for textiles containing cellulose and for leather, method for the preparation thereof; the sulphonyl ureas and process for their preparation - Google Patents

Description

worin R Alkyl oder Alkenyl mit 10 bis 30 C-Atomen, B einer der zweiwertigen Reste

und X ß-Halogenalkyl oder Alkenyl mit jeweils 2 bis 4 C-Atomen ist und R¹ und R² für Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen sowie n für 2,3 oder 4 stehen, und b Gewichtsteilen eines Emulgators, bestehende aus 100-37,5% bekannter nichtionischer Emulgatoren, 0-50% bekannter anionischer Emulaatoren und 0-25% bekannter Licker, c Gewichtsteilen eines Epoxids der Formel 11

worin R³ Alkyl oder Alkenyl mit 15 bis 40 C-Atomen bedeutet, und gegebenenfalls d Gewichtsteilen Wasser oder eines mit Wasser mischbaren organischen Lösungsmittels, wobei a einen Wert von 80 bis 99, b einen Wert von 20 bis 1, c einen Wert von 0 bis 5 und gegebenenfalls

einen Wert von 10 bis 40 hat, bestehen, die Herstellung und Verwendung dieser Mittel sowie die neuen Wirkstoffe der Formel I und deren Herstellung.The present invention relates to softening and waterproofing agents for textile materials made of or containing cellulose and for leather, which are characterized in that they consist of a part by weight of a compound of general formula 1,

wherein R is alkyl or alkenyl having 10 to 30 carbon atoms, B is one of the divalent radicals

and X is β-haloalkyl or alkenyl each having 2 to 4 carbon atoms and R ¹ and R ^{2 are} hydrogen or alkyl having 1 to 4 carbon atoms and n is 2, 3 or 4, and b parts by weight of an emulsifier, existing from 100-37.5% known nonionic emulsifiers, 0-50% known anionic emulators and 0-25% known lickers, c parts by weight of an epoxide of the formula 11

wherein R ^{3 is} alkyl or alkenyl having 15 to 40 C atoms, and optionally d parts by weight of water or a water-miscible organic solvent, where a is from 80 to 99, b is from 20 to 1, c is from 0 to 5 and if necessary

has a value of 10 to 40, exist, the production and use of these agents and the new active compounds of the formula I and their production.

Softening agents are said to give textile materials and leather advantageous surface properties, in particular a pleasant, warm feel. In addition, finishing agents can improve the processing properties of fiber materials. Known conditioning agents are, for example, natural oils and partially saponified natural fats.

These products give the textile materials a full, soft but somewhat dull feel. A particular disadvantage is their sensitivity to water hardness and their tendency to become rancid. Softening agents based on sulfated oils are less sensitive to water hardness. Fats. Other known finishing agents are, for example, primary alkyl sulfates, such as cetyl and stearyl sulfate. In addition to the anionic softening agents, cationic softening agents based on quaternary ammonium bases with at least one long-chain alkyl radical, such as e.g. in the Swiss patent 130 881 or the German Reich patent 546 406. The cationic softening agents give a pleasantly soft feel, but tend to yellowing at high temperatures. They can also lead to color changes and reduce the lightfastness of dyeings. A certain improvement with regard to the tendency to yellowing while influencing the light-fastness of dyeings was achieved by the conditioning agents described in US Pat. No. 2,304,369 and in German Patent 1,048,412, containing predominantly carbonamide or urea groups.

In addition to the effect of aviva, it is often desirable to bring the textile material or leather to be hydrophobic. Known possibilities for the hydrophobization of textile material and leather are the treatment with solutions or emulsions of paraffin hydrocarbons, waxes or the like. Metal soaps have also already been used for hydrophobic purposes. Combinations of metal salts and paraffin and wax emulsions which can be considered for hydrophobic purposes are known from DRP 702 628 and from US Pat. No. 2,015,864. Metal complexes which, like metal soaps, can be used for water repellency purposes are known from US Pat. No. 2,273,040.

A disadvantage of all of the finishing and hydrophobizing agents mentioned above is their inadequate wet and wash fastness. Attempts have therefore already been made to bring about hydrophobization by chemical reaction with the cellulose. So it is known from DRP 542 186, cellulose materials to be treated with anhydrides or chlorides of fatty acids. In practice, however, this method could not be used. The water-repellent treatment of cellulose materials with long-chain isocyanates, for example stearyl isocyanate, is known from American patent specification 2 173 029. However, this process has the disadvantage that the hydrophobization must be carried out in the organic solvent. Certain improvements in this process using isocyanate adducts are known from British Patent 716,232 and US Patent 2,746,988. Other known hydrophobizing agents are alkoxy-methyl-pyridinium compounds with a long-chain alkoxy radical (DRP 613 735) and the similarly constructed N-alkanoylamino-methyl-pyridinium chloride (British Patent 466 817) with a long-chain alkanoyl radical, and in particular those known from DRP 681 520 N-alkyl-N'-ethylene ureas with long-chain alkyl radical.

However, these known products have a number of disadvantages, e.g. their poor resistance to water and, associated with this, a decrease in reactivity after prolonged storage, not always sufficient water repellency effect, the need to bring about the chemical bond between water repellent and cellulose fiber by heating to temperatures of 120-150 ° C. The fiber-reactive water repellents known from DRP 681 520 indeed give good water repellency effects, but they still leave something to be desired in terms of durability, since they tend to autopolymerize under the action of light, heat or traces of acid with a weakening effect. In addition, their manufacture poses considerable problems on the apparatus side.

Other disadvantages of known products are, for example, poor compatibility with other finishing agents for textiles and / or leather or with acidic dyes, which can lead to a shift in shades of color, not uniformly good effects on different materials, such as vegetable tanned or chrome-tanned leather, poor resistance to hydrophobization and finishing effects compared to chemical cleaning and "greasiness" when applied to suede.

The present invention now relates to finishing agents and water repellents which give an excellent improvement in the grip of cellulose textile material and leather and, at the same time, excellent water repellency effects. The effects achieved have a very good wet, wash and chemical cleaning resistance and they can be achieved on different cellulose materials and very different types of leather. In addition, the substrate-reactive active ingredients of the formula I contained in the finishing and hydrophobizing agents to be used according to the invention can be prepared in a technically simple manner.

worin R Alkyl oder Alkenyl mit 10 bis 30 C-Atomen, B einer der zweiwertigen Reste

und X ß-Halogenalkyl oder Alkenyl mit jeweils 2 bis 4 C-Atomen ist und R¹ und R2 für Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen sowie n für 2, 3 oder 4 stehen, und b Gewichtsteilen eines Emulgators, bestehend aus 100-37,5% bekannter nichtionischer Emulgatoren, 0-50% bekannter anionischer Emul-, gatoren und 0-25% bekannter Licker, c Gewichtsteilen eines Epoxids der Formel 11

• worin R³ Alkyl oder Alkenyl mit 15 bis 40 C-Atomen bedeutet, und gegebenenfalls
• d Gewichsteilen Wasser oder eines mit Wasser mischbaren organischen Lösungsmittels, wobei a einen Wert von 80 bis 99,
• b einen Wert von 20 bis 1,
• c einen Wert von 0 bis 5

und gegebenenfalls

einen Wert von 10 bis 40 hat, bestehen.The softening and waterproofing agents to be used according to the invention for textile materials made of or containing cellulose and for leather are characterized in that they consist of a part by weight of a compound of general formula I.

wherein R is alkyl or alkenyl having 10 to 30 carbon atoms, B is one of the divalent radicals

and X is β-haloalkyl or alkenyl each having 2 to 4 carbon atoms and R ¹ and R2 are hydrogen or alkyl having 1 to 4 carbon atoms and n is 2, 3 or 4, and b parts by weight of an emulsifier consisting of 100-37.5% of known nonionic emulsifiers, 0-50% of known anionic emulsifiers, gators and 0-25% of known lickers, c parts by weight of an epoxide of the formula 11

• wherein R ^{3 is} alkyl or alkenyl having 15 to 40 carbon atoms, and optionally
• d parts by weight of water or a water-miscible organic solvent, where a is from 80 to 99,
• b a value from 20 to 1,
• c a value from 0 to 5

and if necessary

has a value of 10 to 40.

Aids according to the invention have particularly favorable properties with 95 to 99 parts by weight of the active ingredient of the formula I and 1 to 5 parts by weight of the emulsifier in 100 parts by weight of the aid.

The long-chain alkyl radicals R of the active compounds of the formula I with 10 to 30 carbon atoms contained in the auxiliary preparations according to the invention are preferably only weakly branched or linear. Preferred active compounds of the formula I have alkyl radicals R having 12 to 22 carbon atoms. Examples of alkyl radicals which can be in the active compounds of the formula R are: decyl, undecyl, duodecyl, 8-ethyl-decyl (10), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 6-hexylduodecyl (12) , Nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, triacontyl.

In the β-haloalkyl radical representing X, the halogen has, for example, the meaning of bromine, iodine, but especially chlorine. Examples of the β-haloalkyl radical are in particular / 3-chloroethyl, β-chloropropyl and β-chlorobutyl, examples of the alkenyl representing X are vinyl, propenyl, 1-butenyl and 2-butenyl.

Mixtures of compounds of the formula I according to the invention in which the radicals R are based on their number of carbon atoms and their molar fraction in the mixture of the statistical composition are likewise preferred, both in terms of the action, emulsifiability and performance properties, and for reasons of easy accessibility of the corresponding starting materials which correspond to carboxylic acids in natural fats, such as tallow fat, coconut fat, stearin, soybean oil or palm oil. R radicals which stand for such a group of alkyl radicals are usually. designated with tallow fatty alkyl, coconut fatty alkyl, etc. For example, "stearylalkyl" consists essentially of alkyl radicals with 16 to 18 carbon atoms, 'tallow fatty alkyl "essentially consists of alkyl radicals with 14, 16, 18 carbon atoms and the octadecen (9) -yl- (1) radical and" oleyl -alkyl "from alkyl radicals with 16-18 carbon atoms and the octadecen- (9) -yl- (1) radical.

ist.Another group of preferred active compounds of the formula I are those in which B is one of the divalent radicals

is.

Because of their particularly advantageous reactivity and favorable accessibility, active compounds of the formula 1 are preferred in which X is for a β-chloroalkyl group having 2 to 4 carbon atoms, such as, for example, stands for the β-chloroethyl-β-chloropropyl or β-chloro butyl group.

The active compounds of formula 1 to be used according to the invention behave particularly favorably with regard to their joint use with other agents required for textile or leather treatment or finishing and with regard to their emulsifiability in aqueous liquors. This advantageous property of the active ingredients contained in the finishing and hydrophobicizing agents according to the invention opens up the possibility of varying the emulsifier required for the emulsification of the active ingredient in water in a variety of ways and thus of producing agents which find special use either for textiles or for leather , or such aids that can be used universally both for cellulose textiles and for leather.

worin

• A verzweigtes oder unverzweigtes Alkyl oder Alkenyl mit 10 bis 22 C-Atomen, Alkylphenyl mit insgesamt 6 bis 12 C-Atomen in den Alkylresten,
  • verzweigtes oder unverzweigtes Alkanoyl oder Alkenoyl mit 10 bis 22 C-Atomen,
  • Aralkyl mit 7 bis 15 C-Atomen,
  • Aralkyl-aryl mit 13 bis 25 C-Atomen,
  • Reste der Wollfettbestandteile oder Acyloxyalkyl mit insgesamt 10 bis 30 C-Atomen;
• R⁴ Wasserstoff oder Alkyl mit 1 bis 2 C-Atomen und
• n eine Zahl zwischen 10 und 60 ist,
• zusammenfassen lassen.

It is also quite expedient to use this possibility and to adapt the emulsifier contained in the finishing and hydrophobizing agents according to the invention to the main application area of the agent that may be envisaged. In any case, the emulsifier contains a proportion of known nonionic emulsifiers, which can be found under the general formula III

wherein

• A branched or unbranched alkyl or alkenyl with 10 to 22 carbon atoms, alkylphenyl with a total of 6 to 12 carbon atoms in the alkyl radicals,
  • branched or unbranched alkanoyl or alkenoyl with 10 to 22 carbon atoms,
  • Aralkyl with 7 to 15 carbon atoms,
  • Aralkyl-aryl with 13 to 25 carbon atoms,
  • Residues of the wool fat components or acyloxyalkyl with a total of 10 to 30 carbon atoms;
• R ^{4 is} hydrogen or alkyl having 1 to 2 carbon atoms and
• n is a number between 10 and 60,
• summarize.

Nonionic emulsifiers of the general formula III given above are obtained by reacting hydroxyl-containing compounds AOH with alkylene oxides such as butylene, propylene and preferably ethylene oxide. Conditioning and hydrophobizing agent preparations according to the invention, in which ethylene oxide reaction products with 10 to 30 mol ethylene oxide are contained as nonionic emulsifiers, provide particularly stable emulsions.

• Carbonsäuren mit 10 bis 22 Kohlenstoffatomen, insbesondere auch hier die natürlichen Fettsäuren, wie Stearinsäure, Palmitinsäure, Ölsäure oder natürliche vorkommende Fettsäuregemische, wie Cocosfettsäure oder Talgfettsäure;
• Alkylphenole mit 4-9 Kohlenstoffatomen in den Alkylresten, wie beispielsweise p-t-Butylphenol, p-Nonylphenol, Tri-isopropyl- und Tri-iso-butylphenole, beispielsweise 2,4,6-Tri-(n)-butylphenol, 2,4,6-Tri-iso-butylphenol oder 2,4,6-Tri-tert.-butylphenol,
• Aralkanole, insbesondere Phenyl- und Diphenyl-alkanole, wie z.B. Benzylalkohol, /3-Phenyl-äthanoi, /}-(4-Methyl-phenyl)-äthanoi, β-(4-lsopropyl-phenyl)-äthanol, 4'-Methyl-4-β-hydroxyäthyldiphenyl; Hydroxy-aralkyl-aryle, insbesondere aralkylierte Phenole und Hydroxydiphenyle, wie z.B. 4-Hydroxydiphenylmethan, 4-Hydroxy-4'-methyl-diphenylmethan, 2-Hydroxy-4'-methyl-diphenylmethan, 4-Benzyl-2'-hydroxydiphenyl oder 2-Benzyl-2'-hydroxydiphenyl, 4-(p-Tolyl)-4'-hydroxydiphenyl; teilweise mit langkettigen Fettsäuren veresterte mehrwertige Alkohole, wie beispielsweise Fettsäuremono- und -diglyceride, Fettsäureester des Sorbits und Sobitans, wobei als Fettsäurekomponenten insbesondere die natürlichen, wie Laurinsäure, Palmitinsäure, Stearinsäure, Ölsäure oder natürlich vorkommende Fettsäuregemische, wie Cocosfettsäure oder Talgfettsäure, in Betracht kommen;
• die Wollfettbestandteile, wie Palmitinsäure, Cerotinsäure, Capronsäure, Ölsäure, Lanocerinsäure, Myristinsäure, Lanopalminsäure, Colesterin, Lanosterin, Agnosterin, Cetylalkohol, Cerylalkohol, die vorteilhafterweise in Form des naturlichen Lanolins eingesetzt werden.

Hydroxyl group-containing organic compounds AOH, which are suitable for the preparation of the nonionic emulsifiers contained in the auxiliary preparation according to the invention, are, for example, long-chain alkanols and alkenols having 10 to 22 carbon atoms, in particular those which differ from the natural fatty acids such as stearic acid, palmitic acid, oleic acid or the natural ones Derive fatty acid mixtures as they are present in coconut fatty acid or tallow fatty acid;

• Carboxylic acids with 10 to 22 carbon atoms, especially here also the natural fatty acids, such as stearic acid, palmitic acid, oleic acid or naturally occurring fatty acid mixtures, such as coconut fatty acid or tallow fatty acid;
• Alkylphenols with 4-9 carbon atoms in the alkyl radicals, such as, for example, pt-butylphenol, p-nonylphenol, tri-isopropyl- and tri-iso-butylphenols, for example 2,4,6-tri (n) -butylphenol, 2,4, 6-tri-iso-butylphenol or 2,4,6-tri-tert-butylphenol,
• Aralkanols, especially phenyl and diphenyl alkanols, such as, for example, benzyl alcohol, / 3-phenyl-ethanoi, /} - (4-methyl-phenyl) -ethanoi, β- (4-isopropyl-phenyl) -ethanol, 4'-methyl -4-β-hydroxyethyl diphenyl; Hydroxy-aralkyl-aryls, in particular aralkylated phenols and hydroxydiphenyls, such as, for example, 4-hydroxydiphenylmethane, 4-hydroxy-4'-methyldiphenylmethane, 2-hydroxy-4'-methyldiphenylmethane, 4-benzyl-2'-hydroxydiphenyl or 2 -Benzyl-2'-hydroxydiphenyl, 4- (p-tolyl) -4'-hydroxydiphenyl; polyhydric alcohols partially esterified with long-chain fatty acids, such as, for example, fatty acid mono- and diglycerides, fatty acid esters of sorbitol and sobitan, the natural fatty acids such as lauric acid, palmitic acid, stearic acid, oleic acid or naturally occurring fatty acid mixtures such as coconut fatty acid or tallow fatty acid being suitable as fatty acid components ;
• the wool fat components, such as palmitic acid, cerotinic acid, caproic acid, oleic acid, lanoceric acid, myristic acid, lanopalmic acid, colesterine, lanosterol, agnosterol, cetyl alcohol, ceryl alcohol, which are advantageously used in the form of natural lanolin.

Reaction products of lanolin with 10-30 mol of ethylene oxide are particularly valuable for use in the auxiliary preparations according to the invention because they give particularly stable emulsions or dispersions of the auxiliary according to the invention in aqueous treatment liquors.

Aid preparations according to the invention, which are preferably intended for textile use, contain essentially, preferably 100%, nonionic emulsifiers. Aid preparations according to the invention which are specifically intended for use in the leather sector do not contain any epoxides of the formula II, but up to 50% of the nonionic emulsifier can be replaced by anionic emulsifiers. In softening and waterproofing preparations according to the invention, the emulsifier can be composed of 100 to 50% of nonionic emulsifiers and 0 to 50% of anionic emulsifiers. Known emulsifiers used in technical leather processing processes are, for example, sulfated fats or oils, such as sulfated tran or sulfated sperm, palm or claw oil,
sulfonated or sulfated paraffin hydrocarbons, chlorinated paraffin hydrocarbons, olefins, fatty alcohols with a chain length of 10-30 C atoms, their salts and their derivatives chemically modified on the sulfo group such as sulfotaurides, sulfoamides or imides, sulfoesters, chemically modified fatty acids with ₁₀ - _{50 C} - Atoms, such as, for example, fatty acid taurides, oxaethanesulfonates, alkylarylsulfonic acid or their salts with an alkyl radical having 5 to 30 carbon atoms.

It is also possible with the auxiliary preparations according to the invention to grease the leather with a fat licker simultaneously with the finishing and hydrophobicization of the leather. In this case, it is also possible to directly incorporate at least a part of the fat licker required for the greasing of the leather into the auxiliary preparations according to the invention. This fat-licker portion generally replaces part of the emulsifiers contained in the auxiliary preparations to be used according to the invention. It is easily possible to replace up to 25% by weight of the emulsifier with fat licker. In such a finishing agent and water repellent according to the invention intended for the leather sector, the emulsifier accordingly consists of 95.0 to 37.5% by weight of known nonionic emulsifiers, 0 to 50% by weight of known anionic emulsifiers and 5 to 30% by weight of known lickers. The emulsifier of the auxiliaries according to the invention intended for leather use preferably contains 90 to 60% by weight of known nonionic emulsifiers, 0 to 20% by weight of known anionic emulsifiers and 10 to 20% by weight of known lickers.

Of the e.g. In "Ullmann's Encyclopedia of Industrial Chemistry", Volume 11, page 567, the known lickers described, which are based on anionic components and free of cationic substances, can be incorporated into the softening and waterproofing agents according to the invention within the scope of the above information.

A distinction is made between the classic licker systems, which are made up of emulsifiers, neutral oils, neutral greases and buffer systems, and the synthetic and semi-synthetic licker systems.

Vegetable and animal-based fatty substances such as tallow, oil of oil, sperm oil, cattle claw oil, castor oil, olive oil, linseed oil, stearin, wool fat are suitable for the classic lickers. Waxes such as beeswax, carnauba wax or montan wax as well as mineral oil and linear chlorinated paraffins with 18-30 C atoms and 10-50% by weight chain chlorine are possible. To use this classic fatliquor To be able to use licker, there are 2 possibilities by partial reaction with monohydrate or sulfuric acid to produce sulfonated semi-synthetic, easily emulsifiable systems or to convert them into an emulsified form with emulsifiers or emulsifier mixtures in the form of nonionic or preferably anionic compounds. Today, however, synthetic products are increasingly used for leather greasing, which have emulsifier properties and at the same time have a greasy effect.

Examples of groups of synthetic compounds which can be present in part in combination with the above-mentioned water-insoluble natural and synthetic fatliquoring agents, in part also alone as a licker in finishing agents and water repellents according to the invention:

und

Fatty acid esters of β-hydroxyethanesulfonic acid, such as

and

Fatty acid derivatives of amino acetic acid, such as

synthetische Sulfochlorierungsprodukte, wie z.B.

sekundäre Sulfonate-Alkalisalze, wie z.B.

langkettige Sulfamide, wie z.B.

Fatty acid taurides and fatty acid N-methyl taurides, such as

synthetic sulfochlorination products, such as

secondary sulfonate alkali salts, such as

long chain sulfamides, such as

Sulfoxidation products predominantly saturated unbranched paraffins, such as

Alkyl aryl sulfonates and olefin sulfonates.

The good compatibility of the active ingredients of the formula I contained in the auxiliaries according to the invention also makes it possible to use them together with epoxides of the formula II. This is of particular interest if the agents according to the invention for textile use, i.e. are provided for the finishing and hydrophobization of cellulose-containing or cellulose textile materials. Agents intended for this special purpose contain 0.5 to 5 parts by weight per 100 parts by weight of the auxiliary preparation of the epoxides of the formula II. This addition surprisingly achieves a substantial increase in the effect of the preparations according to the invention with regard to the desired improvement in grip and the hydrophobization of the treated textile material.

einen Wert von 10 bis 40 hat. Die Gewichtsmenge d des zuzusetzenden Wassers oder mit Wasser mischbaren organischen Lösungsmittels richtet sich demnach nach den Mengen, a, b und c der übrigen Bestandteile der Zubereitung und ergibt sich aus der obigen Gleichung zu

In order to facilitate the application, handling and metering of the auxiliary preparations according to the invention, it is advantageous to use the mixtures of the active ingredient according to the invention the formula I, emulsifier and optionally epoxides of the formula II to add enough water or water-miscible organic solvents that the resulting products have a content of 10 to 40% by weight with respect to the active ingredient of the formula I, ie if the break

has a value from 10 to 40. The amount by weight d of the water to be added or water-miscible organic solvent accordingly depends on the amounts, a, b and c of the other constituents of the preparation and results from the above equation

Water-miscible organic solvents which may be present in the auxiliary preparations according to the invention are lower alkanols, such as, for example, methanol, ethanol, propanol, isopropanol; Ketones such as acetone, diethyl ketone, methyl ethyl ketone; cyclic ethers such as tetrahydrofuran or dioxane; lower acid amides, such as acetamide or dimethylformamide, dimethylacetamide, dimethyl sulfoxide, glycol mono- or dimethyl ether or diglycol mono- or dimethyl ether. Water is particularly preferred for the stated purpose. Of the organic solvents, the lower alkanols, in particular ethanol, and the propanols are preferred.

worin

• R Alkyl oder Alkenyl mit 10 bis 30 C-Atomen,
• B einer der zweiwertigen Reste
  
• X β-Halogenalkyl oder Alkenyl, mit jeweils 2 bis 4 C-Atomen,
• R¹ und R² für Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen und
• n für 2, 3 oder 4 stehen,
• mit 1 bis 20, vorzugsweise 1 bis 5, Gewichtsteilen eines Emulgators, bestehend aus
• 100 - 37,5 Gew.% bekannter nichtionischer Emulgatoren,
• 0 - 50 Gew.% bekannter anionischer Emulgatoren,
• 0 - 25 Gew.% bekannter Licker und
• 0 - 5 Gewichtsteilen eines Epoxids der Formel II
  

worin R3 Alkyl oder Alkenyl mit 15-40 C-Atomen bedeutet, bei Temperaturen von 20-90°C solange verknetet oder verrührt, bis eine homogene Masse entstanden ist und gegebenenfalls durch Zugabe von Wasser oder eines mit Wasser mischbaren organischen Lösungsmittels auf einen Gehalt von 10 bis 40 Gew.% der Verbindung der allgemeinen Formel I einstellt.The softening and waterproofing agents according to the invention are prepared by adding 80 to 99, preferably 95 to 99, parts by weight of a compound of general formula I.

wherein

• R alkyl or alkenyl with 10 to 30 C atoms,
• B one of the divalent residues
  
• X β-haloalkyl or alkenyl, each having 2 to 4 carbon atoms,
• R ¹ and R ^{2 are} hydrogen or alkyl having 1 to 4 carbon atoms and
• n stands for 2, 3 or 4,
• with 1 to 20, preferably 1 to 5, parts by weight of an emulsifier consisting of
• 100 - 37.5% by weight of known nonionic emulsifiers,
• 0 - 50% by weight of known anionic emulsifiers,
• 0 - 25% by weight of known lickers and
• 0 - 5 parts by weight of an epoxide of the formula II
  

wherein R3 is alkyl or alkenyl with 15-40 C atoms, kneaded or stirred at temperatures of 20-90 ° C until a homogeneous mass has formed and, if appropriate, by adding water or a water-miscible organic solvent to a content of 10 to 40% by weight of the compound of the general formula I is established.

The composition of the emulsifier used here can be adapted in the manner described above to the intended use for the product according to the invention to be produced. In auxiliary preparations according to the invention specifically intended for the leather sector, the addition of the epoxide of the formula II is omitted, while in the preparation of preparations according to the invention which are intended for use in the textile sector, the addition of 0.5 to 5 parts by weight, preferably 0.5 to 2 parts by weight of the epoxy.

The finishing agents and water repellents according to the invention are applied in a manner known per se, as is the case with textile finishing or high-quality finishing and in leather treatment procedure is common. Accordingly, aqueous treatment liquors which contain 5 to 50 g / l of an active ingredient of the general formula are used for the finishing and hydrophobicization of cellulose-containing or cellulose-containing textile materials. This amount of active ingredient is expediently added to the aqueous treatment bath in the form of the auxiliary preparations according to the invention described above. This has the considerable advantage that the active ingredients of the formula I change immediately when added to a fine emulsion or dispersion which are stable even for longer periods or under the conditions of use of the treatment bath. Because of the excellent compatibility of the active ingredients of the formula contained in the auxiliaries according to the invention with other known auxiliaries and finishing agents for textiles and leather, the finishing and hydrophobizing can also be carried out simultaneously with other post-treatment or finishing steps. For this purpose, the auxiliary preparations according to the invention can also be used simultaneously with dye liquors which contain anionic cellulose or leather dyes, in addition to the associated dyeing auxiliaries, such as retarders; Leveling agents, dispersants, neutral salts and, if necessary, additives determining the pH of the liquors are used. Surprisingly, it is also possible to use the auxiliaries according to the invention in combination with known high-quality textile finishing agents based on aminoplast formaldehyde precondensates which are used together with acidic or acid-releasing condensation catalysts.

The textile materials containing and made of cellulose, containing or made from cellulose, which have been rendered active and hydrophobicized using the auxiliary preparations according to the invention, have an excellent fluffy and wool-like feel and have very good water-repellent properties. Leather treated according to the invention has a very soft, delicate surface with a pleasant feel and, compared to untreated goods, a considerably reduced water absorption capacity and greatly reduced dynamic water absorption.

It is also of particular importance that the mentioned advantageous effects of the treatment according to the invention arise both on vegetable-tanned and on chrome-tanned leather, that they can be used equally well on suede of various origins, for example on goat and pig suede, and on the leather surfaces obtained none. Greasy, but give the velor a velvety feel and make it insensitive to hydrophilic dirt and stains from aqueous colorless or colored liquids, e.g. Fruit juices, red wine, ink, blood, etc. can arise.

The effects obtained in the treatment according to the invention on cellulose-containing or consisting of textile materials and on leather have a very good resistance to further post-treatment steps, to water, aqueous detergent solutions and cleaning with organic solvents.

In addition to the particularly advantageous effects of the aftertreatment according to the invention, the finishing agents and water repellents to be used according to the invention have excellent storage stability and durability in aqueous liquors. The aftertreatment process according to the invention for softening and hydrophobizing cellulose-containing or cellulose-containing textile materials and leather and the auxiliary preparations according to the invention used for this method accordingly have a technically particularly advantageous combination of valuable properties and are significantly superior to previously known methods and auxiliaries.

in denen B ein zweiwertiger Rest der Formel

mit B¹ = Wasserstoff und R ein langkettiger Alkylrest sind, sind aus der deutschen Offenlegungsschrift 1 545 871 bekannt. Die Verbindungen werden dort zur Herstellung von Tetrahydro-1,2,4-thiadiazin-3- on-1,1-dioxiden eingesetzt. Dieser Druckschrift ist also kein Hinweis auf die vorliegende Erfindung zu entnehmen.The active ingredients of the general formula I.

in which B is a divalent radical of the formula

with B ¹ = hydrogen and R are a long-chain alkyl radical, are known from German Offenlegungsschrift 1 545 871. The compounds are used there for the preparation of tetrahydro-1,2,4-thiadiazin-3-one-1,1-dioxides. No reference to the present invention can be inferred from this publication.

worin

• R Alkyl oder Alkenyl mit 10 bis 30 C-Atomen,
• B einer der zweiwertigen Reste
  
  und
• X ß-Halogenalkyl oder Alkenyl, mit jeweils 2 bis 4 C-Atomen,
• R¹ für Alkyl mit 1 bis 4 C-Atomen,
• R² für Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen und
• n für 2, 3 oder 4 steht,

sind bisher nicht beschrieben worden.Sulfonylureas of the general formula I

wherein

• R alkyl or alkenyl with 10 to 30 C atoms,
• B one of the divalent residues
  
  and
• X ß-haloalkyl or alkenyl, each with 2 to 4 carbon atoms,
• R ¹ for alkyl with 1 to 4 carbon atoms,
• R ^{2 represents} hydrogen or alkyl having 1 to 4 carbon atoms and
• n represents 2, 3 or 4,

have not yet been described.

These new sulfonylureas, which are used as active ingredients for the preparation of the finishing and hydrophobicizing agents according to the invention, also form part of the subject matter of the invention.

Such sulfonylureas of the formula in which R is alkyl or alkenyl having 12 to 22 C atoms and are in particular coconut fatty alkyl, tallow fatty alkyl or oleyl, but preferably stearyl, are particularly valuable.

ist, und auch solche, in denen X für β-Chloralkyl mit 2 bis 4 C-Atomen wie z.B. für die β-Chloräthyl-, β-Chlorpropyl- oder β-Chlorbutylgruppe steht.Furthermore, those sulfonylureas of the formula I according to the invention are preferred in which B is one of the divalent radicals

is, and also those in which X represents β-chloroalkyl having 2 to 4 carbon atoms, such as, for example, the β-chloroethyl, β-chloropropyl or β-chlorobutyl group.

worin R Alkyl oder Alkenyl mit 10 bis 30 C-Atomen,

• B einer der zweiwertigen Reste
  
  und X ß-Halogenalkyl oder Alkenyl mit jeweils 2 bis 4 C-Atomen ist,
• R¹ für Alkyl mit 1 bis 4 C-Atomen,
• R² für Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen und
• n für 2,3 oder 4 steht, erfolgt in der Weise, daβ ein β-Halogenalkyl-sulfonyl-isocyanat mit 2 bis 4 C-Atomen im Alkylrest der Formel
  
• worin X¹ β-Halogenalkyl mit 2 bis 4 C-Atomen ist, mit einem Amin der Formel
  
• worin B einer der zweiwertigen Reste
  
  ist,
• R Alkyl oder Alkenyl mit 10 bis 30 C-Atomen,
• R¹ Alkyl mit 1 bis 4 C-Atomen
• R² Wasserstoff oder Alkyl mit 1 bis C-Atomen ist und
• n für 2, 3 oder 4 steht,

im Molverhältnis von etwa 1:1 in einem aprotischen organischen Lösungsmittel bei Temperaturen zwischen 20°C und 110°C, vorzugsweise zwischen 30°C und dem Siedepunkt des eingesetzten organischen Lösungsmittels, umgesetzt wird, das Reaktionsprodukt in der üblichen Weise isoliert und, sofern.eine Verbindung der Formel 1 hergestellt werden soll, in der X Alkenyl ist, in an sich bekannter Weise anschließend mit wäßrigem Alkali behandelt wird.The preparation of the sulfonylureas of the general formula I

in which R is alkyl or alkenyl having 10 to 30 C atoms,

• B one of the divalent residues
  
  and X is β-haloalkyl or alkenyl each having 2 to 4 carbon atoms,
• R ¹ for alkyl with 1 to 4 carbon atoms,
• R ^{2 represents} hydrogen or alkyl having 1 to 4 carbon atoms and
• n stands for 2, 3 or 4, takes place in such a way that a β-haloalkyl sulfonyl isocyanate with 2 to 4 carbon atoms in the alkyl radical of the formula
  
• wherein X ^{1 is} β-haloalkyl having 2 to 4 carbon atoms, with an amine of the formula
  
• where B is one of the divalent radicals
  
  is
• R alkyl or alkenyl with 10 to 30 C atoms,
• R ¹ alkyl with 1 to 4 carbon atoms
• R ^{2 is} hydrogen or alkyl having 1 to C atoms and
• n represents 2, 3 or 4,

in a molar ratio of about 1: 1 in an aprotic organic solvent at temperatures between 20 ° C and 110 ° C, preferably between 30 ° C and the boiling point of the organic solvent used, the reaction product is isolated in the usual manner and, if. a compound of formula 1 is to be prepared in which X is alkenyl, is then treated in a manner known per se with aqueous alkali.

• 
  umgesetzt wird, worin
• R Alkyl oder Alkenyl mit 12 bis 22 C-Atomen ist und insbesondere Cocosfettalkyl, Talgfettalkyl oder Oleyl, vorzugsweise Stearyl, steht.
• Gleichfalls bevorzugte erfindungsgemäße Sulfonylharnstoffe werden erhalten, wenn das /3-Halogenalkyl-sulfonyl-isocyanat mit 2 bis 4 C-Atomen im Alkylrest mit einem Amin der Formel
  
  umgesetzt wird, worin
• B einer der zweiwertigen Reste
  
  ist.

Preferred sulfonylureas according to the invention are obtained when the β-haloalkyl-sulfonyl-isocyanate having 2 to 4 carbon atoms in the alkyl radical with an amine of the formula is obtained by the stated processes

• 
  is implemented in what
• R is alkyl or alkenyl having 12 to 22 carbon atoms and in particular is coconut fatty alkyl, tallow fatty alkyl or oleyl, preferably stearyl.
• Likewise preferred sulfonylureas according to the invention are obtained when the / 3-haloalkylsulfonyl isocyanate having 2 to 4 carbon atoms in the alkyl radical with an amine of the formula
  
  is implemented in what
• B one of the divalent residues
  
  is.

A β-chloroalkylsulfonyl isocyanate having 2 to 4 carbon atoms in the alkyl radical is preferably used as the β-haloalkylsulfonyl isocyanate having 2 to 4 carbon atoms in the alkyl radical.

Aprotic organic solvents in which the reaction of ß-halogen-ethylsulphonyl isocyanates with the amines of the. Formula RBH can be carried out, for example, aliphatic hydrocarbons having up to 10, preferably 7, carbon atoms, in particular the representatives of this series which are liquid at normal temperature and mixtures of these hydrocarbons which are liquid at normal temperature, advantageously those having boiling points between 50 and 180 ° C., preferably between 50 and 100 ° C, liquid halogenated hydrocarbons with up to 6 carbon atoms and up to 4 chlorine atoms, benzene, alkylbenzenes with 1 to 3 alkyl radicals each with 1 to 3 carbon atoms and halogenobenzenes, especially chlorobenzenes, with 1 to 3 halogen, especially chlorine atoms.

Examples of solvents that can be used for the process according to the invention are pentane, hexane, heptane, octane, nonane, decane, petroleum ether, light and heavy gasoline, ethylene chloride, chloroform, dichloroethane, trichlorethylene, perchlorethylene, benzene, toluene, o-, m-, p-xylene, ethylbenzene, diethylol, isopropylbenzene, monochlorobenzene, monobromobenzene, o-dichlorobenzene, m-dichlorobenzene, o-, m- or p-chlorotoluene.

Water-immiscible organic solvents which are particularly suitable for carrying out the process according to the invention are the aliphatic chlorinated hydrocarbons, in particular dichloroethane, trichlorethylene, perchlorethylene and the aromatic carbon hydrocarbons, in particular benzene, toluene, o-, m- and p-xylene (also in the form of their technical mixtures) , Monochlorobenzene and o-dichlorobenzene. Monochlorobenzene is particularly preferred.

If it is desired to carry out the reaction at temperatures above the boiling point of the organic solvent used, for example to carry out the reaction at 100 ° C. in benzene, it is possible to work in a pressure-tightly sealed vessel.

An excess of one of the reactants can also be used in the preparation of the sulfonylureas of the invention. In this case too, the chemical conversion takes place in a molar ratio of 1: 1, however, as is known, when the concentration of one of the reactants is increased, the reaction rate is increased by law. A disadvantage of this method is that the excess used may have to be removed from the reaction product.

It is particularly advantageous to carry out the reaction in such a way that the reaction components, each dissolved individually if appropriate, are gradually combined in the desired organic solvent at temperatures between 20 and 50 ° C., preferably 30 and 40 ° C., and the reaction after decay the shade of heat is brought to a boil by heating the reaction mixture.

The reaction products obtained can be isolated in a manner known per se, for example by distilling off the solvent and, if necessary for analytical purposes, purification of the reaction products obtained, for example by recrystallization.

The sulfonylureas known from DOS 1 545 871, which can also be present as active ingredients in the softening and waterproofing agents according to the invention, can also be prepared in a completely analogous manner to that described for the new sulfonylureas according to the invention.

Textile materials can be treated with the treatment liquors containing the finishing and hydrophobicizing agents according to the invention, as is customary, for example by impregnation on a two- or three-roll pad, squeezing and subsequent drying or condensation at temperatures of 90 to 150 ° C. The finishing and water repellant liquors according to the invention are applied to leather, as is generally customary in the leather industry, at temperatures between 15 and 70 ° C., preferably with continuous drumming for 15-60 minutes in a rotating drum, with 2-15% of the agents according to the invention in 20 up to 1000% aqueous liquor, based on the leather weight. However, the treatment can also be carried out by spraying the leather with the treatment liquor, which, in addition to the finishing agents and water repellents according to the invention, can also contain other auxiliaries required for leather finishing, such as, for example, fatliquor or lacquers, and then fixing the invention measured reactive ingredient by heat treatment at 50 to 120 ° C, optionally under pressure, for example in an ironing press.

Leather impregnation with the named sulfoureas from hot or cold aqueous solutions can also be carried out very conveniently in the foulard devices known from the textile sector, which have recently also been introduced in the leather industry, previously mainly for leather dyeing.

You use between 20-300 g / liter. After impregnation and squeezing, the leather is dried and, as described for spray impregnation, fixed hot at 50-120 ° C.

In exceptional cases, especially when it comes to ready-made leather articles, the aqueous solution of the hydrophobizing agent can also be carried out by brushing by hand or by brushing machines, in which case the dispersion penetrates into the leather interior by adding 0-50% of one so-called penetrators, e.g. Butyl diglycol, pentaglycol, dimethylformamide, dimethyl sulfoxide, etc. are supported. After drying, heat is fixed as usual at 50-120 ° C and the temporarily glued velor is straightened up again with a hard brush in a dry state.

The following working examples illustrate the manufacture and use of the softening and waterproofing agents according to the invention and the manufacture of the new sulfonylureas contained as active ingredients in the auxiliaries according to the invention. Parts contained in the present application are parts by weight; Percentages mean percentages by weight.

EXAMPLE 1

81.3 g (0.3 mol) of octadecylamine dissolved at 40 ° C in 280 ml of toluene. 51.9 g (0.306 mol) of β-chloroethylsulfonyl isocyanate are added dropwise to this solution at 40 ° C. in the course of 75 minutes. Then, the reaction is driven by one hour under reflux to cookers end and further stirred two hours at a temperature of 40-50 ^o C. The toluene is then distilled off under vacuum. This gives 126.5 g - 96% of theory. Th. Crude N-octadecyl-N 'β-chloroethylsulfonylurea of mp 89-90 ° C.

N-Hexadecyl-N'-β-chlorätbylsulfonylhanstoff:

Similarly, it is possible to give 55.5 g (0.3 mol) of laurylamine or 72.3 g (0.3 mol) of hexadecylamine with 51.9 g (0.306 mol) of β-chloroethylsulfonyl isocyanate under the reaction conditions described to give N-lauryl-N '-β-chloroethylsulfonylurea or to convert to N-hexadecyl-N'-β-chloroethylsulfonylurea. N-Lauryl-N'-β-chlofthylsulfonylurea: C _1s H ₃₁ CISN ₂ 0 ₃ (354.5) mp 79-80 ^o C

N-hexadecyl-N'-β-chloro-ethyl sulfonyl urea:

• 200 g N-Octadecyl-N'-β-chloräthylsulfonyl-harnstoff werden mit 50 g des Umsetzungsproduktes aus 4-Nonylphenol mit 23 Molen äthylenoxyd bei 65-75°C unter Rühren verschmolzen. Dann werden zu dieser homogenen Schmelze noch 750 g Wasser von 70-80°C langsam zugefügt, eine Stunde bei 70-80°C nachgerührt und die erhaltene Emulsion durch Ausrühren auf Zimmertemperatur fertiggestellt. Anstelle der 750 ml H₂0 können auch 750 ml einer Mischung von Äthanol/Wasser 1:1 oder 750 ml Dimethoxyäthan eingesetzt werden.

The compounds prepared according to the procedure described above are converted into an auxiliary preparation according to the invention in the following way:

• 200 g of N-octadecyl-N'-β-chloroethylsulfonylurea are fused with 50 g of the reaction product of 4-nonylphenol with 23 moles of ethylene oxide at 65-75 ° C. with stirring. Then 750 g of water at 70-80 ° C. are slowly added to this homogeneous melt, the mixture is stirred for one hour at 70-80 ° C. and the emulsion obtained is finished by stirring to room temperature. Instead of the 750 ml H ₂ 0, 750 ml of a mixture of ethanol / water 1: 1 or 750 ml of dimethoxyethane can also be used.

An equally good emulsion is obtained if, instead of the reaction product of 4-nonylphenol with 23 moles of ethylene oxide, the same amount of the reaction product of 2.4.6-tributylphenol with 30 moles of ethylene oxide is used.

It is also possible to work with the reaction product of 2-benzyl-2'-hydroxydiphenyl with 15 moles of ethylene oxide.

An emulsion having extremely high stability and excellent application properties is obtained when 200 g of N-octadecyl-N'-ß-chloroethyl-sulfonylurea with a melting point of 89-90 ^o C in the form of the crude product prepared in the manner described above at 65-70 ° C homogeneously fused with 50 g of a reaction product from lanolin with 20 moles of ethylene oxide; 750 g of water at 70-80 ° C. are slowly added to this melt and the mixture is cooled to room temperature with stirring.

EXAMPLE 2

195 g (1 mole) of coconut fatty amine are dissolved in 500 ml of CHCl ₃ at a temperature of 40-50 ° C. and 177.9 g (1.05 mol) of β-chloroethylsulfonyl isocyanate are added dropwise to this solution. The reaction is brought to an end by heating at 50-60 ° C for one hour. The chloroform is distilled off from the resulting crude product. The yield is 360 g 98.7% of theory. Th. Mp. 75-80 ° C.

The analogous compounds are obtained when, instead of coconut fatty amine, 280 g (1 mol) oleylamine or 270 g (1 mol) tallow fatty amine are reacted with 177.9 g (1.05 mol) β-chloroethylsulfonyl isocyanate.

• 200 g N-Talgfettalkyl-N'-β-chloräthlsulfonylharnstoff werden mit 40 g des Umsetzungsproduktes aus 1 Mol Oleylalkohol mit 23 Molen Äthylenoxyd und 10 g eines epoxydierten C_3o-α-Olefins bei einer Temperatur von 70-80°C. unter Rühren verschmolzen. In diese homogene Schmelze werden 750 ml Wasser von 80-90°C eingerührt. Nach einer Nachrührzeit von zwei Stunden wird die erhaltene Emulsion auf Zimmertemperatur ausgerührt. ,

Aid preparations according to the invention can be produced from these compounds as follows, which are particularly suitable for softening and waterproofing textile materials:

• 200 g of N-tallow fatty alkyl N'-β-chloroethylsulfonylurea are mixed with 40 g of the reaction product from 1 mol of oleyl alcohol with 23 moles of ethylene oxide and 10 g of an epoxidized C _3o- α-olefin at a temperature of 70-80 ° C. melted while stirring. 750 ml of water at 80-90 ° C. are stirred into this homogeneous melt. After a stirring time of two hours, the emulsion obtained is stirred to room temperature. ,

Emulsions of virtually the same quality are obtained if, instead of the reaction product of oleyl alcohol with 23 moles of ethylene oxide, the same amount of the reaction product of octadecyl alcohol with 30 moles of ethylene oxide is used.

EXAMPLE 3

141.5 g (0.5 mol) of N-methyl-octadecylamine are dissolved in toluene at 40-50 ° C. and 88.95 g (0.525 mol) of β-chloroethylsulfonyl isocyanate are then added dropwise to this solution. After a stirring time of two hours at 40-90 ° C, the reaction is complete. Distilling off the toluene in vacuo gives 198.5 g of 93.4% of theory crude N-methyl-N-octadecyl-N'-ß-chloroethylsulfonylurea.

Analogous reaction products are obtained by reacting 92.5 g (0.5 mol) of N-ethyldecylamine or 120.5 (0.5 mol) of N-n-butyldodecylamine with 88.95 g (0.525 mol) of β-chloroethylsulfonyl isocyanate.

By fusing 100 g of the above-described N-methyloctadecyl-N'-β-chloroethylsulfonylurea with 25 g of the reaction product from tallow fatty alcohol with 11 moles of ethylene oxide with vigorous stirring and then adding 375 g of water at 70-80 ° C. a storage stable emulsion with good application properties on textile material and on leather.

EXAMPLE 4

390.75 g (0.75 mol) of N-dioctadecylamine are dissolved in 100 ml of ethylene chloride at 60-70 ° C and 127.1 g (0.75 mol) of β-chloroethylsulfenyl isocyanate dissolved in 150 ml of ethylene chloride, added dropwise at this temperature and 2 Hours stirred. By distilling off the ethylene chloride in vacuo, 498.3 g - 96.2% of theory of crude N, N-dioctadecyl-N'-ß-chloroethylsulfonylurea are obtained.
Mp 104-106 ° C.

In the same way it is possible to use 348.75 g (0.75 mol) of N-di-hexadecylamine with 127.1 g (0.75 mol) of β-chloroethylsulfonyl isocyanate or 432.75 g (0.75 mol) of N- To implement di-eicosylamine with 127.1 g (0.75) mol of β-chloroethylsulfonyl isocyanate to give the corresponding sulfonylureas according to the invention.

100 g of the N-di-octadecyl-N'-β-chloroethylsulfonylurea described above are mixed with 25 g of the reaction product from 1 mol of coconut fatty alcohol and 25 mols of ethylene oxide or with 25 g of the reaction product from 1 mol of coconut fatty alcohol with 15 mols of ethylene oxide at a temperature of 80 ―85 ° C melted and then stirred with the addition of 375 g of water from 70―80 ° C to an emulsion.

It is also possible to produce an equally good emulsion if 25 g of the reaction product of 4-benzyl-2'-hydroxydiphenyl or 2-benzyl-2'-hydroxydiphenyl, each with 12 moles of ethylene oxide, instead of the above-mentioned reaction product of 1 mole of coconut fatty alcohol with 15 or 25 moles of ethylene oxide.

EXAMPLE 5

A cotton fabric of 125 g / m ² is impregnated with a liquor of 25 g / liter of an auxiliary preparation according to the invention produced according to Example 1, squeezed to 80% residual moisture, and dried at 125 ° C. for eight minutes.

The treated fabric has a pleasant, soft feel and good water resistance. The improved grip and the water-repellent effect obtained are resistant to laundry.

EXAMPLE 6

• Unter kräftigem Rühren werden 100 g des nach dem Beispiel 1 hergestellten N-Octadecyl-N'-β-chloräthyl-sulfonylharnstoffs mit 20 g des Umsetzungsproduktes von 1 Mol Oleylalkohol mit 23 Molen Äthylenoxyd und 5 g eines epoxydierten C₃₀-α-Olefins bei 80―85°C verschmolzen. Dann werden in diese homogene Schmelze 375 g 85-90^oC warmes Wasser eingerührt und die feindisperse, stabile Emulsion ausegerührt.

A cotton / polyester blend of 65 parts of cotton / 35 parts of polyester with a weight of 100 g or a cotton / polyamide blend with a proportion of 80/20 and a weight of 115 g are soaked in a liquor which weighs 25 g / Contains liters of an auxiliary preparation according to the invention, which was prepared in the following way:

• With vigorous stirring, 100 g of the N-octadecyl-N'-β-chloroethylsulfonylurea prepared according to Example 1 are mixed with 20 g of the reaction product of 1 mole of oleyl alcohol with 23 moles of ethylene oxide and 5 g of an epoxidized C ₃₀ -α-olefin at 80 ―85 ° C melted. Then 375 g of 85-90 ^o C warm water are stirred into this homogeneous melt and the finely dispersed, stable emulsion is stirred out.

The tissues soaked in the auxiliary liquor are dewatered to 64% or 60% and dried at 125 ° C for eight minutes. The textile structures treated in the manner described above have a pleasant, soft feel. They show good water repellency. The effects obtained are resistant to laundry.

EXAMPLE 7

The finishing of a textile fabric, as described in Example 5, is repeated, except that 25 g / liter of the auxiliary according to the invention produced in Example 3 are used and, in addition, 80 g / liter of a dimethylol-dihydroxyethylene urea is added to the liquor used together with 10 g / liter MgCI, .6H, 0.

The goods treated in this way have, in addition to the advantageous properties brought about by the aminoplast high-finishing agent, a very pleasant, soft feel and very good hydrophobicity. The effects achieved are excellent washable.

EXAMPLE 8

In the following examples, which illustrate the use of the auxiliary preparations according to the invention in the leather sector, the amounts used in percent are based on the dry leather weight. Concentration figures in percent mean percentages by weight.

10 post-chromed, East Indian bastard clothing suede leather with a dry weight of 2.6 kg are drummed with 100% H ₂ 0, 2% NH _Q OH and 0.1-0.2% of an anionic emulsifier for about an hour. The leather is then rinsed with water at 20 ° C.-25 ° C. for five minutes and drummed for one hour in a tanning drum with 100-200% water, 1-2% ammonia 25% and 10% of the auxiliary preparation according to the invention described in Example 1. After this time, the amount of water is increased to a total of 1000% and heated to 60-70 ° C. In this bath, the leather is dyed as usual with anionic dyes and acidified with formic acid, the amount of acid should not be less than 2%.

The leather is placed on a trestle for 24 hours without rinsing, then dried at 60-70 ° C. and finally milled in a full drum for three to four hours.

The treated leather shows a silky, smooth velor handle and has a good gloss effect.

Applied water drops do not penetrate within four hours in the case of leather treated in this way, compared to a penetration time of two to four minutes in the case of untreated leather. The dynamic water absorption according to the disc method is reduced from 140-150% for an untreated leather to 40-50%.

• Zu den Bestimmungen werden stets vergleichbare Lederstücke eingesetzt, die möglichtst aus einem Lederstück nebeneinander ausgeschnitten worden sind.

Working procedure for the determination of the dynamic water absorption of leather according to the disc method:

• Comparable pieces of leather are always used for the provisions, which have been cut out from one piece of leather as far as possible.

3 leather discs of 20 mm each are punched out of the test specimen. The cut surfaces of the slices are coated with a nitrocellulose varnish, dried and each piece weighed individually. The 3 leather samples are then placed in a 50 ml shaking bottle containing 250 ml of demineralized water at 20 ° C. and shaken in a shaker for 15 minutes (180 shaking frequencies per minute).

After shaking, the samples are dabbed with filter paper and weighed.

Calculating the percentage of water absorption:

EXAMPLE 9

20 halves of intermediate-dried, chrome-tanned split suede leather with a dry weight of 60 kg are drummed for about an hour in a tanning drum with 1000% water at 35 ° C., 2% ammonia 25% and 0.2-0.4% of an anionic emulsifier. The leather is then rinsed with water at 20-25 ° C. for about five minutes and treated with 100-200% water, 1-2% ammonia 25% and 5-10% of the auxiliary preparation according to the invention prepared according to Example 3. The pH of the liquor should be between pH 8―9 at the end of the treatment. After this time, depending on the desired shade, 4-8% dye is added in powder form and after a dyeing time of 30-45% minutes the total liquor is increased to 800-1000%, heated to 60-70 "C, and after a further 30 minutes Acidified as usual with formic acid The amount of formic acid should be half of the dye used.

The leather is jacked up for about 24 hours without rinsing, then dried at 60-70 "C and finished as usual.

The split suede treated in this way shows a soft, velvety velor handle and has a good gloss effect.

The penetration time of applied water drops is improved from five to 10 minutes for an untreated leather to two to three hours. The dynamic water absorption according to the disc method is reduced from 80-100% for an untreated leather to 30-50%. This hydrophobizing effect can be increased even further by appropriately hydrophobic greasing.

EXAMPLE 10

10 halves of a seam-damp, chrome-tanned cowhide with a leather thickness of 0.8-1 mm are neutralized as usual, retanned, dyed and greased hydrophobically.

As a final treatment, 1-3% of the auxiliary preparation according to the invention prepared according to Example 1 are added to the acidified, 60-70 ° C. warm dyeing and oiling bath. Before the addition, the auxiliary is diluted with water at 20-30 ° C in a ratio of 1: 3 and adjusted to pH 7.5-8.0 with 25% ammonia. The running time in the barrel is approx. 10-20 minutes. After this time, the leather is jacked up without rinsing and finished as usual.

This final treatment with the reactive auxiliary agent according to the invention, which is to be regarded as potting, gives the leather a wax-like, warm surface grip with a hydrophobic effect. The penetration time of applied water drops is increased from 1-2 minutes for an untreated leather to 1-2 hours for a leather treated as described above.

EXAMPLE 11

Chrome-tanned, dyed and, as usual, finished cow leather for furniture upholstery are finished with a finish made of thermoplastic copolymers with inorganic or organic pigments. The products are applied to the dry leather using a spray gun.

To achieve good rub and water resistance, these leathers are given a final application with water-emulsifiable nitro lacquers.

An additive is stirred into 100 parts of the emulsion lacquer, 10-20 parts of the auxiliary, adjusted to pH 8.0-9.0 with 25% ammonia and diluted with 100 parts of water at 20 ° C. to a ready-to-use concentration. After one or two spraying jobs, the leathers are dried and finally ironed with a hydraulic ironing press at 70-80 "C and 80-150 atm pressure.

EXAMPLE 12

131.5 g (0.3 mol) of N-octadecyl-N'-ß-chloroethyl-sulfonylurea are dissolved in 700 ml of anhydrous dioxane, and 24 g (0.6 mol) of NaOH are slowly dissolved in this solution in a mixture of 250 g Dioxane and 100 ml H ₂ 0 slowly added. Then it is stirred for three to four hours at 70-80 ° C, neutralized with hydrochloric acid and the product isolated.

Yield: 110 g -91.2% of theory N-octadecyl-N'-vinyl sulfonylurea. Mp 100-109 ° C.

In the same way, it is possible to firstly obtain the N-methyl-octadecyl-N'-β from 84.9 g (0.3 mol.) Of N-methyloctadecylamine and 50.8 g (0.3 mol) of B-chloroethyl isocyanate -chloroethyl-sulfonylurea and to produce N-methyl-octadecyl-N'-vinyl-sulfonylurea from this according to the example described above.

EXAMPLE 13

Normally colored chrome split velor (4 kg wilting weight) with a thickness of 1.5 mm is in the Multimac continuous multi-purpose machine (System Dust + Co, Lederwerke Mönnedorf / Switzerland, manufacturer Trockentechnik GmbH., Homberg / Niederrhein) at 60 ° C with an impregnation liquor of Treated 50 g / liter of the dispersion prepared according to Example 3 and 20 g / liter of a 70% Igen sulfonated fish oil (Derminollicker NBR, Hoechst AG). The lead time of the leather was 10 seconds at a belt speed of 3 m / minute.

After passing through the built-in squeeze rollers, the split leather had taken up 980 g of the dispersion.

The leather was hot-air dried as usual at 80 ° C., heat-fixed on an ironing press at 95 ° C., 30 atm pressure, for 5 seconds and, as usual, reground with 220-grit sandpaper on a rotating grinding machine.

You get a velvet-like velor handle with a pleasant "writing effect" and a good bead of water.

EXAMPLE 14

An aqueous solution composed of 50 g / liter of impregnating agent (according to Example 3) and 25 g / liter of butyl diglycol is applied to a ready-made ladies' handbag made from post-chromed East Indian bastard leather with a brush. After drying at 50 ° C, the bag is exposed to heat fixation in a heat cabinet at 100 ° C for 60 minutes.

The temporarily glued velor is brushed with a wire brush. The impregnation treatment gives the bag a greatly improved velor handle with a very good beading effect for dripped water.

Excellent softening and waterproofing effects can also be achieved with the products according to the invention with the compositions given in the following table:

EXAMPLE 15

134.5 g (0.5 mol) of octadecylamine are dissolved in 350 mol of toluene at 40 to 50 ° C. 92.66 g (0.505 mol) of 2-chloropropylsulfonyl isocyanate are added dropwise to this solution at 40 to 50 ° C. in the course of 90 minutes. The reaction is terminated by boiling under reflux conditions for one hour. The toluene is then distilled off under vacuum.

This gives 218.5 g ~ 95.6% of theory on N-octadecyl-N'-2-chloropropylurea.

• In gleicher Weise ist es möglich, anstelle des oben beschrieben Umsetzungsprodukts aus 4-Nonylphenol mit 23 Molen Äthylenoxid das Umsetzungsprodukt aus 2,4,6-Tributylphenol mit 50 Molen Äthylenoxid zu verwenden, um eine Emulsion gleich guter Stabilität zu erhalten.

In the thus-produced crude product of a reaction product of 4-nonylphenol with 23 moles of ethylene oxide the product on 100 g of crude product 25 g melted and druch addition of 375 g of water at a temperature of 80 to 85 ° C, a finely dispersed paste _'prepared:

• In the same way, it is possible to use the reaction product of 2,4,6-tributylphenol with 50 moles of ethylene oxide instead of the reaction product of 4-nonylphenol with 23 moles of ethylene oxide described above, in order to obtain an emulsion of equally good stability.

EXAMPLE 16

80.7 g (0.3 mol) of octadecylamine are dissolved in 300 ml of toluene at a temperature of 40 to 45 ° C. 59.84 g (0.303 mol) of 2-chlorobutylsulfonyl isocyanate are then added dropwise to this solution at a temperature of 50 to 60 ° C. and the mixture is stirred under reflux conditions for 1 hour. Now the toluene is distilled off in vacuo.

It lead: 139 g -98.3% of crude product; Mp: 77 ° to 79 ° C. N-octadecyl-N'-2-chlorobutylurea.

100 g of the crude product thus obtained are reacted with 20 g of a reaction product from castor oleic acid, fused with 36 moles of ethylene oxide and stirred with 380 g of warm water at 80 to 85 ° C. using a turbine stirrer. A finely dispersed paste with the properties according to the invention was obtained.

EXAMPLE 17

226.25 g (0.5 mol) of N-octadeyl-N'-β-chloropropylsulfonylurea are dissolved in 1200 ml of dioxane and 30 g (0.75 mol) of NaOH, dissolved in, at a temperature of 40 to 50 ° C. a mixture of 350 g of dioxane and 140 ml of water was added dropwise. The mixture is then stirred at 40 to 50 ° C for 3 hours, neutralized with 2N hydrochloric acid and the product isolated.

Yield: 198 g ~ 95.2% of theory N-octadecyl-N'-propenyl-2-sulfonylurea; Mp 116-118 ° C.

In the same way. it is possible to use N-octadecyl from 139.5 (0.3 mol) N-octadecyl-N'-ß-chlorobutylsulfonylurea and 18 g (0.45 mol) NaOH, dissolved in dioxane / water under the test conditions described above To produce -N'-butenyl-2-sulfonylurea.

Claims (13)

1. A conditioning and water-repellent agent for textile materials consisting of or containing cellulose and for leather, characterised in that it comprises a parts by weight of the compound of the general formula I

wherein R is alkyl or alkenyl having 10 to 30 carbon atoms, B is one of the divalent radicals

wherein R¹ and R² are hydrogen or alkyl having 1 to 4 carbon atoms and n denotes 2, 3 or 4, and X is β-halogenoalkyl or alkenyl each having 2 to 4 carbon atoms, and b parts by weight of an emulsifier comprising 100-37.5% by weight of known non-ionic emulsifiers, 0-50% of known anionic emulsifiers and 0-25% of known fat liquors, c parts by weight of an epoxide of the formula 11

wherein R³ is alkyl or alkenyl having 15 to 40 carbon atoms, and optionally d parts by weight of water or a water-miscible organic solvent, a having a value from 80 to 99, b a value from 20 to 1, c a value from 0 to 5 and optionally

a value from 10 to 40.

2. The conditioning and water-repellent agent of claim 1, characterised in that a has a value from 95 to 99 and b has a value from 5 to 1.

3. The conditioning and water-repellent agent of claims 1 and 2 for textile use, characterised in that c has a value from 0.5 to 5 and that the emulsifier contains 0% of fat liquor.

4. The conditioning and water-repellent agent of claims 1 and 2 for use on leather, characterised in that c is zero and that the emulsifier contains 5 to 25% of fat liquor.

5. The conditioning and water-repellent agent of claims 1 to 4, characterised in that in the compound of the general formula I R is alkyl or alkenyl having 12 to 22 carbon atoms, preferably stearyl, coconut fat alkyl, tallow fat alkyl or oleyl and B is one of the divalent radicals

and that X is ß-chloroalkyl having 2 to 4 carbon atoms.

6. The conditioning and water-repellent agent of claims 1 to 3, characterised in that the emulsifier contains as known non-ionic emulsifiers such of the general formula III

wherein A is branched or unbranched alkyl or alkenyl having 10 to 22 carbon atoms, alkylphenyl with a total of 6 to 12 carbon atoms in the alkyl radicals, branched or unbranched alkanoyl or alkenoyl having 10 to 22 carbon atoms, aralkyl having 7 to 15 carbon atoms, aralkylaryl having 13 to 25 carbon atoms, radicals of the wool grease components or acyloxyalkyl having a total of 10 to 30 carbon atoms, R⁴ is hydrogen or alkyl having 1 to 2 carbon atoms and n is a number between 10 and 60.

7. A method of preparing a conditioning and water-repellent agent for textile materials consisting of or containing cellulose and for leather, characterised in that 80 to 99 parts by weight of a compound of the general formula I

wherein R is alkyl or alkenyl having 10 to 30 carbon atoms, B is one of the divalent radicals

and X is ß-halogenoalkyl or alkenyl each having 2 to 4 carbon atoms and R¹ and R² represent hydrogen or alkyl having 1 to 4 carbon atoms and n represents 2, 3 or 4, are kneaded or stirred with 1 to 20 parts by weight of an emulsifier consisting of 100 to 37.5% of known non-ionic emulsifiers, 0 to 50% of known anionic emulsifiers and 0 to 25% of known fat liquors and 0 to 5 parts by weight of an epoxide of the formula ll

wherein R³ denotes alkyl or alkenyl having 15 to 40 carbon atoms, at temperatures between 20 and 90°C and until a homogeneous substance is obtained, and are optionally adjusted to a content of 10 to 40 parts by weight of the compound of the general formula I by adding water or a water-miscible organic solvent.

8. A method of conditioning and imparting water repellency to textile materials consisting of or containing cellulose and to leather by treating said textile materials and leather at temperatures up to 150°C with aqueous liquors containing a conditioning and water-repellent agent and the usual auxiliaries known for conditioning and water-repellent liquors as well as optionally agents for the high-grade finishing of textiles or fat liquors and/or textile and leather dyestuffs respectively and the auxiliaries required for dyeing characterised in that 5 to 50 g/I of a sulphonylurea of the general formula I

wherein R is alkyl or alkenyl having 10 to 30 carbon atoms, B is one of the divalent radicals

and X is ß-halogenoalkyl or alkenyl each having 2 to 4 carbon atoms and R¹ and R² represent hydrogen or alkyl having 1 to 4 carbon atoms and n denotes 2, 3 or 4, are added to the liquor as a conditioning and water-repellent agent.

9. The method of claim 8, characterised in that the sulphonylurea of the general formula I is added to the liquor in the form of a conditioning and water-repellent agent preparation of claim 1.

10. Sulphonylureas of the general formula I

wherein R is alkyl or alkenyl having 10 to 30 carbon atoms, B is one of the divalent radicals

and X is ß-halogenoalkyl or alkenyl each having 2 to 4 carbon atoms, and R¹ represents alkyl having 1 to 4 carbon atoms, R² represents hydrogen or alkyl having 1 to 4 carbon atoms and n denotes 2, 3 or 4.

11. Sulphonylureas of formula I and as defined in claim 10, characterised in that R is coconut fat alkyl, tallow fat alkyl, oleyl or in particular stearyl, and B is one of divalent radicals

and X is ß-chloroalkyl having 2 to 4 carbon atoms.

12. A method of preparing sulphonylureas of the general formula I

wherein R is alkyl or alkenyl having 10 to 30 carbon atom, B is one of divalent radicals

and X is β-halogenoalkyl or alkenyl each having 2 to 4 carbon atoms, and R¹ represents alkyl having 1 to 4 carbon atoms, R² represents hydrogen or alkyl having 1 to 4 carbon atoms, and n represents 2, 3 or 4, characterised in that a ß-halogenoalkylsulfonylisocyanate having 2 to 4 carbon atoms in the alkyl radical.of the formula

wherein X¹ is ß-halogenoalkyl having 2 to 4 carbon atoms, is reacted with the amine of the formula

wherein B is one of the divalent radicals

R is alkyl or alkenyl having 10 to 30 carbon atoms, R¹ is alkyl having 1 to 4 carbon atoms, R² is h^y- drogen or alkyl having 1 to 4 carbon atoms, and n denotes 2, 3 or 4, the reaction taking place in a molar ratio of about 1:1 in an aprotic organic solvent at temperatures between 20 and 110°C, and the reaction product is separated in the usual manner and, in case a compound of the formula I in which X is alkenyl is to be prepared, is subsequently treated with aqueous alkali in a manner known per se.

13. The method of claim 12, characterised in that preferably a A-chloroalkylsulfonylisocyanate having 2 to 4 carbon atoms in the alkyl radical is reacted with an amine of the formula

wherein R is alkyl or alkenyl having 12 to 22 carbon atoms preferably coconut fat alkyl, tallow fat alkyl, oleyl or in particular stearyl, and B is one of the divalent radicals