EP0362134B1 - Leather treating agent - Google Patents
Leather treating agent Download PDFInfo
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- EP0362134B1 EP0362134B1 EP89810707A EP89810707A EP0362134B1 EP 0362134 B1 EP0362134 B1 EP 0362134B1 EP 89810707 A EP89810707 A EP 89810707A EP 89810707 A EP89810707 A EP 89810707A EP 0362134 B1 EP0362134 B1 EP 0362134B1
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- Prior art keywords
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- composition according
- treatment composition
- leather treatment
- alkali metal
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- 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
- C14C3/00—Tanning; Compositions for tanning
-
- 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
Definitions
- the present invention relates to leather treatment agents, their production and their use for the production of soft leather.
- the manufacturing process of the leather treatment agent and its use for the production of soft leather form further subject matter of the invention.
- Component (a) is known per se.
- DE-OS-1,669,347 the esterification of alcoholic hydroxyl groups and lipophilic residues containing fat or oil-containing compounds with maleic anhydride.
- EP-A-193 832 also discloses the separate use of a component (a) and a component (b).
- the fatty acids of component (a) have 6 to 24, preferably 12 to 24 carbon atoms and can be saturated or unsaturated, e.g. capric, lauric, myristic, palmitic or stearic acid, or decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic, linolenic or ricinoleic acid.
- Suitable polyols of component (a) are 2- to 6-valent aliphatic alcohols having 2 to 18, preferably 2 to 12, carbon atoms. In particular, they are glycerol, trimethylolpropane, erythritol, mannitol, pentaerythritol and sorbitol.
- the dicarboxylic acids of component (a) can be aliphatically saturated, ethylenically unsaturated or aromatic. Suitable aliphatically saturated dicarboxylic acids are malonic acid, succinic acid or higher homologues such as glutaric acid, adipic acid or pimelic acid or their anhydrides.
- Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid and methylene malonic acid.
- Maleic anhydride is particularly mentioned as the anhydride of these acids.
- Suitable aromatic dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and their anhydrides.
- fatty alcohols are those with 12 to 24, preferably 12 to 22 carbon atoms. These alcohols can be saturated or unsaturated and branched or straight-chain and can be used alone or in a mixture. Natural alcohols such as e.g. Myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols, e.g. Oxo-alcohols such as, in particular, 2-ethylhexanol, furthermore trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or alfoles can be used.
- Natural alcohols such as e.g. Myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols, e.g. Oxo-alcohols such as, in particular, 2-ethylhexanol, furthermore trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or alfoles can
- the focus of interest is as component (a) a reaction product of glycerol, oleic acid and maleic anhydride or a reaction product of stearyl alcohol and maleic anhydride.
- Component (a) is prepared in a manner known per se by esterifying the reaction product from a polyol and a fatty acid as defined or from a fatty alcohol or an alkoxylated fatty alcohol as defined with a dicarboxylic acid or its anhydride, the molar ratio of polyol: fatty acid: Dicarboxylic acid (or anhydride) 1: 1: 2, especially 1: 2: 1 and preferably 1: 2: 2 and the molar ratio of fatty alcohol: dicarboxylic acid (or anhydride) is 1: 1.
- the reaction products obtained can optionally be treated with an alkali or ammonium sulfite, e.g. Na2SO3, Na2S2O5, (NH4) 2SO3 or NaHSO3 can be sulfated.
- an alkali or ammonium sulfite e.g. Na2SO3, Na2S2O5, (NH4) 2SO3 or NaHSO3 can be sulfated.
- component (b) The synthetic aromatic tannins of component (b) are known per se, e.g. from Ullmann's Encyclopedia of Industrial Chemistry Vol. 16, (4) 138-140 (1979) or J. Partridge Chemical Treatment of Hides and Leather, Noyes Data Corporation, Park Ridge N.Y. 1972.
- aromatic tannins also called anionic aromatic syntans
- uncondensed precursors or the alkali metal and ammonium salts of these compounds are synthetic, anionic, aromatic tannins (also called anionic aromatic syntans), as well as their uncondensed precursors or the alkali metal and ammonium salts of these compounds.
- condensation products of types (I) - (III), (V) and (VII) - (X) are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, Vol. 16, (4), 140 (1979) and can be described in the The processes described there can be produced.
- reaction product of type (VI) and its preparation are known from EP-A-0245205. These reaction products can be condensed to products of type (V) by methods known per se (cf. e.g. GB-C-683084).
- the ready-to-use tanning salts that are suitable for the optional component (c) are described in the relevant specialist literature. These are usually chromium, aluminum, iron or zirconium salts. Examples of such salts are basic chromium (III) chloride or sulfate, a chrome alum, optionally basic aluminum chloride or sulfate, an alum, iron (III) chloride or sulfate, zirconium oxychloride and zirconium sulfate. Mixtures of the chlorine and aluminum salts mentioned are also well suited to be used as component (c).
- non-tanning substances such as acidic inorganic salts, inorganic salts in combination with organic acid, non-swelling aromatic sulfonic acid, fluorosilicates or dextrin are suitable.
- non-tanning substances such as acidic inorganic salts, inorganic salts in combination with organic acid, non-swelling aromatic sulfonic acid, fluorosilicates or dextrin are suitable.
- examples of such substances are anhydrous sodium sulfate, sodium bisulfite, chrome alum and alkali fluorosilicates.
- a sodium fluorosilicate or dextrin is preferred.
- the leather treatment composition according to the invention is produced by simply mixing components (a) and (b) and optionally (c) and (d) in the presence of water, the components being mixed at temperatures between 20 and 100 ° C., preferably 20 and 90 ° C takes place. The homogeneous mixture obtained is then dried or spray dried to a powder.
- the leather treatment composition according to the invention advantageously contains, based on the total composition, 10 to 40, preferably 25 to 35% by weight of component (a), 20 to 80, preferably 60 to 70% by weight of component (b), 0 to 50, preferably 0 to 35% by weight of component (c), 0 to 20, preferably 0 to 15% by weight of component (d), and ad 100% water.
- the new treatment agents according to the invention are particularly suitable for the production of soft leathers.
- the present application accordingly also relates to a method for treating leather.
- the process is characterized in that the treatment of these materials is carried out before or very particularly after the dyeing with the leather treatment agent according to the invention.
- the conventional methods are used to treat pale or pretanned leather with an aqueous solution which contains the treatment agent according to the invention and then treat the material thus treated in the usual way, e.g. by neutralizing, washing out, greasing and drying. If desired, staining can be done.
- 50 to 300, preferably 140 to 180 parts by weight of water and 5 to 40 parts by weight of the treatment agent according to the invention are used per 100 parts by weight of leather or leather.
- 100 parts by weight of descaled, preferably decalcified are tanned with 140 to 160 parts by weight of water and 10 to 20 parts of the treatment agent according to the invention, or 100 parts by weight in a conventional manner, chrome-tanned leather neutralized with, for example, formates or bicarbonates, with 140 to 160 parts by weight of water and 5 to 15 parts retanned the treatment agent according to the invention.
- the tanned material is rinsed and, if necessary, subsequently greased with a commercially available fatliquor based on, for example, sulfonated fish oil, sperm oil or claw oil. After drying, a light, brilliant leather is obtained, which has good lightfastness, a firm, compact, smooth grain and a soft handle.
- glycerol monooleate maleate (technical) prepared according to Example 1 are (technically) in a solution of 77.3 parts of sodium salt of polyhydroxypolyphenylsulfonic sulfonic acid, 146 parts of chromium salt, which contains 81.45 parts of Cr (OH) SO4 (corresponding to 25.62 parts of chromium), and 130 parts of water.
- This mixture is sprayed into a dry powder. This gives 288.3 parts of a powder which contains 77.3 parts of phenolic tanning agent, 146 parts of chromium salt, 55 parts of fatliquor and 10 parts of water.
- the viscous emulsion obtained is mixed with a solution of 170 parts of polyhydroxypolyphenylsulfonic sulfonic acid, 40 parts of water and 110 parts of 48% sodium hydroxide solution. This mixture is sprayed into a dry powder. This gives 291 parts of a powder which contains 196 parts of phenolic tanning agent, 90 parts of fatliquor and 5 parts of water.
- 100 parts of decalcified veal pellet are treated with 150 parts of water and 10 parts of the composition prepared according to Example 2 for 24 hours at 20 ° C. in a rolling barrel. After about 10 hours of storage, stretching and then hanging drying, you get an excellent soft leather with a slim handle and good volume.
- the leather After washing out 100 parts of folded, neutralized chrome grain calf leather, the leather is washed with 1 part of the leather dye C.I. Acid Brown 189, dyed at 50 ° C. for 20 minutes, then aftertreated with 10 parts of the composition prepared according to Example 1 for 1 hour at 50 ° C. After acidification with 0.5 part of 85% formic acid, store for 10 hours, stretch out, vacuum dry, 1 minute at 75 ° C and then hang dry, without further softening a brown colored, brilliant soft leather with good fullness is obtained.
- the leather dye C.I. Acid Brown 189 dyed at 50 ° C. for 20 minutes
- 10 parts of the composition prepared according to Example 1 for 1 hour at 50 ° C.
- After acidification with 0.5 part of 85% formic acid store for 10 hours, stretch out, vacuum dry, 1 minute at 75 ° C and then hang dry, without further softening a brown colored, brilliant soft leather with good fullness is obtained.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die vorliegende Erfindung betrifft Lederbehandlungsmittel, deren Herstellung sowie deren Verwendung zur Herstellung von weichen Ledern.The present invention relates to leather treatment agents, their production and their use for the production of soft leather.
Das erfindungsgemässe Lederbehandlungsmittel ist dadurch gekennzeichnet, dass es
- (a) ein gegebenenfalls sulfiertes Umsetzungsprodukt aus einer gesättigten oder ungesättigten Fettsäure mit 6 bis 24 C-Atomen, einem Polyol mit 2 bis 18 C-Atomen und einer aliphatischen oder aromatischen Dicarbonsäure bzw. deren Anhydrid oder aus einem gegebenenfalls alkoxylierten Fettalkohol mit 12 bis 24 C-Atomen und einer Dicarbonsäure bzw. deren Anhydrid,
- (b) einen synthetischen aromatischen Gerbstoff oder dessen nicht kondensiertes Vorprodukt bzw. dessen Alkalimetall- oder Ammoniumsalz und gegebenenfalls
- (c) ein wasserlösliches Chrom-, Aluminium-, Eisen- oder Zirkoniumsalz oder deren Gemische und
- (d) ein Konditioniermittel
- (a) an optionally sulfated reaction product of a saturated or unsaturated fatty acid with 6 to 24 C atoms, a polyol with 2 to 18 C atoms and an aliphatic or aromatic dicarboxylic acid or its anhydride or from an optionally alkoxylated fatty alcohol with 12 to 24 Carbon atoms and a dicarboxylic acid or its anhydride,
- (b) a synthetic aromatic tanning agent or its uncondensed precursor or its alkali metal or ammonium salt and optionally
- (c) a water-soluble chromium, aluminum, iron or zirconium salt or mixtures thereof and
- (d) a conditioning agent
Das Herstellungsverfahren des Lederbehandlungsmittels und seine Verwendung zur Herstellung von weichen Ledern bilden weitere Erfindungsgegenstände.The manufacturing process of the leather treatment agent and its use for the production of soft leather form further subject matter of the invention.
Die Komponente (a) ist an sich bekannt. So beschreibt z.B. die DE-OS-1,669,347 die Veresterung von alkoholischen Hydroxylgruppen sowie lipophile Reste enthaltenden fett- oder ölhaltigen Verbindungen mit Maleinsäureanhydrid. Aus der EP-A-193 832 ist auch die separate Verwendung einer Komponente (a) und eine Komponente (b) bekannt.Component (a) is known per se. For example, DE-OS-1,669,347 the esterification of alcoholic hydroxyl groups and lipophilic residues containing fat or oil-containing compounds with maleic anhydride. EP-A-193 832 also discloses the separate use of a component (a) and a component (b).
Die Fettsäuren der Komponente (a) weisen 6 bis 24, vorzugsweise 12 bis 24 Kohlenstoffatome auf und können gesättigt oder ungesättigt sein, wie z.B. die Caprin-, Laurin-, Myristin-, Palmitin- oder Stearinsäure, bzw. die Decen-, Dodecen-, Tetradecen-, Hexadecen-, Oel-, Linol-, Linolen- oder Rizinolsäure.The fatty acids of component (a) have 6 to 24, preferably 12 to 24 carbon atoms and can be saturated or unsaturated, e.g. capric, lauric, myristic, palmitic or stearic acid, or decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic, linolenic or ricinoleic acid.
Geeignete Polyole der Komponente (a) stellen 2- bis 6-wertige aliphatische Alkohole mit 2 bis 18, vorzugsweise 2 bis 12 Kohlenstoffatomen dar. Es sind insbesondere Glycerin, Trimethylolpropan, Erythrit, Mannit, Pentaerythrit und Sorbit. Die Dicarbonsäuren der Komponente (a) können aliphatisch gesättigt, ethylenisch ungesättigt oder aromatisch sein. Als aliphatisch gesättigte Dicarbonsäuren kommen die Malonsäure, Bernsteinsäure oder höhere Homologe wie die Glutarsäure, Adipinsäure oder Pimelinsäure oder ihre Anhydride in Betracht. Ethylenisch ungesättigte Dicarbonsäuren sind vorzugsweise die Fumarsäure, Maleinsäure oder Itaconsäure, ferner die Mesaconsäure, Citraconsäure, Glutaconsäure und Methylenmalonsäure. Als Anhydrid dieser Säuren sei insbesondere Maleinsäurenanhydrid genannt. Als aromatische Dicarbonsäure kommen die Phthalsäure, Isophthalsäure, Terephthalsäure sowie ihre Anhydride in Betracht.Suitable polyols of component (a) are 2- to 6-valent aliphatic alcohols having 2 to 18, preferably 2 to 12, carbon atoms. In particular, they are glycerol, trimethylolpropane, erythritol, mannitol, pentaerythritol and sorbitol. The dicarboxylic acids of component (a) can be aliphatically saturated, ethylenically unsaturated or aromatic. Suitable aliphatically saturated dicarboxylic acids are malonic acid, succinic acid or higher homologues such as glutaric acid, adipic acid or pimelic acid or their anhydrides. Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid and methylene malonic acid. Maleic anhydride is particularly mentioned as the anhydride of these acids. Suitable aromatic dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and their anhydrides.
Als definitionsgemässe Fettalkohole kommen solche mit 12 bis 24, vorzugsweise 12 bis 22 Kohlenstoffatomen in Betracht. Diese Alkohole können gesättigt oder ungesättigt und verzweigt oder geradkettig sein und können allein oder im Gemisch eingesetzt werden. Es können ferner natürliche Alkohole wie z.B. Myristylalkohol, Cetylalkohol, Stearylalkohol oder Oleylalkohol oder synthetische Alkohole, z.B. Oxo-Alkohole wie insbesondere 2-Ethylhexanol, ferner Trimethylhexanol, Trimethylnonylalkohol, Hexadecylalkohol oder Alfole verwendet werden.As definition fatty alcohols are those with 12 to 24, preferably 12 to 22 carbon atoms. These alcohols can be saturated or unsaturated and branched or straight-chain and can be used alone or in a mixture. Natural alcohols such as e.g. Myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols, e.g. Oxo-alcohols such as, in particular, 2-ethylhexanol, furthermore trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or alfoles can be used.
Im Vordergrund des Interesses steht als Komponente (a) ein Umsetzungsprodukt aus Glycerin, Oelsäure und Maleinsäureanhydrid bzw. ein Umsetzungsprodukt aus Stearylalkohol und Maleinsäureanhydrid.The focus of interest is as component (a) a reaction product of glycerol, oleic acid and maleic anhydride or a reaction product of stearyl alcohol and maleic anhydride.
Die Herstellung der Komponente (a) erfolgt in an sich bekannter Weise durch Veresterung des Umsetzungsproduktes aus einem definitionsgemässen Polyol und einer Fettsäure oder aus einem definitionsgemässen Fettalkohol bzw. einem alkoxylierten Fettalkohol mit einer definitionsgemässen Dicarbonsäure bzw. deren Anhydrid, wobei das Molverhältnis Polyol:Fettsäure:Dicarbonsäure (bzw. Anhydrid) 1:1:2, besonders 1:2:1 und vorzugsweise 1:2:2 und das Molverhältnis Fettalkohol:Dicarbonsäure (bzw. Anhydrid) 1:1 beträgt. Die erhaltenen Umsetzungsprodukte können gegebenenfalls mit einem Alkali- oder Ammoniumsulfit, z.B. Na₂SO₃, Na₂S₂O₅, (NH₄)₂SO₃ oder NaHSO₃ sulfiert werden.Component (a) is prepared in a manner known per se by esterifying the reaction product from a polyol and a fatty acid as defined or from a fatty alcohol or an alkoxylated fatty alcohol as defined with a dicarboxylic acid or its anhydride, the molar ratio of polyol: fatty acid: Dicarboxylic acid (or anhydride) 1: 1: 2, especially 1: 2: 1 and preferably 1: 2: 2 and the molar ratio of fatty alcohol: dicarboxylic acid (or anhydride) is 1: 1. The reaction products obtained can optionally be treated with an alkali or ammonium sulfite, e.g. Na₂SO₃, Na₂S₂O₅, (NH₄) ₂SO₃ or NaHSO₃ can be sulfated.
Die synthetischen aromatischen Gerbstoffe der Komponente (b) sind an sich bekannt, z.B. aus Ullmanns Enzyklopädie der technischen Chemie Bd. 16, (4) 138-140 (1979) oder J. Partridge Chemical Treatment of Hides and Leather, Noyes Data Corporation, Park Ridge N.Y. 1972.The synthetic aromatic tannins of component (b) are known per se, e.g. from Ullmann's Encyclopedia of Industrial Chemistry Vol. 16, (4) 138-140 (1979) or J. Partridge Chemical Treatment of Hides and Leather, Noyes Data Corporation, Park Ridge N.Y. 1972.
Von besonderer Bedeutung sind synthetische, anionische, aromatische Gerbstoffe (auch anionische aromatische Syntane genannt), sowie deren nicht kondensierte Vorprodukte bzw. die Alkalimetall- und Ammoniumsalze dieser Verbindungen.Of particular importance are synthetic, anionic, aromatic tannins (also called anionic aromatic syntans), as well as their uncondensed precursors or the alkali metal and ammonium salts of these compounds.
Als Vorprodukte kommen z.B. Naphthalin, Diphenyl, Terphenyl, Phenole, Kresole, 4,4′-Dihydroxidiphenylsulfon, β-Naphthol, Dihydroxibenzole, Resorcin, 2,2′-Bis-(hydroxyphenyl)-propan und Diarylether wie Diphenylether und Ditolylether in Betracht, die in an sich bekannter Weise zu den anionischen nicht kondensierten Vorprodukten sulfoniert werden.As preliminary products e.g. Naphthalene, diphenyl, terphenyl, phenols, cresols, 4,4'-dihydroxy diphenyl sulfone, β-naphthol, dihydroxy benzenes, resorcinol, 2,2'-bis (hydroxyphenyl) propane and diaryl ethers such as diphenyl ether and ditolyl ether are considered in themselves be sulfonated in a known manner to form the anionic uncondensed precursors.
Als anionische aromatische Syntane sind jene zu erwähnen, welche durch Kondensation der sulfonierten Vorprodukte allein oder zusammen mit weiteren, meist unsulfonierten Vorprodukten mit Formaldehyd und/oder Harnstoff erhältlich sind, wie z.B.
- (I) Kondensationsprodukte aus sulfoniertem Phenol oder Kresol und Formaldehyd,
- (II) Kondensationsprodukte aus Naphthalinsulfonsäure und Formaldehyd,
- (III) Formaldehyd-Kondensationsprodukte von 4,4′-Dihydroxydiphenylsulfonen mit (Hydroxy)arylsulfonsäuren,
- (IV) Formaldehyd-Kondensationsprodukte von sulfogruppenhaltigen aromatischen Hydroxyverbindungen mit Aralkylhalogeniden,
- (V) Harnstoff-Formaldehyd-Kondensationsprodukte von Phenolen und Phenolsulfonsäuren,
- (VI) Umsetzungsprodukt aus Phenol und einem Sulfonierungsmittel, wobei das Molverhältnis (Phenol):(SO₃) (1):(1,1-2,2) beträgt.
- (VII) Kondensationsprodukte aus sulfonierten Diarylethern und Formaldehyd,
- (VIII) Kondensationsprodukte aus sulfonierten Di- oder Terphenylen und Formaldehyd,
- (IX) Kondensationsprodukte aus 4,4′-Dihydroxydiphenylsulfon und sulfoniertem 4,4′-Dihydroxydiphenylsulfon mit Formaldehyd und
- (X) Formaldehyd-Kondensationsprodukte aus Diarylethersulfonsäure und 4,4′-Dihydroxydiphenylsulfon.
- (I) condensation products of sulfonated phenol or cresol and formaldehyde,
- (II) condensation products of naphthalenesulfonic acid and formaldehyde,
- (III) formaldehyde condensation products of 4,4'-dihydroxydiphenyl sulfones with (hydroxy) aryl sulfonic acids,
- (IV) formaldehyde condensation products of sulfo-containing aromatic hydroxy compounds with aralkyl halides,
- (V) urea-formaldehyde condensation products of phenols and phenolsulfonic acids,
- (VI) reaction product of phenol and a sulfonating agent, the molar ratio (phenol) :( SO₃) (1) :( 1.1-2.2).
- (VII) condensation products from sulfonated diaryl ethers and formaldehyde,
- (VIII) condensation products of sulfonated di- or terphenylene and formaldehyde,
- (IX) condensation products of 4,4'-dihydroxydiphenyl sulfone and sulfonated 4,4'-dihydroxydiphenyl sulfone with formaldehyde and
- (X) formaldehyde condensation products from diaryl ether sulfonic acid and 4,4'-dihydroxydiphenyl sulfone.
Die Kondensationsprodukte der Typen (I)-(III), (V) und (VII)-(X) sind z.B. aus Ullmanns Enzyklopädie der technischen Chemie Bd. 16, (4), 140 (1979) bekannt und können nach den in den dort angegebenen Referenzen beschriebenen Verfahren hergestellt werden.The condensation products of types (I) - (III), (V) and (VII) - (X) are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, Vol. 16, (4), 140 (1979) and can be described in the The processes described there can be produced.
Kondensationsprodukte des Typs (IV) und deren Herstellung sind aus GB-C-986621 bekannt.Condensation products of type (IV) and their preparation are known from GB-C-986621.
Kondensationsprodukte des Typs (V) und deren Herstellung sind aus GB-C-890150 und 935678 bekannt.Condensation products of type (V) and their production are known from GB-C-890150 and 935678.
Das Umsetzungsprodukt des Typs (VI) und dessen Herstellung sind aus EP-A-0245205 bekannt. Diese Umsetzungsprodukte können nach an sich bekannten Methoden zu Produkten des Typs (V) kondensiert werden (vgl. z.B. GB-C-683084).The reaction product of type (VI) and its preparation are known from EP-A-0245205. These reaction products can be condensed to products of type (V) by methods known per se (cf. e.g. GB-C-683084).
Die für die fakultative Komponente (c) in Betracht kommenden gebrauchsfertigen Gerbesalze sind in der einschlägigen Fachliteratur beschrieben. Es handelt sich hierbei in der Regel um Chrom-, Aluminium-, Eisen- oder Zirkoniumsalze. Als Beispiele solcher Salze sei basisches Chrom(III)-chlorid oder -sulfat, ein Chromalaun, gegebenenfalls basisches Aluminiumchlorid oder -sulfat, ein Alaun, Eisen(III)-chlorid oder -sulfat, Zirkonoxychlorid und Zirkoniumsulfat genannt. Auch Gemische der genannten Chlor- und Aluminiumsalze eignen sich gut dazu, als Komponente (c) eingesetzt zu werden. Bevorzugt sind indessen [CrCl₂(OH₂)₄]Cl·2 H₂O, [Cr(OH₂)₆]Cl₃, Cr(OH)SO₄, Cr₂(OH)₄SO₄, KCr(SO₄)₂·12 H₂O und Fe₂(SO₄)₃·9 H₂O.The ready-to-use tanning salts that are suitable for the optional component (c) are described in the relevant specialist literature. These are usually chromium, aluminum, iron or zirconium salts. Examples of such salts are basic chromium (III) chloride or sulfate, a chrome alum, optionally basic aluminum chloride or sulfate, an alum, iron (III) chloride or sulfate, zirconium oxychloride and zirconium sulfate. Mixtures of the chlorine and aluminum salts mentioned are also well suited to be used as component (c). Preferred are, however, [CrCl₂ (OH₂) ₄] Cl · 2 H₂O, [Cr (OH₂) ₆] Cl₃, Cr (OH) SO₄, Cr₂ (OH) ₄SO₄, KCr (SO₄) ₂ · 12 H₂O and Fe₂ (SO₄) ₃ · 9 H₂O.
Sofern die fakultative Komponente (d) in dem erfindungsgemässen Lederbehandlungsmittel mitverwendet wird, kommen nicht gerbende Stoffe in Betracht wie saure anorganische Salze, anorganische Salze in Verbindung mit organischer Säure, nichtschwellende aromatische Sulfonsäure, Fluorsilikate oder Dextrin. Beispiele für solche Stoffe sind wasserfreies Natriumsulfat, Natriumbisulfit, Chromalaun und Alkalifluorsilikate. Bevorzugt kommt ein Natriumfluorsilikat oder Dextrin in Betracht.If the optional component (d) is also used in the leather treatment composition according to the invention, non-tanning substances such as acidic inorganic salts, inorganic salts in combination with organic acid, non-swelling aromatic sulfonic acid, fluorosilicates or dextrin are suitable. Examples of such substances are anhydrous sodium sulfate, sodium bisulfite, chrome alum and alkali fluorosilicates. A sodium fluorosilicate or dextrin is preferred.
Die Herstellung des erfindungsgemässen Lederbehandlungsmittels erfolgt durch einfaches Mischen der Komponenten (a) und (b) und gegebenenfalls (c) und (d) in Gegenwart von Wasser, wobei das Mischen der Komponenten bei Temperaturen zwischn 20 und 100°C, vorzugsweise 20 und 90°C erfolgt. Die erhaltene homogene Mischung wird anschliessend getrocknet bzw. zu einem Pulver sprühgetrocknet.The leather treatment composition according to the invention is produced by simply mixing components (a) and (b) and optionally (c) and (d) in the presence of water, the components being mixed at temperatures between 20 and 100 ° C., preferably 20 and 90 ° C takes place. The homogeneous mixture obtained is then dried or spray dried to a powder.
Das erfindungsgemässe Lederbehandlungsmittel enthält mit Vorteil, bezogen auf das gesamte Mittel,
10 bis 40, vorzugsweise 25 bis 35 Gew.-% der Komponente (a),
20 bis 80, vorzugsweise 60 bis 70 Gew.-% der Komponente (b),
0 bis 50, vorzugsweise 0 bis 35 Gew.-% der Komponente (c),
0 bis 20, vorzugsweise 0 bis 15 Gew.-% der Komponente (d),
und ad 100 % Wasser.The leather treatment composition according to the invention advantageously contains, based on the total composition,
10 to 40, preferably 25 to 35% by weight of component (a),
20 to 80, preferably 60 to 70% by weight of component (b),
0 to 50, preferably 0 to 35% by weight of component (c),
0 to 20, preferably 0 to 15% by weight of component (d),
and ad 100% water.
Die neuen, erfindungsgemässen Behandlungsmittel eignen sich besonders zur Herstellung von weichen Ledern.The new treatment agents according to the invention are particularly suitable for the production of soft leathers.
Gegenstand der vorliegenden Anmeldung ist demnach auch ein Verfahren zur Behandlung von Ledern. Das Verfahren ist dadurch gekennzeichnet, dass man die Behandlung dieser Materialien vor, oder ganz besonders nach der Färbung mit dem erfindungsgemässen Lederbehandlungsmittel vornimmt.The present application accordingly also relates to a method for treating leather. The process is characterized in that the treatment of these materials is carried out before or very particularly after the dyeing with the leather treatment agent according to the invention.
Hierbei geht man nach konventionellen Methoden so vor, dass man Blösse oder vorgegerbtes Leder mit einer wässrigen Lösung behandelt, welche das erfindungsgemässe Behandlungsmittel enthält und anschliessend das so behandelte Material auf übliche Weise z.B. durch Neutralisieren, Auswaschen, Fetten und Trocknen fertigstellt. Falls erwünscht, kann eine Färbung durchgeführt werden. In der Regel werden auf 100 Gewichtsteile Blösse oder Leder 50 bis 300, vorzugsweise 140 bis 180 Gewichtsteile Wasser und 5 bis 40 Gewichtsteile des erfindungsgemässen Behandlungsmittels eingesetzt.The conventional methods are used to treat pale or pretanned leather with an aqueous solution which contains the treatment agent according to the invention and then treat the material thus treated in the usual way, e.g. by neutralizing, washing out, greasing and drying. If desired, staining can be done. As a rule, 50 to 300, preferably 140 to 180 parts by weight of water and 5 to 40 parts by weight of the treatment agent according to the invention are used per 100 parts by weight of leather or leather.
Im Einzelnen werden 100 Gewichtsteile vorzugsweise entkalkte Blösse mit 140 bis 160 Gewichtsteilen Wasser und 10 bis 20 Teilen des erfindungsgemässen Behandlungsmittels gegerbt oder 100 Gewichtsteile auf übliche Art und Weise mit z.B. Formiaten oder Bicarbonaten neutralisiertes chromgegerbtes Leder mit 140 bis 160 Gewichtsteilen Wasser und 5 bis 15 Teilen des erfindungsgemässen Behandlungsmittels nachgegerbt. Das gegerbte Material wird nachgespült und gegebenenfalls anschliessend mit einem handelsüblichen Fettungsmittel auf der Basis von z.B. sulfoniertem Fischöl, Spermöl oder Klauenöl gefettet. Nach dem Trocknen erhält man ein helles, brillantes Leder, welches eine gute Lichtechtheit, einen festen, kompakten, glatten Narben und einen weichen Griff aufweist.Specifically, 100 parts by weight of descaled, preferably decalcified, are tanned with 140 to 160 parts by weight of water and 10 to 20 parts of the treatment agent according to the invention, or 100 parts by weight in a conventional manner, chrome-tanned leather neutralized with, for example, formates or bicarbonates, with 140 to 160 parts by weight of water and 5 to 15 parts retanned the treatment agent according to the invention. The tanned material is rinsed and, if necessary, subsequently greased with a commercially available fatliquor based on, for example, sulfonated fish oil, sperm oil or claw oil. After drying, a light, brilliant leather is obtained, which has good lightfastness, a firm, compact, smooth grain and a soft handle.
Die in den nachfolgenden Beispielen angegebenen Prozente und Teile beziehen sich stets auf das Gewicht.The percentages and parts given in the examples below always relate to the weight.
83 Teile (0,215 Mol) Glycerinmonooleat (technisch) werden in einem mit Stickstoffspülung, Rührung und Thermometer versehenen 750 ml Sulfierkolben vorgelegt und bei 85°C mit 21 Teilen (0,215 Mol) Maleinsäureanhydrid versetzt. Nach dem Aufschmelzen des Anhydrids wird noch 1 Stunde bei 100°C gehalten. Der entstandene Maleinsäurehalbester wird bei ca. 60°C in eine Lösung aus 300 Teilen Polyhydroxypolyphenylsulfonsulfonsäure (vgl. EP-A- 0 245 205), 100 Teilen Wasser und 118 Teilen 48%-ige Natronlauge gegehen. Diese Mischung wird zu einem trockenen Pulver versprüht. Man erhält 442,3 Teile eines Pulvers, das 324 Teile phenolischen Gerbstoff, 108,3 Teile Fettungsmittel und 10 Teile Wasser enthält.83 parts (0.215 mol) of glycerol monooleate (technical) are placed in a 750 ml sulfonation flask equipped with nitrogen flushing, stirring and a thermometer, and 21 parts (0.215 mol) of maleic anhydride are added at 85.degree. After the anhydride has melted, the mixture is kept at 100 ° C. for 1 hour. The resulting maleic acid half-ester is dissolved in a solution of 300 parts of polyhydroxypolyphenylsulfone sulfonic acid (cf. EP-A-0 245 205), 100 parts of water and 118 parts of 48% sodium hydroxide solution at about 60 ° C. This mixture is sprayed into a dry powder. This gives 442.3 parts of a powder which contains 324 parts of phenolic tanning agent, 108.3 parts of fatliquor and 10 parts of water.
55 Teile des nach Beispiel 1 hergestellten Glycerinmonooleatmaleinsäurehalbesters (technisch) werden in eine Lösung aus 77,3 Teilen Natriumsalz von Polyhydroxypolyphenylsulfon-sulfonsäure, 146 Teilen Chromsalz, das 81,45 Teile Cr(OH)SO₄ (entsprechend 25,62 Teilen Chrom) enthält, und 130 Teilen Wasser gegeben. Diese Mischung wird zu einem trockenen Pulver versprüht. Man erhält 288,3 Teile eines Pulvers, das 77,3 Teile phenolischen Gerbstoff, 146 Teile Chromsalz, 55 Teile Fettungsmittel und 10 Teile Wasser enthält.55 parts of the glycerol monooleate maleate (technical) prepared according to Example 1 are (technically) in a solution of 77.3 parts of sodium salt of polyhydroxypolyphenylsulfonic sulfonic acid, 146 parts of chromium salt, which contains 81.45 parts of Cr (OH) SO₄ (corresponding to 25.62 parts of chromium), and 130 parts of water. This mixture is sprayed into a dry powder. This gives 288.3 parts of a powder which contains 77.3 parts of phenolic tanning agent, 146 parts of chromium salt, 55 parts of fatliquor and 10 parts of water.
50 Teile (0,18 Mol) Stearylalkohol werden in einem mit Stickstoffspülung, Rührung und Thermometer versehenen 1 l Sulfierkolben vorgelegt und bei 70°C mit 18,3 Teilen (0,18 Mol) Maleinsäureanhydrid versetzt. Nach dem Aufschmelzen wird noch 1 1/2 Stunde bei 90°C gehalten. Der entstandene Maleinsäurehalbester wird bei ca. 70°C in eine Losung von 17,6 Teilen (0,09 Mol) Natriumpyrosulfit in 163,5 Teilen Wasser und 20 Teilen 50%-iger Kalilauge gegeben und bei 90°C noch 2 Stunden gerührt. Die erhaltene dickflüssige Emulsion wird mit einer Lösung aus 170 Teilen Polyhydroxypolyphenylsulfon-sulfonsäure, 40 Teilen Wasser und 110 Teilen 48%-ige Natronlauge gemischt. Diese Mischung wird zu einem trockenen Pulver versprüht. Man erhält 291 Teile eines Pulvers, das 196 Teile phenolischen Gerbstoff, 90 Teile Fettungsmittel und 5 Teile Wasser enthält.50 parts (0.18 mol) of stearyl alcohol are placed in a 1 l sulphonation flask provided with nitrogen flushing, stirring and a thermometer, and 18.3 parts (0.18 mol) of maleic anhydride are added at 70.degree. After melting, the mixture is held at 90 ° C. for a further 1 1/2 hour. The resulting maleic acid half-ester is placed at about 70 ° C. in a solution of 17.6 parts (0.09 mol) of sodium pyrosulfite in 163.5 parts of water and 20 parts of 50% potassium hydroxide solution and stirred at 90 ° C. for a further 2 hours. The viscous emulsion obtained is mixed with a solution of 170 parts of polyhydroxypolyphenylsulfonic sulfonic acid, 40 parts of water and 110 parts of 48% sodium hydroxide solution. This mixture is sprayed into a dry powder. This gives 291 parts of a powder which contains 196 parts of phenolic tanning agent, 90 parts of fatliquor and 5 parts of water.
108,3 Teile des nach Beispiel 1 hergestellten Natriumsalzes von Glycerinmonooleatmaleinsäurehalbester (technisch) werden in einer Mischung aus 348 Teilen eines Natriumsalzes von Formaldehyd-Polyhydroxypolyphenylsulfon-sulfonsäure-Kondensat (vgl. DP-C-961 351), 70 Teilen Natriumfluorsilikat und 300 Teilen Wasser gegeben. Diese Mischung wird zu einem trockenen Pulver versprüht. Man erhält 546,3 Teile eines Pulvers, das 348 Teile phenolischen Gerbstoff, 108,3 Teile Fettungsmittel, 70 Teile Natriumfluorsilikat und 20 Teile Wasser enthält.108.3 parts of the sodium salt of glycerol monooleate maleate (technical) prepared according to Example 1 are mixed in a mixture of 348 parts of a sodium salt of formaldehyde-polyhydroxypolyphenylsulfone-sulfonic acid condensate (cf. DP-C-961 351), 70 parts of sodium fluorosilicate and 300 parts of water given. This mixture is sprayed into a dry powder. This gives 546.3 parts of a powder which contains 348 parts of phenolic tanning agent, 108.3 parts of fatliquor, 70 parts of sodium fluorosilicate and 20 parts of water.
114 Teile (0,30 Mol) Sorbitmonolaurat (technisch) werden in einem mit Stickstoffspülung, Rührung und Thermometer versehenen 750 ml Sulfierkolben vorgelegt und bei 95°C mit 30 Teilen (0,30 Mol) Bernsteinsäureanhydrid versetzt. Nach dem Aufschmelzen des Anhydrids wird noch 1 Stunde bei 100°C gehalten. Der entstandene Bernsteinsäurehalbester wird bei 60°C in eine Lösung aus 340 Teilen Polyhydroxypolyphenylsulfonsäure (vgl. EP. A-0 245 205), 150 Teilen Wasser und ca 162 Teilen 48 %-ige Natronlauge gegeben. Diese Mischung wird einem trockenen Pulver versprüht. Man erhält 535 Teile eines Pulvers, das 367 Teile phenolischen Gerbstoff, 156 Teile Fettungsmittel und 12 Teile Wasser enthält.114 parts (0.30 mol) of sorbitol monolaurate (technical) are placed in a 750 ml sulfonation flask equipped with nitrogen flushing, stirring and a thermometer, and 30 parts (0.30 mol) of succinic anhydride are added at 95.degree. After the anhydride has melted, the mixture is kept at 100 ° C. for 1 hour. The resulting succinic acid half-ester is placed at 60 ° C. in a solution of 340 parts of polyhydroxypolyphenylsulfonic acid (cf. EP. A-0 245 205), 150 parts of water and approx. 162 parts of 48% sodium hydroxide solution. This mixture is sprayed onto a dry powder. This gives 535 parts of a powder which contains 367 parts of phenolic tanning agent, 156 parts of fatliquor and 12 parts of water.
100 Teile entkalkte Kalbsblösse werden mit 150 Teilen Wasser und 10 Teilen der gemäss Beispiel 2 hergestellten Zusammensetzung während 24 Stunden bei 20°C im rollenden Fass behandelt. Nach ca. 10 Stunden lagern, ausrecken und anschliessendem Hängetrocknen erhält man ein hervorragendes weiches Leder mit schmalzigem Griff und guter Fülle.100 parts of decalcified veal pellet are treated with 150 parts of water and 10 parts of the composition prepared according to Example 2 for 24 hours at 20 ° C. in a rolling barrel. After about 10 hours of storage, stretching and then hanging drying, you get an excellent soft leather with a slim handle and good volume.
Nach dem Auswaschen von 100 Teilen gefalztem, neutralisiertem Chromnarbenkalbsleder wird das Leder mit 1 Teil des Lederfarbstoffes C.I. Acid Brown 189, 20 Minuten bei 50°C gefärbt dann mit 10 Teilen der gemäss Beispiel 1 hergestellten Zusammensetzung während 1 Stunde bei 50°C nachbehandelt. Nach Ansäuern mit 0,5 Teilen 85%-iger Ameisensäure, 10 Stunden lagern, ausrecken, vakuumantrocknen, 1 Minute bei 75°C und anschliessendem Hängetrocknen erhält man ohne weitere Weichmachung ein braun gefärbtes, brillantes weiches Leder mit guter Fülle.After washing out 100 parts of folded, neutralized chrome grain calf leather, the leather is washed with 1 part of the leather dye C.I. Acid Brown 189, dyed at 50 ° C. for 20 minutes, then aftertreated with 10 parts of the composition prepared according to Example 1 for 1 hour at 50 ° C. After acidification with 0.5 part of 85% formic acid, store for 10 hours, stretch out, vacuum dry, 1 minute at 75 ° C and then hang dry, without further softening a brown colored, brilliant soft leather with good fullness is obtained.
Claims (21)
- A leather treatment composition which comprises(a) a reaction product or sulfonated reaction product of a saturated or unsaturated fatty acid of 6 to 24 carbon atoms, a polyol of 2 to 18 carbon atoms, and an aliphatic or aromatic dicarboxylic acid or the anhydride thereof, or of a fatty alcohol of 12 to 24 carbon atoms or alkoxylated fatty alcohol of 12 to 24 carbon atoms and a dicarboxylic acid or the anhydride thereof.(b) a synthetic aromatic tanning agent or the non-condensed precursor thereof or the alkali metal salt or ammonium salt thereof, and, as additional optional components(c) a water-soluble chromium, aluminium, iron or zirconium salt or a mixture thereof, and(d) a conditioning agent.
- A leather treatment composition according to claim 1, wherein, in component (a), the fatty acid contains 12 to 14 carbon atoms, the polyol 2 to 12 carbon atoms and the fatty alcohol 12 to 24 carbon atoms.
- A leather treatment composition according to claim 1, wherein component (a) is a reaction product of glycerol, oleic acid and maleic anhydride.
- A leather treatment composition according to claim 1, wherein component (a) is a reaction product of stearyl alcohol and maleic anhydride.
- A leather treatment composition according to claim 1, wherein component (b) is a synthetic anionic aromatic tanning agent or the non-condensed precursor thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a condensate of sulfonated phenol or cresol and formaldehyde, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a condensate of naphthalenesulfonic acid and formaldehyde, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a formaldehyde condensate of a 4,4'-dihydroxydiphenyl sulfone with a (hydroxy)arylsulfonic acid, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a formaldehyde condensate of a sulfo-containing aromatic hydroxyl compound with an aralkyl halide, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a urea/formaldehyde condensate of a phenol or phenolsulfonic acid, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a condensate of a sulfonated diaryl ether and formaldehyde, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a condensate of a sulfonated diphenyl or terphenyl and formaldehyde, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a condensate of 4,4'-dihydroxydiphenyl sulfone and sulfonated 4,4'-dihydroxydiphenyl sulfone with formaldehyde, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a condensate of diaryl ether sulfonic acid and 4,4'-dihydroxydiphenyl sulfone and formaldehyde, or the alkali metal salt or ammonium salt thereof.
- A leather treatment composition according to claim 5, wherein component (b) is a reaction product of phenol and a sulfonating agent, or the alkali metal salt or ammonium salt thereof, the molar ratio of (phenol):(SO₃) being (1):(1.1-2.2).
- A leather treatment composition according to claim 1, which contains a chromium salt as optional component (c).
- A leather treatment composition according to claim 1, which comprises
10 to 40 % by weight of component (a),
20 to 80 % by weight of component (b),
0 to 50 % by weight of component (c), and
0 to 20 % by weight of component (d), and
water to make up 100 % by weight. - Use of a leather treatment composition according to any one of claims 1 to 17 for making soft leathers.
- A process for treating leathers, which comprises treating these materials, during or after dyeing, with a composition which comprises(a) a reaction product or sulfonated reaction product of a saturated or unsaturated fatty acid of 6 to 24 carbon atoms, a polyol of 2 to 18 carbon atoms, and an aliphatic or aromatic dicarboxylic acid or the anhydride thereof, or of a fatty alcohol of 12 to 24 carbon atoms or alkoxylated fatty alcohol of 12 to 24 carbon atoms and a dicarboxylic acid or the anhydride thereof.(b) a synthetic aromatic tanning agent or the non-condensed precursor thereof or the alkali metal salt or ammonium salt thereof, and, as additional optional components(c) a water-soluble chromium, aluminium, iron or zirconium salt or a mixture thereof, and(d) a conditioning agent.
- A process according to claim 19, wherein treatment with the composition is carried out after dyeing.
- Leather treated according to either claim 19 or claim 20.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3613/88 | 1988-09-28 | ||
| CH361388 | 1988-09-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0362134A2 EP0362134A2 (en) | 1990-04-04 |
| EP0362134A3 EP0362134A3 (en) | 1992-01-08 |
| EP0362134B1 true EP0362134B1 (en) | 1994-11-30 |
Family
ID=4259749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89810707A Expired - Lifetime EP0362134B1 (en) | 1988-09-28 | 1989-09-19 | Leather treating agent |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0362134B1 (en) |
| JP (1) | JPH02133500A (en) |
| KR (1) | KR900004943A (en) |
| AR (1) | AR245225A1 (en) |
| BR (1) | BR8904924A (en) |
| DE (1) | DE58908686D1 (en) |
| ES (1) | ES2064485T3 (en) |
| MX (1) | MX170257B (en) |
| PT (1) | PT91819B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948714B (en) * | 2010-09-13 | 2012-05-30 | 四川亭江新材料股份有限公司 | Method for preparing cation synthetic sperm oil fat liquor |
| CN103290148B (en) * | 2013-06-13 | 2015-06-24 | 浙江金鑫皮革有限公司 | Process for making goat denim line simulated upper leather |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1669347A1 (en) * | 1967-03-25 | 1971-05-06 | Henkel & Cie Gmbh | Process for greasing leather |
| FR2348975A1 (en) * | 1976-04-23 | 1977-11-18 | Jallatte Sa | Alkali resistant leather prodn. in three stage treatment - by retanning, nourishing and waterproofing |
| DE3419405A1 (en) * | 1984-05-24 | 1985-11-28 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING LEATHER AND FURS |
| DE3507241A1 (en) * | 1985-03-01 | 1986-09-04 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING WATERPROOF LEATHER OR FUR |
-
1989
- 1989-09-19 ES ES89810707T patent/ES2064485T3/en not_active Expired - Lifetime
- 1989-09-19 DE DE58908686T patent/DE58908686D1/en not_active Expired - Fee Related
- 1989-09-19 EP EP89810707A patent/EP0362134B1/en not_active Expired - Lifetime
- 1989-09-26 MX MX017690A patent/MX170257B/en unknown
- 1989-09-26 AR AR89315017A patent/AR245225A1/en active
- 1989-09-27 KR KR1019890013882A patent/KR900004943A/en not_active Application Discontinuation
- 1989-09-27 PT PT91819A patent/PT91819B/en not_active IP Right Cessation
- 1989-09-28 BR BR898904924A patent/BR8904924A/en not_active Application Discontinuation
- 1989-09-28 JP JP1250830A patent/JPH02133500A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| PT91819B (en) | 1995-08-09 |
| DE58908686D1 (en) | 1995-01-12 |
| KR900004943A (en) | 1990-04-13 |
| BR8904924A (en) | 1990-05-08 |
| PT91819A (en) | 1990-03-30 |
| EP0362134A2 (en) | 1990-04-04 |
| MX170257B (en) | 1993-08-12 |
| ES2064485T3 (en) | 1995-02-01 |
| AR245225A1 (en) | 1993-12-30 |
| JPH02133500A (en) | 1990-05-22 |
| EP0362134A3 (en) | 1992-01-08 |
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