EP0002773A2 - Process for conditioning and hydrophobing of leather - Google Patents

Abstract

The softening and waterproofing agents for textile materials and for leather consist of 10 to 35% by weight of a compound of the general formula I R-NH-CO-NHn (CH2OH) m (I) where R is linear or branched alkyl or alkenyl with 14-22 C atoms, m is a number from 1.0 to 1.5 and n = 2-m; b% by weight of known nonionic and c% by weight of known anionic emulsifiers, where: b = 0 to 10 c = 0 to 3 and b + c = 0.5 to 10; 0 to 5% by weight of an epoxide of the formula II <IMAGE> in which R 1 is alkyl or alkenyl having 15 to 40 C atoms; 0 to 25% by weight of known lickers and 25 to 89.5% by weight of water or a water-miscible organic solvent.

Description

worin

• R lineares oder verzweigtes Alkyl oder Alkenyl mit 14 - 22 C-Atomen und
• m eine Zahl von 1,0 bis 1,5 bedeuten und
• n - 2 - m ist;
• b Gew.% bekannter nichtionischer und
• c Gew.% bekannter anionischer Emulgatoren, wobei gilt
  • b - O bis 10
  • c = O bis 3 und b+c - 0,5 bis 10;
• O bis 5 Gew.% eines Epoxids der Formel II
  
  worin
  • R¹ Alkyl oder Alkenyl mit 15 bis 40 C-Atomen bedeutet; O bis 25 Gew.% bekannter Licker und
  • 25 bis 89,5 Gew.% Wasser oder eines mit Wasser mischbaren organischen Lösungsmittels, ihre Herstellung und Verwendung.

The present invention relates to softening and waterproofing agents for textile materials made of or containing cellulose and for leather, consisting of 10 to 35% by weight of a compound of general formula I.

wherein

• R linear or branched alkyl or alkenyl with 14-22 C atoms and
• m is a number from 1.0 to 1.5 and
• n - 2 - m;
• b% by weight of known nonionic and
• c% by weight of known anionic emulsifiers, where applies
  • b - O to 10
  • c = O to 3 and b + c - 0.5 to 10;
• 0 to 5% by weight of an epoxide of the formula II
  
  wherein
  • R ¹ denotes alkyl or alkenyl with 15 to 40 C atoms; 0 to 25% by weight of known licker and
  • 25 to 89.5% by weight of water or a water-miscible organic solvent, their preparation and use.

Softeners are said to give textile materials and leather advantageous surface shadows, in particular a pleasant, warm feel. In addition, finishing agents can improve the processing properties of fiber materials. Known anti-aging 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 chew. 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 have also become known on the Lasis quaternary ammonium bases with at least one long-chain alkyl radical, such as those e.g. in the Swiss patent 130 881 or the German imperial patent 5.16 406. The cationic softening agents give a pleasantly soft feel, but tend to yellowing at high temperatures. They may 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 aviva effect, it is often desirable to bring the textile material or the leather to be hydrophobic. Known options for waterproofing textile materials and leather are treatment with solutions or emulsions of paraffin hydrocarbons, waxes or the like. Metal soaps have also already been used for waterproofing purposes. Combinations of metal salt and paraffin and wax emulsions which can be considered for hydrophobic purposes are known from DKP 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 hydronic agents mentioned above is their insufficient wet and wash fastness. Attempts have therefore already been made to bring about hydrophobization by chemical reaction with the cellulose. It is known from DRP 542 18G to treat cellulose materials with anhydrides or chlorides of fatty acids. However, this procedure could not be used in the practice. 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 by using isocyanate adducts are known from British patent specification 716 232 and American patent specification 2,746,988. Other known water repellents 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, such as, for example, their poor resistance to water and, associated with this, a decrease in the reactivity with prolonged prolongation, the water-repellent effect, which is not always sufficient, and the need for the chemical bond between the hydrophobicizing agent and cellulose fiber by heating Temperatu temperatures of 120 - 150 ° C. The fiber-reactive water repellents known from DRP 681 520 do indeed have good water repellency effects, but they still leave something to be desired in terms of durability, since under the action of light, heat or traces of acid they tend to autopolymerize with a reduced effect. In addition, their manufacture poses considerable problems on the apparatus side.

From US Pat. No. 2,361,185 it is known, inter alia, monomethylol compounds of longer-chain alkylureas (called octadecyl-ureido-methanol) or a mixture of the corresponding alkylureas themselves and formaldehyde in the presence of acidic catalysts with aliphatic alcohols, such as methanol, ethanol, or isopropanol Octanol to implement. The ethers thus obtained are e.g. recommended as a fabric softener. However, it has been shown that these products have an unsatisfactorily greasy feel on cellulose fibers.

• a) wenigstens einem Mono- und/oder Dimethylolalkylharnstoff mit 12 bis 22 Kohlenstoffatomen im Alkylrest und
• b) wenigstens einem Butyläther eines Mono- und/oder Dimethylolalkylharnstoffes mit 12 bis 22 Kohlenstoffatomen im Alkylrest, in denen das Gewichtsverhältnis a : b von 2 : 1 bis 1 : 2 beträgt,

eingesetzt werden. Derartige teilverätherte Produkte weisen jedoch den Nachteil auf, daß vor ihrer Fixierung auf dem Substrat zunächst die Äthergruppe wieder abgespalten werden muß. Dies erfolgt durdi eine thermische Behandlung in Gegenwart relativ hoher Mengen von Säuraioder Säure abgebenden Produkten. Dies kann bei empfindlichen Textilmaterialien bereits zu einer Schädigung der Fasern, z.B. zur Spaltung von Zellulosemolekülen und damit einer Verringerung der Faserfestigkeit,oder zu einer Veränderung der Textur evtl. im Textilmaterial enthaltener synthetischer Fasern führen. Weitere Schwierigkeiten beim Einsatz dieser Produkte ergeben sich, wenn gleichzeitig eine Textilhochveredelung auf Basis von Methylolmelamin- bzw. Methylolharnstoffen durchgeführt werden soll. Hierbei können durch die drastischen Fixierbedingungen dieser bekannten Avivagemittel Überhärtungen des Textilhochveredelungsmittels eintreten, die zu einer erheblichen Beeinträchtigung des Warengriffes führen können.To overcome this disadvantage, according to German Auslegeschrift 23 20 302 mixtures

• a) at least one mono- and / or dimethylolalkylurea with 12 to 22 carbon atoms in the alkyl radical and
• b) at least one butyl ether of a mono- and / or dimethylolalkylurea with 12 to 22 carbon atoms in the alkyl radical, in which the weight ratio a: b is from 2: 1 to 1: 2,

be used. Such partially etherified products have the disadvantage, however, that the ether group must first be split off again before they are fixed on the substrate. This is done by thermal treatment in the presence of relatively large amounts of acid or acid donating products. In the case of sensitive textile materials, this can already lead to damage to the fibers, for example to the splitting of cellulose molecules and thus a reduction in the fiber strength, or to a change in the texture of synthetic fibers possibly contained in the textile material. Further difficulties in use These products result when a high-level textile finishing based on methylol melamine or methylol ureas is to be carried out at the same time. In this case, the drastic fixing conditions of these known finishing agents can result in over-hardening of the high-quality textile finishing agent, which can lead to a considerable impairment of the handle of the goods.

From German Auslegeschrift 1 934 177, plasticizers are reaction products of at least 3 moles of formaldehyde and 1 mole of N-alkylurea or N-alkylbiuret compounds with about 14 to 22 carbon atoms in the alkyl radical. When these products are applied to high-quality textile materials and leather, however, the handle is much too hard, and moreover the ready-to-use emulsions prepared with such compounds and the usual emulsifiers are not sufficiently stable in storage and cannot be distributed with the fine distribution required for technical use getting produced.

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, non-uniformly good effect on various 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 applied to different cellulose materials and achieve very different types of leather. In addition, the substrate-reactive active ingredients of the formula I contained in the finishing and hydrophobicizing agents to be used according to the invention can be prepared in a technically simple manner.

worin

• R lineares oder verzweigtes Alkyl oder Alkenyl mit 14 - 22 C-Atomen und
• m eine Zahl von 1,0 bis 1,5 bedeuten und
• n = 2-m ist;
• b Gew.% bekannter nichtionischer und
• c Gew.% bekannter anionischer Emulgatoren,
  wobei gilt
  • b = O bis 10
  • c = O bis 3 und b+c - 0,5 bis 10;
• O bis 5 Gew.% eines Epoxids der Formel II
  
  worin R¹ Alkyl oder Alkenyl mit 15 bis 40 C-Atomen bedeutet; O bis 25 Gew.% bekannter Licker und
  25 bis 89,5 Gew.% Wasser oder eines mit Wasser mischbaren organischen Lösungsmittels.

The softening and waterproofing agents to be used according to the invention for textile materials made of or containing cellulose and for leather consist of 10 to 35% by weight of a compound of the general formula I.

wherein

• R linear or branched alkyl or alkenyl with 14-22 C atoms and
• m is a number from 1.0 to 1.5 and
• n = 2-m;
• b% by weight of known nonionic and
• c% by weight of known anionic emulsifiers,
  where applies
  • b = 0 to 10
  • c = O to 3 and b + c - 0.5 to 10;
• 0 to 5% by weight of an epoxide of the formula II
  
  wherein R ^{1 is} alkyl or alkenyl having 15 to 40 carbon atoms; 0 to 25% by weight of known licker and
  25 to 89.5% by weight of water or a water-miscible organic solvent.

Auxiliaries according to the invention have particularly favorable properties with 10 to 25% by weight of the active ingredient of the formula I and 1 to 5% by weight of nonionic and anionic emulsifiers.

The long-chain alkyl radicals R of the active compounds of the formula I with 14 to 22 carbon atoms contained in the auxiliary preparations according to the invention are preferably only weakly branched or linear. Examples of alkyl radicals which can be R in the active compounds of the formula I 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.

Both in terms of the effect, emulsifiability and performance properties and for reasons of easy accessibility of the corresponding starting materials, mixtures of the compounds of the formula I according to the invention are also preferred in which the radicals R in terms of their number of carbon atoms and their molar fraction in the mixture of the statistical composition of the Carboxylic acids in natural fats, such as tallow fat, coconut fat, stearin, soybean oil or palm oil correspond. R radicals which stand for such a group of alkyl radicals are usually designated as 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.

The active compounds of the formula I 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 with nonionic and anionic emulsifiers in aqueous liquors. This advantageous property of the active ingredients contained in the softening and waterproofing 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 are special Application, either for textiles or for leather, or such aids that can be used universally both for cellulose textiles and for leather.

worin

• A unverzweigtes Alkyl oder Alkenyl mit 10 bis 22 C-Atomen, Alkylphenyl, Dialkylphenyl, Trialkylphenyl mit insgesamt 4 bis 12 C-Atomen in den Alkylresten,
• R ⁴ Wasserstoff oder Alkyl mit 1 bis 2 C-Atomen und
• n eine Zahl zwischen 8 und 14 ist,

zusammenfassen .It is also entirely expedient to use this possibility and to adapt the combinations of nonionic and anionic emulsifiers contained in the finishing and hydrophobizing agents according to the invention to the main application area of the agent which may be envisaged. The nonionic emulsifiers known per se contained in the finishing agents and water repellents according to the invention can be obtained using the general formula III

wherein

• A unbranched alkyl or alkenyl with 10 to 22 carbon atoms, alkylphenyl, dialkylphenyl, trialkylphenyl with a total of 4 to 12 carbon atoms in the alkyl radicals,
• R ^{4 is} hydrogen or alkyl having 1 to 2 carbon atoms and
• n is a number between 8 and 14,

sum up .

Nonionic emulsifiers of the general formula III given above are obtained by reacting hydroxyl-containing compounds AOH with 8 to 14 moles of alkylene oxides, such as butylene, propylene and preferably ethylene oxide.

Hydroxy group-containing organic compounds AOH which are suitable for the preparation of the nonionic emulsifiers present in the auxiliary preparations according to the invention, are, for example, long-chain alkanols and alkenols with 10 to 22 carbon atoms, in particular those which are derived from the natural fatty acids, such as stearic acid, palmitic acid, oleic acid or the natural fatty acid mixtures which are present in coconut fatty acid or tallow fatty acid, and synthetic alcohols with a C. ₁₀ to C15 alkyl chain distribution; Alkylphenols, dialkylphenols or trialkylphenols with 4 - 9 C atoms in the individual alkyl radicals and with a total of 4 - 12 C atoms in all alkyl radicals together, such as p-tert-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.

Aid preparations according to the invention, which are preferably intended for textile use, contain essentially, preferably exclusively, nonionic emulsifiers. Aid preparations according to the invention, which are specifically intended for use in the leather sector, contain predominantly or even exclusively known anionic emulsifiers. Known anionic emulsifiers used in industrial 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 carbon 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, e.g. Fatty acid taurides, oxaethane sulfonates; Alkylarylsulfonic acid or its salts with an alkyl radical having 5 to 30 carbon atoms.

Further anionic emulsifiers which contain at least one -OS0 ₃ H or a -S0 ₃ H group are, for example, the sulfuric acid half-esters of nonionic emulsifiers based on ethylene oxide adducts with organic compounds containing OH groups, which are optionally subsequently neutralized with inorganic bases, such as NaOH, Na ₂ C0 ₃ or with organic amines, such as diethanolamine, ethanolamine or triethanolamine, were converted into the salts. As starting compounds The following are suitable for ethylene oxide base: reaction products of 4-nonylphenol, 2,4,6-tritertiary butylphenol, 4-benzyl-2'-hydroxy-diphenyl, 2-benzyl-2'-hydroxydiphenyl with 8-30 moles of ethylene oxide,
Reaction products of ethoxylated alkanols based on natural products such as stearyl alcohol, coconut fatty alcohol, tallow fatty alcohol and oleyl alcohol with 8 - 30 moles of ethylene oxide. It is also possible to use emulsifiers which are obtained when stearoyl chloride, oleyl chloride or coconut fatty acid chloride are reacted with taurine or N-methyl taurine to give the corresponding taurides.

The inventive compositions containing the above-described emulsifiers as well as mixtures of these emulsifiers have very good performance properties and show an optimal fine distribution of the emulsified active substances and thus a high storage stability of the emulsions. In particular, it has been shown that the combination of the nonionic and the anionic emulsifiers, which have at least one -OS0 ₃ H or one -S03H group in the form of the alkali metal, NH ₄ ^⊕ - or alkylammonium salts, succeeds in their molecule, to increase the fine distribution of the active substances claimed to such an extent that colloidal solutions are formed when diluted to 1 to 0.1% solutions.

Particularly preferred for the combination with anionic emulsifiers are nonionic emulsifiers of the general formula III, in which A is unbranched or slightly branched alkyl or alkenyl having 10-22 carbon atoms.

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 are intended for textile use, ie for the finishing and hydrophobizing of cellulose-containing or cellulose-containing textile materials. Agents intended for this special purpose contain 0.5 to 5% by weight 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.

Aid preparations according to the invention which are to be applied to leather are preferably free of epoxides of the formula II.

With the auxiliary additives according to the invention, it is also possible to grease the leather with a fat licker at the same time as 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 25% 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, sperm oil, rin, are suitable for the classic licker claw oil, castor oil, olive oil, linseed oil, stearin, wool fat; 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. In order to be able to use these classic fatliquoring agents as lickers, there are two possibilities, by partial reaction with monohydrate or sulfuric acid, to produce sulfonated semisynthetic, easily emulsifiable systems or with emulsifiers or emulsifier mixtures in the form of nonionic or, preferably, anionic compounds in an emulsified form convict. Today, however, synthetic products are increasingly used for leather greasing, which have emulsifier properties and at the same time have a greasy effect.

• Fettsäureester der ß'hydroxyäthansulfonsäure, wie z.B.
  
  und
  
• Fettsäurederivate der Aminoessigsäure, wie z.B.
  
• Fettsäuretauride und Fettsäure-N-methyltauride, wie z.B.
  
• synthetische Sulfochlorierungsprodukte, wie z.B.
  
• sekundäre Sulfonate - Allcalisalze, wie z.B.
  
• langkettige Sulfamide, wie z.B.
  
• Sulfoxydationsprodukte vorwiegend gesättigter unverzweigter Paraffine, wie z.B.
  C₁₈H₃₇-SO₃Na,
  
  oder
  

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:

• Fatty acid esters of ß'hydroxyethanesulfonic acid, such as
  
  and
  
• Fatty acid derivatives of amino acetic acid, such as
  
• Fatty acid taurides and fatty acid N-methyl taurides, such as
  
• synthetic sulfochlorination products, such as
  
• secondary sulfonates - Allcalisalze, such as
  
• long chain sulfamides, such as
  
• Sulfoxidation products predominantly saturated unbranched paraffins, such as
  C ₁₈ H ₃₇ -SO ₃ Na,
  
  or
  

Alkyl aryl sulfonates and olefin sulfonates.

Aid preparations according to the invention which are intended for textile use expediently contain no licker.

In order to facilitate the application, handling and metering of the auxiliary preparations according to the invention, it is expedient to add enough water or water-miscible organic solvents to the mixtures of the active compound of the formula I, emulsifier and, if appropriate, epoxides of the formula II according to the invention that the resulting products have a content of 10 to 75% by weight with respect to the active ingredient of formula 1.

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, especially ethanol, and the propanols are preferred.

In principle, the finishing agents and water repellents according to the invention can be prepared by homogenizing the N-methylol-N'-alkylureas of the formula 1, which are to be regarded as the main active ingredients of the preparation, with the nonionic and / or anionic emulsifiers of the type described above and, if the preparation is specifically for textile materials or leather of particularly suitable finishing and hydrophobizing agents is desired, with epoxides of the formula II or known lickers.

hergestellt. Die Methylolierung kann im Prinzip nach allen bekannten Methoden durch Umsetzung der Harnstoffderivate mit Formaldehyd oder Formaldehyd abspaltenden Mitteln bei Temperaturen zwischen Zimmertemperatur und ca. 150°C durchgeführt werden. Besonders vorteilhaft können Harnstoffe der Formel IV methyloliert werden durch Umsetzung mit Paraformaldehyd in der Schmelze oder mit wäßriger Formaldehydlösung in einem mit Wasser nicht mischbaren organischen Lösungsmittel. Die Reaktionstemperaturen liegen bei diesem Verfahren zwischen 60 und 150°C. Bei der Durchführung der Methylolierungsreaktion in der Schmelze arbeitet man vorzugsweise zwischen 100 und 130°C, bei der Durchführung im inerten mit Wasser nicht mischbaren organischen Lösungsmittel wird mit Rücksicht auf eine möglichst hohe Reaktionsgeschwindigkeit in der Nähe des Siedepunktes des Lösungsmittels, insbesondere bei Rückflußtemperatur der Reaktionsmischung, gearbeitet. Als wäßrige Formaldehydlösung wird zweckmäßigerweise die handelsübliche konzentrierte wäßrige Formaldehydlösung mit einem Gehalt von ca. 39 % Formaldehyd eingesetzt. Geeignete inerte mit Wasser nicht mischbare organische Lösungsmittel, die für die Durchführung der Methylolierung geeignet sind, sind beispielsweise Erdölfraktionen mit einem Siedepunkt zwischen 60 und 150°C, vorzugsweise 80 und 110°C, Halogenkohlenwasserstoffe, wie beispielsweise Tetrachlorkohlenstoff, Trichloräthylen, Perchloräthylen, Dichloräthan oder Tetrachloräthan, insbesondere aber aromatische Kohlenwasserstoffe, wie Benzol, Toluol und die Xylole sowie Halogenkohlenwasserstoffe, wie beispielsweise Monochlorbenzol. Bei Verwendung organischer Lösungsmittel mit niedrigeren Siedepunkten, insbesondere Siedepunkten unterhalb 60°C, wie beispielsweise Chloroform oder Methylenchlorid, ist eine wesentliche Verlängerung der Methylolierungsdauer in Kauf zu nehmen.However, the N-methylol-N'-alkylureas of the formula I are expediently obtained immediately before the preparation of the preparations according to the invention by methylolation of the corresponding N-alkylureas of the formula IV

manufactured. In principle, the methylolation can be carried out by all known methods by reacting the urea derivatives with formaldehyde or formaldehyde-releasing agents at temperatures between room temperature and about 150 ° C. Urea of the formula IV can be methylolated particularly advantageously by reaction with paraformaldehyde in the melt or with aqueous formaldehyde solution in a water-immiscible organic solvent. The reaction temperatures in this process are between 60 and 150 ° C. When the methylolation reaction is carried out in the melt, the reaction is preferably carried out between 100 and 130 ° C., when carrying out the reaction in an inert water-immiscible organic solvent, the highest possible reaction rate is in the vicinity of the boiling point of the solvent, in particular at the reflux temperature of the reaction mixture , worked. The commercially available concentrated aqueous formaldehyde solution with a content of about 39% formaldehyde is expediently used as the aqueous formaldehyde solution. Suitable inert water-immiscible organic solvents which are suitable for carrying out the methylolation are, for example, petroleum fractions with a boiling point between 60 and 150 ° C, preferably 80 and 110 ° C, halogenated hydrocarbons, such as carbon tetrachloride, trichlorethylene, perchlorethylene, dichloroethane or Tetrachloroethane, but especially aromatic hydrocarbons, such as benzene, toluene and the xylenes, and halogenated hydrocarbons, such as monochlorobenzene. If organic solvents with lower boiling points, in particular boiling points below 60 ° C., such as chloroform or methylene chloride, are used, a substantial extension of the methylolation time must be accepted.

It is known that methylolation reactions are catalyzed by acids and bases. For the preparation of the compounds of the formula I, it is advantageous to work under the pH values between 5 and 9, preferably between 7 and 8.5, which are described, for example, in French Patent 1,374,705. The pH from 5 to 9 can be adjusted by adding weak organic or inorganic acids or bases to the methylolation mixture. The preferred pH range from 7 to 8.5 is achieved by adding weak inorganic or organic bases. Suitable inorganic bases are, for example, sodium hydrogen carbonate or sodium carbonate in the form of concentrated aqueous solutions. The use of organic bases which cannot be methylolated is particularly advantageous. In particular, low-odor, low-volatile tertiary amines such as e.g. Triethanolamine, N-methylmorpholine, N-ß-hydroxyethylmorpholine, N-methylthiomorpholine, N-ß-hydroxyethylthiomorpholine and N, N-dimethylethanolamine. After methylolation has ended, the compounds of the formula I which have been obtained in the melt can be used directly without further purification operations to prepare the preparations according to the invention. When the methylolation is carried out in the organic solvent, this is distilled off azeotropically together with the water contained in the aqueous formaldehyde solution after the methylolation has ended.

It has proven to be particularly advantageous to add some or all of the amount of the emulsifiers to be incorporated into the softening and waterproofing agents according to the invention to the reaction mixture before or during the methylolation reaction. After the methylolation reaction has ended and, if appropriate, organic solvent and water have been distilled off, products which can be emulsified directly in water are obtained which have a particularly good fine distribution of the N-methylol-N'-alkylureas of the formula I and have an extraordinarily high resistance and outstanding activity.

The N-methylol-N'-alkylureas of the formula I can also be prepared from the N-alkylureas of the formula IV immediately after the preparation of these ureas from the corresponding alkyl isocyanates. This procedure offers particular advantages when the methylolation is carried out in an organic solvent. In this case, it is expedient to use the same organic solvent for the reaction of the isocyanates with ammonia to the ureas of the formula IV and for the subsequent methylolation of the ureas. In this case, the reaction mixtures obtained in the reaction of the isocyanates with NH ₃ can be used for the subsequent methylolation without intermediate isolation of the ureas of the formula IV.

The amount of formaldehyde to be used in the methylolation. Paraformaldehyde depends on the desired degree of methylolation m of the methylolalkylureas of formula I to be prepared. The degree of methylolation m should be between 1 and 1.5. Accordingly, at least 1 to 1.5 moles of formaldehyde or paraformaldehyde are used per mole of the urea of the formula IV. As a rule, an excess of 20 - 50% is necessary.

Depending on whether the methylolation has already been carried out in the presence of part or all of the emulsifiers present in the finishing agents according to the invention, products are obtained which contain no emulsifier or part or all of the emulsifiers. After completion of the methylolation reaction, the remaining amounts of emulsifier and, if desired, epoxides of the formula II or known lickers are then homogenized with the products of the methylolation reaction and finally the products obtained are adjusted to a total solids content of 10 to 75% by adding water or water-miscible organic solvents. 0 to 10 parts by weight of nonionic and 0 to 3 parts by weight of anionic emulsifiers are used for the preparation of 100 g each of finishing and hydrophobicizing agents according to the invention, the total amount of emulsifiers being 0.5 to 10 parts by weight.

The amount of the urea of the formula IV to be used for the preparation of 100 parts by weight of a finishing and hydrophobizing agent according to the invention results from the amount a of the N-methylol-N'-alkylurea of the formula I contained therein, by mixing this amount with the factor M, in which M is the molecular weight M + 30m of the alkyl urea of formula IV used and m is the degree of methylolation, multiplied.

If the finishing agents according to the invention to be produced are preferably used for textile materials, epoxides of the formula II in which R has the above meanings are advantageously incorporated in an amount of 0 to 5 parts by weight for every 100 parts by weight of finishing and hydrophobicizing agents according to the invention, in addition to the emulsifiers mentioned above. If products according to the invention are to be produced, which are preferably intended for use on leather, no epoxides of the formula II are incorporated into the preparations, but it is then advantageous to use known lickers in an amount of 0 to 25 parts by weight, based on 100 parts by weight finishing agent to be manufactured, incorporated and homogenized. The incorporation and homogenization of the individual components of the finishing agents and water repellents according to the invention is carried out in a manner known per se by kneading or stirring in the plastic or molten state. As a rule, a temperature between 50 and 120 ° C., preferably 60 to 100 ° C., is required for this. It is particularly advantageous to use a high-speed stirrer with which the solid components are first homogenized in the upper part of the specified temperature range and then gradually, in the course of 20 to 200 minutes, the desired amount of water or in the middle to lower part of the specified temperature range. water-miscible solvent, preferably preheated to about the temperature of the solid mixture introduced, metered in.

Gewichtsteile eines Harnstoffs der Formel IV

mit mindestens der m-fachen Molmenge von entweder Paraformaldehyd, gerechnet als Formaldehyd, in der Schmelze oder wäßriger Formaldehydlösung in Gegenwart eines mit Wasser nicht mischbaren inerten Lösungsmittels in Gegenwart von

• h Gewichtsteilen bekannter nichtionischer und p Gewichtsteilen bekannter anionischer Emulgatoren unter an sich bekannten Bedingungen methyloliert, ein gegebenenfalls vorhandenes mit Wasser nicht mischbares inertes Lösungsmittel abdestilliert und den Rückstand mit (b - h) Gewichtsteilen bekannter nichtionischer und (c - p) Gewichtsteilen bekannter anionischer Emulgatoren, d Gewichtsteilen eines Epoxids der obigen Formel 11 und e Gewichtsteilen bekannter Licker im plastischen oder geschmolzenen Zustand homogenisiert und anschließend f Gewichtsteile Wasser oder eines mit Wasser mischbaren organischen Lösungsmittels unter ständiger Zumischung zufügt und erneut homogenisiert, wobei gilt
  a + b + c + d + e + f - 100
  a - 10 bis 35
  b - 0 bis 10
  c - 0 bis 3
  b + c - 0,5 bis 10
  d - 0 bis 5
  e - O bis 25
  f - 25 bis 89,5,
  h ≤ b und p ≤ c.

According to the above explanations, the finishing agents according to the invention are accordingly produced by:

Parts by weight of a urea of the formula IV

with at least m times the molar amount of either paraformaldehyde, calculated as formaldehyde, in the melt or aqueous formaldehyde solution in the presence of a water-immiscible inert solvent in the presence of

• h parts by weight of known nonionic and p parts by weight of known anionic emulsifiers methylolated under conditions known per se, any water-immiscible inert solvent distilled off and the residue with (b - h) parts by weight of known nonionic and (c - p) parts by weight of known anionic emulsifiers, d parts by weight of an epoxide of the above formula 11 and e parts by weight of known lickers are homogenized in the plastic or molten state and then f parts by weight of water or a water-miscible organic solvent are added with constant addition and homogenized again, where applicable
  a + b + c + d + e + f - 100
  a - 10 to 35
  b - 0 to 10
  c - 0 to 3
  b + c - 0.5 to 10
  d - 0 to 5
  e - O to 25
  f - 25 to 89.5,
  h ≤ b and p ≤ c.

The finishing agents and lyophilizing agents according to the invention are applied in a manner known per se, as is customary in textile finishing or high-textile finishing and in leather treatment processes. Accordingly, aqueous treatment liquors which contain 5 to 50 g / 1 of an active ingredient of the general formula 1 are used for the finishing and hydrophobization 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 inventive inventive preparations 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. Due to the excellent compatibility of the active ingredients of the formula I contained in the auxiliaries according to the invention with other known auxiliaries and finishing agents for textiles and leather, the finishing and hydrophobing 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 aids, such as retarders, leveling agents, dispersants, neutral salts and, if appropriate, additives which determine the pII value of the liquors. It is surprisingly 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 treatment of textile materials with the treatment liquors containing the softening and waterproofing agents according to the invention can be carried out as usual, for example by impregnation on a two- or three-roll pad, squeezing and subsequent drying or condensing at temperatures from 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 to 1000% aqueous liquor, based on the weight of leather. However, the treatment can also be carried out by spraying the leather with the treatment liquor, which, in addition to the finishing and water-repellent agents according to the invention, can also contain other auxiliaries required for leather finishing, such as greasing agents or lacquers, and then fixing the reactive active ingredient according to the invention by heat treatment 50 to 120 ° C, optionally under pressure, for example in an ironing press.

Leather impregnation with the auxiliaries according to the invention can be carried out very conveniently from hot or cold aqueous solutions 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 in the S ^p rühimprägnierung, at 50 - 120 ° C heat set.

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, with penetration of the dispersion into the leather interior by adding 0 - 50% of one so-called penetrators, for example butyl diglycol, pentaglycol, dimethylformamide, dimethyl sulfoxide, etc., under o supports. After drying, heat is fixed as usual at 50 - 120 C and the temporarily glued velor is re-erected in a dry state with a hard brush.

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 advantageous effects of the treatment according to the invention mentioned 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 have no greasiness, but give the velor a velvety feel and make it insensitive to hydrophilic dirt and stains from aqueous colorless or colored liquids, such as 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 hydrophobicizing cells Textile materials containing loose or consisting of cellulose and leather as well as 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 auxiliary substances.

The following exemplary embodiments illustrate the preparation and use of the finishing agents and water repellents according to the invention, and the preparation of the N-methylol-N'-alkylureas of the formula I contained as active ingredients in the auxiliaries according to the invention. The details of parts contained in the present application are parts by weight; Percentages mean percentages by weight.

example 1

312 g (1 mol) of N-octadecyl-urea are melted under a N ₂ atmosphere at a temperature of 120-130 ° C., mixed with 3 g of triethanolamine as a catalyst and 39 g (1.3 mol ) Paraformaldehyde added. In this case, reaction with dissolution of the paraformaldehyde occurs under the influence of heat. The crude product obtained has a melting point range of 60 - 62 ⁰ C, one after recrystallization from dioxane
Mp 67-69 ° C.
Yield: 338 g

Analysis: HCHO (bound)
calculated: 8.77% based on 1 mole
found: 10.2% ~ 1.16 mole -CH ₂ OH groups
Free HCHO <0.1%

• 3 H - CH₃-Gruppe bei 0,9 ppm
• 32 H - (CH₂)-Gruppen bei 1 - 2 ppm
• 2 H -
  
  bei 3,2 ppm
• 2 H - NH-CH₂-0- bei 4,5 ppm
• 3 H - beweglich

NMR data of the recorded product, solvent CDC1 ₃

• 3 H - CH ₃ group at 0.9 ppm
• 32 H - (CH ₂ ) groups at 1-2 ppm
• 2 H -
  
  at 3.2 ppm
• 2 H - NH-CH ₂ -0- at 4.5 ppm
• 3 H - flexible

Example 2

a) 30 g of the N-methylol-N'-octadecylurea prepared in Example 1 are at a temperature of 90-100 C with 6 g of a reaction product of 2,4,6-tri-tert-butylphenol with 9 moles of ethylene oxide and 1.5 g of an epoxy wax, which was produced by oxidation of a C ₃₀ -α-olefin, fused. The mixture is then stirred vigorously for 20 minutes using a high-speed stirrer and 112.5 ml of warm water are slowly added. Then it is homogenized for 1 hour at 60-70 ° C and stirred to 20-30 ° C in the bath.

The emulsion obtained is characterized by excellent storage stability.

If, instead of the reaction product of 2,4,6-tri-tert-butylphenol with 9 moles of ethylene oxide used above, the same amount of the reaction product from 2,4,6-tri-tert-butylphenol with 25 moles of ethylene oxide is used to prepare the emulsion , you get a product with an extremely short shelf life of, at most, one day. Instead of 2,4,6-tri-tert-butylphenol, 2,4,6-tri-iso-butylphenol or 2,4,6-tri-n-butylphenol can also be used with the same result.

According to the following paragraphs b) and c), finishing agents according to the invention with excellent performance properties, such as pourability, emulsion stability and effectiveness, are likewise obtained.

b) 30 g of the reaction product obtained according to Example 1 are melted at a temperature of 90 to 100 ° C. with 7.5 g of a reaction product of 1 mol of oleyl alcohol with 10 moles of ethylene oxide and 112.5 ml of warm H ₂ O are stirred in with a high-speed stirrer. The mixture is then stirred for a further 1 hour at 90-100 ° C. and then, with slow cooling, the emulsion obtained is stirred to a temperature of 20-30 ° C.

c) In the same way it is possible, instead of the reaction product from oleyl alcohol with 10 moles of ethylene oxide, to fuse with the same amount of a reaction product from oleyl alcohol with 8 moles of ethylene oxide or from oleyl alcohol with 13 moles of ethylene oxide.

Example 3

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

The treated fabric has a pleasant, soft feel and very good water repellency. The improved grip and the water-repellent effect are resistant to delicates.

Example 4

44.85 g (0.152 mol) of octadecyl isocyanate are dissolved in 269.1 ml of technical toluene and 2.6 g (0.152 mol) of gaseous NH ₃ are passed in at 35-40 ° C. until the reaction is alkaline. Then 0.35 g of triethanolamine, 11.25 g of a reaction product of oleyl alcohol with 10 moles of ethylene oxide and 17.54 g (0.228 mol) of 39% aqueous HCHO solution are added and the mixture is heated to reflux. The mixture is then heated to boiling under reflux and then 13.1 ml of H ₂ O are distilled off on a water separator. Finally, the toluene is distilled off quantitatively from the reaction product obtained first under normal pressure and finally in a water jet vacuum at 14-15 torr.

Mp. 52 - ₅₇ ^o _C.

Yield: 63.7 g

• gefunden 8.3 % ~ Methylolierungsgrad 1.2 berechnet auf Produkt mit Emulgator
• freier HCHO < 0,1 %

Analysis: HCHO (bound):

• found 8.3% ~ degree of methylolation 1.2 calculated on product with emulsifier
• free HCHO <0.1%

36 g of the product thus produced are melted at a temperature of 90 to 100 ° C. with 1.5 g of an epoxy wax, which has been prepared by epoxidation of a C _30- a-olefin, and at this temperature with 112.5 ml of H ₂ O slowly stirred. Then stirring is continued for a further 1 hour with a high-speed stirrer and the finely dispersed emulsion formed is slowly stirred to room temperature.

Example 5

A cotton / polyester blend of 65 parts of cotton and 35 parts of polyester with a weight of 100 g / m2 or a cotton / polyamide blend with a fiber ratio of 80/20 and a weight of 115 g / m ² is soaked in a liquor containing 25 g / liter of an emulsion preparation prepared in accordance with paragraph b). The soaked fabrics are squeezed to 64% or 60% and dried at 125 ° C for eight minutes. The textile fabrics treated in the manner described above have a pleasant, soft feel. They show good water repellency, and the effects found are resistant to delicates at 60 ° C.

Example 6

The finishing of a textile fabric, as described in Example 5, is repeated, but in addition to 25 g / liter of the aid produced in Example 4, an additional 80 g / liter of a dimethylol-dihydroxyethylene urea together with 10 g / liter of Mg C1 _2nd 6 H ₂ 0 can be used.

The goods treated in this way have, in addition to the properties caused by the aminoplast high-refining agent, a very pleasant, soft feel and have a very good hydrophobicity with excellent wash resistance.

Example 7

47.8 g (0.2 mol) of tetradecyl isocyanate are dissolved in 280 ml of technical toluene and 3.4 g (0.2 mol) of gaseous NH ₃ gas at a temperature of 35-40 ° C. until an alkaline reaction occurs (pH, measured in the toluene / H ₂ O mixture, 9.5).

Now 0.35 g of N-dimethylethanolamine, 23.08 g (0.3 mol) of 39% aqueous formaldehyde solution and 11.95 g of a reaction product of tallow fatty alcohol with 14 moles of ethylene oxide are added. The mixture is then heated to boiling under reflux for 4 hours and then 17 ml of water are separated off on a water separator. The solvent toluene is first completely distilled off at normal pressure and later in vacuo.

Mp 47-49 ° C

Yield: 72 g

Analysis: HCH _O (bound)

found: 11.96% ~ degree of methylolation 1.5 calculated on crude product with emulsifier

30 g of the distillation residue obtained are melted at a temperature of 60 to 70 ° C and adjusted to a final content of 20% by adding 120 ml of hot water.

An emulsion with the same performance properties is obtained if, instead of the oxyethyl tallow fatty alcohol, the reaction product of a synthetic alcohol with an alkyl chain of C ₉ -C ₁₂ and 10 moles of ethylene oxide is used as an emulsifier.

Example 8:

80.75 g (0.25 mol) of eicosyl isocyanate are dissolved in 350 ml of technical toluene, and 4.25 g (0.25 mol) of liquid NH _{3 are} slowly added in a pressure vessel with stirring at a temperature of 50-60 ° C. After stirring for 30 minutes, the N-eicosylurea is isolated.

This intermediate product is transferred to a 500 ml three-necked flask with stirrer and thermometer and reflux condenser after suspension in 200 ml of toluene. 31 g of the sulfuric acid half-ester of a reaction product of 1 mol of stearyl alcohol with 12 mols of ethylene oxide, 0.2 g of N-methylmorpholine and finally 27 g (0.35 mol) of an aqueous 39% formaldehyde solution are then added. The mixture is then heated to boiling under reflux for 4 hours, then the H ₂ 0 and the solvent are distilled off.

The resulting crude melt containing emulsifier is converted into a 30% aqueous emulsion by adding hot H ₂ O while stirring vigorously with a high-speed stirrer.

In the same way, from the intermediate product described above and 200 ml of toluene with the addition of 31 g of the sulfuric acid half ester of a reaction product of 1 mol of stearyl alcohol with 12 mols of ethylene oxide, 58.7 g of a 70% sulfonated fish oil ®Derminollicker NBR, HOECHST AG ), 0.2 g of N-methylmorpholine and 27 g (0.35 mol) of 39% aqueous formaldehyde solution prepare a preparation for the finishing and waterproofing of leather.

This preparation is distinguished by an excellent storage stability and an excellent improvement in the grip of the leather without a so-called "fatiness" being observed on the treated materials.

Example 9:

140.4 g (0.4 mol) of docosyl isocyanate are dissolved in 400 ml of xylene and 6.8 g (0.4 mol) of gaseous NH ₃ gas are introduced until the batch undergoes an alkaline reaction (pH, measured in a toluene / H ₂ 0 mixture, 9.2).

Now 1.5 g of triethanolamine are added and then 34.6 g (0.45 mol) of 39% aqueous formaldehyde solution are added. The mixture is then heated to boiling under reflux for 4 hours, then water and the xylene are distilled off.

Yield: 157 g of crude product N-docosyl-N'-methylol-urea

Analysis: HCHO (bound)

found: 7.6% corresponding to a degree of methylolation of 1.0

100 g of the methyloldocosylurea obtained in the manner described above with a degree of methylolation of 1.2 are melted at a temperature of 80-85 ° C., with 5 g of the triethanolamine salt of the sulfuric acid half-ester from a reaction product of oleyl alcohol and 13 moles of ethylene oxide and homogeneously fused with 20 g of the reaction product of stearyl alcohol and 14 moles of ethylene oxide. 475 ml of warm water at 70-80 ° C. are then stirred into this homogeneous melt with good stirring using a high-speed stirrer.

An emulsion according to the invention for hydrophobizing and improving the grip of textiles and leather with excellent performance properties is obtained.

Example 10:

In the following examples, which illustrate the use of the auxiliary preparations according to the invention in the leather sector, the amounts used in% are based on the dry leather weight.

10 post-chromed, East Indian bastard clothing suede leather with a dry weight of 2.6 kg are drummed with 100% H ₂ O, 2% NH ₄ 0H and 0.1 to 0.2% an anionic emulsifier for about 1 hour. The leathers are then rinsed with water at 20-25 ° C. for five minutes and drummed for one hour in a tanning drum with 100-200% water, 1 to 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 leathers are dyed as usual with anionic dyes and then acidified with formic acid, the amount of acid should not be less than 2%.

The leathers are placed on a trestle for 24 hours without rinsing, then dried at 60-70 ° C. and finally milled in a full drum for 3-4 hours. The leathers treated in this way have a silky, smooth velor handle and have a good gloss effect.

Applied water drops do not penetrate within 4 hours in the case of a leather treated in this way, compared to a penetration time of two to four minutes in the case of an untreated leather.

The dynamic water absorption according to the disc method is reduced from 140 - 150% for an untreated leather to 45 - 35%.

• Zu den Bestimmungen werden stets vergleichbare LederstUcke eingesetzt, die möglichst 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 leather pieces that have been cut out from a piece of leather side by side are always used for the provisions.

3 leather discs of 20 mm 0 each are punched out of a 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 500 ml shaking bottle containing 250 ml of demineralized water at 20 ° C. and shaken in the shaker for 15 minutes (shaking frequency:
180 min ^-1 ).

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

• % Wasseraufnahme
  
• ^G _naß - Gewicht des nassen Leders
• ^Gtrocken = Gewicht des trockenen Leders.

Calculating the percentage of water absorption:

• % Water absorption
  
• ^G _wet - weight of wet leather
• ^G dry = weight of the dry leather.

Example 11:

20 halves of intermediate-dried chrome-tanned split suede leather with a dry weight of 60 kg are mixed with 1000% water at 35 ° C, 2% NH ₃ , 25%, and 0.2 - 0.4% of an anionic emulsifier in a tanning drum for about 1 hour tumbled. The leathers are then rinsed with water at 20-25 ° C. for about 5 minutes and treated with 100-200% water, 1-2% ammonia, 25% strength and 5-10% of the auxiliary preparation according to the invention prepared according to Example 4. The pH should be between 6 and 9 at the end of treatment. After this time, depending on the desired shade, 4-8% dye, powdered, is added 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 running time as usually acidified with formic acid. The amount of formic acid should be half of the amount of dye used.

The treated leathers are jacked up about 24 hours without rinsing, then 60 - 70 ⁰ C dried and finished as usual.

The split suede treated in this way has a soft velvet-like velor handle and has a good gloss effect.

The penetration time of applied water drops is improved from 5 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 20 to 30%. This hydrophobizing effect can be increased by additional hydrophobic greasing.

Example 12:

10 halves of a seam-damp chrome-tanned cowhide with a leather thickness of 0.8 to 1 mm are neutralized as usual, highly tanned, dyed and greased hydrophobically. As a final treatment, 1-3% of the auxiliary preparation according to the invention described in Example 9 are added to the acidified approx. 60-70 ° C dyeing and oiling bath. Before the addition of this auxiliary preparation, the auxiliary is diluted 1: 3 with water at 20-30.degree. C. and adjusted to a pH of 7.5-8.0 with 25% ammonia.

The running time in the barrel is about 10 - 20 minutes.

After this time, the treated leather is jacked up without rinsing and finished as usual.

As a result of this final treatment with the reactive auxiliary according to the invention, which is to be regarded as potting, these leathers obtain a wax-like warm surface grip with a simultaneous hydrophobizing finish.

This final treatment increases the penetration time of water drops from 1-2 minutes to 1-2 hours.

Example 13:

Chrome-tanned, dyed and, as usual, finished cow leather for furniture covers are finished with a finish made of thermoplastic copolymers with organic and inorganic pigments. These products are applied with a spray gun. In order to achieve good rubbing and water fastness as required by the application, these leathers are additionally given a final application with nitro lacquers emulsified in aqueous systems.

10-20 g of an auxiliary preparation prepared according to Example 4 are stirred into 100 g of emulsion varnish for the final treatment of chrome leather, adjusted to pH 8.0-9.0 with ammonia, 25%, and then with 100 parts of water at 20 ° C. a ready-to-use concentration is diluted. After 2 Spritx orders, the treated leather is dried and then finally ironed with a hydraulic ironing press at 70 - 80 ° C and 80 - 150 atm.

The leathers obtained in this way are considerably superior in terms of friction and water fastness to those which have been aftertreated with the same lacquer system, but without the addition of the product from Example 4.

Example 14:

Normally colored chrome split suede leather (4 kg off-weight) with a thickness of 1.5 mm is treated in the continuous multi-purpose machine at 60 ° C. with an impregnation liquor of 50 g / liter of the emulsion produced according to Example 2 and 20 g / liter of a 70% strength sul fonated fish oil (® DERMINOL LICICER ONLY, Höchst AG) treated. The lead time of the leather was 10 seconds at a belt speed of 3 m / minute.

After squeezing to 980 g of liquor pickup, the leather was then hot-air dried as usual at 80 ° C. on an ironing press

at 95 ° C, 30 atm pressure, heat-fixed for 5 seconds and, as usual, reground with 220-grit sandpaper on a rotating grinding machine.

This gives a napped velor handle with a pleasant "S _c hreibeffekt" and a good water-repellent effect of water on the processed material.

With the preparations according to the invention given in the table below, excellent softening and water repellent effects can be achieved in the same way on high-quality textile materials or on leather.

Claims (10)

1. softening and waterproofing agents for textile materials made of or containing cellulose and for leather, consisting of 10 to 35% by weight of a compound of general formula I.

wherein R linear or branched alkyl or alkenyl with 14-22 C atoms and m represents a number from 1.0 to 1.5 and n is 2-m; b% by weight of known nonionic and c% by weight of known anionic emulsifiers,
where: b - 0 to 10 c - O to 3 and b + c - O, 5 to 10; 0 to 5% by weight of an epoxide of the formula II

wherein R ^{1 is} alkyl or alkenyl having 15 to 40 carbon atoms; 0 to 25% by weight of known licker and
25 to 89.5% by weight of water or a water-miscible organic solvent. 2. softening and waterproofing agent according to claim 1 consisting of
10 to 25% by weight of a compound of the general formula I

wherein R linear or branched alkyl or alkenyl with 14 to 22 carbon atoms and m represents a number from 1.0 to 1.5 and n is 2-m; b% by weight of known nonionic and c% by weight of known anionic emulsifiers,
where applies b - 0 to 5 c = 0 to 3 and b + c - 1 to 5; 0 to 5% by weight of an epoxide of the formula II

wherein R ^{1 is} alkyl or alkenyl having 15 to 40 carbon atoms; 0 to 25% by weight of known licker and
40 to 89.0% by weight of water or a water-miscible organic solvent. 3. softening and waterproofing agent according to claims 1 and 2 for textile use, characterized in that it is up to 5 wt.% Of the epoxide of formula II and
Contains 0% licker. 4. softening and waterproofing agent according to claims 1 and 2 for use on leather, characterized in that it contains no epoxy of formula II and 5 to 25% licker. 5. softening and waterproofing agent according to claims 1 to 4, characterized in that in the compound of general formula 1 R is stearyl, coconut fatty alkyl, tallow fatty alkyl or oleyl. 6. softening and waterproofing agents according to claims 1 to 5, characterized in that known, nonionic emulsifiers are those of the general formula III

are included in what A unbranched alkyl or alkenyl with 10 to 22 carbon atoms, alkylphenyl, dialkylphenyl or trialkylphenyl with a total of 4 to 12 carbon atoms in the alkyl radicals, R ^{4 is} hydrogen or alkyl having 1 to 2 carbon atoms and n is a number between 8 and 14. 7. softening and waterproofing agents according to claims 1 to 6, characterized in that known nonionic emulsifiers are those of the general formula III, wherein
A is stearyl, coconut fatty alkyl, tallow fatty alkyl or oleyl and R ^{4 is} hydrogen. 8. Process for the production of finishing and water repellents for textile materials made of or containing cellulose and for leather consisting of
10 to 35% by weight of a compound of the general formula I

wherein R linear or branched alkyl or alkenyl with 14-22 C atoms and m is a number from 1.0 to 1.5 and n = 2-m; b% by weight of known nonionic and c% by weight of known anionic emulsifiers, where applies b - O to 10 c = O to 3 and b + c = O, 5 to 10; 0 to 5% by weight of an epoxide of the formula II

wherein R ¹ denotes alkyl or alkenyl with 15 to 40 C atoms; 0 to 25% by weight of known licker and ₂ 5 to 89.5 wt.% Water or a water-miscible organic solvent, characterized in that

Parts by weight of a urea of the formula IV

with at least m times the molar amount of either paraformaldehyde (calculated as formaldehyde) in the melt or aqueous formaldehyde solution in the presence of an inert water-immiscible solvent
in the presence of h parts by weight of known nonionic and p parts by weight of known anionic emulsifiers methylolated under conditions known per se, any water-immiscible inert solvent distilled off and the residue with (bh) parts by weight of known nonionic, (cp) parts by weight of known anionic emulsifiers, d parts by weight of an epoxide of formula II and e parts by weight of known licker homogenized in the plastic or molten state and then f Add parts by weight of water or a water-miscible organic solvent with constant mixing and homogenize again,
where applies a + b + c + d + e + f = 100, a - 10 to 35 b - 0 to 10 c - 0 to 3 b + c - 0.5 to 10 d - O to 5 e = O to 25 f - 25 to 89.5, h ≤ b and p ≤ c. 9. Use of the agents of claim 3 for softening and waterproofing textile materials consisting of or containing cellulose. 10th Use of the agent of claim 4 for finishing and waterproofing leather.