EP0814168A1 - Process for tanning of leather - Google Patents
Process for tanning of leather Download PDFInfo
- Publication number
- EP0814168A1 EP0814168A1 EP97109282A EP97109282A EP0814168A1 EP 0814168 A1 EP0814168 A1 EP 0814168A1 EP 97109282 A EP97109282 A EP 97109282A EP 97109282 A EP97109282 A EP 97109282A EP 0814168 A1 EP0814168 A1 EP 0814168A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tanning
- iii
- groups
- chromium
- weight
- 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.)
- Granted
Links
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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
-
- 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
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
Definitions
- the invention relates to a method for pretanning and tanning leather using blocked polyisocyanates containing ether groups and mineral tanning agents.
- the tanning transforms animal skins into leather by cross-linking the collagen.
- One of the most important characteristics of leather is the increased shrinking temperature compared to untanned hides, i.e. the improved hot water resistance, and the white appearance (non-transparent, non-pigment-like) after drying.
- the still dominant type of tanning is chrome tanning, in which covalent bonds with the carboxyl groups of the collagen are formed using chromium (III) compounds under the influence of OH ions.
- the hydrogen bonds to the amide groups of collagen that can be obtained with polyfunctional vegetable tannins are much weaker, which also results in a moderately increased shrinking temperature.
- Aliphatic aldehydes e.g. Glutaraldehyde, which leads to crosslinking via the primary amino groups of collagen, has been recommended as a tanning agent (US Pat. No. 2,941,859).
- the resulting aldimines can reversibly react back to aldehyde and amine in the presence of water.
- aliphatic diisocyanates such as hexamethylene diisocyanate (DE-PS 72 981) has not been able to gain acceptance for toxicological reasons.
- the use of the bisulfite-blocked polyisocyanates containing polyethylene oxide groups and described in EP-A 690 135 has application-technical advantages because residual liquors of the tanning are obtained which are free of heavy metal ions.
- the shrinking temperatures of the leather that can be achieved with these products are included more than 80 ° C within the shrinking temperatures required for most types of leather. But if you want to produce shoes very efficiently, you have to use the so-called thermosetting process. Here, shoe uppers are pulled onto lasts and fixed by heat (> 100 ° C) and water vapor (> 80% relative humidity). This process makes it possible to significantly shorten the manufacturing time of the shoe and to make better use of the expensive lasts. If you want to use the thermosetting process, the materials used for this must withstand these processing conditions.
- the invention relates to a method for tanning using
- reaction products to be used according to the invention can be obtained from the intermediates obtainable from A, B and optionally C with NCO contents of 3 to 50, preferably 5 to 45, in particular 20 to 45% by weight (based on the intermediate) by subsequently blocking the free ones Obtained isocyanate groups.
- the products according to the invention then - calculated as sodium salt and based on solids - contain 9.7 to 78, preferably 14 to 74, in particular 46.5 to 74% by weight of carbamoyl sulfonate groups.
- Suitable organic polyisocyanates A) are aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates as described, for example, by W. Siefken in Liebigs Annalen der Chemie 562 , pages 75 to 136.
- Preferred polyisocyanates A) are compounds of the formula Q (NCO) n with an average molecular weight below 800, where n is a number of at least 2, preferably from 2 to 4, Q is an aliphatic C 4 -C 12 -hydrocarbon radical, a cycloaliphatic C 6 - C 15 hydrocarbon radical, an araliphatic C 7 -C 15 hydrocarbon radical or a heterocyclic C 2 -C 12 radical with 1 to 3 heteroatoms from the series oxygen, sulfur, nitrogen, for example (i) diisocyanates such as ethylene diisocyanate, 1.4 -Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-2-isocyana
- polyisocyanates produced by trimerization are the trimerizate of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane obtainable by isocyanurate formation and the isocyanurate groups containing isocyanurate groups obtainable by trimerization of hexamethylene diisocyanate, optionally in a mixture with 2,4-diisocyanatotoluene Polyisocyanates.
- polyisocyanates produced by biuretization are tris (isocyanatohexyl) biuret and its mixtures with its higher homologs, as are accessible, for example, according to DE-OS 23 08 015.
- Particularly preferred polyisocyanates A are those with a molecular weight of 140 to 400 with NCO groups bound to aliphatics or cycloaliphatics, such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethylpentane, 2 , 2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,3- and 1,4-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 1-isocyanato-1-methyl-4-isocyanatomethyl-cyclohexane and 4,4'-diisocyanatodicyclohexyl-methane, and any mixtures of such diisocyanates.
- araliphatic polyisocyanates such as the xylylene diisocyanates of
- diisocyanates are preferably used.
- monofunctional aliphatic isocyanates such as, for example, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate or dodecyl isocyanate and / or polyisocyanates with an average functionality of 2.2 to 4.2.
- the higher-functionality polyisocyanates are preferably essentially composed of trimeric 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and optionally dimeric 1,6-diisocyanatohexane or 1-isocyanato-3 , 3,5-trimethyl-5-isocyanatomethyl-cyclohexane and the correspondingly higher homologues of isocyanurate groups and optionally uretdione groups containing polyisocyanate mixtures with an NCO content of 19 to 24 wt .-%, as obtained by known catalytic trimerization and under isocyanurate Formation of 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane can be obtained and which preferably have an (average) NCO functionality of 3.2 to 4.2.
- polyisocyanates A are polyisocyanates prepared by modifying aliphatic or cycloaliphatic diisocyanates with uretdione and / or isocyanurate, urethane and / or allophanate, biuret or oxadiazine structure, as described, for example, in DE-OS 1 670 666, 3 700 209 and 3 900 053 and are described by way of example in EP 336 205 and 339 396.
- Suitable polyisocyanates are e.g. also the ester group-containing polyisocyanates, e.g.
- triisocyanates accessible by reacting pentaerythritol or trimethylolpropane silyl ethers with isocyanatocaproic acid chloride (cf. DE-OS 3 743 782). It is also possible to use triisocyanates such as e.g. Tris-isocyanatodicyclohexylmethane to use.
- the use of monofunctional and more than difunctional isocyanates is preferably limited to amounts of at most 10 mol%, based on all polyisocyanates A.
- the polyether alcohols B are accessible in a manner known per se by alkoxylation of suitable starter molecules. Any mono- or polyhydric alcohols with a molecular weight of 32 to 250 can be used as starter molecules to produce the polyether alcohols. Monofunctional aliphatic C 1 -C 18 , preferably C 1 -C 4 alcohols are preferably used as starter molecules.
- the use of methanol, butanol, ethylene glycol monomethyl ether or ethylene glycol monobutyl ether as starter is particularly preferred.
- Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any order. Any other epoxides such as butylene oxide, dodecene oxide or styrene oxide can also be used. Pure polyethylene oxide alcohols are particularly preferred.
- Polyalkylene oxide alcohols containing ester groups can also be used.
- Suitable polyalkylene oxide alcohols containing ester groups are OH-terminated polyester ethers which, by reacting aliphatic C 2 -C 8 -dicarboxylic acids or their esters or acid chlorides with polyethers from the group consisting of polyethylene oxides, polypropylene oxides, their mixtures or mixed polyethers, with 0 per OH equivalent of the polyether, 8 to 0.99 equivalents of carboxyl groups or their derivatives are used, are available and have an average molecular weight below 10,000, preferably below 3,000.
- the optionally used NCO-reactive components C include conventional mono- to tetrafunctional building blocks used in polyurethane chemistry, such as alcohols, amines, amino alcohols and mercaptans with molecular weights below 6,000, preferably below 2,000, such as e.g. Polyesters, polyether esters, aminopolyethers and polycarbonates, unless they fall under definition B.
- Preferred components C are long-chain, optionally branched, so-called fatty alcohols or fatty amines with 12 to 30 carbon atoms which have a "fatty" or “re-fatty” effect, and esters of natural fatty acids, such as stearic acid, oleic acid, palmitic acid, linoleic acid, linolenic acid, etc., which contain OH groups.
- Very particularly preferred components C are natural fats and oils carrying OH groups, such as castor oil.
- reaction products from components A to D to be used according to the invention can contain up to 20% by weight of component C.
- Preferred blocking agents D are the sodium salts of sulphurous or disulphurous acid, ie sodium bisulphite (NaHSO 3 ) or sodium disulphite (Na 2 S 2 O 5 ).
- alkali and ammonium salts of these acids namely potassium bisulfite, potassium disulfite, lithium bisulfite, lithium disulfite, ammonium bisulfite, ammonium disulfite, and simple tetraalkylammonium salts of these acids, such as, for example, tetramethylammonium bisulfite, tetraethylammonium bisulfite, etc., can also be used advantageously Solutions with solids contents of 5 to 40% by weight are used.
- reaction products to be used according to the invention can be prepared, for example, as follows:
- the polyisocyanate is reacted with the polyether alcohol B until all OH groups have been urethanized.
- the NCO-terminated prepolymer thus obtained is then blocked in a second step with alkali metal or ammonium bisulfite or disulfite until all NCO groups have been reacted.
- the entire process is particularly preferably carried out solvent-free as a one-pot process.
- the reaction (1st step) is carried out in the temperature range up to 130 ° C., preferably in the range between 50 ° C. and 120 ° C., particularly preferably between 80 ° C. and 110 ° C.
- the reaction can be followed by titration of the NCO content or by measuring the IR spectra and evaluating the carbonyl band at approx. 2 100 cm -1 and is complete when the isocyanate content is not more than 0.1% by weight above the value which is to be achieved with complete sales. As a rule, response times of less than 4 hours are sufficient.
- the reaction can be accelerated by using catalysts such as dibutyltin dilaurate, tin (II) octoate or 1,4-diazabicyclo [2.2.2] octane in amounts of 10 to 1000 ppm, based on the reaction components.
- catalysts such as dibutyltin dilaurate, tin (II) octoate or 1,4-diazabicyclo [2.2.2] octane in amounts of 10 to 1000 ppm, based on the reaction components.
- the NCO prepolymers thus obtained with NCO contents of 5 to 45% by weight are then in a second step at 0 to 60 ° C, preferably at 10 to 40 ° C, with aqueous solutions of alkali or ammonium sulfites and Water reacted until all NCO groups have reacted. This generally requires reaction times of 1 to 12, preferably 3 to 8 hours.
- the end products are optically clear aqueous solutions, in a few individual cases stable, fine-particle emulsions with average particle diameters below 8000 nanometers. It may be advantageous to initially add 20 to 50% by weight of the NCO prepolymers implement aqueous solutions of the alkali metal or ammonium bisulfites or disulfites and add the remaining water after 5 to 45 minutes, so that the solids content of the aqueous preparations is 10 to 50% by weight, preferably 25 to 40% by weight .
- a low pH is not required, as is customary in mineral tanning. This can save you the addition of salt (pimples). Nakedness is e.g. decalcified to a pH of 5 to 8, preferably by 7, the reaction product to be used according to the invention is added and the basification is started after one hour's running time. (In the case of annealed magnesium oxide, the addition can be started immediately).
- the pre-tanning and preferably the simultaneous basification can be completed in 4 to 6 hours.
- the mixture is left to run overnight in a further 2 steps (each after 1 hour running time), rinsing the next morning and continuing as usual.
- reaction products to be used according to the invention amounts of 1 to 20% by weight, preferably 3 to 15% by weight, of the reaction product are generally used, based on the weight of the raw material.
- Suitable mineral tannins are salts of aluminum, chromium, iron, titanium and zircon.
- 100 ° C. is reached and - depending on the amount used and the process control (pH, temperature etc.) - clearly exceeded.
- a particularly preferred working method is the use of tanning chromium compounds that are stable at high pH values.
- pH-resistant chromium compounds are described, for example, in EP-A 304 677; there one uses an aqueous solution of basic chromium (III) sulfate and, per mole of chromium oxide of the basic chromium (III) sulfate, 0.2 to 0.8 mol of aliphatic C 4 -C 6 dicarboxylic acid and subsequent adjustment of the theoretical Basicity to 0 to 50% prepared reaction product, the addition of the reaction product to the pickling liquor as an aqueous solution with a chromium oxide content of at least 5% by weight or in powdered form in an amount of 0.9 to 1.5% by weight chromium oxide (based on pelt weight), the liquor volume is less than 100% by weight (based on pelt weight), the final pH is above 4.0 and the final temperature is above 40 ° C.
- a chromium (III) compound is t
- Example 1 of EP-A 304 677 describes a product which has 0.2 mol of glutaric acid with a basicity of 30 per mol of Cr 2 O 3 .
- This product can be added free of salt and pimples in a short liquor of up to pH 9, preferably 5-8, to the material to be tanned without spontaneous precipitation.
- the tanning proceeds without having to be basified.
- Shrinking temperatures of approximately 100 ° C. are achieved with quantities of 1.25% by weight of Cr 2 O 3 (based on shaved weight).
- a particular advantage of such a combined procedure is the high exhaustion of chromium III salt from the residual liquor of the tanning: With a liquor length of, for example, 50% by weight at 40 ° C, after 1 to 3 hours, the seam is folded to approx. 1 mm Leather tanned through (with a Cr 2 O 3 content in the leather of approx. 3% by weight) and in the remaining liquor of this tanning a Cr 2 O 3 content of 0.4 g per liter at a final pH (the pH -Value drops due to the added tanning agent) of 4.1 found.
- example A 66 describes a tanning process in which formic acid and then a commercially available, self-dulling chrome tanning agent were added after pretanning with carbamoyl sulfonate.
- This type of tanning already provides leather with a high shrinking temperature and residual liquors with sufficiently good chromium exhaustion.
- a formate- or dicarboxylate-stabilized chromium tanning agent according to EP-A 304 677 is used, there is a further reduction in the chromium 3+ ion content of the remaining liquor.
- retanning can be carried out with synthetic organic polymers (incl. Resin tanning agents) or with vegetable tanning agents.
- the average molecular weights mentioned in this application are number average molecular weights.
- the percentages in the following examples relate to the weight and to the bare / leather.
- the liquor is drained, the leathers are rinsed for 10 minutes at room temperature, then they are wilted and folded to a thickness of 1 mm.
- the folded leather is placed in a barrel and washed for 10 minutes with 200% (based on the fold weight) of water (from room temperature). The fleet is released.
- the subsequent mineral tanning is initiated by 50% water at 35 ° C. (the pH value has reached 6.8) and 5% of a product which has been prepared according to Example 1 of EP-A 304677. After 150 minutes of movement, the pH value becomes 4.1.
- the fleet is drained, the leathers have a Ts of 100 ° C. After washing with 300% water at 40 ° C (10 minutes), the liquor is drained off. In the neutralization which now begins, 200% water (40 ° C), 3% TANIGAN PAK-N are left to act for 1 hour (pH 4.7), then 4% CUTAPOL TIS-MF (diluted 1: 4) for 30 minutes. Then it is drained and washed with 200% water (35 ° C.) for 10 minutes.
- the retanning is started with 150% water (40 ° C): 3% TANIGAN BN and 2% TANIGAN LF for 20 minutes, then a solution of 3% BAYGENAL Braun CGG and 2% BAYKANOL TF-2N (1:20 at 60 ° C warm water) added. After 60 minutes, 100% water (70 ° C.) is added, after another 10 minutes 2% formic acid (diluted 1: 5) is added and the mixture is left to run for 30 minutes (pH 3.4).
- Example A 1 of EP-A 690 135 12 pieces of 100 g of bare bark in 40% liquor with 0.35% magnesium oxide were allowed to run for 1 hour in a test kettle from Dose (pH 7.4), then 7 , 5% (active substance) of a product according to Example 1 of EP-A 690 135 added, after 3 hours a further 0.35% magnesium oxide (pH 6.6) and then run overnight.
- the resulting leather had a Ts of 77 ° C. 5 of these leathers were treated in 100% liquor with 0.05% formic acid and 0.08% sulfuric acid to a pH of 3, a further 3 with 0.08% sulfuric acid to a pH of 4, and one each with 0.
- tanning agents analogous to those of EP-A 304 677 are recommended if, at the same time, you value high consumption from the remaining liquors of the tanning process.
Landscapes
- 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)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Vorgerbung und Ausgerbung von Leder unter Verwendung Ethergruppen-haltiger blockierter Polyisocyanate und mineralischer Gerbstoffe .The invention relates to a method for pretanning and tanning leather using blocked polyisocyanates containing ether groups and mineral tanning agents.
Die Gerbung überführt tierische Häute unter Vernetzung des Kollagens in Leder. Eines der wichtigsten Merkmale von Leder ist die gegenüber ungegerbten Häuten erhöhte Schrumpfungstemperatur, d.h. die verbesserte Heißwasserbeständigkeit, und das weiße Aussehen (nicht-transparent, nichtpigmentartig) nach dem Trocknen.The tanning transforms animal skins into leather by cross-linking the collagen. One of the most important characteristics of leather is the increased shrinking temperature compared to untanned hides, i.e. the improved hot water resistance, and the white appearance (non-transparent, non-pigment-like) after drying.
Die heute immer noch dominierende Art der Gerbung ist die Chromgerbung, bei der unter Verwendung von Chrom(III)-verbindungen unter dem Einfluß von OH-Ionen vernetzend wirkende kovalente Bindungen mit den Carboxylgruppen des Kollagens ausgebildet werden. Die mit polyfunktionellen Vegetabilgerbstoffen erhältlichen Wasserstoffbrückenbindungen zu den Amidgruppen des Kollagens sind dagegen viel schwächer, was sich auch in einer nur mäßig erhöhten Schrumpfungstemperatur auswirkt. Auch aliphatische Aldehyde, wie z.B. Glutaraldehyd, die zu einer Vernetzung über die primären Aminogruppen des Kollagens führen, hat man als Gerbstoffe empfohlen (US-PS 2 941 859). Die entstehenden Aldimine können jedoch in Gegenwart von Wasser reversibel zu Aldehyd und Amin zurückreagieren.The still dominant type of tanning is chrome tanning, in which covalent bonds with the carboxyl groups of the collagen are formed using chromium (III) compounds under the influence of OH ions. In contrast, the hydrogen bonds to the amide groups of collagen that can be obtained with polyfunctional vegetable tannins are much weaker, which also results in a moderately increased shrinking temperature. Aliphatic aldehydes, e.g. Glutaraldehyde, which leads to crosslinking via the primary amino groups of collagen, has been recommended as a tanning agent (US Pat. No. 2,941,859). However, the resulting aldimines can reversibly react back to aldehyde and amine in the presence of water.
Die Verwendung von aliphatischen Diisocyanaten wie Hexamethylendiisocyanat (DE-PS 72 981) hat sich aus toxikologischen Gründen nicht durchsetzen können.The use of aliphatic diisocyanates such as hexamethylene diisocyanate (DE-PS 72 981) has not been able to gain acceptance for toxicological reasons.
Die in den US-PS 2 923 594 und 4 413 997 empfohlene Verwendung von Bisulfit-blockierten aliphatischen, cycloaliphatischen oder aromatischen Diisocyanaten wie Hexamethylendiisocyanat, Isophorondiisocyanat und Toluylendiisocyanat als Gerbstoffe ergibt zwar helle, lichtechte Leder, die Gerbflotten sind jedoch nicht pH-stabil.Although the use of bisulfite-blocked aliphatic, cycloaliphatic or aromatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate and tolylene diisocyanate as tannins, as recommended in US Pat. Nos. 2,923,594 and 4,413,997, gives light, lightfast leather, the tanning liquors are not pH-stable.
Die Verwendung der in EP-A 690 135 beschriebenen, Polyethylenoxidgruppenhaltigen Bisulfit-blockierten Polyisocyanaten hat anwendungstechnische Vorteile, weil man Restflotten der Gerbung erhält, die frei von Schwermetallionen sind. Die mit diesen Produkten erreichbaren Schrumpfungstemperaturen der Leder liegen mit mehr als 80°C innerhalb der für die meisten Lederarten erforderlichen Schrumpfungstemperaturen. Wenn man aber hochrationell Schuhe herstellen will, so muß man sich des sog. Thermosetting-Verfahrens bedienen. Dabei werden Schuhschäfte auf Leisten gezogen und durch Hitze ( > 100°C) und Wasserdampf (> 80% relative Feuchte) fixiert. Dieses Verfahren ermöglicht es, die Herstellungszeit des Schuhes deutlich zu verkürzen und die teuren Leisten besser auszunutzen. Wenn man das Thermosettingverfahren einsetzen will, so müssen die dafür benutzten Materialien diese Verarbeitungsbedingungen aushalten.The use of the bisulfite-blocked polyisocyanates containing polyethylene oxide groups and described in EP-A 690 135 has application-technical advantages because residual liquors of the tanning are obtained which are free of heavy metal ions. The shrinking temperatures of the leather that can be achieved with these products are included more than 80 ° C within the shrinking temperatures required for most types of leather. But if you want to produce shoes very efficiently, you have to use the so-called thermosetting process. Here, shoe uppers are pulled onto lasts and fixed by heat (> 100 ° C) and water vapor (> 80% relative humidity). This process makes it possible to significantly shorten the manufacturing time of the shoe and to make better use of the expensive lasts. If you want to use the thermosetting process, the materials used for this must withstand these processing conditions.
Es hat sich gezeigt, daß für diesen und ähnliche Einsatzzwecke Leder benötigt werden, deren Schrumpfungstemperaturen (Ts) im trockenen Zustand etwa 100°C betragen. Andererseits möchte man die ökologischen Vorteile, die mit dem der EP-A 690 135 zugrunde liegenden Verfahren erreicht werden, nicht aufgeben. Es bestand also Bedarf nach einem Verfahren, das mineralgerbstoffhaltige Leder liefert und mit möglichst geringen Umweltbelastungen verknüpft ist.It has been shown that leather is required for these and similar purposes, the shrinking temperatures (Ts) of which are approximately 100 ° C. in the dry state. On the other hand, one does not want to give up the ecological advantages which are achieved with the process on which EP-A 690 135 is based. There was therefore a need for a process which supplies leather containing mineral tannins and which is associated with the lowest possible environmental impact.
-
I. Carbamoylsulfonatgtuppen-haltiger Umsetzungsprodukte aus
- A. organischem Polyisocyanat,
- B. pro Isocyanatgruppe von A. 0,01 bis 0,4 Äquivalenten Polyetheralkohol mit eingebauten Polyalkylenoxideinheiten (die Äquivalente beziehen sich auf die Hydroxylgruppen des Polyetheralkohols), wobei die Polyalkylenoxideinheiten zu 40 bis 100, vorzugsweise 50 bis 100 Mol-% aus Polyethylenoxideinheiten einer Sequenzlänge von 5 bis 70, vorzugsweise 6 bis 60, insbesondere 7 bis 40, bestehen,
- C. gegebenenfalls anderen NCO-reaktiven Komponenten, und
- D. Ammonium- oder Alkalibisulfiten oder -disulfiten,
- A. organic polyisocyanate,
- B. per isocyanate group of A. 0.01 to 0.4 equivalents of polyether alcohol with built-in polyalkylene oxide units (the equivalents relate to the hydroxyl groups of the polyether alcohol), the polyalkylene oxide units being 40 to 100, preferably 50 to 100 mol% of polyethylene oxide units of a sequence length from 5 to 70, preferably 6 to 60, in particular 7 to 40,
- C. optionally other NCO-reactive components, and
- D. ammonium or alkali bisulfites or disulfites,
- II. mineralischer Gerbstoffe aus der Reihe Chrom(III), Eisen(II), Eisen(III), Aluminium(III), Titan(IV) und Zirkon(IV) ohne Pickel bei einem pH-Wert über 4, vorzugsweise über 5.II. Mineral tanning agents from the series chromium (III), iron (II), iron (III), aluminum (III), titanium (IV) and zirconium (IV) without pimples at a pH value above 4, preferably above 5.
Die erfindungsgemäß zu verwendenden Umsetzungsprodukte lassen sich aus den aus A, B und gegebenenfalls C erhältlichen Zwischenprodukten mit NCO-Gehalten von 3 bis 50, vorzugsweise 5 bis 45, insbesondere 20 bis 45 Gew.-% (bezogen auf Zwischenprodukt) durch anschließende Blockierung der freien Isocyanatgruppen erhalten. Die erfindungsgemäßen Produkte enthalten dann - berechnet als Natriumsalz und festkörperbezogen - 9,7 bis 78, vorzugsweise 14 bis 74, insbesondere 46,5 bis 74 Gew.-% Carbamoylsulfonatgruppen.The reaction products to be used according to the invention can be obtained from the intermediates obtainable from A, B and optionally C with NCO contents of 3 to 50, preferably 5 to 45, in particular 20 to 45% by weight (based on the intermediate) by subsequently blocking the free ones Obtained isocyanate groups. The products according to the invention then - calculated as sodium salt and based on solids - contain 9.7 to 78, preferably 14 to 74, in particular 46.5 to 74% by weight of carbamoyl sulfonate groups.
Als organische Polyisocyanate A) kommen aliphatische, cycloaliphatische, araliphatische, aromatische oder heterocyclische Polyisocyanate in Betracht, wie sie z.B. von W. Siefken in Liebigs Annalen der Chemie 562, Seiten 75 bis 136, beschrieben werden.Suitable organic polyisocyanates A) are aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates as described, for example, by W. Siefken in Liebigs Annalen der Chemie 562 , pages 75 to 136.
Bevorzugte Polyisocyanate A) sind Verbindungen der Formel Q(NCO)n mit einem mittleren Molekulargewicht unter 800, worin n eine Zahl von mindestens 2, vorzugsweise von 2 bis 4, Q einen aliphatischen C4-C12-Kohlenwasserstoffrest, einen cycloaliphatischen C6-C15-Kohlenwasserstoffrest, einen araliphatischen C7-C15-Kohlenwasserstoffrest oder einen heterocyclischen C2-C12-Rest mit 1 bis 3 Heteroatomen aus der Reihe Sauerstoff, Schwefel, Stickstoff bedeuten, beispielsweise (i) Diisocyanate wie Ethylendiisocyanat, 1,4-Tetramethylendiisocyanat, 1,6-Hexamethylendiisocyanat, 1,12-Dodecandiisocyanat, Cyclobutan-1,3-diisocyanat, Cyclohexan-1,3- und -1,4-diisocyanat sowie beliebige Gemische dieser Isomeren, 1-Isocyanato-2-isocyanatomethyl-cyclopentan, 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexan, 2,4- und 2,6-Hexahydrotoluylendiisocyanat sowie beliebige Gemische dieser Isomeren, Hexahydro-1,3- und/oder -1,4-phenylendiisocyanat, Perhydro-2,4'- und/oder -4,4'-diphenylmethyl-diisocyanat, 1,3- und 1,4-Phenylen-diisocyanat, 2,4- und 2,6-Toluylendiisocyanat sowie beliebige Gemische dieser Isomeren, Diphenylmethan-2,4'- und/oder -4,4'-diisocyanat, Naphthalin-1,5-diisocyanat, Uretdiongruppen enthaltende Polyisocyanate wie z.B. das Bis-(6-isocyanatohexyl)-uretdion oder das die Uretdion-Struktur enthaltende Dimere des 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexans und beliebige Mischungen der vorgenannten Polyisocyanate; (ii) tri- und höherfunktionelle Polyisocyanate wie die Isomeren der Triisocyanatotriphenylmethanreihe (wie Triphenylmethan-4,4',4''-triisocyanat) und ihre Gemische; (iii) durch Allophanatisierung, Trimerisierung oder Biuretisierung aus den Polyisocyanaten (i) und/oder (ii) hergestellte Verbindungen, die mindestens 3 Isocyanatgruppen pro Molekül aufweisen. Beispiele für durch Trimerisierung hergestellte Polyisocyanate sind das durch Isocyanurat-Bildung erhältliche Trimerisat des 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexans und die durch Trimerisierung von Hexamethylendiisocyanat, gegebenenfalls im Gemisch mit 2,4-Diisocyanatotoluol, erhältlichen Isocyanuratgruppen enthaltenden Polyisocyanate. Beispiele für durch Biuretisierung hergestellte Polyisocyanate sind Tris-(isocyanatohexyl)-biuret und dessen Gemische mit seinen höheren Homologen, wie sie z.B. gemäß DE-OS 23 08 015 zugänglich sind.Preferred polyisocyanates A) are compounds of the formula Q (NCO) n with an average molecular weight below 800, where n is a number of at least 2, preferably from 2 to 4, Q is an aliphatic C 4 -C 12 -hydrocarbon radical, a cycloaliphatic C 6 - C 15 hydrocarbon radical, an araliphatic C 7 -C 15 hydrocarbon radical or a heterocyclic C 2 -C 12 radical with 1 to 3 heteroatoms from the series oxygen, sulfur, nitrogen, for example (i) diisocyanates such as ethylene diisocyanate, 1.4 -Tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-2-isocyanatomethyl- cyclopentane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4- phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmet hyl diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate , Naphthalene-1,5-diisocyanate, uretdione group-containing polyisocyanates such as bis- (6-isocyanatohexyl) uretdione or the uretdione structure-containing dimer of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and any Mixtures of the aforementioned polyisocyanates; (ii) trifunctional and higher functional polyisocyanates such as the isomers of Triisocyanatotriphenylmethane series (such as triphenylmethane 4,4 ', 4''triisocyanate) and their mixtures; (iii) Compounds prepared by allophanatization, trimerization or biuretization from the polyisocyanates (i) and / or (ii) which have at least 3 isocyanate groups per molecule. Examples of polyisocyanates produced by trimerization are the trimerizate of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane obtainable by isocyanurate formation and the isocyanurate groups containing isocyanurate groups obtainable by trimerization of hexamethylene diisocyanate, optionally in a mixture with 2,4-diisocyanatotoluene Polyisocyanates. Examples of polyisocyanates produced by biuretization are tris (isocyanatohexyl) biuret and its mixtures with its higher homologs, as are accessible, for example, according to DE-OS 23 08 015.
Besonders bevorzugte Polyisocyanate A sind solche mit einem Molekulargewicht von 140 bis 400 mit an Aliphaten oder Cycloaliphaten gebundenen NCO-Gruppen, wie z.B. 1,4-Diisocyanatobutan, 1,6-Diisocyanatohexan, 1,5-Diisocyanato-2,2-dimethylpentan, 2,2,4- bzw. 2,4,4-Trimethyl-1,6-diisocyanatohexan, 1,3- und 1,4-Diisocyanatohexan, 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexan, 1-Isocyanato-1-methyl-4-isocyanatomethyl-cyclohexan und 4,4'-Diisocyanatodicyclohexyl-methan, und beliebige Gemische solcher Diisocyanate. Auch araliphatische Polyisocyanate wie die Xylylendiisocyanate der Formeln
Bevorzugt verwendet werden obige Diisocyanate. Man kann aber auch monofunktionelle aliphatische Isocyanate wie beispielsweise Butylisocyanat, Hexylisocyanat, Cyclohexylisocyanat, Stearylisocyanat oder Dodecylisocyanat und/oder Polyisocyanate mit einer durchschnittlichen Funktionalität von 2,2 bis 4,2 mitverwenden.The above diisocyanates are preferably used. However, it is also possible to use monofunctional aliphatic isocyanates such as, for example, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate or dodecyl isocyanate and / or polyisocyanates with an average functionality of 2.2 to 4.2.
Bevorzugt handelt es sich bei den höherfunktionellen Polyisocyanaten um im wesentlichen aus trimerem 1,6-Diisocyanatohexan oder 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexan und gegebenenfalls dimerem 1,6-Diisocyanatohexan oder 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexan und den entsprechend höheren Homologen bestehenden Isocyanuratgruppen und gegebenenfalls Uretdiongruppen aufweisenden Polyisocyanatgemischen mit einem NCO-Gehalt von 19 bis 24 Gew.-%, wie sie durch an sich bekannte katalytische Trimerisierung und unter Isocyanurat-Bildung von 1,6-Diisocyanatohexan oder 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexan erhalten werden und die vorzugsweise eine (mittlere) NCO-Funktionalität von 3,2 bis 4,2 aufweisen.The higher-functionality polyisocyanates are preferably essentially composed of trimeric 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and optionally dimeric 1,6-diisocyanatohexane or 1-isocyanato-3 , 3,5-trimethyl-5-isocyanatomethyl-cyclohexane and the correspondingly higher homologues of isocyanurate groups and optionally uretdione groups containing polyisocyanate mixtures with an NCO content of 19 to 24 wt .-%, as obtained by known catalytic trimerization and under isocyanurate Formation of 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane can be obtained and which preferably have an (average) NCO functionality of 3.2 to 4.2.
Weitere geeignete Polyisocyanate A sind durch Modifizierung aliphatischer oder cycloaliphatischer Diisocyanate hergestellte Polyisocyanate mit Uretdion- und/oder Isocyanurat-, Urethan- und/oder Allophanat-, Biuret- oder Oxadiazinstruktur, wie sie beispielsweise in den DE-OS 1 670 666, 3 700 209 und 3 900 053 und in den EP 336 205 und 339 396 beispielhaft beschrieben sind. Geeignete Polyisocyanate sind z.B. auch die estergruppenhaltigen Polyisocyanate, wie z.B. die durch Umsetzung von Pentaerythrit- oder Trimethylolpropan-silylethern mit Isocyanatocapronsäurechlorid zugänglichen Tetrakis- bzw. Triisocyanate (vgl. DE-OS 3 743 782). Außerdem ist es auch möglich, Triisocyanate wie z.B. Tris-isocyanatodicyclohexylmethan zu verwenden.Further suitable polyisocyanates A are polyisocyanates prepared by modifying aliphatic or cycloaliphatic diisocyanates with uretdione and / or isocyanurate, urethane and / or allophanate, biuret or oxadiazine structure, as described, for example, in DE-OS 1 670 666, 3 700 209 and 3 900 053 and are described by way of example in EP 336 205 and 339 396. Suitable polyisocyanates are e.g. also the ester group-containing polyisocyanates, e.g. the tetrakis or triisocyanates accessible by reacting pentaerythritol or trimethylolpropane silyl ethers with isocyanatocaproic acid chloride (cf. DE-OS 3 743 782). It is also possible to use triisocyanates such as e.g. Tris-isocyanatodicyclohexylmethane to use.
Die Verwendung von monofunktionellen und von mehr als difunktionellen Isocyanaten wird in beiden Fällen vorzugsweise auf Mengen von je maximal 10 Mol-%, bezogen auf sämtliche Polyisocyanate A, beschränkt.In both cases, the use of monofunctional and more than difunctional isocyanates is preferably limited to amounts of at most 10 mol%, based on all polyisocyanates A.
Ganz besonders bevorzugt sind jedoch die obengenannten aliphatischen, cycloaliphatischen und araliphatischen Diisocyanate.However, the abovementioned aliphatic, cycloaliphatic and araliphatic diisocyanates are very particularly preferred.
Die Polyetheralkohole B sind in an sich bekannter Weise durch Alkoxylierung geeigneter Startermoleküle zugänglich. Zur Herstellung der Polyetheralkohole können beliebige ein- oder mehrwertige Alkohole des Molekulargewichts 32 bis 250 als Startermoleküle eingesetzt werden. Bevorzugt werden als Startermoleküle monofunktionelle aliphatische C1-C18-, vorzugsweise C1-C4-Alkohole verwendet. Besonders bevorzugt ist die Verwendung von Methanol, Butanol, Ethylenglykolmonomethylether oder Ethylenglykolmonobutylether als Starter.The polyether alcohols B are accessible in a manner known per se by alkoxylation of suitable starter molecules. Any mono- or polyhydric alcohols with a molecular weight of 32 to 250 can be used as starter molecules to produce the polyether alcohols. Monofunctional aliphatic C 1 -C 18 , preferably C 1 -C 4 alcohols are preferably used as starter molecules. The use of methanol, butanol, ethylene glycol monomethyl ether or ethylene glycol monobutyl ether as starter is particularly preferred.
Für die Alkoxylierungsreaktion geeignete Alkylenoxide sind insbesondere Ethylenoxid und Propylenoxid, die in beliebiger Reihenfolge bei der Alkoxylierungsreaktion eingesetzt werden können. Auch beliebige andere Epoxide wie beispielsweise Butylenoxid, Dodecenoxid oder Styroloxid können mitverwendet werden. Reine Polyethylenoxidalkohole sind besonders bevorzugt.Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any order. Any other epoxides such as butylene oxide, dodecene oxide or styrene oxide can also be used. Pure polyethylene oxide alcohols are particularly preferred.
Auch estergruppenhaltige Polyalkylenoxidalkohole können mitverwendet werden. Geeignete estergruppenhaltige Polyalkylenoxidalkohole sind OH-terminierte Polyesterether, die durch Umsetzung von aliphatischen C2-C8-Dicarbonsäuren oder deren Estern oder Säurechloriden mit Polyethern aus der Gruppe der Polyethylenoxide, Polypropylenoxide, deren Gemische oder Mischpolyether, wobei pro OH-Äquivalent des Polyethers 0,8 bis 0,99 Äquivalente an Carboxylgruppen oder deren Derivate eingesetzt werden, erhältlich sind und ein mittleres Molekulargewicht unter 10 000, vorzugsweise unter 3 000 aufweisen.Polyalkylene oxide alcohols containing ester groups can also be used. Suitable polyalkylene oxide alcohols containing ester groups are OH-terminated polyester ethers which, by reacting aliphatic C 2 -C 8 -dicarboxylic acids or their esters or acid chlorides with polyethers from the group consisting of polyethylene oxides, polypropylene oxides, their mixtures or mixed polyethers, with 0 per OH equivalent of the polyether, 8 to 0.99 equivalents of carboxyl groups or their derivatives are used, are available and have an average molecular weight below 10,000, preferably below 3,000.
Die gegebenenfalls mitverwendeten NCO-reaktiven Komponenten C umfassen übliche, in der Polyurethanchemie verwendete mono- bis tetrafunktionelle Bausteine wie Alkohole, Amine, Aminoalkohole und Mercaptane mit Molekulargewichten unter 6 000, bevorzugt unter 2 000, wie z.B. Polyester, Polyetherester, Aminopolyether und Polycarbonate, sofern sie nicht unter die Definition B fallen.The optionally used NCO-reactive components C include conventional mono- to tetrafunctional building blocks used in polyurethane chemistry, such as alcohols, amines, amino alcohols and mercaptans with molecular weights below 6,000, preferably below 2,000, such as e.g. Polyesters, polyether esters, aminopolyethers and polycarbonates, unless they fall under definition B.
Bevorzugte Komponenten C sind "fettend" bzw. "nachfettend" wirkende langkettige, gegebenenfalls verzweigte sogenannte Fettalkohole oder Fettamine mit 12 bis 30 Kohlenstoffatomen sowie OH-Gruppen tragende Ester natürlicher Fettsäuren wie Stearinsäure, Ölsäure, Palmitinsäure, Linolsäure, Linolensäure etc.Preferred components C are long-chain, optionally branched, so-called fatty alcohols or fatty amines with 12 to 30 carbon atoms which have a "fatty" or "re-fatty" effect, and esters of natural fatty acids, such as stearic acid, oleic acid, palmitic acid, linoleic acid, linolenic acid, etc., which contain OH groups.
Ganz besonders bevorzugte Komponenten C sind OH-Gruppen tragende natürliche Fette und Öle wie beispielsweise Rizinusöl.Very particularly preferred components C are natural fats and oils carrying OH groups, such as castor oil.
Die erfindungsgemäß zu verwendenden Umsetzungsprodukte aus den Komponenten A bis D können bis zu 20 Gew.-% der Komponente C enthalten.The reaction products from components A to D to be used according to the invention can contain up to 20% by weight of component C.
Bevorzugte Blockierungsmittel D sind die Natriumsalze der schwefligen bzw. dischwefligen Säure, d.h. Natriumhydrogensulfit (NaHSO3) bzw. Natriumdisulfit (Na2S2O5).Preferred blocking agents D are the sodium salts of sulphurous or disulphurous acid, ie sodium bisulphite (NaHSO 3 ) or sodium disulphite (Na 2 S 2 O 5 ).
Vorteilhaft verwendet werden können auch die anderen Alkali- und Ammoniusalze dieser Säuren, nämlich Kaliumbisulfit, Kaliumdisulfit, Lithiumbisulfit, Lithiumdisulfit, Ammoniumbisulfit, Ammoniumdisulfit sowie einfache Tetraalkylammoniumsalze dieser Säuren wie beispielsweise Tetramethylammonium-bisulfit, Tetraethylammonium-bisulfit usw. Zur Blockierung werden die Salze bevorzugt als wäßrige Lösungen mit Festkörpergehalten von 5 bis 40 Gew.-% eingesetzt.The other alkali and ammonium salts of these acids, namely potassium bisulfite, potassium disulfite, lithium bisulfite, lithium disulfite, ammonium bisulfite, ammonium disulfite, and simple tetraalkylammonium salts of these acids, such as, for example, tetramethylammonium bisulfite, tetraethylammonium bisulfite, etc., can also be used advantageously Solutions with solids contents of 5 to 40% by weight are used.
Die erfindungsgemäß zu verwendenden Umsetzungsprodukte lassen sich beispielsweise folgendermaßen herstellen:The reaction products to be used according to the invention can be prepared, for example, as follows:
In einem ersten Schritt wird das Polyisocyanat mit dem Polyetheralkohol B umgesetzt, bis sämtliche OH-Gruppen urethanisiert sind. Das so erhaltene NCO-endständige Präpolymer wird dann in einem zweiten Schritt mit Alkali- oder Ammonium-bisulfit oder -disulfit blockiert, bis sämtliche NCO-Gruppen umgesetzt sind.In a first step, the polyisocyanate is reacted with the polyether alcohol B until all OH groups have been urethanized. The NCO-terminated prepolymer thus obtained is then blocked in a second step with alkali metal or ammonium bisulfite or disulfite until all NCO groups have been reacted.
Das gesamte Verfahren wird besonders bevorzugt lösungsmittelfrei als Eintopfverfahren durchgeführt. Die Reaktion (1. Schritt) wird im Temperaturbereich bis 130°C, vorzugsweise im Bereich zwischen 50°C und 120°C, besonders bevorzugt zwischen 80°C und 110°C durchgeführt. Die Reaktion kann durch Titration des NCO-Gehaltes oder durch Messung der IR-Spektren und Auswertung der Carbonylbande bei ca. 2 100 cm-1 verfolgt werden und ist beendet, wenn der Isocyanatgehalt nicht mehr als 0,1 Gew.-% oberhalb des Wertes liegt, der bei vollständigem Umsatz erreicht werden soll. In der Regel sind Reaktionszeiten von weniger als 4 Stunden ausreichend.The entire process is particularly preferably carried out solvent-free as a one-pot process. The reaction (1st step) is carried out in the temperature range up to 130 ° C., preferably in the range between 50 ° C. and 120 ° C., particularly preferably between 80 ° C. and 110 ° C. The reaction can be followed by titration of the NCO content or by measuring the IR spectra and evaluating the carbonyl band at approx. 2 100 cm -1 and is complete when the isocyanate content is not more than 0.1% by weight above the value which is to be achieved with complete sales. As a rule, response times of less than 4 hours are sufficient.
Durch die Mirverwendung von Katalysatoren wie Dibutylzinndilaurat, Zinn-(II)-octoat oder 1,4-Diazabicyclo-[2.2.2]octan in Mengen von 10 bis 1 000 ppm, bezogen auf die Reaktionskomponenten, kann die Reaktion beschleunigt werden. Die so erhaltenen NCO-Präpolymeren mit NCO-Gehalten von 5 bis 45 Gew.-% werden nun in einem 2. Schritt bei 0 bis 60°C, bevorzugt bei 10 bis 40°C, mit wäßrigen Lösungen von Alkali- bzw. Ammoniumsulfiten und Wasser umgesetzt, bis alle NCO-Gruppen reagiert haben. Dazu sind im allgemeinen Reaktionszeiten von 1 bis 12, vorzugsweise 3 bis 8 Stunden notwendig. Die Endprodukte sind optisch klare wäßrige Lösungen, in wenigen Einzelfällen stabile, feinteilige Emulsionen mit mittleren Teilchendurchmessern unter 8000 Nanometer. Es kann vorteilhaft sein, die NCO-Präpolymeren zunächst mit 20 bis 50 gew.-%igen wäßrigen Lösungen der Alkali- oder Ammonium-bisulfite oder -disulfite umzusetzen und nach 5 bis 45 Minuten das restliche Wasser zuzusetzen, so daß dann ein Festkörpergehalt der wäßrigen Zubereitungen von 10 bis 50 Gew.-%, vorzugsweise 25 bis 40 Gew.-% resultiert.The reaction can be accelerated by using catalysts such as dibutyltin dilaurate, tin (II) octoate or 1,4-diazabicyclo [2.2.2] octane in amounts of 10 to 1000 ppm, based on the reaction components. The NCO prepolymers thus obtained with NCO contents of 5 to 45% by weight are then in a second step at 0 to 60 ° C, preferably at 10 to 40 ° C, with aqueous solutions of alkali or ammonium sulfites and Water reacted until all NCO groups have reacted. This generally requires reaction times of 1 to 12, preferably 3 to 8 hours. The end products are optically clear aqueous solutions, in a few individual cases stable, fine-particle emulsions with average particle diameters below 8000 nanometers. It may be advantageous to initially add 20 to 50% by weight of the NCO prepolymers implement aqueous solutions of the alkali metal or ammonium bisulfites or disulfites and add the remaining water after 5 to 45 minutes, so that the solids content of the aqueous preparations is 10 to 50% by weight, preferably 25 to 40% by weight .
In der ersten Stufe einer solchen kombinierten Gerbung wird, wie in EP-A 690 135 beschrieben, gegebenenfalls unter Zuhilfename eines Basifizierungsmittels mit 0,1 - 30, vorzugsweise 0,5 - 10, ganz besonders bevorzugt 1 - 7, Gew.-% Carbamoylsulfonat bei pH 5 - 14, vorzugsweise 7,5 - 9,5 vorgegerbt. Zur Basifizierung sind alle bekannten, in der Gerberei üblichen Abstumpfmittel geeignet:
Natriumcarbonat und -hydrogencarbonat, Magnesiumoxid, Dolomit, tertiäre Amine usw. Auch die kontrollierte Zugabe von Natrium- oder Kaliumhydroxid ist generell möglich (aber ungebräuchlich). Besonders bevorzugt ist Magnesiumoxid.In the first stage of such a combined tanning, as described in EP-A 690 135, optionally with the aid of a base agent, 0.1-30, preferably 0.5-10, very particularly preferably 1-7,% by weight of carbamoyl sulfonate pre-tanned at pH 5-14, preferably 7.5-9.5. All known tamping agents commonly used in tannery are suitable for basification:
Sodium carbonate and bicarbonate, magnesium oxide, dolomite, tertiary amines, etc. The controlled addition of sodium or potassium hydroxide is generally possible (but not common). Magnesium oxide is particularly preferred.
Bei der Vorgerbung mit den erfindungsgemäß zu verwendenden Umsetzungsprodukten benötigt man keinen niedrigen pH-Wert, wie er bei der Mineralgerbung üblich ist. Dadurch kann man sich den Salzzusatz (Pickel) ersparen. Blöße wird z.B. bis auf einen pH-Wert von 5 bis 8, vorzugsweise um 7, entkälkt, das erfindungsgemäß zu verwendende Umsetzungsprodukt zugegeben und nach einer Stunde Laufzeit mit der Basifizierung begonnen. (Im Falle von geglühtem Magnesiumoxid kann sofort mit der Zugabe begonnen werden). Je nach mechanischer Walkwirkung und Dicke sowie Aufschluß (z.B. enzymatisch) der Blöße kann die Vorgerbung und vorzugsweise die gleichzeitig stattfindende Basifizierung in 4 bis 6 Stunden abgeschlossen sein. Im allgemeinen läßt man aber - wie bei der Chromgerbung üblich - nach dem Vorlauf von 1 Stunde sowie nach Zugabe des Basifizierungsmittels in weiteren 2 Schritten (jeweils nach 1 Stunde Laufzeit) über Nacht laufen, spült am nächsten Morgen und arbeitet wie gewöhnlich weiter.When tanning with the reaction products to be used according to the invention, a low pH is not required, as is customary in mineral tanning. This can save you the addition of salt (pimples). Nakedness is e.g. decalcified to a pH of 5 to 8, preferably by 7, the reaction product to be used according to the invention is added and the basification is started after one hour's running time. (In the case of annealed magnesium oxide, the addition can be started immediately). Depending on the mechanical flexing effect and thickness as well as the digestion (e.g. enzymatically) of the bare, the pre-tanning and preferably the simultaneous basification can be completed in 4 to 6 hours. In general, however - as is customary in chrome tanning - after running for 1 hour and after adding the base agent, the mixture is left to run overnight in a further 2 steps (each after 1 hour running time), rinsing the next morning and continuing as usual.
Von den erfindungsgemäß zu verwendenden Umsetzungsprodukten verwendet man im allgemeinen Mengen von 1 bis 20, vorzugsweise 3 bis 15 Gew.-% Umsetzungsprodukt, bezogen auf Blößengewicht. Dabei dienen die mit dem Umsetzungsprodukt gegerbten Leder mit Schrumpfungstemperaturen von über 70°C, vorzugsweise über 75°C, als Vorstufe (analog wet blue) für die Ausgerbung.Of the reaction products to be used according to the invention, amounts of 1 to 20% by weight, preferably 3 to 15% by weight, of the reaction product are generally used, based on the weight of the raw material. The leather tanned with the reaction product with shrinking temperatures of above 70 ° C., preferably above 75 ° C., serves as a preliminary stage (analogue wet blue) for tanning.
Dann kann man bei einem pH-Wert über 4, vorzugsweise über 5, mit minimaler Mineralgerbstoffmenge pickel- und salzfrei ausgerben. Geeignete Mineralgerbstoffe sind Salze des Aluminiums, Chroms, Eisens, Titans und Zirkons. Die bei Aluminium (Ts= 70 - 80°C) , Eisen (Ts= 70 - 80°C), Titan (Ts= 75 - 85°C) oder Zirkon (Ts= 70 - 80°C) laut J. Kochta et al., Das Leder, Aug. 1990, maximal erreichbaren Schrumpfungstemperaturen werden durch diese kombinierte Gerbung z.T. erhöht. Beim erfindungsgemäßen Verfahren werden 100°C erreicht und - in Abhängigkeit der Einsatzmenge und Prozeßführung (pH, Temperatur etc.) - deutlich überschritten.Then, at a pH value above 4, preferably above 5, you can tan free of pimples and salt-free with a minimal amount of mineral tanning agent. Suitable mineral tannins are salts of aluminum, chromium, iron, titanium and zircon. The aluminum (Ts = 70 - 80 ° C), iron (Ts = 70 - 80 ° C), titanium (Ts = 75 - 85 ° C) or zirconium (Ts = 70 - 80 ° C) according to J. Kochta et al., Das Leder, Aug. 1990, maximum achievable shrinkage temperatures are partially increased by this combined tanning. In the process according to the invention, 100 ° C. is reached and - depending on the amount used and the process control (pH, temperature etc.) - clearly exceeded.
Eine besonders bevorzugte Arbeitsmethode besteht in der Verwendung von gerbenden Chromverbindungen, die bei hohen pH -Werten beständig sind. Solche pH-beständigen Chromverbindungen werden z.B. in der EP-A 304 677 beschrieben; dort verwendet man ein in wäßriger Lösung aus basischen Chrom(III)-sulfat und, pro Mol Chromoxid des basischen Chrom(III)-sulfats, 0,2 bis 0,8 mol aliphatische C4-C6-Dicarbonsäure und anschließendes Einstellen der theoretischen Basizität auf 0 bis 50 % hergestelltes Reaktionsprodukt, wobei die Zugabe des Reaktionsprodukts zur Pickelflotte als wäßrige Lösung mit einem Chromoxidgehalt von mindestens 5 Gew.-% bzw. in pulverisierter Form in einer Menge von 0,9 bis 1,5 Gew.-% Chromoxid (bezogen auf Blößengewicht) erfolgt, das Flottenvolumen weniger als 100 Gew.-% (bezogen auf Blößengewicht) beträgt, der End-pH-Wert über 4,0 liegt und die Endtemperatur über 40°C beträgt. Ob eine Chrom(III)-Verbindung gerbt oder nicht, wird durch ihre Basizität bestimmt (s. F. Stather, Gerbereichemie und Gerbereitechnologie, Leipzig, 1967, S. 409, 458-459).A particularly preferred working method is the use of tanning chromium compounds that are stable at high pH values. Such pH-resistant chromium compounds are described, for example, in EP-A 304 677; there one uses an aqueous solution of basic chromium (III) sulfate and, per mole of chromium oxide of the basic chromium (III) sulfate, 0.2 to 0.8 mol of aliphatic C 4 -C 6 dicarboxylic acid and subsequent adjustment of the theoretical Basicity to 0 to 50% prepared reaction product, the addition of the reaction product to the pickling liquor as an aqueous solution with a chromium oxide content of at least 5% by weight or in powdered form in an amount of 0.9 to 1.5% by weight chromium oxide (based on pelt weight), the liquor volume is less than 100% by weight (based on pelt weight), the final pH is above 4.0 and the final temperature is above 40 ° C. Whether a chromium (III) compound is tanned or not is determined by its basicity (see F. Stather, Gerbereichemie und Gerfertechnologie, Leipzig, 1967, p. 409, 458-459).
In Beispiel 1 der EP-A 304 677 wird ein Produkt beschrieben, das pro Mol Cr2O3 0,2 mol Glutarsäure bei einer Basizität von 30 hat. Dieses Produkt kann salz- und pickelfrei in kurzer Flotte von bis zu pH 9, vorzugsweise 5 - 8, dem zu gerbenden Material zugegeben werden, ohne daß es spontan zu Ausfällungen kommt. Die Gerbung verläuft, ohne daß basifiziert werden muß. Bereits mit Mengen von 1,25 Gew.-% Cr2O3 (bezogen auf Falzgewicht) werden Schrumpfungstemperaturen von ca. 100°C erzielt. Ein besonderer Vorteil einer solchen kombinierten Arbeitsweise ist die hohe Auszehrung an Chrom-III-salz aus der Restflotte der Gerbung: Bei einer Flottenlänge von beispielsweise 50 Gew.-% bei 40°C wird nach 2 - 3 Stunden ein auf ca. 1 mm gefalztes Leder durchgegerbt (mit einem Cr2O3-Gehalt im Leder von ca. 3 Gew.-%) und in der Restflotte dieser Gerbung ein Cr2O3-Gehalt von 0,4 g pro Liter bei einem End-pH (der pH-Wert sinkt infolge des zugesetzten Gerbstoffes) von 4,1 gefunden.Example 1 of EP-A 304 677 describes a product which has 0.2 mol of glutaric acid with a basicity of 30 per mol of Cr 2 O 3 . This product can be added free of salt and pimples in a short liquor of up to pH 9, preferably 5-8, to the material to be tanned without spontaneous precipitation. The tanning proceeds without having to be basified. Shrinking temperatures of approximately 100 ° C. are achieved with quantities of 1.25% by weight of Cr 2 O 3 (based on shaved weight). A particular advantage of such a combined procedure is the high exhaustion of chromium III salt from the residual liquor of the tanning: With a liquor length of, for example, 50% by weight at 40 ° C, after 1 to 3 hours, the seam is folded to approx. 1 mm Leather tanned through (with a Cr 2 O 3 content in the leather of approx. 3% by weight) and in the remaining liquor of this tanning a Cr 2 O 3 content of 0.4 g per liter at a final pH (the pH -Value drops due to the added tanning agent) of 4.1 found.
Rein rechnerisch ergibt sich z.B. gegenüber dem Beispiel 12 der EP-A 304 677, das ein im Hinblick auf Auszehrung optimiertes Verfahren darstellt, folgendes Bild:
In EP-A 690 135 wird im Beispiel A 66 eine Gerbung beschrieben, bei der nach einer Vorgerbung mit Carbamoylsulfonat Ameisensäure und dann ein handelsüblicher, selbstabstumpfender Chromgerbstoff zugefügt wurde. Diese Art der Gerbung liefert bereits Leder hoher Schrumpfungstemperatur und Restflotten ausreichend guter Chromauszehrung. Setzt man aber einen formiat- oder dicarboxylatstabilisierten Chromgerbstoff gemäß EP-A 304 677 ein, ergibt sich eine weitere Erniedrigung des Gehalts an Chrom-3+-ionen der Restflotte.In EP-A 690 135, example A 66 describes a tanning process in which formic acid and then a commercially available, self-dulling chrome tanning agent were added after pretanning with carbamoyl sulfonate. This type of tanning already provides leather with a high shrinking temperature and residual liquors with sufficiently good chromium exhaustion. However, if a formate- or dicarboxylate-stabilized chromium tanning agent according to EP-A 304 677 is used, there is a further reduction in the chromium 3+ ion content of the remaining liquor.
Sofern man also einen stabilisierten selbstabstumpfenden Chromgerbstoff verwendet, kann man nach der Vorgerbung, gegebenenfalls nach dem Falzen, ohne pH-Wert-Erniedrigung und ohne Pickel bei einem pH-Wert von mindestens 4 gerben und anschließend in gewohnter Weise nachgerben.If you use a stabilized, self-dulling chrome tanning agent, you can tan after pretanning, if necessary after folding, without lowering the pH value and without pimples at a pH of at least 4 and then retanning in the usual way.
Die Nachgerbung kann, wie üblich, mit synthetischen organischen Polymeren (incl. Harzgerbstoffen) oder mit Vegetabilgerbstoffen erfolgen.As usual, retanning can be carried out with synthetic organic polymers (incl. Resin tanning agents) or with vegetable tanning agents.
Die in dieser Anmeldung genannten mittleren Molekulargewichte sind als Zahlenmittel bestimmte Molekulargewichte.The average molecular weights mentioned in this application are number average molecular weights.
Die Prozentangaben der nachfolgenden Beispiele beziehen sich jeweils auf das Gewicht und auf Blöße/Leder.The percentages in the following examples relate to the weight and to the bare / leather.
- ®BAYCHROM A®BAYCHROM A
- selbstabstumpfender Chromgerbstoff der Bayer AG mit 21 % Chromoxidself-dulling chrome tanning agent from Bayer AG with 21% chromium oxide
- ®BAYKANOL TF-2N®BAYKANOL TF-2N
- Färbereihilfsmittel auf Basis aromatischer Sulfonsäure der Bayer AGDyeing aids based on aromatic sulfonic acid from Bayer AG
- ®BAYGENAL Braun CGG®BAYGENAL Braun CGG
- Acid Brown 83 der Bayer AGAcid Brown 83 from Bayer AG
- ®BAYMOL FD fl.®BAYMOL FD fl.
- 80 %ige wäßrige Lösung eines nichtionischen Emulgators der Bayer AG80% aqueous solution of a nonionic emulsifier from Bayer AG
- ®BLANCOROL ZB 33®BLANCOROL ZB 33
- 0 % basisches Zirkonsulfat mit 33 % Zirkonoxid der Bayer AG0% basic zirconium sulfate with 33% zirconium oxide from Bayer AG
- ®BLANCOROL ZBE®BLANCOROL ZBE
- 50 % basisches Zirkonsulfat mit 31 % Zirkonoxid der Bayer AG50% basic zirconium sulfate with 31% zirconium oxide from Bayer AG
- ®TANIGAN BN®TANIGAN BN
- Organisch synthetischer Austauschgerbstoff der Bayer AG auf Basis Dioxy-diphenyl-sulfon und Naphthalinsulfosäure; Säurezahl 85Organic synthetic exchange tanning agent from Bayer AG based on dioxydiphenyl sulfone and naphthalenesulfonic acid; Acid number 85
- ®TANIGAN LF®TANIGAN LF
- Synthetischer Austausch- und Weißgerbstoff der Bayer AGSynthetic exchange and white tanning agents from Bayer AG
- ®TANIGAN PAK-N®TANIGAN PAK-N
- Neutralisationsgerbstoff auf Basis aromatischer, Sulfonsäure der Bayer AGNeutralization tanning agent based on aromatic, sulfonic acid from Bayer AG
- ®TANIGAN OS®TANIGAN OS
- analog TANIGAN BN aufgebauter Austauschgerbstoff der Bayer AG der Säurezahl 32Analogue TANIGAN BN replacement tanning agent from Bayer AG with acid number 32
- ®RETINGAN R7®RETINGAN R7
- anionischer Harzgerbstoff der Bayer AG mit selektiver Füllwirkung auf Basis Dicyandiamidanionic resin tanning agent from Bayer AG with selective filling effect based on dicyandiamide
- Quebracho, Mimosa, Kastanie:Quebracho, Mimosa, Chestnut:
- handelsübliche Vegetabilgerbstoffecommercially available vegetable tanning agents
- ®CUTAPOL TIS-MF®CUTAPOL TIS-MF
- sulfitiertes Fischöl, 65 % WS von Dr.Th.Böhmesulfited fish oil, 65% WS by Dr.Th.Böhme
- ®CORIPOL MK®CORIPOL MK
- Mischung aus sulfitierten, natürlichen Ölen und synthetischen Sulfoestern von Stockhausen & Cie.Mixture of sulfited, natural oils and synthetic sulfoesters from Stockhausen & Cie.
- ®LUTAN BN®LUTAN BN
- basisches Aluminiumchlorid der BASF AGbasic aluminum chloride from BASF AG
- ®TETRAPOL SAF®TETRAPOL SAF
- weichmachendes Stabilisierungsmittel auf Grundlage von Fettalkoholen von Stockhausen & Cie.softening stabilizer based on fatty alcohols from Stockhausen & Cie.
- ®POLYZIM 202®POLYZIM 202
- proteolytisches Beizmittel auf Basis Pankreas der Fa. Diamaltproteolytic mordant based on pancreas from Diamalt
- MagnesiumoxidMagnesium oxide
- Magnesia 322 der Fa. Magnesia GmbH, LüneburgMagnesia 322 from Magnesia GmbH, Lüneburg
Betriebsüblich geäscherte Blöße wird auf 2 mm gespalten. Dann wird die Blöße in ein übliches Gerbfaß gegeben und einmal mit 200 % (%-Angaben beziehen sich hier und im folgenden auf Spaltgewicht) Wasser von 35°C 15 Minuten lang gewaschen. Dann läßt man die Flotte ab. In der anschließenden Entkälkung wird 30 % Wasser von 35°C, 2% Ammoniumsulfat und 0,2 % Natrium-meta-bisulfit zugegeben und 10 Minuten bewegt. Danach gibt man 0,2 % Ameisensäure (1:10 verdünnt) und 0,2 % BAYMOL FD flüssig und laßt 20 Minuten laufen. Mit 0,5 % Polyzim 202 wird 30 Minuten in der gleichen Flotte gebeizt. Es resultiert ein pH-Wert von 7,9 (Schnitt der Blöße mit Phenolphthalein farblos). Dann läßt man die Flotte ab.Normally ashed nakedness is split to 2 mm. Then the pelts are placed in a conventional tanning drum and washed once with 200% (percentages refer here and hereinafter to the gap weight) of water at 35 ° C. for 15 minutes. Then let the fleet down. In the subsequent descaling, 30% water at 35 ° C, 2% ammonium sulfate and 0.2% sodium meta-bisulfite is added and agitation is carried out for 10 minutes. Then add 0.2% formic acid (diluted 1:10) and 0.2% BAYMOL FD liquid and let it run for 20 minutes. Stain with 0.5% Polyzim 202 in the same liquor for 30 minutes. The result is a pH of 7.9 (cut the nakedness with colorless phenolphthalein). Then let the fleet down.
Man wäscht 2 mal mit 150 % Wasser (von Raumtemperatur) und die Flotte wird abgelassen.It is washed twice with 150% water (from room temperature) and the liquor is drained off.
In der jetzt beginnenden Gerbung wird 30 % Wasser von 30°C eingefüllt und 0,35 % Magnesiumoxid (Magnesia 322) und nach 60 Minuten 7,5 % (bezogen auf Wirksubstanz) eines Produktes, das nach Beispiel 1 der EP-A 690 135 hergestellt worden war, zugegeben. Nach einer Laufzeit von 6 Stunden stellt sich ein pH-Wert von 7,1 ein; man fügt weitere 0,35 % Magnesiumoxid (Magnesia 322) zu und läßt über Nacht laufen (End-pH-Wert 6,8).
Am nächsten Morgen hat das entstandene Leder eine Schrumpfungstemperatur von 78°C.30% of water at 30 ° C. and 0.35% of magnesium oxide (Magnesia 322) are introduced into the tanning now beginning, and after 60 minutes 7.5% (based on active substance) of a product which is described in Example 1 of EP-A 690 135 manufactured had been admitted. After a running time of 6 hours, a pH of 7.1 is established; another 0.35% magnesium oxide (Magnesia 322) is added and the mixture is left to run overnight (final pH 6.8).
The next morning the resulting leather has a shrinking temperature of 78 ° C.
Die Flotte wird abgelassen, die Leder werden 10 Minuten bei Raumtemperatur gespült, dann werden sie abgewelkt und auf 1 mm Stärke gefalzt.
Man gibt die gefalzten Leder in ein Faß und wäscht sie 10 Minuten lang mit 200 % (bezogen auf Falzgewicht) Wasser (von Raumtemperatur). Man läßt die Flotte ab.The liquor is drained, the leathers are rinsed for 10 minutes at room temperature, then they are wilted and folded to a thickness of 1 mm.
The folded leather is placed in a barrel and washed for 10 minutes with 200% (based on the fold weight) of water (from room temperature). The fleet is released.
Die anschließende Mineralgerbung wird durch 50 % Wasser von 35°C (der pH-Wert hat sich auf 6,8 eingestellt) sowie von 5 % eines Produktes, das nach Beispiel 1 der EP-A 304677 hergestellt wurde, eingeleitet. Nach 150 Minuten Bewegung stellt sich ein pH-Wert 4,1 ein.The subsequent mineral tanning is initiated by 50% water at 35 ° C. (the pH value has reached 6.8) and 5% of a product which has been prepared according to Example 1 of EP-A 304677. After 150 minutes of movement, the pH value becomes 4.1.
Die Flotte wird abgelassen, die Leder haben eine Ts von 100°C. Nach einer Wäsche mit 300 % Wasser von 40°C (10 Minuten) wird die Flotte abgelassen. In der jetzt einsetzenden Neutralisation wird 200 % Wasser (40°C), 3 % TANIGAN PAK-N 1 Stunde (pH-Wert 4,7), dann 4 % CUTAPOL TIS-MF (1:4 verdünnt) 30 Minuten einwirken lassen. Dann wird abgelassen und 10 Minuten mit 200 % Wasser (35°C) gewaschen. Mit 150 % Wasser (40°C) wird die Nachgerbung angefangen: 3 % TANIGAN BN und 2 % TANIGAN LF 20 Minuten, sodann eine Lösung aus 3 % BAYGENAL Braun CGG und 2 % BAYKANOL TF-2N (1:20 in 60°C warmem Wasser) zugefügt. Nach 60 Minuten wird 100 % Wasser (70°C) zugefügt, nach weiteren 10 Minuten 2 % Ameisensäure (1:5 verdünnt) zugesetzt und 30 Minuten laufen lassen (pH-Wert 3,4). Nach Ablassen der Flotte wird in 200 % Wasser (50°C) mit einer Mischung aus 8 % CORIPOL MK, 6 % CUTAPOL TIS-MF und 1 % TETRAPOL SAF (1:4 mit 60°C Wasser verdünnt) 90 Minuten gefettet. Danach kommt 1,5 % Ameisensäure (1:5 verdünnt) für 45 Minuten dazu (pH-Wert 3.1); die Flotte wird klar. Nach Ablassen der Flotte wird zweimal mit 200 % Wasser von Raumtemperatur jeweils 10 Minuten gewaschen. Die Leder kommen auf Bock, werden naß gespannt, klimatisiert, gestollt, gemillt, gespannt und beurteilt.The fleet is drained, the leathers have a Ts of 100 ° C. After washing with 300% water at 40 ° C (10 minutes), the liquor is drained off. In the neutralization which now begins, 200% water (40 ° C), 3% TANIGAN PAK-N are left to act for 1 hour (pH 4.7), then 4% CUTAPOL TIS-MF (diluted 1: 4) for 30 minutes. Then it is drained and washed with 200% water (35 ° C.) for 10 minutes. The retanning is started with 150% water (40 ° C): 3% TANIGAN BN and 2% TANIGAN LF for 20 minutes, then a solution of 3% BAYGENAL Braun CGG and 2% BAYKANOL TF-2N (1:20 at 60 ° C warm water) added. After 60 minutes, 100% water (70 ° C.) is added, after another 10 minutes 2% formic acid (diluted 1: 5) is added and the mixture is left to run for 30 minutes (pH 3.4). After draining the liquor, grease for 90 minutes in 200% water (50 ° C) with a mixture of 8% CORIPOL MK, 6% CUTAPOL TIS-MF and 1% TETRAPOL SAF (diluted 1: 4 with 60 ° C water). Then 1.5% formic acid (diluted 1: 5) is added for 45 minutes (pH 3.1); the fleet becomes clear. After draining the liquor, it is washed twice with 200% water at room temperature for 10 minutes each. The leathers are put on jack, are wet-tensioned, air-conditioned, stolled, grilled, tensioned and assessed.
In Anlehnung an Beispiel A 1 der EP-A 690 135 wurden 12 Stücke von 100 g Rindblöße in 40 % Flotte mit 0,35 % Magnesiumoxid 1 Stunde in einem Versuchsfäßchen der Firma Dose vorlaufen lassen (pH-Wert 7,4), dann 7,5 % (Wirksubstanz) eines Produktes gemäß Beispiel 1 der EP-A 690 135 zugegeben, nach 3 Stunden weitere 0,35 % Magnesiumoxid (pH-Wert 6,6) und dann über Nacht laufen lassen. Das resultierende Leder hatte eine Ts von 77°C. 5 dieser Leder wurden in 100 % Flotte mit 0,05 % Ameisensäure und 0,08 % Schwefelsäure auf einen pH-Wert von 3, weitere 3 mit 0,08 % Schwefelsäure auf einen pH-Wert von 4, und je eines mit 0,03 % Ameisensäure auf pH von 5, eines bei 6,6 (vorliegend belassen) und eines mit 0,04 % 42 %iger wäßriger Natronlauge auf 8,2 eingestellt.
Alle diese Leder wurden nun mineralisch nachgegerbt.
All of these leathers have now been retanned minerally.
Das in EP-A 690 135 unter A 66 aufgeführte Beispiel wurde nachgearbeitet (Beispiele 3 bis 5) und mit dem erfindungsgemäßen Verfahren verglichen (Beispiel 6). Die erhaltenen Leder wurden auf Schrumpfungstemperatur untersucht und die Chromgehalte der Leder und der Restflotten ermittelt.
Um mit der Gerbmethode der EP-A 690 135 zu Ledern hoher Schrumpfungstemperatur zu kommen, sollte man - um Ausfallungen zu verhindern - pickeln. Wenn man aber auf das Pickeln verzichten will, sind Gerbstoffen analog denen der EP-A 304 677 zu empfehlen, wenn man gleichzeitig Wert auf hohe Auszehrung aus den Restflotten der Gerbung legt.To get leather with a high shrinking temperature using the tanning method of EP-A 690 135, you should pick - to prevent failures. However, if you want to do without pimples, tanning agents analogous to those of EP-A 304 677 are recommended if, at the same time, you value high consumption from the remaining liquors of the tanning process.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19624821 | 1996-06-21 | ||
DE19624821A DE19624821A1 (en) | 1996-06-21 | 1996-06-21 | Leather tanning process |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0814168A1 true EP0814168A1 (en) | 1997-12-29 |
EP0814168B1 EP0814168B1 (en) | 2000-10-18 |
Family
ID=7797601
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97109282A Expired - Lifetime EP0814168B1 (en) | 1996-06-21 | 1997-06-09 | Process for tanning of leather |
Country Status (5)
Country | Link |
---|---|
US (1) | US5820634A (en) |
EP (1) | EP0814168B1 (en) |
JP (1) | JPH1060499A (en) |
DE (2) | DE19624821A1 (en) |
ES (1) | ES2152594T3 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1647563A2 (en) | 2004-10-15 | 2006-04-19 | Lanxess Deutschland GmbH | Tanning agents based on isocyanates |
CN102168154A (en) * | 2011-03-24 | 2011-08-31 | 黄石圣康医药化工有限公司 | Method for preparing polynuclear low-chromium leather tanning agent |
CN102242228A (en) * | 2011-05-18 | 2011-11-16 | 齐河力厚化工有限公司 | Novel salt-free pickling leather additive |
CN102321771A (en) * | 2011-08-22 | 2012-01-18 | 温州大学 | Chrome-free metal composite tanning agent and preparation method thereof |
EP2415879A1 (en) | 2010-08-06 | 2012-02-08 | LANXESS Deutschland GmbH | Compositions comprising at least one compound containing carbamoylsulfonate groups and their use as tanning agents |
EP2508627A1 (en) | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Solid, particular material on the basis of compounds containing carbamoylsulfonate groups |
EP2508626A1 (en) | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Solid, particular tanning agent preparations |
EP2540753A1 (en) | 2011-06-29 | 2013-01-02 | LANXESS Deutschland GmbH | Compound on the basis of compounds containing carbamoylsulfonate groups |
WO2013001077A1 (en) | 2011-06-29 | 2013-01-03 | Lanxess Deutschland Gmbh | Composition based on compounds containing carbamoylsulfonate groups |
EP2557224A1 (en) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Method for colouring substrates containing collagen fibres |
EP2557181A1 (en) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Method for hydrophobic finishing of substrates containing collagen fibre |
CN103060484A (en) * | 2013-01-24 | 2013-04-24 | 焦作隆丰皮草企业有限公司 | Salt-free tanning method |
CN104046707A (en) * | 2014-06-30 | 2014-09-17 | 四川大学 | Iron-zirconium-aluminum compound tanning agent and preparation method thereof |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2607499A3 (en) * | 2013-02-14 | 2013-07-10 | Basf Se | Method for producing leather |
CN104073575B (en) * | 2014-07-16 | 2016-07-06 | 四川大学 | Fur tanning agent based on isocyanates and preparation method thereof |
CN105969920B (en) * | 2016-07-25 | 2018-02-27 | 兴业皮革科技股份有限公司 | A kind of Chrome-free hygrometric state dyeing and finishing technology that cattle hide upper leather is prepared based on ferrozirconium aluminum complex |
CN114479061A (en) * | 2022-01-21 | 2022-05-13 | 四川大学 | Polyether amine chlorotriazine telechelic polymer tanning agent, and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0001067A1 (en) * | 1977-09-01 | 1979-03-21 | Bayer Ag | Water-soluble cationic oligourethane resins and their use in the treatment of hides or leather |
US4413997A (en) * | 1983-02-07 | 1983-11-08 | The United States Of America As Represented By The Secretary Of Agriculture | Dicarbamoylsulfonate tanning agent |
EP0290143A1 (en) * | 1987-04-24 | 1988-11-09 | I.C.I. Francolor Snc | Tanning agent |
US5417723A (en) * | 1993-03-25 | 1995-05-23 | Bayer Aktiengesellschaft | Use of ester urethanes for retanning |
EP0690135A1 (en) * | 1994-06-28 | 1996-01-03 | Bayer Ag | Hydrogen sulfite blocked polyisocyanates as tanning agents |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2923594A (en) * | 1958-05-29 | 1960-02-02 | Ethicon Inc | Method of tanning |
US2941859A (en) * | 1959-04-08 | 1960-06-21 | Martin L Fein | Tanning with glutaraldehyde |
US3748329A (en) * | 1970-07-08 | 1973-07-24 | Bayer Ag | Compounds containing the 2,4,6-triketo-1,3,5-oxadiazine ring |
DE2308015B2 (en) * | 1973-02-17 | 1980-07-31 | Bayer Ag, 5090 Leverkusen | Process for the production of polyisocyanates with a biuret structure |
US3976622A (en) * | 1973-02-17 | 1976-08-24 | Bayer Aktiengesellschaft | Process for the production of polyisocyanates with a biuret structure |
ATE21935T1 (en) * | 1981-05-19 | 1986-09-15 | Inst Chimii Tech Redkik | TANNING AGENTS FOR HIDES AND PROCESS FOR PRODUCTION THEREOF. |
GB8426851D0 (en) * | 1984-10-24 | 1984-11-28 | British Leather Manufacturers | Tanning agents |
DE3700209A1 (en) * | 1987-01-07 | 1988-07-21 | Bayer Ag | METHOD FOR PRODUCING POLYISOCYANATES WITH BIURET STRUCTURE |
DE3726796A1 (en) * | 1987-08-12 | 1989-02-23 | Bayer Ag | METHOD FOR HIGHLY EXHAUSTING CHROME TANNING |
DE3743782A1 (en) * | 1987-12-23 | 1989-07-13 | Bayer Ag | ESTER URETHANE (METH) ACRYLIC ACID DERIVATIVES |
DE3811350A1 (en) * | 1988-04-02 | 1989-10-19 | Bayer Ag | METHOD FOR THE PRODUCTION OF ISOCYANURATE POLYISOCYANATES, THE COMPOUNDS OBTAINED BY THIS PROCESS AND THEIR USE |
DE3814167A1 (en) * | 1988-04-27 | 1989-11-09 | Bayer Ag | METHOD FOR PRODUCING POLYISOCYANATES CONTAINING ISOCYANURATE GROUPS AND THE USE THEREOF |
DE3900053A1 (en) * | 1989-01-03 | 1990-07-12 | Bayer Ag | PROCESS FOR THE PREPARATION OF POLYISOCYANATES USING URETDION AND ISOCYANATE GROUPS, THE POLYISOCYANATES AVAILABLE FOR THIS PROCESS, AND THEIR USE IN TWO-COMPONENT POLYURETHANE VARNISHES |
-
1996
- 1996-06-21 DE DE19624821A patent/DE19624821A1/en not_active Withdrawn
-
1997
- 1997-06-09 EP EP97109282A patent/EP0814168B1/en not_active Expired - Lifetime
- 1997-06-09 DE DE59702486T patent/DE59702486D1/en not_active Expired - Fee Related
- 1997-06-09 ES ES97109282T patent/ES2152594T3/en not_active Expired - Lifetime
- 1997-06-17 JP JP9175148A patent/JPH1060499A/en active Pending
- 1997-06-17 US US08/877,381 patent/US5820634A/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0001067A1 (en) * | 1977-09-01 | 1979-03-21 | Bayer Ag | Water-soluble cationic oligourethane resins and their use in the treatment of hides or leather |
US4413997A (en) * | 1983-02-07 | 1983-11-08 | The United States Of America As Represented By The Secretary Of Agriculture | Dicarbamoylsulfonate tanning agent |
EP0290143A1 (en) * | 1987-04-24 | 1988-11-09 | I.C.I. Francolor Snc | Tanning agent |
US5417723A (en) * | 1993-03-25 | 1995-05-23 | Bayer Aktiengesellschaft | Use of ester urethanes for retanning |
EP0690135A1 (en) * | 1994-06-28 | 1996-01-03 | Bayer Ag | Hydrogen sulfite blocked polyisocyanates as tanning agents |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1647563A2 (en) | 2004-10-15 | 2006-04-19 | Lanxess Deutschland GmbH | Tanning agents based on isocyanates |
CN103080341A (en) * | 2010-08-06 | 2013-05-01 | 朗盛德国有限责任公司 | Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents |
US9376729B2 (en) * | 2010-08-06 | 2016-06-28 | Lanxess Deutschland Gmbh | Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents |
RU2578611C2 (en) * | 2010-08-06 | 2016-03-27 | ЛЕНКСЕСС Дойчланд ГмбХ | Compositions containing at least one compound, possessing carbamoylsulphonate groups, and application thereof as tanning substances |
EP2415879A1 (en) | 2010-08-06 | 2012-02-08 | LANXESS Deutschland GmbH | Compositions comprising at least one compound containing carbamoylsulfonate groups and their use as tanning agents |
WO2012016907A1 (en) | 2010-08-06 | 2012-02-09 | Lanxess Deutschland Gmbh | Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents |
CN103080341B (en) * | 2010-08-06 | 2015-11-25 | 朗盛德国有限责任公司 | Comprise at least one containing the composition of compound of formamyl sulfonate ester group and the purposes as tanning agent thereof |
KR101439070B1 (en) * | 2010-08-06 | 2014-09-05 | 란세스 도이치란트 게엠베하 | Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents |
US20130288066A1 (en) * | 2010-08-06 | 2013-10-31 | Lanxess Deutschland Gmbh | Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents |
CN102168154A (en) * | 2011-03-24 | 2011-08-31 | 黄石圣康医药化工有限公司 | Method for preparing polynuclear low-chromium leather tanning agent |
CN102168154B (en) * | 2011-03-24 | 2013-05-08 | 黄石圣康医药化工有限公司 | Method for preparing polynuclear low-chromium leather tanning agent |
EP2508626A1 (en) | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Solid, particular tanning agent preparations |
EP2508627A1 (en) | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Solid, particular material on the basis of compounds containing carbamoylsulfonate groups |
CN103502477B (en) * | 2011-04-04 | 2017-03-15 | 朗盛德国有限责任公司 | Solid particulate materials containing carbamyl sulfonate ester group |
WO2012136565A1 (en) | 2011-04-04 | 2012-10-11 | Lanxess Deutschland Gmbh | Solid, particulate tanning agent preparations |
CN103502477A (en) * | 2011-04-04 | 2014-01-08 | 朗盛德国有限责任公司 | Solid, particulate material based on compounds containing carbamoylsulfonate groups |
WO2012136559A1 (en) | 2011-04-04 | 2012-10-11 | Lanxess Deutschland Gmbh | Solid, particulate material based on compounds containing carbamoylsulfonate groups |
CN102242228A (en) * | 2011-05-18 | 2011-11-16 | 齐河力厚化工有限公司 | Novel salt-free pickling leather additive |
WO2013001077A1 (en) | 2011-06-29 | 2013-01-03 | Lanxess Deutschland Gmbh | Composition based on compounds containing carbamoylsulfonate groups |
EP2540753A1 (en) | 2011-06-29 | 2013-01-02 | LANXESS Deutschland GmbH | Compound on the basis of compounds containing carbamoylsulfonate groups |
WO2013023980A1 (en) | 2011-08-12 | 2013-02-21 | Lanxess Deutschland Gmbh | Method for hydrophobing substrates containing collagen fibers |
WO2013023979A1 (en) | 2011-08-12 | 2013-02-21 | Lanxess Deutschland Gmbh | Method for dyeing substrates containing collagen fibre |
EP2557224A1 (en) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Method for colouring substrates containing collagen fibres |
EP2557181A1 (en) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Method for hydrophobic finishing of substrates containing collagen fibre |
CN102321771A (en) * | 2011-08-22 | 2012-01-18 | 温州大学 | Chrome-free metal composite tanning agent and preparation method thereof |
CN103060484A (en) * | 2013-01-24 | 2013-04-24 | 焦作隆丰皮草企业有限公司 | Salt-free tanning method |
CN103060484B (en) * | 2013-01-24 | 2015-03-11 | 焦作隆丰皮草企业有限公司 | Salt-free tanning method |
CN104046707A (en) * | 2014-06-30 | 2014-09-17 | 四川大学 | Iron-zirconium-aluminum compound tanning agent and preparation method thereof |
CN104046707B (en) * | 2014-06-30 | 2016-05-11 | 四川大学 | Iron-zirconium-aluminium coordinates tanning agent and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
US5820634A (en) | 1998-10-13 |
DE59702486D1 (en) | 2000-11-23 |
JPH1060499A (en) | 1998-03-03 |
EP0814168B1 (en) | 2000-10-18 |
DE19624821A1 (en) | 1998-01-02 |
ES2152594T3 (en) | 2001-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0814168B1 (en) | Process for tanning of leather | |
EP2601317B1 (en) | Compositions comprising at least one compound containing a carbamoyl sulfonate group and use of the same as tanning agents | |
EP1647563A2 (en) | Tanning agents based on isocyanates | |
EP0963445A1 (en) | Biologically degradable leather | |
EP0690135B1 (en) | Hydrogen sulfite blocked polyisocyanates as tanning agents | |
WO2013023979A1 (en) | Method for dyeing substrates containing collagen fibre | |
EP0717114A2 (en) | Aqueous composition for pretanning hides or retanning of leather | |
EP3924523B1 (en) | Leather agents for beamhouse | |
EP0429830A2 (en) | Method of tanning hides and retanning chrome-tanned leather | |
EP0533011B1 (en) | Process for producing chrome-tanned leather | |
AT409384B (en) | AQUEOUS COMPOSITION FOR PRELIMINATING SKIN BALES OR LEAVING LEATHER | |
EP0526815B1 (en) | Process for tanning/impregnation and/or post-tanning of leather | |
EP0347373B1 (en) | Aqueous solutions of synthetic tanning agents | |
DE2504081C3 (en) | Process for tanning or retanning of pelts or leather with hydrophilic oligourethanes | |
DE19707578A1 (en) | Production of leather | |
EP3390673B1 (en) | Method for the manufacture of semi-finished products of leather or fur | |
EP0574800B1 (en) | Process for tanning leather and furs | |
DE1284028C2 (en) | METHOD OF RAPID SKIN TANNING | |
DE19736309A1 (en) | Leather, used for clothes, shoes, furniture covers and automobile interiors | |
DE1494839C3 (en) | Process for the rapid tanning of leather | |
DE3306374A1 (en) | METHOD FOR TANNING SKIN WITH A HIGH BASIC CHROME TANNER | |
DE1000563B (en) | Tanning of hides and skins | |
DE1289941B (en) | Water-soluble condensation products from dicyandiamide, oxo compounds and salts of sulphurous acid for tanning skins or pelts | |
DE4421292A1 (en) | Retanning of chrome-tanned leather | |
WO2001002533A1 (en) | Device and method for producing semifinished leather products |
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): DE ES GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19980629 |
|
AKX | Designation fees paid |
Free format text: DE ES GB IT NL SE |
|
RBV | Designated contracting states (corrected) |
Designated state(s): DE ES GB IT NL SE |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
17Q | First examination report despatched |
Effective date: 19991019 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE ES GB IT NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20001018 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20001018 |
|
REF | Corresponds to: |
Ref document number: 59702486 Country of ref document: DE Date of ref document: 20001123 |
|
ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2152594 Country of ref document: ES Kind code of ref document: T3 |
|
EN | Fr: translation not filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20010515 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20010605 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20010606 Year of fee payment: 5 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20010630 Year of fee payment: 5 |
|
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 |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
EUG | Se: european patent has lapsed |
Ref document number: 97109282.0 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020609 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020610 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030101 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030101 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20020609 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20030101 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030711 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050609 |