EP0002773B1 - Procédé de l'avivage et de l'hydrofugation du cuir - Google Patents

Procédé de l'avivage et de l'hydrofugation du cuir Download PDF

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Publication number
EP0002773B1
EP0002773B1 EP78101747A EP78101747A EP0002773B1 EP 0002773 B1 EP0002773 B1 EP 0002773B1 EP 78101747 A EP78101747 A EP 78101747A EP 78101747 A EP78101747 A EP 78101747A EP 0002773 B1 EP0002773 B1 EP 0002773B1
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Prior art keywords
water
leather
weight
percent
alkyl
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Expired
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EP78101747A
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German (de)
English (en)
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EP0002773A2 (fr
EP0002773A3 (en
Inventor
Gustav Hudec
Karl-Heinz Dr. Keil
Volker Köhler
Kurt Dr. Rosenbusch
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Sanofi Aventis Deutschland GmbH
Original Assignee
Cassella AG
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Publication of EP0002773A3 publication Critical patent/EP0002773A3/xx
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Publication of EP0002773B1 publication Critical patent/EP0002773B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • 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 finish is intended to give leather advantageous surface properties, in particular a pleasant, warm feel.
  • Known conditioning agents are, for example, natural oils and partially saponified natural fats. When finishing, it is often desirable to also make the leather hydrophobic.
  • Known options for waterproofing leather are treatment with solutions or emulsions of paraffin hydrocarbons, waxes or the like.
  • Metal soaps have also already been used for hydrophobic purposes, as have combinations of metal salts and paraffin or wax emulsions.
  • Metal complexes, which, like metal soaps, can be used for water repellency purposes are known from US Pat. No. 2,273,040.
  • Further known hydrophobizing agents are the N-alkyl-N'-ethyleneureas with long-chain alkyl radical known from DRP 6 81 520.
  • the present invention now relates to a finishing and water-repellent process by means of which an excellent improvement in the grip of leather is achieved, while at the same time excellent water-repellent effects.
  • the effects achieved have a very good wet, wash and chemical cleaning resistance, and they can be achieved on very different types of leather.
  • the substrate-reactive active compounds of the formula I to be used in the process according to the invention can be prepared in a technically simple manner.
  • the long-chain alkyl radicals R of the active compounds of the formula 1 with 14 to 22 carbon atoms contained in the softening and waterproofing agent are preferably only weakly branched or linear.
  • alkyl radicals which can be R in the active compounds of formula 1 are:
  • stearylalkyl essentially consists 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
  • the active compounds of the formula behave particularly favorably with regard to their joint use with other agents required for 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 finishing and hydrophobicizing agents to be used according to the invention opens up the possibility of varying the emulsifier required for emulsifying the active ingredient in water in a variety of ways. It is also quite expedient to use this option and that in the finishing and water repellents Combinations of non-ionic and anionic emulsifiers contained in the leather that may be envisaged.
  • nonionic emulsifiers known per se and contained in the finishing agents and water repellents can be obtained using the general formula II wherein A is 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 with 1 to 2 carbon atoms and n is a number between 8 and 14 is summarized.
  • Nonionic emulsifiers of the general formula 11 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 are, for example, long-chain alkanols and alkenols having 10 to 22 carbon atoms, in particular those which differ from the natural fatty acids such as stearic acid, palmitic acid, oleic acid or the natural fatty acid mixtures as described in the coconut fatty acid or tallow fatty acid are present, derived, and synthetic alcohols with a C lo - 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, for example, p-tert-butylphenol, p-nonylphenol, tri-iso-propyl and Tri-iso-butylphenols, for example 2,4,6-tri- (n) -butylphenol, 2,4,6-
  • sulfated fats or oils such as. B. 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 carbon atoms such as B. fatty acid taurides, -oxethanesulfonates
  • anionic emulsifiers which contain at least one -OS0 3 H or a -SOaH group are, for. B. the sulfuric acid half-esters of nonionic emulsifiers based on ethylene oxide adducts with OH groups containing organic compounds, which may then be neutralized with inorganic bases, such as. B. NaOH, Na 2 C0 3 or with organic amines, such as. As diethanolamine, ethanolamine or triethanolamine, have been converted into the salts.
  • the softeners and water repellents containing the emulsifiers described above, ie also mixtures of these emulsifiers, have very good application properties and show an optimal fine distribution of the emulsified active substances and thus a high storage stability of the emulsion.
  • the combination of the nonionic and the anionic emulsifiers which have at least one -OS0 3 H or one -S0 3 H group in the form of the alkali metal, NH 4 ⁇ - or alkylammonium salts in their molecule, succeeds in increasing the fine distribution of the active substances to such an extent that colloidal solutions are formed when diluted to 1 to 0.1% solutions.
  • nonionic emulsifiers of the general formula II, in which A is unbranched or slightly branched alkyl or alkenyl having 10-22 carbon atoms.
  • the leather in the method according to the invention, it is also possible to grease the leather with a fat licker simultaneously with the finishing and hydrophobicization of the leather.
  • a fat licker in this case, it is also possible to directly incorporate at least a part of the fat licker required for greasing the leather into the softening and waterproofing agents to be used according to the invention.
  • This fat-licker portion usually replaces some of the emulsifiers. It is easily possible to replace up to 25 percent by weight of the emulsifier with fat licker.
  • the emulsifier accordingly consists of 95.0 to 37.5 percent by weight of known nonionic emulsifiers, 0 to 50 percent by weight of known anionic emulsifiers and 5 to 25 percent by weight of known lickers.
  • the emulsifier preferably contains 90 to 60 percent by weight of known nonionic emulsifiers, 0 to 20 percent by weight of known anionic emulsifiers and 10 to 20 percent by weight of known lickers.
  • Sulfoxidation products predominantly saturated unbranched paraffins, such as or Alkyl aryl sulfonates and olefin sulfonates.
  • Water-miscible organic solvents which can be contained in the finishing and hydrophobizing agents 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.
  • finishing agents and water repellents to be used in the process according to the invention can be prepared by homogenizing the N-methylol-N'-alkylureas of the formula 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 appropriate, with known ones Lickern done.
  • the N-methylol-N'-alkylureas of the formula are expediently obtained immediately before the preparation of the finishing and hydrophobizing agents by methylolation of the corresponding N-alkylureas of the formula III produced.
  • 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 III 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.
  • the process is preferably carried out between 100 and 130 ° C, when carrying out the reaction in an inert water-immiscible organic solvent, taking into account the highest possible reaction rate 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 to 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.
  • 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.
  • methylolation reactions are catalyzed by acids and bases.
  • 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, non-methylolizable bases is particularly advantageous. As such, especially low-odor, low-volatile tertiary amines, such as. B.
  • the N-methylol-N'-alkylureas of the formula I can also be prepared from the N-alkylureas of the formula 111 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.
  • 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 III.
  • the amount of formaldehyde or paraformaldehyde to be used in the methylolation depends on the desired degree of methylolation m of the methylolalkylureas of the 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 111. As a rule, an excess of 20-50% is necessary.
  • products are obtained which contain no emulsifier or part or all of the emulsifiers.
  • the remaining amounts of emulsifier and, if desired, known licker 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 to prepare 100 g of softening and hydrophobicizing agents, the total amount of emulsifiers being 0.5 to 10 parts by weight.
  • the amount of to be used to produce 100 parts by weight of the finishing and hydrophobicity which can be used in the process according to the invention by means of the urea of the formula III results from the amount a of the N-methylol-N'-alkylurea of the formula 1 contained therein by adding this amount to the factor where M is the molecular weight of the alkyl urea of the formula III used and m is the degree of methylolation.
  • Known lickers are incorporated and homogenized in an amount of 0 to 25 parts by weight, based on 100 parts by weight of finishing agents to be produced.
  • the incorporation and homogenization of the individual components of the finishing and hydrophobizing agents 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. with water-miscible solvent, preferably preheated to about the temperature of the solid mixture introduced, metered in.
  • the finishing agents and water repellents are applied in a manner known per se, as is customary in the leather treatment process.
  • the process of finishing and water-repellent treatment according to the invention can also be carried out simultaneously with other post-treatment or finishing steps.
  • the finishing and hydrophobizing agents can also be used simultaneously with liquors containing leather dyes, in addition to the associated dyeing aids such as retardants, leveling agents, dispersants, neutral salts and, if necessary, additives which determine the pH of the liquors.
  • the process according to the invention is carried out, as is generally customary in the leather industry, at temperatures between 15 and -0.degree.
  • 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, may contain auxiliaries such as, for example, greasing agents or varnishes, which are required in the leather finishing, and subsequent fixation of the reactive active ingredient by heat treatment at 50 up to 120 ° C, optionally under pressure, for example in an ironing press.
  • auxiliaries such as, for example, greasing agents or varnishes, which are required in the leather finishing, and subsequent fixation of the reactive active ingredient by heat treatment at 50 up to 120 ° C, optionally under pressure, for example in an ironing press.
  • the process according to the invention can also be carried out very conveniently using 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. 20 to 300 g of finishing and water repellant / liter are used. After impregnation and squeezing, the leather is dried and, as described for spray impregnation, hot fixed at 50 to 120 ° C.
  • the aqueous solution of the finishing and water repellent can also be carried out by brushing on by hand or by brushing machines, the penetration of the dispersion into the leather interior by adding 0- 50% of a so-called penetrator, for example butyl diglycol, pentaglycol, dimethylformamide, dimethyl sulfoxide etc., is 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.
  • a so-called penetrator for example butyl diglycol, pentaglycol, dimethylformamide, dimethyl sulfoxide etc.
  • leather treated according to the invention has a very soft, delicate surface with a pleasant feel and, compared to untreated goods, a significantly reduced water absorption capacity and greatly reduced dynamic water absorption. It is also of particular importance that the mentioned advantageous effects of the treatment according to the invention arise both on vegetable-tanned and on chrome-tanned leather, that they can be used equally well on suede of various origins, for example on goat and pig suede, and on the leather surfaces obtained have no greasiness, but give the velor a velvety feel and make it insensitive to hydrophilic dirt and stains, which can arise from aqueous colorless or colored liquids, such as fruit juices, red wine, ink, blood, etc.
  • the effects obtained in the treatment according to the invention have very good resistance to further post-treatment steps, to water, aqueous detergent solutions and cleaning with organic solvents.
  • the softening and waterproofing agents to be used have an excellent shelf life and durability in aqueous liquors.
  • the process according to the invention for finishing and hydrophobicizing leather and the auxiliary preparations used for this process accordingly have a technically particularly advantageous combination of valuable properties and are significantly superior in this respect to previously known processes and auxiliaries.
  • the following exemplary embodiments illustrate the preparation and use of the finishing agents and water repellents and the preparation of the N-methylol-N'-alkylureas of the formula I contained as active ingredients in the auxiliaries.
  • the details of parts contained in the present application are parts by weight; Percentages mean percentages by weight.
  • 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 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.
  • This preparation is characterized 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.
  • the leather is placed on a trestle for 24 hours without rinsing, then dried at 60-70 ° C and then milled in a 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 2 to 4 minutes in the case of an untreated leather.
  • the dynamic water absorption according to the disc method is reduced from 140-150 ° C to 45-35% for an untreated leather.
  • the treated leathers are jacked up for about 24 hours without rinsing, then dried at 60 to 70 ° C. 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 2 to 3 hours.
  • the dynamic water absorption according to the disc method is reduced from 80 to 100% for an untreated leather to 20 to 30%. This hydrophobizing effect can be increased by additional hydrophobic greasing.
  • 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 2a and 20 g / liter of a 70% strength sulfonated fish oil ( @ DERMINOL LICKER NBR, absolute AG) treated.
  • the lead time of the leather was 10 seconds at a hand speed of 3 m / minute.
  • the leather was then hot-air dried as usual at 80 ° C., heat-fixed on an ironing press at 95 ° C., 30 bar pressure, for 5 seconds and, as usual, reground on a rotating grinding machine with 220-grit sandpaper.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Coloring (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Claims (9)

1. Procédé d'avivage et d'hydrofugeage du cuir, caractérisé en ce qu'on traite le cuir, de manière connue, par un bain aqueux contenant un agent d'avivage et d'hydrofugeage du cuir, agent qui est constitué de:
a = 10 à 35% en poids d'un composé répondant à la formule générale 1
Figure imgb0027
dans laquelle R représente un radical alkyle ou alcényle linéaire ou ramifié, renfermant de 14 à 22 atomes de carbone, m désigne un nombre de 1,0 à 1,5 et n un nombre égal à2--m;
b % en poids d'émulsionnants non ioniques connus,
c % en poids d'émulsionnants anioniques connus, b étant un nombre de 0 à '10, c un nombre de 0 à 3 et la somme b + étant un nombre de 0,5 à 10,
de 0 à 25% en poids de nourritures connues et de 25 à 89,5% en poids d'eau ou d'un solvant organique miscible à l'eau.
2. Procédé selon la revendication 1, caractérisé en ce que a=10 à 25% en poids.
3. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que l'agent d'avivage et d'hydrofugeage contient de 5 à 25% d'une nourriture (ou »licker«).
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que, dans le composé de formule générale I, le symbole R représente un radical stéaryle, un radical alkyle provenant du coco, un radical alkyle provenant du suif ou un radic?' léyle.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'agent d'avivage et d'hydrofugeage contient, comme émulsionnants non ionogènes connus, des composés répondant à la formule générale 111
Figure imgb0028
dans laquelle A représente un radical alkyle ou alcényle non ramifié contenant de 10 à 22 atomes de carbone, ou un radical alkylphényle, dialkylphényle ou trialkylphényle contenant au total, dans les radicaux alkyles, de 4 à 12 atomes de carbone, R4 représente l'hydrogène ou un radical alkyle contenant de 1 à 2 atomes de carbone et n désigne un nombre compris entre 8 et 14.
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'agent d'avivage et d'hydrofugeage contient, comme émulsionnants non ionogènes connus, des composés de formule générale III dans lesquels A représente un radical stéaryle, un radical alkyle provenant du coco, un radical alkyle provenant du suif ou un radical oléyle et R4 représente l'hydrogène.
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le bain aqueux contient de 2 à 15% de l'agent d'avivage et d'hydrofugeage.
8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le traitement est effectué à une température comprise entre 15 et 70° C,
9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que la somme b+c est un nombre de 1 à 5.
EP78101747A 1977-12-23 1978-12-18 Procédé de l'avivage et de l'hydrofugation du cuir Expired EP0002773B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2757582 1977-12-23
DE19772757582 DE2757582A1 (de) 1977-12-23 1977-12-23 Verfahren zur herstellung lagerstabiler waessriger emulsionen von n.alkyl-n'-alkylol-harnstoffen und deren anwendung zum weichmachen von leder und textilmaterial

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EP0002773A2 EP0002773A2 (fr) 1979-07-11
EP0002773A3 EP0002773A3 (en) 1979-07-25
EP0002773B1 true EP0002773B1 (fr) 1981-09-23

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US (1) US4289665A (fr)
EP (1) EP0002773B1 (fr)
JP (1) JPS5495988A (fr)
AR (1) AR222165A1 (fr)
BR (1) BR7808476A (fr)
CS (1) CS209402B2 (fr)
DE (2) DE2757582A1 (fr)
ES (1) ES476247A1 (fr)
HU (1) HU181652B (fr)
YU (1) YU303978A (fr)
ZA (1) ZA787212B (fr)

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US8551551B2 (en) 2012-01-06 2013-10-08 Perlman Consulting, Llc Stabilization of omega-3 fatty acids in saturated fat microparticles having low linoleic acid content

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE418549A (fr) * 1935-05-12
US2361185A (en) * 1941-12-30 1944-10-24 Du Pont Process of making ether compounds
US3147138A (en) * 1961-01-28 1964-09-01 Bayer Ag Method of coating leather
US3510245A (en) * 1967-02-13 1970-05-05 Pers Pro Tan Leathers Inc Ph 3.9 to 4.4 impregnation of an acidic vegetable tanned,fat-liquored leather with a dimethylol urea solution
DE2133820B2 (de) * 1971-07-07 1977-09-15 Cassella Farbwerke Mainkur Ag, 6000 Frankfurt Verfahren zur herstellung von niedermolekularen, veraetherten methylolharnstoffen bzw. -thioharnstoffen
DE2152596C2 (de) * 1971-10-22 1982-09-30 Uhde Gmbh, 4600 Dortmund Verfahren zur Herstellung eines durch chemische Mittel gebundenen nicht gewebten Faserflächengebildes mit hoher Wasserdampfaufnahmefähigkeit und guten Wärmeisolationseigenschaften
US3965015A (en) * 1972-08-01 1976-06-22 Colgate-Palmolive Company Bleach-resistant fabric softener
DE2259613A1 (de) * 1972-12-06 1974-06-12 Hoechst Ag Mittel und verfahren zur oel- und wasserabweisenden ausruestung von flaechenoder formgebilden aus polyurethan mit veloursartiger oberflaeche
CH573006B5 (fr) * 1973-04-21 1976-02-27 Basf Ag
DE2730042A1 (de) * 1977-07-02 1979-01-11 Cassella Farbwerke Mainkur Ag Avivage- und hydrophobiermittel fuer zellulose-textilien und leder

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CS209402B2 (en) 1981-12-31
DE2757582A1 (de) 1979-06-28
US4289665A (en) 1981-09-15
BR7808476A (pt) 1979-08-21
JPS5495988A (en) 1979-07-28
DE2861125D1 (en) 1981-12-10
ZA787212B (en) 1979-12-27
EP0002773A2 (fr) 1979-07-11
ES476247A1 (es) 1979-04-16
EP0002773A3 (en) 1979-07-25
AR222165A1 (es) 1981-04-30
YU303978A (en) 1983-10-31
HU181652B (en) 1983-10-28

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