EP0000201B1 - Produits d'avivage et d'hydrofugeage contenant des sulfonylurées pour matériaux textiles contenant de la cellulose, et pour cuir, procédé pour leur préparation; les sulfonylurées et procédé pour leur préparation - Google Patents

Produits d'avivage et d'hydrofugeage contenant des sulfonylurées pour matériaux textiles contenant de la cellulose, et pour cuir, procédé pour leur préparation; les sulfonylurées et procédé pour leur préparation Download PDF

Info

Publication number
EP0000201B1
EP0000201B1 EP78100278A EP78100278A EP0000201B1 EP 0000201 B1 EP0000201 B1 EP 0000201B1 EP 78100278 A EP78100278 A EP 78100278A EP 78100278 A EP78100278 A EP 78100278A EP 0000201 B1 EP0000201 B1 EP 0000201B1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
alkyl
water
alkenyl
leather
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100278A
Other languages
German (de)
English (en)
Other versions
EP0000201A1 (fr
Inventor
Gustav Hudec
Karl-Heinz Dr. Keil
Volker Köhler
Joachim Dr. Ribka
Kurt Dr. Rosenbusch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sanofi Aventis Deutschland GmbH
Original Assignee
Cassella AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cassella AG filed Critical Cassella AG
Publication of EP0000201A1 publication Critical patent/EP0000201A1/fr
Application granted granted Critical
Publication of EP0000201B1 publication Critical patent/EP0000201B1/fr
Expired legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/438—Sulfonamides ; Sulfamic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides

Definitions

  • 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 ⁇ -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,
  • Softening agents are said to give textile materials and leather advantageous surface properties, in particular a pleasant, warm feel.
  • finishing agents can improve the processing properties of fiber materials.
  • Known conditioning agents are, for example, natural oils and partially saponified natural fats.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the halogen has, for example, the meaning of bromine, iodine, but especially chlorine.
  • the ⁇ -haloalkyl radical are in particular / 3-chloroethyl, ⁇ -chloropropyl and ⁇ -chlorobutyl, examples of the alkenyl representing X are vinyl, propenyl, 1-butenyl and 2-butenyl.
  • 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
  • oleyl -alkyl from alkyl radicals with 16-18 carbon atoms and the octadecen- (9) -yl- (1) radical.
  • Another group of preferred active compounds of the formula I are those in which B is one of the divalent radicals is.
  • active compounds of the formula 1 are preferred in which X is for a ⁇ -chloroalkyl group having 2 to 4 carbon atoms, such as, for example, stands for the ⁇ -chloroethyl- ⁇ -chloropropyl or ⁇ -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.
  • 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.
  • 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.
  • the emulsifier can be composed of 100 to 50% of nonionic emulsifiers and 0 to 50% of anionic emulsifiers.
  • 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.
  • sulfated fats or oils such as sulfated tran or sulfated sperm, palm or
  • auxiliary preparations according to the invention 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.
  • 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.
  • 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.
  • 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.
  • Fatty acid esters of ⁇ -hydroxyethanesulfonic acid such as and
  • 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 are 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the finishing and hydrophobizing can also be carried out simultaneously with other post-treatment or finishing steps.
  • 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.
  • dye liquors which contain anionic cellulose or leather dyes
  • the associated dyeing auxiliaries such as retarders
  • Leveling agents, dispersants, neutral salts and, if necessary, additives determining the pH of the liquors are used.
  • 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.
  • 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.
  • 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 ⁇ -chloroalkyl having 2 to 4 carbon atoms, such as, for example, the ⁇ -chloroethyl, ⁇ -chloropropyl or ⁇ -chlorobutyl group.
  • a ⁇ -chloroalkylsulfonyl isocyanate having 2 to 4 carbon atoms in the alkyl radical is preferably used as the ⁇ -haloalkylsulfonyl isocyanate having 2 to 4 carbon atoms in the alkyl radical.
  • 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.
  • solvents examples include 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.
  • An excess of one of the reactants can also be used in the preparation of the sulfonylureas of the invention.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • penetrators e.g. Butyl diglycol, pentaglycol, dimethylformamide, dimethyl sulfoxide, etc.
  • N-Lauryl-N'- ⁇ -chlofthylsulfonylurea C 1s H 31 CISN 2 0 3 (354.5) mp 79-80 o C N-hexadecyl-N'- ⁇ -chloro-ethyl sulfonyl urea:
  • 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.
  • 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) ⁇ -chloroethylsulfonyl isocyanate.
  • 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.
  • 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 ⁇ -chloroethylsulfonyl isocyanate.
  • N-dioctadecylamine 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 ⁇ -chloroethylsulfenyl isocyanate dissolved in 150 ml of ethylene chloride, added dropwise at this temperature and 2 Hours stirred.
  • 498.3 g - 96.2% of theory of crude N N-dioctadecyl-N'-ß-chloroethylsulfonylurea are obtained.
  • 100 g of the N-di-octadecyl-N'- ⁇ -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.
  • 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.
  • 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 5 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.
  • 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%.
  • 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).
  • 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.
  • auxiliary preparation according to the invention prepared according to Example 1 are added to the acidified, 60-70 ° C. warm dyeing and oiling bath.
  • 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 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.
  • 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.
  • 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.
  • the leathers are dried and finally ironed with a hydraulic ironing press at 70-80 "C and 80-150 atm pressure.
  • N-methyl-octadecyl-N'- ⁇ 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.
  • the split leather 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.
  • 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.
  • 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. Agent d'avivage et d'imperméabilisation pour des matières textiles cellulosiques ou contenant de la cellulose et pour du cuir, cet agent étant caractérisé en ce qu'il consiste en (a) parties en poids d'un composé de formule générale (I)
Figure imgb0101
(dans laquelle R est une groupe alkyle ou alcényle ayant 10 à 30 atomes de carbone; B est l'un des radicaux divalents
Figure imgb0102
et X est un groupe béta-halogénoalkyle ou alcényle ayant chacun 2 à 4 atomes de carbone; R1 et R 2 sont chacun un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone et n vaut 2, 3 our 4) et (b) parties en poids d'un émulsifiant consistant en 100 à 37,5% d'émulsifiants non-ioniques connus, 0 à 50% d'émulsifiants anioniques connus et 0 à 25% de produits connus pour la nourriture du cuir; (c) parties en poids d'un époxyde de formule (II)
Figure imgb0103
(dans laquelle R3 est un groupe alkyle ou alcényle ayant 15 à 40 atomes de carbone) et éventuellement en (d) parties en poids d'eau ou d'un solvant organique miscible à l'eau, a valant 80 à 99, b 20 à 1, c 0 à 5 et, s'il y a lieu, l'expression
Figure imgb0104
valant 10 à 40.
2. Agent d'avivage et d'imperméabilisation selon la revendication 1, caractérisé en ce que a vaut 95 à 99 et b 5à 1.
3. Agent d'avivage et d'imperméabilisation selon l'une des revendications 1 et 2 pour application sur des textiles, cet agent étant caractérisé en ce que c vaut 0,5 à 5 et l'émulsifiant contient 0% d'un produit pour la nourriture de cuir.
4. Agent d'avivage et d'imperméabilisation selon l'une des revendications 1 et 2, destiné à une application sur le cuir, caractérisé en ce que c est nul et en ce que l'émulsifiant contient 5 à 25% d'un produit pour la nourriture du cuir.
5. Agent d'avivage et d'imperméabilisation selon d'une quelconque des revendications 1 à 4, caractérisé en ce que, dans le composé de formule générale (1), R est un groupe alkyle ou alcényle ayant 12 à 22 atomes de carbone, de préférence un groupe stéaryle, alkyle de graisse de noix de coco, alkyle de graisse de suif ou oléyle, B est l'une des restes divalents
Figure imgb0105
atomes de carbone.
6. Agent d'avivage ed d'imperméabilisation selon l'une quelconques des revendications 1 à 3, caractérisé en ce que l'emulsifiant contient comme émulsifiant non-ionique connu ceux repondant à la formule générale (lll)
Figure imgb0106
(dans laquelle A représente un groupe alkyle ou alcényle, ramifié ou non, ayant 10 à 22 atomes de carbone, un groupe alkylphényle ayant au total 6 à 12 atomes de carbone dans le groupe alkyle, un groupe alcanoyle ou alcénoyle, ramifié ou non, ayant 10 à 22 atomes de carbone, un groupe aralkyle ayant 7 à 15 atomes de carbone, un groupe aralkylaryle ayant 13 à 25 atomes de carbone, des restes ayant la composition de la lanoline ou un groupe acyloxyalkyle ayant au total 10 à 30 atomes de carbone, R4 est un atome d'hydrogène ou un groupe alkyle ayant 1 ou 2 atomes de carbone, et n est un nombre valant 10 et 60).
7. Procédé pour produire un agent d'avivage et d'imperméabilisation pour les matières textiles cellulosiques ou contenant de la cellulose et pour du cuir, caractérisé en ce qu'on malaxe ou remue 80 à 99 parties en poids d'un composé de formule générale (1)
Figure imgb0107
(dans laquelle R est un groupe alkyle ou alcényle ayant 10 à 30 atomes de carbone, B est l'un des restes divalents
Figure imgb0108
et X un groupe béta-halgénoalkyle ou alcényle ayant chacun 2 à 4 atomes de carbone, R1 et R2 sont chacun un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de cabone, et n vaut 2, 3 ou 4) avec 1 à 20 parties en poids d'un émulsifiant consistant en 100 à 37,5% d'agents émulsifiants non-ioniques connus, 0 à 50% d'agents émulsifiants anioniqùes connus et 0 à 25% de produits connus pour la nourriture du cuir, et 0 à 5 parties en poids d'un époxyde de formule (II)
Figure imgb0109
dans laquelle R3 est un groupe alkyle ou alcényle ayant 15 à 40 atomes de carbone) à des températures de 20° à 90°C jusqu'à obtention d'une masse homogène et en ce que éventuellement, par addition d'eau ou d'un solvant organique miscible à l'eau, on ajuste à une velour de 10 à 40% en poids la teneur en le composé de formule générale (1).
8. Procédé pour l'avivage et l'imperméabilisation des matières textiles cellulosiques ou contenant de la cellulose et du cuir, par traitement des matières par des bains aqueux contenant des agents d'avivage et d'imperméabilisation et les adjuvants connus usuels pour les bains d'avivage et d'imperméabilisation et éventuellement aussi des agents pour l'apprêt noble des textiles ou pour la nourriture du cuir ou des colorants pour textiles ou uirs ainsi que les adjuvants nécessaires à la teinture, à des temperatures allant jusqu'à 150°C, ce procédé étant caractérisé en ce qu'on ajoute au bain, comme agent d'avivage et d'imperméabilisation, 5 à 50 g/I de sulfonylurée de formule générale (I)
Figure imgb0110
(dans laquelle R est un groupe alkyle ou alcényle ayant 10 à 30 atomes de carbone, B est l'un des restes divalents
Figure imgb0111
est X es un groupe béta-halogénoalkyle ou alcényle ayant chacun 2 à 4 atomes de carbone, R1 et R2 sont chacun un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone, et n vaut 2, 3 ou 4).
9. Procédé selon la revendication 8, caractérisé en ce qu' on ajoute au bain la sulfonylurée de formule générale (I) sous forme d'une préparation pour l'avivage et l'imperméabilisation selon la revendication 1.
10. Sulfonylurée de la formule générale (1)
Figure imgb0112
(dans laquelle R est un groupe alkyle ou alcényle ayant 10 à 30 atomes de carbone, B est l'un des restes divalents
Figure imgb0113
et X est un groupe béta-halogénoalkyle ou alcényle ayant chacun 2 à 4 atomes de carbone, R1 est un groupe alkyle ayant 1 à 4 atomes de carbone, R2 est un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone, et n vaut 2, 3 ou 4).
11. Sulfonylurée selon la revendication 10, caractérisé en ce que, dans la formule (I), R représente un group alkyie de graisse de noix de coco, alkyle de graisse de suif, oléyle ou en particulier stéaryle, B est l'un des restes divalents
Figure imgb0114
et X est un groupe béta-chloralkyle ayant 2 à 4 atomes de carbone.
12. Procédé pour produire des sulfonylurées de formule générale (l)
Figure imgb0115
(dans laquelle R est un groupe alkyle ou alcényle ayant 10 à 30 atomes de carbone, B est l'un des restes divalents
Figure imgb0116
ou ―NH―CnH2n―N― et X est un groupe béta-halogénoalkyle ou alcényle ayant chacun 2 à 4 atomes de carbone, R1 est un groupe alkyle ayant 1 à 4 atomes de carbone, R2 un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone, et n vaut 2, 3 ou 4), caractérisé en ce qu'on fait réagir un isocyanate de béta-halogénoalkyl-sulfonyle ayant 2 à 4 atomes de carbone dans son reste alkyle et répondant à la formule:
Figure imgb0117
(dans laquelle X1 est un groupe béta-halogénoalkyle ayant 2 à 4 atomes de carbone) avec une amine de formule:
Figure imgb0118
(dans laquelle B est l'un des restes divalents
Figure imgb0119
R est un groupe alkyle ou alcényle ayant 10 à 30 atomes de carbone, R1 est un groupe alkyle ayant 1 à 4 atomes de carbone, R2 est un atome d'hydrogène ou un groupe alkyle ayant 1 à 4 atomes de carbone, et n vaut 2, 3 ou 4), selon un rapport molaire d'environ 1:1 dans un solvant organique aprotique à des températures comprises entre 20°C et 110°C, on isole de façon, usuelle le produit de la réaction et, dans la mesure où l'on doit produire un composé de formule (l) dans laquelle X est un groupe alcényle, on traite ensuite de façon connue avec une solution alcaline aqueuse.
13. Procédé selon la revendication 12, caractérisé en ce qu'on fait réagir de préférence un isocyanate de béta-chloralkylsulfonyle, ayant 2 à 4 atomes de carbone dans le reste alkyle, avec une amine de formule
Figure imgb0120
dans laquelle R est un groupe alkyle ou alcényle ayant 12 à 22 atomes de carbone, de préférence un groupe alkyle de graisse de noix de coco, alkyle de graisse de suif, oléyle ou en particulier stéaryle, et B est l'un des restes divalents
Figure imgb0121
EP78100278A 1977-07-02 1978-06-29 Produits d'avivage et d'hydrofugeage contenant des sulfonylurées pour matériaux textiles contenant de la cellulose, et pour cuir, procédé pour leur préparation; les sulfonylurées et procédé pour leur préparation Expired EP0000201B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772730042 DE2730042A1 (de) 1977-07-02 1977-07-02 Avivage- und hydrophobiermittel fuer zellulose-textilien und leder
DE2730042 1977-07-02

Publications (2)

Publication Number Publication Date
EP0000201A1 EP0000201A1 (fr) 1979-01-10
EP0000201B1 true EP0000201B1 (fr) 1981-01-07

Family

ID=6013063

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100278A Expired EP0000201B1 (fr) 1977-07-02 1978-06-29 Produits d'avivage et d'hydrofugeage contenant des sulfonylurées pour matériaux textiles contenant de la cellulose, et pour cuir, procédé pour leur préparation; les sulfonylurées et procédé pour leur préparation

Country Status (8)

Country Link
US (1) US4149979A (fr)
EP (1) EP0000201B1 (fr)
BR (1) BR7804208A (fr)
CS (3) CS208476B2 (fr)
DE (2) DE2730042A1 (fr)
ES (2) ES471328A1 (fr)
HU (1) HU177572B (fr)
IT (1) IT1118230B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2757582A1 (de) * 1977-12-23 1979-06-28 Cassella Ag Verfahren zur herstellung lagerstabiler waessriger emulsionen von n.alkyl-n'-alkylol-harnstoffen und deren anwendung zum weichmachen von leder und textilmaterial

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR919464A (fr) * 1944-12-28 1947-03-10 Geigy Ag J R Urées substituées et procédé de préparation de ces produits
US2487383A (en) * 1945-04-18 1949-11-08 Ciba Ltd Urea derivatives and process of making same
FR1180621A (fr) * 1955-08-08 1959-06-08 Hoechst Ag Sulfonylurées et leur procédé de préparation
US2976317A (en) * 1955-10-19 1961-03-21 Hoechst Ag N(alkyl-, cycloalkyl-, and cycloalkylalkylsulfonyl)-n'(alkyl-, alkenyl-, cycloalkyl,and cycloalkylalkyl)-ureas
US3069466A (en) * 1959-04-21 1962-12-18 Anton Von Waldheim New n1-halogenoalkyl-phenyl-sulfonyl-n2-substituted ureas, and the corresponding cyclohexyl compounds
US3420697A (en) * 1965-08-25 1969-01-07 Allied Chem Perfluoroalkyl-substituted polyamide oil-repellency compound and textile materials treated therewith
BE686440A (fr) * 1965-09-20 1967-02-15
CH1160169D (fr) * 1968-08-01 1900-01-01
NL6908449A (fr) * 1969-06-03 1970-12-07
BE790518A (fr) * 1971-10-26 1973-04-25 Bayer Ag Production et application de perfluoro-alcane-sulfonamides
BE792563A (fr) * 1971-12-10 1973-06-12 Bayer Ag Perfluoralcane sulfonamides et leur preparation
US3965015A (en) * 1972-08-01 1976-06-22 Colgate-Palmolive Company Bleach-resistant fabric softener

Also Published As

Publication number Publication date
EP0000201A1 (fr) 1979-01-10
DE2860405D1 (en) 1981-02-26
IT1118230B (it) 1986-02-24
HU177572B (en) 1981-11-28
DE2730042A1 (de) 1979-01-11
IT7825227A0 (it) 1978-06-30
US4149979A (en) 1979-04-17
ES471328A1 (es) 1979-09-01
CS208476B2 (en) 1981-09-15
ES478660A1 (es) 1979-07-01
CS208478B2 (en) 1981-09-15
BR7804208A (pt) 1979-04-03
CS208477B2 (en) 1981-09-15

Similar Documents

Publication Publication Date Title
DE605973C (de) Verfahren zur Herstellung von AEthern aus hydroxylhaltigen organischen Verbindungen und AEthylenoxyd
DE667744C (de) Verfahren zur Herstellung von in Wasser loeslichen oder leicht verteilbaren Kondensationsprodukten
EP1485533B1 (fr) Preparations a base d'eau et/ou de solvants organiques et leur utilisation comme appret sur des produits plats
EP0638128B1 (fr) Procede et dispositif d'impermeabilisation de materiaux a structure fibreuse
EP0036076A2 (fr) Procédé de préparation d'apprêts exempts de formaldéhyde pour matières textiles cellulosiques et leurs applications
EP0000137A1 (fr) Esters polyglycoliques; procédé de préparation et utilisation comme agents tensioactifs
CH671052A5 (fr)
EP0000201B1 (fr) Produits d'avivage et d'hydrofugeage contenant des sulfonylurées pour matériaux textiles contenant de la cellulose, et pour cuir, procédé pour leur préparation; les sulfonylurées et procédé pour leur préparation
DE2152705A1 (de) Verfahren zur herstellung von textilausruestungsmitteln
DE1594966A1 (de) Verfahren und Mittel zur Behandlung von Haushaltstextilien
US2040997A (en) Esters of boric acid
EP0002773B1 (fr) Procédé de l'avivage et de l'hydrofugation du cuir
DE3903926A1 (de) Faerbereihilfsmittel
EP0013388A2 (fr) Agent d'apprêt textile et procédé pour sa préparation ainsi que son utilisation
DE2056083A1 (de) Verfahren zur Ausrüstung von Textil stoffen
EP0022067B1 (fr) Procédé de teinture et de tannage en un seul bain de peaux et de fourrures
EP0044275B1 (fr) Mélanges de produits de réaction à base d'époxydes, d'amines primaires et d'acides gras et de précondensats d'aminoplaste, leur préparation et leur utilisation comme agents de corroyage du cuir
EP0415279B1 (fr) Utilisation d'amides d'acides gras éthoxylés comme adoucissants
CH676012A5 (fr)
DE1418650B2 (de) Verfahren zur Herstellung von oberflächenaktiven Schwefelsäureestern bzw. deren Salzen
DE2327505C3 (de) Mittel zum gleichzeitigen chemischen Reinigen und Hydrophobieren von konfektionierten Textilien und deren Verwendung
DE1594952A1 (de) Verfahren und Mittel zur Behandlung von Haushaltstextilien
AT236335B (de) Mittel zum Wasserabweisendmachen von Fasermaterialien
DE1419367C (de) Mittel zum Wasserabweisendmachen von Fasermaterialien
DE3837199A1 (de) Verwendung von amino-alkylenoxidaddukten als lederfaerbehilfsmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB NL

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE CH DE FR GB NL

REF Corresponds to:

Ref document number: 2860405

Country of ref document: DE

Date of ref document: 19810226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19810629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19810630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19820101

KL Correction list

Free format text: 82/01

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19820101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19830201

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19830331

KL Correction list

Free format text: 83/02 RECHERCHENBERICHT

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881117

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT