EP0648846B1 - Retans with softening and hydrophobic action - Google Patents
Retans with softening and hydrophobic action Download PDFInfo
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- EP0648846B1 EP0648846B1 EP94115468A EP94115468A EP0648846B1 EP 0648846 B1 EP0648846 B1 EP 0648846B1 EP 94115468 A EP94115468 A EP 94115468A EP 94115468 A EP94115468 A EP 94115468A EP 0648846 B1 EP0648846 B1 EP 0648846B1
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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
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
Definitions
- the invention relates to improved retanning agents for making softer hydrophobic leather.
- retanning means aftertreatment of pre-tanned (generally chrome-tanned) Leather to color, levelness, softness, fullness as well as the behavior towards water (Hydrophobicity) to optimize and fix tannins.
- Retanning agents do not meet all the expectations placed on them, because they are either insufficiently hydrophobic or because of the handle, the colorability, the grain or the subsequent finishing of the leather disadvantageous influence.
- the multitude of desirable properties compels one Compromise.
- Retanning agents are desired that give the leather an optimal look Provide hydrophobicity (i.e. the leather while maintaining the water vapor permeability make it as impermeable as possible), but handle, colorability, firm grain and do not adversely affect the applicability of the subsequent dressing.
- Preferred monomers c) include, for example, styrene, ⁇ -methylstyrene, p-methylstyrene, Vinyl acetate, allyl acetate, isobutyl vinyl ether, allyl alcohol and methallyl alcohol.
- Terpolymers from a), b) and c) are known; see. e.g. DE-OS 27 01 760. You can be produced by free radical polymerization.
- the Polymerization takes place in an inert atmosphere under polymerization conditions organic solvents, especially in an aromatic solvent such as toluene or xylene.
- Suitable radical formers include, for example, diacyl peroxides such as diacetyl peroxide, Dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, peroxy esters such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, alkyl peroxides such as bis (tert.-butylperoxybutane), dicumyl peroxide, tert.-butylcumyl peroxide, hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, ketone peroxides such as Cyclohexanone hydroperoxide, methyl ethyl ketone hydroperoxide, acetylacetone peroxide or azoisobutyrodinitrile.
- diacyl peroxides such as diacetyl peroxide, Dibenzoyl peroxid
- the reaction of the terpolymers A with the alcohols B can either be direct in the solution of the terpolymers A or after isolation of the solid terpolymers A in substance, solution or suspension.
- the reaction can Temperatures of 60 to 180, preferably 80 to 140 ° C are carried out.
- Primary and secondary alcohols B are preferred. Suitable representatives include for example n-hexanol, cyclohexanol, n-octanol, 2-ethylhexanol, n-dodecanol, n-tetradecanol, n-hexadecanol, stearyl alcohol, eicosanol and behenyl alcohol or their mixtures.
- the reaction can be carried out in the presence or absence of an acid catalyst be performed.
- Mineral acids such as are suitable as such Sulfuric acid or anhydrous hydrogen chloride, aliphatic and aromatic Sulphonic acids such as methanesulphonic acids and p-toluenesulphonic acid, fluorinated aliphatic Carboxylic acids such as perfluorobutanoic or octanoic acid, and acidic ion exchangers.
- mineral acids such as are suitable as such Sulfuric acid or anhydrous hydrogen chloride, aliphatic and aromatic Sulphonic acids such as methanesulphonic acids and p-toluenesulphonic acid, fluorinated aliphatic Carboxylic acids such as perfluorobutanoic or octanoic acid, and acidic ion exchangers.
- esterified in the presence of an acidic catalyst then it is useful to remove the water of reaction in a with water not miscible organic solvents, e
- Base C preferably as an aqueous solution.
- Suitable bases C include, for example, alkali metal hydroxides and alcoholates as well as ammonia and primary, secondary and tertiary aliphatic amines with bis to 6 carbon atoms per molecule (which carry up to 1 hydroxyl group per alkyl radical can), especially sodium and potassium hydroxides and ammonia, Ethylamine, propylamine, n-butylamine, diethanolamine, dimethylamine and Triethylamine.
- Base C can be the polymer melt or solution or dispersion are added.
- the amount of base C is such that at least 20% of the carboxyl groups remaining after the esterification reaction be implemented. A conversion of all remaining carboxyl groups is possible; but it can also be advantageous to use only 20 to 80% of the remaining To neutralize carboxyl groups (In this context, the esterification reaction unreacted anhydride groups formally as 2 carboxyl groups be counted).
- the esterification reaction unreacted anhydride groups formally as 2 carboxyl groups be counted.
- the aqueous solutions or dispersions obtained are preferably based on neutralized wet blue material used, i.e. on chrome leather, which by Common neutralizing agents (e.g. sodium bicarbonate, formate, etc.) or neutralizing tanning agents adjusted to a pH of 4 to 7, preferably 5.5 to 6.5 has been.
- Common neutralizing agents e.g. sodium bicarbonate, formate, etc.
- neutralizing tanning agents adjusted to a pH of 4 to 7, preferably 5.5 to 6.5 has been.
- the neutralized wet blue material can be used possibly with commercially available retanning agents (replacement, white, resin and polymeric tanning agents), Vegetable tanning agents and fatliquors are treated. Want to produce dyed leather is dyed with dyes. Beyond that it is also possible, the solutions or dispersions on vegetable tanned purely vegetable Use leather for retanning before dyeing and greasing.
- aqueous solutions or dispersions obtained can also be used in others Stages of retanning, e.g. after treatment with exchange, white or Vegetable tanning agents can be used.
- the leather retanned according to the invention is distinguished by a very soft and full grip as well as good scar strength and scar smoothness from and have a clear pigmentation. Because of their high light fastness and Their good thermal yellowing resistance makes them ideal for Manufacture of light leather. In addition, show with the dispersions of the invention retanned leather has water-repellent properties.
- dispersion IV After a running time of 15 minutes, 1%, based on dry substance, of dispersion IV according to the invention is added as a 20.7% setting and the mixture is left to run for a further 45 minutes.
- the liquor pH is around 5.2.
- the resulting leathers are of good fullness and softness and stand out with excellent scar smoothness.
- the light fastness is level 5 to 6 (Xeno test), and the heat yellowing (24 hours, 120 ° C) is level 3 to 4 (Gray scale).
- dispersion III After a running time of 15 minutes, 1.5%, based on dry substance, of dispersion III according to the invention is added as a 15.7% setting and the mixture is left to run for a further 45 minutes.
- the liquor pH is around 5.0.
- the pH is adjusted by adding 1.5% Sodium formate and 0.4% sodium bicarbonate raised to approximately 6.0 and the liquor drained after 40 minutes.
- the resulting leathers are of good fullness and softness and stand out with excellent smooth scars with fine mill grain.
- dispersion I according to the invention (see preparation example 1) is added as a 12.7% setting and the mixture is left to run for 30 minutes.
- the liquor pH is around 5.0.
- split leather 25 kg are made in the usual way Chromium column (gap thickness approx. 1.3 mm) in 200% water (based on gap weight as all of the following) washed at 50 ° C for 10 minutes.
- the leathers After draining the liquor, the leathers are soaked in 200% water for 10 minutes Washed 60 ° C and in 100% water of 60 ° C with 7.0% of a commercially available Fat mixture greased.
- the liquor pH is around 4.5.
- the leather is added by adding 0.5% formic acid (85%, 1:10 diluted with water) acidified to a pH of approx. 4.0.
- the leather are rinsed in the usual way (water at 20 ° C, 5 minutes), stretched out, vacuum and hang-dried, air-conditioned, tunneled, aired, rerolled and again vacuum dried (1/2 minute, 70 ° C).
- the resulting gaps have a very high degree of whiteness and stand out with a soft full grip, the velor side having a soft, uniform short cut.
- 20 kg of New Zealand sheep wet blue are used to manufacture clothing nappa in 200% water (based on shaved weight, like all the following information) from Washed 40 ° C and 0.5% of a commercially available emulsifier for 20 minutes. After draining the liquor in 100% water at 40 ° C with a commercial self-dulling chrome-syntan retanning agent re-chromed for 15 minutes, 1% of a commercial synthetic fatliquor added and after 45 minutes running time with 3% of a commercial neutralization tanning agent and 0.3% sodium bicarbonate to pH 5.5 over 45 minutes neutralized.
- dispersion III according to the invention from preparation example 3 is added as a 15.7% setting and drummed for 45 minutes.
- the leathers are rinsed cold and finished in the usual way (dried, milled, minced etc.).
- the leathers have a soft full grip and are characterized by a fine smooth scars and a uniform, brilliant color.
- Vegetable uppers are made in the usual way tanned leather in 300% water (based on shaved weight, like all of the following Details) of 30 ° C for 10 minutes and after draining the liquor in 100% water at 30 ° C with 1% of a commercial bleaching agent over 20 Minutes bleached (pH of the liquor: approx. 3.3) and with 300% water at 40 ° C washed.
- the resulting leathers are soft, of good fullness and have a pleasant feel slimy grip.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Die Erfindung betrifft verbesserte Nachgerbstoffe zur Herstellung weicher hydrophober Leder.The invention relates to improved retanning agents for making softer hydrophobic leather.
Während die Gerbung zu einer Erhöhung der Schrumpftemperatur des Leders führt, hat die Nachgerbung darauf kaum Einfluß. Unter "Nachgerbung" versteht man die Nachbehandlung von vorgegerbtem (im allgemeinen chromgegerbtem) Leder, um Farbe, Egalität, Weichheit, Fülle sowie das Verhalten gegen Wasser (Hydrophobie) zu optimieren und Gerbstoffe zu fixieren.During the tanning process an increase in the shrinking temperature of the leather retanning has hardly any influence on it. Under "retanning" means aftertreatment of pre-tanned (generally chrome-tanned) Leather to color, levelness, softness, fullness as well as the behavior towards water (Hydrophobicity) to optimize and fix tannins.
Die heute wichtigsten Nachgerbstoffe sind neben der Gruppe der sogenannten Syntane Carboxylgruppen-haltige Polymerisate in Salzform (EP-A-118 023 und 372 746, DE-OS 39 31 039). Aber auch Polyurethane, die gegebenenfalls Polyethylenoxidgruppen, ionische Gruppen bzw. Methylolgruppen enthalten, sind schon zur Nachgerbung eingesetzt worden (DE-OS 25 04 081).The most important retanning agents today are alongside the group of so-called Syntane carboxyl group-containing polymers in salt form (EP-A-118 023 and 372 746, DE-OS 39 31 039). But also polyurethanes, which may contain polyethylene oxide groups, contain ionic groups or methylol groups are already have been used for retanning (DE-OS 25 04 081).
Die bislang bekannten Nachgerbstoffe erfüllen nicht alle an sie gestellten Erwartungen, weil sie entweder ungenügend hydrophobieren oder den Griff, die Färbbarkeit, die Festnarbigkeit oder die nachfolgende Zurichtung der Leder nachteilig beeinflussen. Die Vielzahl wünschenswerter Eigenschaften zwingt zu einem Kompromiß. Erwünscht sind Nachgerbstoffe, die dem Leder eine optimale Hydrophobie verleihen (also das Leder unter Erhalt der Wasserdampfdurchlässigkeit möglichst wasserundurchlässig machen), aber Griff, Färbbarkeit, Festnarbigkeit und die Applizierbarkeit der nachfolgenden Zurichtung nicht negativ beeinflussen.The retanning agents known to date do not meet all the expectations placed on them, because they are either insufficiently hydrophobic or because of the handle, the colorability, the grain or the subsequent finishing of the leather disadvantageous influence. The multitude of desirable properties compels one Compromise. Retanning agents are desired that give the leather an optimal look Provide hydrophobicity (i.e. the leather while maintaining the water vapor permeability make it as impermeable as possible), but handle, colorability, firm grain and do not adversely affect the applicability of the subsequent dressing.
Es wurde nun überraschenderweise gefunden, daß man durch Verwendung bestimmter Copolymerisate, die eingebaute Reste langkettiger Alkohole und neutralisierte (und gegebenenfalls freie) Carboxylgruppen enthalten, eine glückliche Kombination von Hydrophobie, Weichheit und Festnarbigkeit erhält.It has now surprisingly been found that by using certain copolymers, the built-in residues of long-chain alcohols and contain neutralized (and optionally free) carboxyl groups, one lucky combination of hydrophobicity, softness and firmness.
Gegenstand der Erfindung ist also die Verwendung von Umsetzungsprodukten aus
- R1
- Wasserstoff oder Methyl,
- R2
- Wasserstoff, Methyl, Ethyl, -OR3, gegebenenfalls durch C1-C4-Alkyl substituiertes Phenyl oder Hydroxymethyl und
- R3
- C1-C4-Alkyl bedeuten,
- R 1
- Hydrogen or methyl,
- R 2
- Hydrogen, methyl, ethyl, -OR 3 , phenyl or hydroxymethyl optionally substituted by C 1 -C 4 alkyl and
- R 3
- C 1 -C 4 alkyl,
Maleinsäureanhydrid (Monomer a) und Diisobutylen (Monomer b) polymerisieren in der Regel alternierend. Bei Anwesenheit eines dritten Comonomeren c) entstehen ebenfalls alternierende Copolymerisate, wobei das Molverhältnis von a:(b+c) im Copolymerisat etwa 1:1 beträgt.Polymerize maleic anhydride (monomer a) and diisobutylene (monomer b) usually alternating. In the presence of a third comonomer c) alternating copolymers are also formed, the molar ratio of a: (b + c) in the copolymer is about 1: 1.
Bevorzugte Monomere c) umfassen beispielsweise Styrol, α-Methylstyrol, p-Methylstyrol, Vinylacetat, Allylacetat, Isobutylvinylether, Allylalkohol und Methallylalkohol.Preferred monomers c) include, for example, styrene, α-methylstyrene, p-methylstyrene, Vinyl acetate, allyl acetate, isobutyl vinyl ether, allyl alcohol and methallyl alcohol.
Terpolymerisate aus a), b) und c) sind bekannt; vgl. z.B. DE-OS 27 01 760. Sie können durch radikalisch initiierte Polymerisation hergestellt werden. Die Polymerisation erfolgt dabei in einem unter Polymerisationsbedingungen inerten organischen Lösungsmittel, insbesondere in einem aromatischen Lösungsmittel wie Toluol oder Xylol.Terpolymers from a), b) and c) are known; see. e.g. DE-OS 27 01 760. You can be produced by free radical polymerization. The Polymerization takes place in an inert atmosphere under polymerization conditions organic solvents, especially in an aromatic solvent such as toluene or xylene.
Geeignete Radikalbildner umfassen beispielsweise Diacylperoxide wie Diacetylperoxid, Dibenzoylperoxid, Di-p-chlorbenzoylperoxid, Peroxyester wie tert.-Butylperoxyacetat, tert.-Butyl-peroxybenzoat, Dicyclohexylperoxydicarbonat, Alkylperoxide wie Bis-(tert.-butylperoxybutan), Dicumylperoxid, tert.-Butylcumylperoxid, Hydroperoxide wie Cumolhydroperoxid, tert.-Butylhydroperoxid, Ketonperoxide wie Cyclohexanon-hydroperoxid, Methylethylketonhydroperoxid, Acetylacetonperoxid oder Azoisobutyrodinitril. Die üblichen Mengen betragen 0,01 bis 5 Gew.-%, bevorzugt 0,1 bis 3 Gew.-%, bezogen auf die Summe der zu polymerisierenden Monomeren a), b) und c).Suitable radical formers include, for example, diacyl peroxides such as diacetyl peroxide, Dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, peroxy esters such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, alkyl peroxides such as bis (tert.-butylperoxybutane), dicumyl peroxide, tert.-butylcumyl peroxide, hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, ketone peroxides such as Cyclohexanone hydroperoxide, methyl ethyl ketone hydroperoxide, acetylacetone peroxide or azoisobutyrodinitrile. The usual amounts are 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the sum of those to be polymerized Monomers a), b) and c).
Die Umsetzung der Terpolymerisate A mit den Alkoholen B kann entweder direkt in der Lösung der Terpolymerisate A oder nach Isolierung der festen Terpolymerisate A in Substanz, Lösung oder Suspension erfolgen. Die Reaktion kann bei Temperaturen von 60 bis 180, vorzugsweise 80 bis 140°C durchgeführt werden. The reaction of the terpolymers A with the alcohols B can either be direct in the solution of the terpolymers A or after isolation of the solid terpolymers A in substance, solution or suspension. The reaction can Temperatures of 60 to 180, preferably 80 to 140 ° C are carried out.
Primäre und sekundäre Alkohole B werden bevorzugt. Geeignete Vertreter umfassen beispielsweise n-Hexanol, Cyclohexanol, n-Octanol, 2-Ethylhexanol, n-Dodecanol, n-Tetradecanol, n-Hexadecanol, Stearylalkohol, Eicosanol und Behenylalkohol oder deren Gemische.Primary and secondary alcohols B are preferred. Suitable representatives include for example n-hexanol, cyclohexanol, n-octanol, 2-ethylhexanol, n-dodecanol, n-tetradecanol, n-hexadecanol, stearyl alcohol, eicosanol and behenyl alcohol or their mixtures.
Die Umsetzung kann in Ab- oder Anwesenheit eines sauren Katalysators durchgeführt werden. Als solche eignen sich beispielsweise Mineralsäuren wie Schwefelsäure oder wasserfreier Chlorwasserstoff, aliphatische und aromatische Sulfonsäuren wie Methansulfonsäuren und p-Toluolsulfonsäure, fluorierte aliphatische Carbonsäuren wie Perfluorbutan- oder -octansäure, und saure Ionenaustauscher. Wird in Gegenwart eines sauren Katalysators verestert, dann ist es zweckmäßig, zur Entfernung des Reaktionswassers in einem mit Wasser nicht mischbaren organischen Lösungsmittel, wie z.B. Toluol oder Xylol, zu arbeiten und das entstandene Reaktionswasser azeotrop abzutrennen. Bei Veresterung in Abwesenheit eines Katalysators erhält man aus den Anhydridgruppen hauptsächlich den Halbester, bei sauer katalysierter Veresterung Mischungen von Halb- und Diester der Dicarbonsäurereste.The reaction can be carried out in the presence or absence of an acid catalyst be performed. Mineral acids such as are suitable as such Sulfuric acid or anhydrous hydrogen chloride, aliphatic and aromatic Sulphonic acids such as methanesulphonic acids and p-toluenesulphonic acid, fluorinated aliphatic Carboxylic acids such as perfluorobutanoic or octanoic acid, and acidic ion exchangers. If esterified in the presence of an acidic catalyst, then it is useful to remove the water of reaction in a with water not miscible organic solvents, e.g. Toluene or xylene and azeotropically separate the water of reaction formed. When esterified in The absence of a catalyst is mainly obtained from the anhydride groups the half ester, in the case of acid-catalyzed esterification mixtures of half and Diester of dicarboxylic acid residues.
Zur Überführung der erhaltenen Veresterungsprodukte in eine wasserlösliche oder - dispergierbare Form wird Base C zugegeben - vorzugsweise als wäßrige Lösung. Geeignete Basen C umfassen beispielsweise Alkalihydroxide und -alkoholate sowie Ammoniak und primäre, sekundäre und tertiäre aliphatische Amine mit bis zu 6 C-Atomen pro Molekül (die bis zu 1 Hydroxylgruppe pro Alkylrest tragen können), insbesondere Natrium- und Kaliumhydroxide sowie Ammoniak, Ethylamin, Propylamin, n-Butylamin, Diethanolamin, Dimethylamin und Triethylamin. Die Base C kann der Polymerschmelze oder -lösung bzw. -dispersion zugesetzt werden. Die Menge der Base C wird so bemessen, daß mindestens 20 % der nach der Veresterungsreaktion verbliebenen Carboxylgruppen umgesetzt werden. Eine Umsetzung aller verbliebenen Carboxylgruppen ist möglich; es kann aber auch vorteilhaft sein, nur 20 bis 80 % der verbliebenen Carboxylgruppen zu neutralisieren (In diesem Zusammenhang sollen in der Veresterungsreaktion nicht umgesetzte Anhydridgruppen formal als 2 Carboxylgruppen gezählt werden). Bei der Umsetzung restlicher Anhydridgruppen mit Alkalilauge entstehen die entsprechenden Carboxylate, während mit Ammoniak, primären und sekundären Aminen die Halbamid-/Halbammoniumsalze und mit tertiären aliphatischen Aminen in der Regel die Diammoniumsalze (jeweils bezogen auf 1 ursprüngliche Anhydridgruppe) erhalten werden. Durch die Umsetzung mit Base C entstehen wäßrige Lösungen bzw. Dispersionen, die noch organisches Lösungsmittel enthalten können. Sie können direkt als solche oder nach der Entfernung des Lösungsmittels zur Nachgerbung von Leder eingesetzt werden. Insbesondere eignen sie sich für alle den von Chromleder (Rind, Ziege, Schwein etc.).To convert the esterification products obtained into a water-soluble or - Dispersible form is added to Base C - preferably as an aqueous solution. Suitable bases C include, for example, alkali metal hydroxides and alcoholates as well as ammonia and primary, secondary and tertiary aliphatic amines with bis to 6 carbon atoms per molecule (which carry up to 1 hydroxyl group per alkyl radical can), especially sodium and potassium hydroxides and ammonia, Ethylamine, propylamine, n-butylamine, diethanolamine, dimethylamine and Triethylamine. Base C can be the polymer melt or solution or dispersion are added. The amount of base C is such that at least 20% of the carboxyl groups remaining after the esterification reaction be implemented. A conversion of all remaining carboxyl groups is possible; but it can also be advantageous to use only 20 to 80% of the remaining To neutralize carboxyl groups (In this context, the esterification reaction unreacted anhydride groups formally as 2 carboxyl groups be counted). When implementing residual anhydride groups with The corresponding carboxylates are formed in alkali lye, while with ammonia, primary and secondary amines the half amide / half ammonium salts and with tertiary aliphatic amines usually the diammonium salts (each based on 1 original anhydride group) can be obtained. Through the Reaction with base C result in aqueous solutions or dispersions that still can contain organic solvent. You can directly as such or used for retanning leather after removing the solvent will. They are particularly suitable for all those of chrome leather (cow, goat, Pig etc.).
Die erhaltenen wäßrigen Lösungen bzw. Dispersionen werden vorzugsweise auf neutralisiertem Wet-blue-Material eingesetzt, d.h. auf Chromleder, welches durch übliche Neutralisationsmittel (z.B. Natriumbicarbonat, -formiat usw.) oder Neutralisationsgerbstoffe auf einen pH-Wert von 4 bis 7, vorzugsweise 5,5 bis 6,5 eingestellt worden ist. Im allgemeinen kommen Mengen von 0,5 bis 8, vorzugsweise 1 bis 4, insbesondere 1 bis 2 Gew.-%, berechnet als Trockensubstanz und bezogen auf Wet-blue-Falzgewicht, zur Anwendung.The aqueous solutions or dispersions obtained are preferably based on neutralized wet blue material used, i.e. on chrome leather, which by Common neutralizing agents (e.g. sodium bicarbonate, formate, etc.) or neutralizing tanning agents adjusted to a pH of 4 to 7, preferably 5.5 to 6.5 has been. In general, amounts of 0.5 to 8, preferably 1 to 4, in particular 1 to 2 wt .-%, calculated as dry matter and related on wet-blue fold weight, for use.
Im weiteren Fortgang der Nachgerbung kann das neutralisierte Wet-blue-Material evtl. mit handelsüblichen Nachgerbstoffen (Austausch-, Weiß-, Harz- und Polymergerbstoffen), Vegetabilgerbstoffen sowie Fettungsmitteln behandelt werden. Will man gefärbte Leder herstellen, wird mit Farbstoffen gefärbt. Darüber hinaus ist es auch möglich, die Lösungen bzw. Dispersionen auf rein vegetabil gegerbten Ledern zur Nachgerbung vor der Färbung und Fettung einzusetzen.In the further course of retanning, the neutralized wet blue material can be used possibly with commercially available retanning agents (replacement, white, resin and polymeric tanning agents), Vegetable tanning agents and fatliquors are treated. Want to produce dyed leather is dyed with dyes. Beyond that it is also possible, the solutions or dispersions on vegetable tanned purely vegetable Use leather for retanning before dyeing and greasing.
Die erhaltenen wäßrigen Lösungen bzw. Dispersionen können auch in anderen Stadien der Nachgerbung, z.B. nach der Behandlung mit Austausch-, Weiß- oder Vegetabilgerbstoffen, eingesetzt werden.The aqueous solutions or dispersions obtained can also be used in others Stages of retanning, e.g. after treatment with exchange, white or Vegetable tanning agents can be used.
Die erfindungsgemäß nachgegerbten Leder zeichnen sich durch einen sehr weichen und vollen Griff sowie durch gute Narbenfestigkeit und Narbenglätte aus und weisen eine deutliche Pigmentierung auf. Wegen ihrer hohen Lichtechtheit und ihrer guten thermischen Vergilbungsresistenz eignen sie sich ausgezeichnet zur Herstellung heller Leder. Außerdem zeigen die mit den erfindungsgemäßen Dispersionen nachgegerbten Leder wasserabstoßende Eigenschaften.The leather retanned according to the invention is distinguished by a very soft and full grip as well as good scar strength and scar smoothness from and have a clear pigmentation. Because of their high light fastness and Their good thermal yellowing resistance makes them ideal for Manufacture of light leather. In addition, show with the dispersions of the invention retanned leather has water-repellent properties.
Die nachfolgenden Beispiele zeigen die Herstellung der erfindungsgemäß zu verwendenden wäßrigen Lösungen bzw. Dispersionen und ihre Anwendung in unterschiedlichen Rezepturen zur Nachgerbung verschiedener Ledertypen. The following examples show the preparation of the invention using aqueous solutions or dispersions and their application in different recipes for retanning different types of leather.
Die Prozentangaben der nachfolgenden Beispiele beziehen sich, sofern nicht anders angegeben, jeweils auf das Gewicht. Mischungs- und Verdünnungsverhältnisse beziehen sich, sofern nicht anders angegeben, ebenfalls auf das Gewicht. The percentages in the following examples relate, if not otherwise stated, each on the weight. Mixing and dilution ratios unless otherwise stated, also relate to the weight.
Zur Herstellung von Möbelledern werden 50 kg in der üblichen Weise chromgegerbte und auf 1,2 bis 1,4 mm gefalzte wet-blues im Gerbfaß zunächst in 250 bis 350 % Wasser (bezogen auf Falzgewicht, wie alle folgenden %-Angaben) von 40°C sowie Zusatz von 0,3 bis 0,5 % Ameisensäure (85 %ig, 1:10 mit Wasser verdünnt) und 2,0 % eines lichtechten handelsüblichen Weißgerbstoffes 30 Minuten lang gewalkt. Der pH-Wert der Flotte liegt bei ca. 3,8. Die Flotte wird abgelassen und anschließend wird in 300 % Wasser von 40°C 10 Minuten gewaschen.To produce furniture leather, 50 kg are chrome-tanned in the usual way and on 1.2 to 1.4 mm folded wet blues in the tanning drum, first in 250 up to 350% water (based on shaved weight, like all the following% data) from 40 ° C and addition of 0.3 to 0.5% formic acid (85%, 1:10 with water diluted) and 2.0% of a lightfast commercial white tanning agent 30 Walked for minutes. The pH of the fleet is around 3.8. The fleet will drained and then in 300% water at 40 ° C for 10 minutes washed.
Nach dem Ablassen der Flotte wird in 150 % Wasser von 40°C mit 1 % eines handelsüblichen Chromgerbstoffes und 3 % eines handelsüblichen, selbstabstumpfenden Chrom-Syntan-Mischgerbstoffes in 45 Minuten nachchromiert, mit 7 % eines handelsüblichen synthetischen Fettungsmittels in 30 Minuten gefettet und anschließend 1,5 % eines handelsüblichen, lichtechten Neutralisationsgerbstoffes, 4,0 % eines handelsüblichen Weißgerbstoffes sowie 3,0 % eines handelsüblichen Harzgerbstoffes zugegeben.After draining the liquor in 150% water at 40 ° C with 1% commercially available chrome tanning agent and 3% of a commercially available, self-dulling Chrome-Syntan mixed tanning agent after-chrome-plated in 45 minutes, with 7% of a commercially available synthetic fatliquor greased in 30 minutes and then 1.5% of a commercially available, lightfast neutralizing tanning agent, 4.0% of a commercially available white tanning agent and 3.0% of a commercially available Resin tanning agent added.
Nach 15 Minuten Laufzeit wird 1 %, bezogen auf Trockensubstanz, der erfindungsgemäßen Dispersion IV als 20,7 %ige Einstellung zugesetzt und weitere 45 Minuten laufen gelassen.After a running time of 15 minutes, 1%, based on dry substance, of dispersion IV according to the invention is added as a 20.7% setting and the mixture is left to run for a further 45 minutes.
Der Flotten-pH-Wert liegt bei ca. 5,2. The liquor pH is around 5.2.
1,5 % Natriumformiat und 0,5 % Natriumbicarbonat werden zugegeben (Flotten-pH-Wert: ca. 6,1) und die Flotte nach 40 Minuten abgelassen. Die Leder werden anschließend mit 300 % Wasser von 40°C 10 Minuten lang gewaschen, gefettet und betriebsüblich fertiggestellt (ausgereckt, naß gespannt und getrocknet, klimatisiert, gestollt, gemillt und gespannt).1.5% sodium formate and 0.5% sodium bicarbonate are added (liquor pH: 6.1) and the liquor drained after 40 minutes. The leathers will then washed with 300% water at 40 ° C for 10 minutes, greased and completed in the normal way (stretched, stretched and dried, air-conditioned, stollen, grilled and tense).
Die resultierenden Leder sind von guter Fülle und Weichheit und zeichnen sich durch hervorragende Narbenglätte aus. Die Lichtechtheit beträgt Stufe 5 bis 6 (Xeno-Test), und die Hitzevergilbung (24 Stunden, 120°C) liegt bei Stufe 3 bis 4 (Grauskala).The resulting leathers are of good fullness and softness and stand out with excellent scar smoothness. The light fastness is level 5 to 6 (Xeno test), and the heat yellowing (24 hours, 120 ° C) is level 3 to 4 (Gray scale).
Zur Herstellung von Autopolsterledern werden 50 kg in der üblichen Weise chromgegerbte und auf 1,1 bis 1,3 mm gefalzte wet blues im Gerbfaß wie in Beispiel 1 beschrieben, gewaschen, mit Ameisensäure versetzt, mit einem Weißgerbstoff vorgegerbt, erneut gewaschen, chromnachgegerbt, gefettet und mit 1,5 % (bezogen auf Falzgewicht, wie alle folgenden %-Angaben) eines handelsüblichen Neutralisationsgerbstoffes, 4,0 % eines handelsüblichen Austauschgerbstoffes sowie 3 % eines handelsüblichen Harzgerbstoffes nachgegerbt.For the production of car upholstery leather 50 kg are used in the usual way Chrome-tanned and folded to 1.1 to 1.3 mm wet blues in the tanning drum as in Example 1 described, washed, mixed with formic acid, with a White tanning agent pre-tanned, washed again, retanned chrome, greased and with 1.5% (based on fold weight, like all the following% data) of a commercially available Neutralization tanning agent, 4.0% of a commercially available replacement tanning agent and retanned 3% of a commercially available resin tanning agent.
Nach 15 Minuten Laufzeit wird 1,5 %, bezogen auf Trockensubstanz, der erfindungsgemäßen Dispersion III als 15,7 %ige Einstellung zugesetzt und weitere 45 Minuten laufen gelassen.After a running time of 15 minutes, 1.5%, based on dry substance, of dispersion III according to the invention is added as a 15.7% setting and the mixture is left to run for a further 45 minutes.
Der Flotten-pH-Wert liegt bei ca. 5,0. Der pH-Wert wird durch Zugabe von 1,5 % Natriumformiat und 0,4 % Natriumbicarbonat auf ca. 6,0 angehoben und die Flotte nach 40 Minuten abgelassen.The liquor pH is around 5.0. The pH is adjusted by adding 1.5% Sodium formate and 0.4% sodium bicarbonate raised to approximately 6.0 and the liquor drained after 40 minutes.
Nach 10-minütigem Waschen in 300 % Wasser von 40°C und Ablassen der Flotte wird in 30 % Wasser von 25°C unter Zusatz von 1,0 % eines handelsüblichen Färbereihilfsmittels mit 5,0 % einer Mischung von handelsüblichen Lederfarbstoffen in 30 Minuten durchgefärbt.After washing for 10 minutes in 300% water at 40 ° C and draining the liquor is in 30% water of 25 ° C with the addition of 1.0% of a commercial Dyeing aid with 5.0% of a mixture of commercially available leather dyes dyed through in 30 minutes.
Nach Zugabe von 10 % eines synthetischen Fettungsmittels wird 30 Minuten gefettet. Anschließend werden 150 % Wasser von 70°C zugegeben und nach 5 Minuten der Farbstoff durch Zugabe von 2,5 % Ameisensäure (85 %ig, 1:10 mit Wasser verdünnt, Zugabe in 2 Raten) fixiert. Der Flotten-pH-Wert liegt bei ca. 4,0.After adding 10% of a synthetic fatliquor 30 minutes greased. Then 150% water at 70 ° C is added and after 5 Minutes the dye by adding 2.5% formic acid (85%, 1:10 with Diluted water, addition in 2 installments) fixed. The liquor pH is approx. 4.0.
Nach dem Ablassen der Flotte wird mit 300 % Wasser von 40°C gewaschen, 10 Minuten bei 25°C gespült und anschließend die Leder betriebsüblich fertiggestellt.After draining the liquor, wash with 300% water at 40 ° C, 10 Rinsed minutes at 25 ° C and then finished the leather as usual.
Die resultierenden Leder sind von guter Fülle und Weichheit und zeichnen sich durch hervorragende glatte Narben mit feinem Millkorn aus.The resulting leathers are of good fullness and softness and stand out with excellent smooth scars with fine mill grain.
Zur Herstellung von Schuhoberleder werden 35 kg in der üblichen Weise chromgegerbte und auf 1,6 bis 1,7 mm gefalzte wet blues im Gerbfaß zunächst in 200 % Wasser (bezogen auf Falzgewicht, wie alle folgen %-Angaben), von 50°C sowie 0,4 % Ameisensäure (85 %ig, TAPE 2, 1:10 mit Wasser verdünnt) 15 Minuten gewaschen. Nach dem Ablassen der Flotte wird in 100 % Wasser von 40°C mit 2 % eines handelsüblichen Neutralisationsgerbstoffes und 0,8 % Natriumbicarbonat neutralisiert. Der Flotten-pH-Wert beträgt nach 45 Minuten Neutralisation ca. 5,2.To produce upper leather, 35 kg are chrome-tanned in the usual way and to 1.6 to 1.7 mm folded wet blues in the tanning drum, initially in 200% Water (based on fold weight, as all follow%), from 50 ° C as well 0.4% formic acid (85%, TAPE 2, 1:10 diluted with water) for 15 minutes washed. After draining the liquor in 100% water at 40 ° C with 2% of a commercial neutralization tanning agent and 0.8% sodium bicarbonate neutralized. After 45 minutes of neutralization, the liquor pH is approx. 5.2.
Anschließend wird 1,5 %, bezogen auf Trockensubstanz, der erfindungsgemäßen Dispersion I (siehe Herstellungsbeispiel 1) als 12,7 %ige Einstellung zugesetzt und 30 Minuten laufen gelassen. Der Flotten-pH-Wert liegt bei ca. 5,0.Then 1.5%, based on dry substance, of dispersion I according to the invention (see preparation example 1) is added as a 12.7% setting and the mixture is left to run for 30 minutes. The liquor pH is around 5.0.
3 % eines handelsüblichen Austauschgerbstoffes, 4 % Quebracho und 1,5 % Farbstoff werden zugegeben und nach 90 Minuten Laufzeit mit 0,5 % Ameisensäure (85 %ig, 1:10 mit Wasser verdünnt) auf einen pH-Wert von ca. 4,2 abgesäuert.3% of a commercial replacement tanning agent, 4% quebracho and 1.5% dye are added and after 90 minutes running time with 0.5% formic acid (85%, 1:10 diluted with water) acidified to a pH of approx. 4.2.
Nach dem Ablassen der Flotte wird in 100 % Wasser von 50°C gefettet, nochmals mit Ameisensäure auf einen pH-Wert von 3,9 angesäuert und die Flotte erneut abgelassen. Nach 10-minütigem Spülen in 25°C warmem Wasser werden die Leder betriebsüblich ausgereckt, vakuum- und hängegetrocknet, klimatisiert, gestollt und nochmals vakuumgetrocknet (1/2 Minute bei 70°C). Die resultierenden Leder zeichnen sich durch eine gleichmäßige Färbbarkeit mit vollem weichem Griff bei guter Festnarbigkeit aus. After draining the liquor, grease in 100% water at 50 ° C, again acidified to a pH of 3.9 with formic acid and the liquor again drained. After rinsing in warm water at 25 ° C for 10 minutes, the Leather stretched out as usual, vacuum and hanging dried, air-conditioned, tunneled and vacuum dried again (1/2 minute at 70 ° C). The resulting Leather are characterized by an even dyeability with full soft Grip with good firm grain.
Zur Herstellung von Spaltleder werden 25 kg in der üblichen Weise hergestellte Chromspalte (Spaltstärke ca. 1,3 mm) in 200 % Wasser (bezogen auf Spaltgewicht wie alle folgenden Angaben) von 50°C 10 Minuten lang gewaschen.For the production of split leather 25 kg are made in the usual way Chromium column (gap thickness approx. 1.3 mm) in 200% water (based on gap weight as all of the following) washed at 50 ° C for 10 minutes.
Nach dem Ablassen der Flotte wird in 100 % Wasser von 40°C mit 2 % eines handelsüblichen Neutralisationsgerbstoffes und 1,5 % Natriumbicarbonat über 90 Minuten auf einen pH-Wert von ca. 5,8 neutralisiert.After draining the liquor in 100% water at 40 ° C with 2% one commercial neutralization tanning agent and 1.5% sodium bicarbonate over 90 Minutes neutralized to a pH of about 5.8.
Nach der Vorfettung mit 2 % eines synthetischen Fettungsmittels über 15 Minuten werden 1,2 %, bezogen auf Trockensubstanz, der erfindungsgemäßen Dispersion II nach Herstellungsbeispiel 2 als 9,5 %ige Einstellung zugesetzt und die Spaltleder 45 Minuten gewalkt.After pre-greasing with 2% of a synthetic fatliquoring agent for 15 minutes, 1.2%, based on dry matter, of the dispersion II according to the invention from preparation example 2 is added as a 9.5% setting and the split leather is drummed for 45 minutes.
Anschließend werden 6,0 % eines handelsüblichen Weißgerbstoffes zugegeben und nach 45 Minuten der pH-Wert von ca. 5,5 durch Zugabe von 0,5 % Ameisensäure (85 %ig, 1:10 mit Wasser verdünnt) über 15 Minuten auf ca. 4,5 gesenkt.Then 6.0% of a commercially available white tanning agent is added and after 45 minutes the pH of approx. 5.5 by adding 0.5% formic acid (85%, 1:10 diluted with water) reduced to about 4.5 over 15 minutes.
Nach dem Ablassen der Flotte werden die Leder in 200 % Wasser 10 Minuten bei 60°C gewaschen und in 100 % Wasser von 60°C mit 7,0 % einer handelsüblichen Fettmischung gefettet.After draining the liquor, the leathers are soaked in 200% water for 10 minutes Washed 60 ° C and in 100% water of 60 ° C with 7.0% of a commercially available Fat mixture greased.
Der Flotten-pH-Wert liegt bei ca. 4,5.The liquor pH is around 4.5.
Es ist nun möglich zur Erzielung einer größeren Fülle und Weichheit in die Fettung gegebenenfalls nochmals 0,5 %, bezogen auf Trockensubstanz, der obengenannten Dispersion zuzusetzen.It is now possible to achieve greater fullness and softness in the Fatting if necessary again 0.5%, based on dry matter add the above dispersion.
Abschließend werden die Leder durch Zusatz von 0,5 % Ameisensäure (85 %ig, 1:10 mit Wasser verdünnt) auf einen pH-Wert von ca. 4,0 abgesäuert. Die Leder werden betriebsüblich gespült (Wasser von 20°C, 5 Minuten), ausgereckt, vakuum- und hängegetrocknet, klimatisiert, gestollt, abgelüftet, nachgestollt und nochmals vakuumgetrocknet (1/2 Minute, 70°C). Finally, the leather is added by adding 0.5% formic acid (85%, 1:10 diluted with water) acidified to a pH of approx. 4.0. The leather are rinsed in the usual way (water at 20 ° C, 5 minutes), stretched out, vacuum and hang-dried, air-conditioned, tunneled, aired, rerolled and again vacuum dried (1/2 minute, 70 ° C).
Die resultierenden Spalte besitzen einen sehr hohen Weißgrad und zeichnen sich durch einen weichen vollen Griff aus, wobei die Velourseite einen weichen, gleichmäßigen Kurzschliff aufweist.The resulting gaps have a very high degree of whiteness and stand out with a soft full grip, the velor side having a soft, uniform short cut.
Zur Herstellung von Bekleidungsnappa werden 20 kg Neuseeland-Schaf-wet blue in 200 % Wasser (bezogen auf Falzgewicht, wie alle folgenden Angaben) von 40°C und 0,5 % eines handelsüblichen Emulgators 20 Minuten gewaschen. Nach dem Ablassen der Flotte wird in 100 % Wasser von 40°C mit einem handelsüblichen selbstabstumpfenden Chrom-Syntan-Nachgerbstoff über 15 Minuten nachchromiert, 1 % eines handelsüblichen synthetischen Fettungsmittels zugegeben und nach 45 Minuten Laufzeit mit 3 % eines handelsüblichen Neutralisationsgerbstoffes und 0,3 % Natriumbicarbonat auf einen pH-Wert von 5,5 über 45 Minuten neutralisiert.20 kg of New Zealand sheep wet blue are used to manufacture clothing nappa in 200% water (based on shaved weight, like all the following information) from Washed 40 ° C and 0.5% of a commercially available emulsifier for 20 minutes. After draining the liquor in 100% water at 40 ° C with a commercial self-dulling chrome-syntan retanning agent re-chromed for 15 minutes, 1% of a commercial synthetic fatliquor added and after 45 minutes running time with 3% of a commercial neutralization tanning agent and 0.3% sodium bicarbonate to pH 5.5 over 45 minutes neutralized.
Nach Zugabe von 300 % Wasser von 40°C wird nach 10 Minuten die Flotte abgelassen.After adding 300% water at 40 ° C, the liquor is drained off after 10 minutes.
Anschließend werden in 100 % Wasser von 40°C 1,5 %, bezogen auf Trockensubstanz, der erfindungsgemäßen Dispersion III nach Herstellungsbeispiel 3 als 15,7 %ige Einstellung zugesetzt und 45 Minuten gewalkt.Subsequently, in 100% water at 40 ° C., 1.5%, based on dry matter, of dispersion III according to the invention from preparation example 3 is added as a 15.7% setting and drummed for 45 minutes.
Es werden 3 % eines handelsüblichen Austauschgerbstoffes zugegeben und nach 20 Minuten Laufzeit 3 % Farbstoff zugesetzt. Nach 40 Minuten wird mit 2 % Ameisensäure (85 %ig, 1:10 mit Wasser verdünnt) auf einen pH-Wert von ca. 3,8 über 30 Minuten abgesäuert.3% of a commercially available replacement tanning agent is added and after 20% runtime 3% dye added. After 40 minutes with 2% Formic acid (85%, 1:10 diluted with water) to a pH of approx.3.8 acidified over 30 minutes.
Nach dem Ablassen der Flotte wird in 200 % Wasser von 50°C mit 1,5 % Farbstoff überfärbt und noch 20 Minuten mit 1,5 % Ameisensäure (85 %ig, 1:10 mit Wasser verdünnt) auf einen pH-Wert von 3,5 abgesäuert.After draining the liquor is in 200% water at 50 ° C with 1.5% dye over-colored and for another 20 minutes with 1.5% formic acid (85%, 1:10 with Diluted water) acidified to pH 3.5.
Die Leder werden kalt gespült und betriebsüblich fertiggestellt (getrocknet, gemillt, gestollt etc.). The leathers are rinsed cold and finished in the usual way (dried, milled, minced etc.).
Die Leder besitzen einen weichen vollen Griff und zeichnen sich durch einen feinen glatten Narben sowie durch eine gleichmäßige, brillante Färbung aus.The leathers have a soft full grip and are characterized by a fine smooth scars and a uniform, brilliant color.
Zur Herstellung von Vegetabil-Oberleder werden in der üblichen Weise vegetabil gegerbte Leder in 300 % Wasser (bezogen auf Falzgewicht, wie alle folgenden Angaben) von 30°C 10 Minuten gewaschen und nach Ablassen der Flotte in 100 % Wasser von 30°C mit 1 % eines handelsüblichen Bleichgerbstoffes über 20 Minuten gebleicht (pH-Wert der Flotte: ca. 3,3) und mit 300 % Wasser von 40°C gewaschen.Vegetable uppers are made in the usual way tanned leather in 300% water (based on shaved weight, like all of the following Details) of 30 ° C for 10 minutes and after draining the liquor in 100% water at 30 ° C with 1% of a commercial bleaching agent over 20 Minutes bleached (pH of the liquor: approx. 3.3) and with 300% water at 40 ° C washed.
Nach dem Ablassen der Flotte wird in 100 % Wasser von 40°C mit 1,5 %, bezogen auf Trockensubstanz, der erfindungsgemäßen Dispersion IV nach Herstellungsbeispiel 4 als 20,7 %ige Einstellung über 20 Minuten behandelt. Der pH-Wert der Flotte liegt bei ca. 4,3.After the liquor has been drained, 100% water at 40 ° C. is treated with 1.5%, based on dry substance, of the dispersion IV according to the invention from preparation example 4 as a 20.7% setting over 20 minutes. The pH of the liquor is around 4.3.
Anschließend wird mit 1,3 % einer handelsüblichen Farbstoffmischung 20 Minuten lang gefärbt und mit ca. 9 % einer handelsüblichen Fettmischung aus synthetischen und natürlichen Fetten über 20 Minuten gefettet (pH-Wert: ca. 4,2).Then with 1.3% of a commercially available dye mixture for 20 minutes long colored and with approx. 9% of a commercially available fat mixture synthetic and natural fats greased over 20 minutes (pH value: approx. 4.2).
Abschließend wird 0,5 % Ameisensäure (85 %ig, 1:10 mit Wasser verdünnt) zur Fixierung zugegeben (pH-Wert: ca. 3,4). Die Leder werden gewaschen (300 % Wasser von 20°C) und betriebsüblich fertiggestellt (ausgestoßen, vakuum- und hängegetrocknet, klimatisiert, gestollt und 1/2 Minute vakuumgetrocknet bei 60°C).Finally, 0.5% formic acid (85%, 1:10 diluted with water) is used Fixation added (pH value: approx.3.4). The leathers are washed (300% Water of 20 ° C) and normally completed (ejected, vacuum and hang-dried, air-conditioned, rolled and vacuum-dried for 1/2 minute 60 ° C).
Die resultierenden Leder sind weich, von guter Fülle und besitzen einen angenehmen schmalzigen Griff.The resulting leathers are soft, of good fullness and have a pleasant feel slimy grip.
Claims (3)
- Use of reaction products obtained from(A) a terpolymer having molecular weights
M n, determined as number average, of 5000 to 60 000 made ofa) maleic anhydride,b) 80 to 120 mol%, relative to component a), of diisobutylene, and- R1
- denotes hydrogen or methyl,
- R2
- denotes hydrogen, methyl, ethyl,-OR3, unsubstituted or C1-C4-alkyl substituted phenyl or hydroxymethyl, and
- R3
- denotes C1-C4-alkyl,
(B) an aliphatic and/or cycloaliphatic monohydric C6-C24-alcohol, and(C) a base, - Use according to Claim 1, wherefor monomer c) is selected from the series consisting of styrene, α-methylstyrene, p-methylstyrene, vinyl acetate, allyl acetate, isobutyl vinyl ether, allyl alcohol, methyl alcohol and mixtures thereof.
- Use according to Claim 1, wherefor 30 to 75% of the carboxyl groups corresponding to the anhydride groups of the terpolymer have been esterified with alcohol B.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4334796 | 1993-10-13 | ||
DE4334796A DE4334796A1 (en) | 1993-10-13 | 1993-10-13 | Softening and hydrophobic retanning agents |
Publications (3)
Publication Number | Publication Date |
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EP0648846A2 EP0648846A2 (en) | 1995-04-19 |
EP0648846A3 EP0648846A3 (en) | 1995-11-29 |
EP0648846B1 true EP0648846B1 (en) | 1998-12-23 |
Family
ID=6499990
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP94115468A Expired - Lifetime EP0648846B1 (en) | 1993-10-13 | 1994-09-30 | Retans with softening and hydrophobic action |
Country Status (4)
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US (1) | US5472741A (en) |
EP (1) | EP0648846B1 (en) |
DE (2) | DE4334796A1 (en) |
ES (1) | ES2126036T3 (en) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19612986A1 (en) | 1996-04-01 | 1997-10-02 | Basf Ag | Use of copolymers based on ethylenically unsaturated dicarboxylic acids or dicarboxylic acid anhydrides, lower olefins and hydrophobic comonomers for retanning, greasing or hydrophobicizing leather and fur skins |
US6248827B1 (en) | 1997-12-22 | 2001-06-19 | Bridgestone Corporation | Centipede polymers and preparation and application in rubber compositions |
US6248825B1 (en) | 1998-05-06 | 2001-06-19 | Bridgestone Corporation | Gels derived from extending grafted centipede polymers and polypropylene |
US6204354B1 (en) | 1998-05-06 | 2001-03-20 | Bridgestone Corporation | Soft compounds derived from polypropylene grafted disubstituted ethylene- maleimide copolymers |
US6207763B1 (en) | 1998-06-12 | 2001-03-27 | Bridgestone Corporation | Application of disubstituted ethylene-maleimide copolymers in rubber compounds |
US6184292B1 (en) | 1998-10-05 | 2001-02-06 | Bridgestone Corporation | Soft gel polymers for high temperature use |
US6191217B1 (en) | 1998-11-17 | 2001-02-20 | Bridgestone Corporation | Gels derived from polypropylene grafted alkyl vinylether-maleimide copolymers |
US6133354A (en) * | 1998-11-17 | 2000-10-17 | Bridgestone Corporation | Copolymers as additives in thermoplastic elastomer gels |
US6395040B1 (en) * | 2000-04-28 | 2002-05-28 | Wolverine World Wide, Inc. | Process for producing leather |
US6476117B1 (en) | 2000-06-05 | 2002-11-05 | Bridgestone Corporation | Grafted near-gelation polymers having high damping properties |
US6384134B1 (en) | 2000-06-05 | 2002-05-07 | Bridgestone Corporation | Poly(alkenyl-co-maleimide) and maleated polyalkylene grafted with grafting agent, and epoxy polymer |
US6350800B1 (en) | 2000-06-05 | 2002-02-26 | Bridgestone Corporation | Soft polymer gel |
US6417259B1 (en) | 2000-06-05 | 2002-07-09 | Bridgestone Corporation | Polyalkylene grafted centipede polymers |
US6353054B1 (en) | 2000-07-31 | 2002-03-05 | Bridgestone Corporation | Alkenyl-co-maleimide/diene rubber copolymers and applications |
US6359064B1 (en) | 2000-09-08 | 2002-03-19 | Bridgestone Corporation | Compound of polyester and polyalkylene grafted comb polymer |
DE10304959A1 (en) * | 2003-02-06 | 2004-08-19 | Basf Ag | Process for the production of leather |
US20060288494A1 (en) * | 2005-06-24 | 2006-12-28 | Wolverine World Wide, Inc. | Process for producing leather |
US20060288493A1 (en) * | 2005-06-24 | 2006-12-28 | Wolverine World Wide, Inc. | Process For Producing Leather Footwear Lining |
WO2009086519A2 (en) | 2007-12-28 | 2009-07-09 | Bridgestone Corporation | Interpolymers containing isobutylene and diene mer units |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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US4190687A (en) * | 1972-05-09 | 1980-02-26 | Sumitomo Chemical Company, Limited | Method for treating leather |
IT1035147B (en) * | 1974-04-04 | 1979-10-20 | Bayer Ag | PROCEDURE FOR TANNING LEATHER WITH HYDROPHILIC OLIGOIURETHANS |
JPS50136315A (en) * | 1974-04-17 | 1975-10-29 | ||
DE2701760C3 (en) * | 1977-01-18 | 1982-04-01 | Bayer Ag, 5090 Leverkusen | Process for the production of paper sizing agents |
DE2840501A1 (en) * | 1978-09-18 | 1980-03-27 | Basf Ag | METHOD FOR PRODUCING COPOLYMERISATS FROM MALEIC ACID ANHYDRIDE AND ALKENES |
DE3304120A1 (en) * | 1983-02-08 | 1984-08-09 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING WATERPROOF LEATHER AND FURS |
DE3529248A1 (en) * | 1985-08-16 | 1987-02-26 | Bayer Ag | TERPOLYMERISATE |
TNSN89128A1 (en) * | 1988-12-02 | 1991-02-04 | Rohn And Haas Company Independance Mall West | LEATHER TREATMENT WITH SELECTED AMPHIPHITE COPOLYMERS |
DE3931039A1 (en) * | 1989-09-16 | 1991-03-28 | Basf Ag | USE OF COPOLYMERISATS BASED ON LONG-CHAIN UNSATURATED ESTERS AND ETHYLENICALLY UNSATURATED CARBONIC ACIDS FOR THE HYDROPHOBICATION OF LEATHER AND FUR SKINS |
US5348807A (en) * | 1991-02-05 | 1994-09-20 | Rohm And Haas Company | Polymeric retan fatliquor for low fogging upholstery leather |
-
1993
- 1993-10-13 DE DE4334796A patent/DE4334796A1/en not_active Withdrawn
-
1994
- 1994-09-30 EP EP94115468A patent/EP0648846B1/en not_active Expired - Lifetime
- 1994-09-30 DE DE59407529T patent/DE59407529D1/en not_active Expired - Fee Related
- 1994-09-30 ES ES94115468T patent/ES2126036T3/en not_active Expired - Lifetime
- 1994-10-06 US US08/319,191 patent/US5472741A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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EP0648846A3 (en) | 1995-11-29 |
DE4334796A1 (en) | 1995-04-20 |
DE59407529D1 (en) | 1999-02-04 |
EP0648846A2 (en) | 1995-04-19 |
US5472741A (en) | 1995-12-05 |
ES2126036T3 (en) | 1999-03-16 |
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