EP0100493B1 - Process for finishing leather or leather substitutes - Google Patents

Process for finishing leather or leather substitutes Download PDF

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Publication number
EP0100493B1
EP0100493B1 EP83107140A EP83107140A EP0100493B1 EP 0100493 B1 EP0100493 B1 EP 0100493B1 EP 83107140 A EP83107140 A EP 83107140A EP 83107140 A EP83107140 A EP 83107140A EP 0100493 B1 EP0100493 B1 EP 0100493B1
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Prior art keywords
weight
leather
copolymer
dispersion
methacrylamide
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EP83107140A
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German (de)
French (fr)
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EP0100493A1 (en
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Karl Fischer
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BASF SE
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BASF SE
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Priority claimed from DE19823228128 external-priority patent/DE3228128A1/en
Priority claimed from DE19833307431 external-priority patent/DE3307431A1/en
Application filed by BASF SE filed Critical BASF SE
Priority to AT83107140T priority Critical patent/ATE17023T1/en
Publication of EP0100493A1 publication Critical patent/EP0100493A1/en
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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
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds

Definitions

  • the invention relates to a novel process for finishing leather or synthetic leather replacement material - leather is to be referred to in the following for the sake of simplicity - with a purely aqueous system which is free from organic solvents and in which certain aqueous polymer dispersions are used for priming and the finish are used.
  • the aim of a leather dressing (coating) is to give the tanned, greased and possibly colored raw leather the desired appearance, special gripping properties and the necessary fastness to use, such as. B. to give kink elasticity, water fastness and wet and dry rub fastness.
  • these properties could only be optimally achieved with systems that contained organic solvents.
  • the modern requirements regarding health and environmental protection made it necessary to realize leather finishing with purely aqueous systems. Previous attempts on this basis have so far not been satisfactory because at least one of the required properties has always not been achieved.
  • the object of the invention is a purely aqueous dressing process for leather, which should fully meet the above objectives.
  • the invention accordingly relates to a process for finishing leather or synthetic leather exchange material by applying a primer based on aqueous acrylic resin dispersions, intermediate drying and then applying a finish with an aqueous styrene-acrylate dispersion, which is characterized in that the primer a dispersion reaches the insert, the at least one copolymer a, which - based on the copolymer - 30 to 85 wt .-% of a C 2 to C 6 alkyl ester of (meth) acrylic acid, 1 to 8 wt .-% of a carboxyl-containing monomers and 7 to 65 wt .-% of at least one copolymerizable with the aforementioned monomers from the group of acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinyl acetate and styrene, copolymerized, and a copolymer b, which - based on the copolymer - 50 to 90 wt
  • the primer is carried out with a dispersion which contains at least one copolymer a and one copolymer b.
  • a and b are in a ratio of 2 to 5: 1, preferably 2 to 4.5: 1, and together they are present in the dispersion in an amount of 30 to 70, preferably 35 to 60% by weight.
  • the copolymer a is a typical acrylic resin known in terms of its composition. It contains 30 to 85, preferably 60 to 75% by weight of a C 2 -C 6 -alkyl ester of (meth) acrylic acid, preferably ethyl, n-propyl or n-butyl acrylate, as a monomer unit. It also contains 1 to 8% by weight of a monomer containing carboxyl groups, such as (meth) acrylic acid, crotonic acid, maleic acid or acrylamidoglycolic acid. Up to 2 to 5% by weight of these comonomers are preferably copolymerized in the copolymer; acrylic acid is preferred as the comonomer.
  • Comonomers which can be copolymerized with the abovementioned are also present in amounts of 7 to 65, preferably 20 to 38% by weight, and acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinyl acetate and / or styrene are to be mentioned here in particular .
  • the copolymer b contains 50 to 90, preferably 55 to 70% by weight of vinylidene chloride as main constituents. It also contains a C 2 -C 4 -alkyl ester of (meth) acrylic acid in an amount of 10 to 50, preferably 25 to 40% by weight. Ethyl or butyl acrylate is preferably used here.
  • N-methylol (meth) acrylamide which is copolymerized in amounts of 1 to 5, preferably 1 to 3,% by weight is particularly worth mentioning as the crosslinking comonomer.
  • copolymerized (b) (meth) acrylamide can optionally be copolymerized in the copolymer, specifically 1 to 5, preferably 1 to 3,% by weight.
  • the copolymer a can consist of a mixture of two copolymers according to definition a, based on the total quantity, exist. If a second copolymer is used, a copolymer of the composition according to a with proportions of 65 to 85% by weight of one of the abovementioned alkyl esters of (meth) acrylic acid is preferred. This softens the primer.
  • the dispersion for the subsequent finishing of the primed leather contains a salt of a divalent metal, such as zinc, cadmium, calcium or magnesium, which causes the polymers contained therein to ionize.
  • a divalent metal such as zinc, cadmium, calcium or magnesium
  • the chlorides, sulfates, acetates, nitrates, oxalates or carbonates are expediently used as salts.
  • zinc and magnesium zinc oxide or magnesium oxide can also be used.
  • the advantageous amounts of metal compound are 0.3 to 3, preferably 0.5 to 2% by weight, based on the aforementioned dispersion.
  • the copolymer c used here contains 20 to 40% by weight of styrene, 50 to 75% by weight of at least one C 1 to C 6 alkyl ester of (meth) acrylic acid, preferably methyl, ethyl and / or n Butyl acrylate, 1 to 10% by weight of (meth) acrylic acid, preferably 2 to 9% by weight, and 1 to 5, preferably 2 to 4% by weight of a monomer capable of covalent crosslinking, such as N - methylol ( meth) acrylamide.
  • the aqueous dispersion of the copolymer c to be used in the finish expediently has a content of 10 to 50, preferably 15 to 30,% by weight.
  • the dispersion c used for finishing contains, based on the total weight, 0.5 to 20, preferably 2 to 8% by weight of shellac modified with acrylates and 0.5 to 3% by weight.
  • additives based on the dispersion, in an amount of 1 to 10, preferably 1 to 6,% by weight of high-boiling polyglycols, phthalic acid esters, ethylene glycol, waxes of natural or synthetic origin as plasticizers, and also fungicides, such as the Na salt of diazenium dioxide cyclohexane.
  • these additives also apply to the primer dispersion, as can be seen from the examples.
  • this simplification has the consequence that leather prepared by this process is resistant to amien in addition to the known usage fastnesses. What is meant is that the applied film does not yellow under the influence of amines. This advantageous result of the amine resistance while maintaining the other usage fastnesses, such as water resistance, elasticity, adhesion to leather, light fastness and hot storage stability, were not predictable.
  • the amine resistance of the leather preparation according to the invention to free amines is of particular advantage for shoe leather in shoe manufacture when foaming polyurethane soles on the upper leather and, for example, in polyurethane foam fillings for furniture leather.
  • the leather is finished with the dispersions to be used according to the invention in a manner which is conventional per se.
  • the primer dispersion can also be applied in several steps, each interrupted by intermediate drying.
  • the dispersion for the final finish is then applied in a customary manner in amounts of 10 to 30 g of solid per square meter of leather. It is first dried at 60 to 80 ° C, ironed at 140 to 170 ° C and optionally ironed at 80 to 100 ° C under reduced pressure.
  • pigment preparations and / or dyes can be used in the primer and finish dispersion for the primer. It is advantageous to add 1 to 5 g of pigment preparation and / or commercial dye - based on 10 g of the solids present in the dispersions.
  • Hot ironing should be understood to mean that e.g. B. the leather is ironed at a temperature of 90 to 180 ° C, preferably at 120 to 170 ° C, with a conventional continuous ironing machine.
  • the leather sprayed in this way was dried at 70 ° C. after each spray application and ironed in at 70 ° C. and 50 bar after the first spray application.
  • Application rate 45 g solids / m 2 .
  • the preparation was sprayed on by means of a compressed air gun with two spraying jobs, intermediate and final drying at 70 ° C, then ironed at 170 ° C on the continuous ironing machine.
  • the leather obtained has the sensory properties desired for a shoe upper leather (feel, gloss, etc.) and also fulfills the fastness properties required in practice, e.g. Water resistance, elasticity and amine resistance.
  • Cowhide nappa leather for clothing was coated with the following primer preparation:
  • the leather treated in this way was intermediate dried at 70 ° C. after each of the three spray applications.
  • the leather was then sprayed with the following finish preparation:
  • the leather obtained showed all the properties required for clothing, such as Handle, abrasion resistance or waterfastness.
  • Cowhide for upholstery purposes was similarly coated with a primer mixture of the following composition (order quantity:
  • Two spraying jobs each dried at 70 ° C, ironed at 150 ° C (continuous ironing machine) and ironed at 90 ° C on the hydraulic ironing machine.
  • the leather thus obtained has all the properties desired for upholstered leather, such as. B. coefficients of friction, elasticity, light fastness, abrasion resistance, amine resistance and hot iron fastness.
  • the leather was coated once with this primer mixture with the puddle board, then dried at 70 ° C, ironed at 70 ° C, plushed again and with intermediate drying sprayed at 70 ° C with two spray jobs (air pressure gun).
  • Application quantity 80 g solid / m 2 .
  • the primed leather was then coated with the following finish: Application quantity: 30 g / m 2 .
  • This preparation was applied using a compressed air gun with two spraying jobs, dried at 70 ° C and ironed at 100 ° C on the continuous ironing machine.
  • the leather obtained has the properties desired for upper leather. It is lightfast, amine-resistant, waterproof and has sufficient elasticity.
  • the primed leather was then finished with a preparation of the following composition:
  • the leather obtained is waterproof and mechanically stressable without the finish peeling off.
  • the leather obtained showed all the properties desired for clothing purposes in terms of grip, abrasion resistance and waterfastness.
  • Goat leather was similarly made with a mixture of (30 g / m 2 )
  • the leather obtained has all the properties that are desired for handbags and briefcases.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Description

Die Erfindung betrifft ein neuartiges Verfahren zur Zurichtung von Leder oder synthetischem Lederaustauschmaterial - im folgenden soll der Einfachheit halber von Leder die Rede sein - mit einem rein wässerigen System, das frei von organischen Lösungsmitteln ist, und bei dem bestimmte wässerige Polymerisat-Dispersionen bei der Grundierung und der Appretur zum Einsatz gelangen.The invention relates to a novel process for finishing leather or synthetic leather replacement material - leather is to be referred to in the following for the sake of simplicity - with a purely aqueous system which is free from organic solvents and in which certain aqueous polymer dispersions are used for priming and the finish are used.

Das Ziel einer Lederzurichtung (Beschichtung) besteht darin, dem gegerbten, gefetteten und ggf. gefärbten Rohleder das gewünschte Aussehen, spezielle griffliche Eigenschaften sowie die notwendigen Gebrauchsechtheiten, wie z. B. Knickelastizität, Wasserechtheit und Nass- und Trokkenreibechtheit zu verleihen. In optimaler Weise waren diese Eigenschaften bisher nur mit Systemen zu erzielen, die organische Lösungsmittel enthielten. Die modernen Anforderungen bezüglich des Gesundheits- und Umweltschutzes machten es jedoch erforderlich, die Lederzurichtung mit rein wässerigen Systemen zu realisieren. Bisherige Versuche auf dieser Basis konnten bisher noch nicht befriedigen, weil immer zumindest eine der geforderten Eigenschaften nicht erreicht werden konnte.The aim of a leather dressing (coating) is to give the tanned, greased and possibly colored raw leather the desired appearance, special gripping properties and the necessary fastness to use, such as. B. to give kink elasticity, water fastness and wet and dry rub fastness. Up until now, these properties could only be optimally achieved with systems that contained organic solvents. However, the modern requirements regarding health and environmental protection made it necessary to realize leather finishing with purely aqueous systems. Previous attempts on this basis have so far not been satisfactory because at least one of the required properties has always not been achieved.

Die Aufgabe der Erfindung ist ein rein wässeriges Zurichtverfahren für Leder, das den obengenannten Zielen voll gerecht sein sollte.The object of the invention is a purely aqueous dressing process for leather, which should fully meet the above objectives.

Sie wurde gelöst mit einem Verfahren, das darauf beruht, dass bei der Grundierung Dispersionen, die mindestens zwei chemisch verschiedene Copolymerisate eindispergiert enthalten und bei der Appretur eine zweiwertige Metallionen enthaltende Copolymerisat-Dispersion, wie im Patentanspruch definiert ist, verwendet wird.It was achieved with a method which is based on the fact that dispersions containing at least two chemically different copolymers are dispersed in the primer and that a copolymer dispersion containing divalent metal ions is used in the finish, as defined in the patent claim.

Gegenstand der Erfindung ist demnach ein Verfahren zum Zurichten von Leder oder synthetischem Lederaustauschmaterial durch Aufbringen einer Grundierung auf der Basis von wässerigen Acrylharz-Dispersionen, Zwischentrocknen und anschliessendes Auftragen einer Appretur mit einerwässerigen Styrol-Acrylat-Dispersion, das dadurch gekennzeichnet ist, dass bei der Grundierung eine Dispersion zum Einsatz gelangt, die mindestens ein Copolymerisat a, das - bezogen auf das Copolymerisat - 30 bis 85 Gew.-% eines C2- bis C6-Alkylesters der (Meth)Acrylsäure, 1 bis 8 Gew.-% eines carboxylgruppenhaltigen Monomeren und 7 bis 65 Gew.-% mindestens eines mit den vorgenannten Monomeren copolymerisierbaren Monomeren aus der gruppe Acrylnitril, Acrylamid, Methacrylamid, Vinylchlorid, Vinylacetat und Styrol, einpolymerisiert enthält, und ein Copolymerisat b, das - bezogen auf das Copolymerisat - 50 bis 90 Gew.-% Vinylidenchlorid, 10 bis 50 Gew.-% eines C2- bis C4-Alkylesters der (Meth)Acrylsäure und 1 bis 5 Gew.-% N-Methylol-(meth)acrylamid, das eine zur Vernetzung des Copolymerisats befähigte Gruppe trägt, als Comonomer und ggf. 1 bis 5 Gew.-% (Meth)Acrylamid einpolymerisiert enthält, oder der Zusammensetzung 50 bis 90 Gew.-% Vinylchlorid und 10 bis 50 Gew.-% eines C1- bis C4-Alkylesters der (Meth)Acrylsäure sowie 0 bis 5 Gew.-% (Meth)Acrylamid im Verhältnis a:b wie 2 bis 5:1 eindispergiert enthält, und dass als Appretur eine 2-wertige Metallionen enthaltende Dispersion verwendet wird, die ein Copolymerisat c eindispergiert enthält, das - bezogen auf das Copolymerisat - 20 bis 40 Gew.-% Styrol, 50 bis 75 Gew.-% mindestens eines C1- bis C6-Alkyl- esters der (Meth)Acrylsäure, 1 bis 10 Gew.-% (Meth)Acrylsäure und 1 bis 5 Gew.-% N-Methylol-(meth)acrylamid, das eine zur Vermetzung des Copolymerisats befähigte Gruppe trägt, einpolymerisiert enthält.The invention accordingly relates to a process for finishing leather or synthetic leather exchange material by applying a primer based on aqueous acrylic resin dispersions, intermediate drying and then applying a finish with an aqueous styrene-acrylate dispersion, which is characterized in that the primer a dispersion reaches the insert, the at least one copolymer a, which - based on the copolymer - 30 to 85 wt .-% of a C 2 to C 6 alkyl ester of (meth) acrylic acid, 1 to 8 wt .-% of a carboxyl-containing monomers and 7 to 65 wt .-% of at least one copolymerizable with the aforementioned monomers from the group of acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinyl acetate and styrene, copolymerized, and a copolymer b, which - based on the copolymer - 50 to 90 wt .-% vinylidene chloride, 10 to 50 wt .-% of a C 2 - to C 4 alkyl ester of (meth) acrylic acid and 1 bi s contains 5% by weight of N-methylol (meth) acrylamide, which carries a group capable of crosslinking the copolymer, as a comonomer and, if appropriate, 1 to 5% by weight of (meth) acrylamide in copolymerized form, or of the composition 50 to 90 % By weight of vinyl chloride and 10 to 50% by weight of a C 1 -C 4 -alkyl ester of (meth) acrylic acid and 0 to 5% by weight of (meth) acrylamide in a: b ratio as 2 to 5: 1 contains dispersed, and that as a finish a dispersion containing divalent metal ions is used, which contains a copolymer c dispersed, which - based on the copolymer - 20 to 40 wt .-% styrene, 50 to 75 wt .-% of at least one C 1 to C 6 alkyl esters of (meth) acrylic acid, 1 to 10% by weight of (meth) acrylic acid and 1 to 5% by weight of N-methylol- (meth) acrylamide, which enabled one to crosslink the copolymer Group carries, polymerized contains.

Wenn die angegebenen und im folgenden noch näher beschriebenen Bedingungen eingehalten werden, erhält man einwandfreie zugerichtete Leder, deren spezielle Eigenschaften durch Variation der Zusammensetzung der Dispersionen und der sonstigen Arbeitsbedingungen, wie der Temperaturführung bei den Trocknungs- und Bügelvorgängen jeweils eingestellt werden können. Die Grundierung wird dabei mit einer Dispersion durchgeführt, die mindestens ein Copolymerisat a und ein Copolymerisat b enthält. a und b liegen im Verhältnis 2 bis 5:1, vorzugsweise 2 bis 4,5:1 vor, und sind in der Dispersion zusammen zu 30 bis 70, vorzugsweise 35 bis 60 Gew.-% anwesend.If the specified conditions and those described in more detail below are observed, perfectly prepared leather is obtained, the special properties of which can be adjusted by varying the composition of the dispersions and the other working conditions, such as the temperature control during the drying and ironing processes. The primer is carried out with a dispersion which contains at least one copolymer a and one copolymer b. a and b are in a ratio of 2 to 5: 1, preferably 2 to 4.5: 1, and together they are present in the dispersion in an amount of 30 to 70, preferably 35 to 60% by weight.

Das Copolymerisat a ist ein typisches und hinsichtlich seiner Zusammensetzung dem Fachmann bekanntes Acrylharz. Es enthält 30 bis 85, vorzugsweise 60 bis 75 Gew.-% eines C2- bis C6-Alkylesters der (Meth)Acrylsäure, vorzugsweise Ethyl-, n-Propyl- oder n-Butylacrylat als Monomerbaustein. Weiterhin enthält es 1 bis 8 Gew.-% eines carboxylgruppenhaltigen Monomeren, wie (Meth)Acrylsäure, Crotonsäure, Maleinsäure oder Acrylamidoglykolsäure. Bevorzugt sind diese Comonomeren zu bis 2 bis 5 Gew.-% im Copolymerisat einpolymerisiert, bevorzugt ist als Comonomer Acrylsäure.The copolymer a is a typical acrylic resin known in terms of its composition. It contains 30 to 85, preferably 60 to 75% by weight of a C 2 -C 6 -alkyl ester of (meth) acrylic acid, preferably ethyl, n-propyl or n-butyl acrylate, as a monomer unit. It also contains 1 to 8% by weight of a monomer containing carboxyl groups, such as (meth) acrylic acid, crotonic acid, maleic acid or acrylamidoglycolic acid. Up to 2 to 5% by weight of these comonomers are preferably copolymerized in the copolymer; acrylic acid is preferred as the comonomer.

Des weiteren sind Comonomere, die mit den vorgenannten copolymerisierbar sind, in Mengen von 7 bis 65, bevorzugt 20 bis 38 Gew.-% enthalten, und es sind hier vor allem Acrylnitril, Acrylamid, Methacrylamid, Vinylchlorid, Vinylacetat und/oder Styrol zu nennen.Comonomers which can be copolymerized with the abovementioned are also present in amounts of 7 to 65, preferably 20 to 38% by weight, and acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinyl acetate and / or styrene are to be mentioned here in particular .

Das Copolymerisat b enthält als Hauptbestandteile 50 bis 90, vorzugsweise 55 bis 70 Gew.-% Vinylidenchlorid einpolymerisiert. Weiter enthält es einen C2- bis C4-Alkylester der (Meth)Acrylsäure in einer Menge von 10 bis 50, vorzugsweise 25 bis 40 Gew.-%. Hier wird bevorzugt Ethyl- oder Butylacrylat eingesetzt.The copolymer b contains 50 to 90, preferably 55 to 70% by weight of vinylidene chloride as main constituents. It also contains a C 2 -C 4 -alkyl ester of (meth) acrylic acid in an amount of 10 to 50, preferably 25 to 40% by weight. Ethyl or butyl acrylate is preferably used here.

Als vernetzendes Comonomeres ist vor allem N-Methylol-(meth)acrylamid zu nennen, das in Mengen von 1 bis 5, vorzugsweise 1 bis 3 Gew.-% einpolymerisiert ist.N-methylol (meth) acrylamide, which is copolymerized in amounts of 1 to 5, preferably 1 to 3,% by weight is particularly worth mentioning as the crosslinking comonomer.

Ausserdem kann ggf. im Copolymerisat b (Meth)Acrylamid in geringen Mengen einpolymerisiert sein, und zwar 1 bis 5, vorzugsweise 1 bis 3 Gew.-%.In addition, small amounts of copolymerized (b) (meth) acrylamide can optionally be copolymerized in the copolymer, specifically 1 to 5, preferably 1 to 3,% by weight.

In der Grundierdispersion kann das Copolymerisat a aus einer Mischung von zwei Copolymerisaten gemäss Definition a, bezogen auf die Gesamtmenge, bestehen. Bei Verwendung eines zweiten Copolymerisats ist ein Copolymerisat der Zusammensetzung gemäss a mit Anteilen von 65 bis 85 Gew.-% eines der oben genannten Alkylester der (Meth)Acrylsäure bevorzugt. Die Grundierung wird dadurch weicher.In the primer dispersion, the copolymer a can consist of a mixture of two copolymers according to definition a, based on the total quantity, exist. If a second copolymer is used, a copolymer of the composition according to a with proportions of 65 to 85% by weight of one of the abovementioned alkyl esters of (meth) acrylic acid is preferred. This softens the primer.

Die Dispersion für die anschliessenden Appretur des grundierten Leders enthält ein Salz eines 2- wertigen Metalles, wie des Zinks, Cadmiums, Calciums oder Magnesiums, das eine ionische Vernezung der darin enthaltenen Polymerisate bewirkt. Zweckmässig werden als Salze die Chloride, Sulfate, Acetate, Nitrate, Oxalate oder Carbonate verwendet. Im Falle des Zinks und Magnesiums kann auch das Zinkoxid oder Magnesiumoxid eingesetzt werden. Die vorteilhaften Mengen an Metallverbindung liegen bei 0,3 bis 3, vorzugsweise 0,5 bis 2 Gew.-%, bezogen auf die vorgenannte Dispersion.The dispersion for the subsequent finishing of the primed leather contains a salt of a divalent metal, such as zinc, cadmium, calcium or magnesium, which causes the polymers contained therein to ionize. The chlorides, sulfates, acetates, nitrates, oxalates or carbonates are expediently used as salts. In the case of zinc and magnesium, zinc oxide or magnesium oxide can also be used. The advantageous amounts of metal compound are 0.3 to 3, preferably 0.5 to 2% by weight, based on the aforementioned dispersion.

Das hierbei verwendete Copolymerisat c enthält 20 bis 40 Gew.-% Styrol, 50 bis 75 Gew.-% mindestens eines C1- bis C6-Alkylesters der (Meth)-Acrylsäure, vorzugsweise Methyl-, Ethyl- und/ oder n-Butylacrylat, 1 bis 10 Gew.-% (Meth)-Acrylsäure, vorzugsweise 2 bis 9 Gew.-%, und 1 bis 5, vorzugsweise 2 bis 4 Gew.-% eines zur kovalenten Vernetzung befähigten Monomeren, wie N - Methylol-(meth)acrylamid.The copolymer c used here contains 20 to 40% by weight of styrene, 50 to 75% by weight of at least one C 1 to C 6 alkyl ester of (meth) acrylic acid, preferably methyl, ethyl and / or n Butyl acrylate, 1 to 10% by weight of (meth) acrylic acid, preferably 2 to 9% by weight, and 1 to 5, preferably 2 to 4% by weight of a monomer capable of covalent crosslinking, such as N - methylol ( meth) acrylamide.

Die bei der Appretur zu verwendende wässerige Dispersion des Copolymerisats c weist zweckmässigerweise einen Gehalt von 10 bis 50, bevorzugt 15 bis 30 Gew.-% auf.The aqueous dispersion of the copolymer c to be used in the finish expediently has a content of 10 to 50, preferably 15 to 30,% by weight.

In einer bevorzugten Ausführungsform bei Anwendung in der Praxis enthält die für die Appretur verwendete Dispersion c, bezogen auf das Gesamtgewicht, 0,5 bis 20, bevorzugt 2 bis 8 Gew.-% mit Acrylaten modifizierten Schellak und 0,5 bis 3 Gew.-% Verdickungsmittel auf Basis von Polyglykolpolyurethanen, Vinylpyrrolidon oder hochmolekulare Copolymerisate auf Basis Acrylsäure.In a preferred embodiment when used in practice, the dispersion c used for finishing contains, based on the total weight, 0.5 to 20, preferably 2 to 8% by weight of shellac modified with acrylates and 0.5 to 3% by weight. % Thickener based on polyglycol polyurethanes, vinyl pyrrolidone or high molecular weight copolymers based on acrylic acid.

Es können natürlich noch übliche Zusätze, bezogen auf die Dispersion in einer Menge von 1 bis 10, bevorzugt 1 bis 6 Gew.-% hochsiedende Polyglykole, Phthalsäureester, Ethylenglykol, Wachse natürlicher oder synthetischer Herkunft als Weichmacher sowie auch Fungizide, wie das Na-Salz des Diazeniumdioxidcyclohexans, enthalten sein. Diese Zusätze gelten auch für die Grundierdispersion, wie aus den Beispielen hervorgeht.Of course, it is also possible to use conventional additives, based on the dispersion, in an amount of 1 to 10, preferably 1 to 6,% by weight of high-boiling polyglycols, phthalic acid esters, ethylene glycol, waxes of natural or synthetic origin as plasticizers, and also fungicides, such as the Na salt of diazenium dioxide cyclohexane. These additives also apply to the primer dispersion, as can be seen from the examples.

Es wurde gefunden, dass man im Hinblick auf die Gebrauchsechtheiten besonders vorteilhafte Ergebnisse erhält, wenn man ein Copolymerisat b der Zusammensetzung 50 bis 90, bevorzugt 65 bis 85 Gew.-% Vinylchlorid und 10 bis 50, bevorzugt 15 bis 35 Gew.-% eines Ci - bis CQ-Alkylesters der (Meth)Acrylsäure sowie 0 bis 5, bevorzugt 0 bis 3 Gew.-% (Meth)Acrylamid verwendet.It has been found that particularly advantageous results with regard to the fastness to use are obtained if a copolymer b having the composition 50 to 90, preferably 65 to 85% by weight of vinyl chloride and 10 to 50, preferably 15 to 35% by weight of one C i to C Q alkyl esters of (meth) acrylic acid and 0 to 5, preferably 0 to 3% by weight of (meth) acrylamide are used.

Überraschenderweise hat diese Vereinfachung zur Folge, dass nach diesem Verfahren zugerichtetes Leder zusätzlich zu den bekannten Gebrauchsechtheiten beständig gegenüber Amien ist. Gemeint ist, dass der aufgetragene Film unter dem Einfluss von Aminen nicht vergilbt. Dieses vorteilhafte Ergebnis der Aminbeständigkeit unter Beibehaltung der übrigen Gebrauchsechtheiten, wie Wasserfestigkeit, Elastizität, Haftung zum Leder, Lichtechtheit und Heisslagerstabilität, waren nicht vorhersehbar.Surprisingly, this simplification has the consequence that leather prepared by this process is resistant to amien in addition to the known usage fastnesses. What is meant is that the applied film does not yellow under the influence of amines. This advantageous result of the amine resistance while maintaining the other usage fastnesses, such as water resistance, elasticity, adhesion to leather, light fastness and hot storage stability, were not predictable.

Die Aminbeständigkeit der erfindungsgemässen Lederzurichtung gegenüber freien Aminen ist von besonderem Vorteil für Schuhleder bei der Schuhherstellung beim Anschäumen von Polyurethansohlen an das Oberleder sowie beispielsweise bei Polyurethanschaumstoffüllungen für Möbelleder.The amine resistance of the leather preparation according to the invention to free amines is of particular advantage for shoe leather in shoe manufacture when foaming polyurethane soles on the upper leather and, for example, in polyurethane foam fillings for furniture leather.

Im übrigen erfolgt die Zurichtung der Leder mit den erfindungsgemäss zu verwendenden Dispersionen in an sich üblicher Weise.Otherwise, the leather is finished with the dispersions to be used according to the invention in a manner which is conventional per se.

Zunächst plüscht, bürstet, giesst oder sprüht man die Grundierdispersion in einer Menge auf das Leder, dass pro qm Lederfläche 20 bis 70 g Feststoff aufgebracht werden und trocknet das Material bei 60 bis 80° C innerhalb weniger Minuten. Das Auftragen der Grundierdispersion kann auch in mehreren Schritten, jeweils durch Zwischentrocknung unterbrochen, durchgeführt werden.First plush, brush, pour or spray the primer dispersion onto the leather in an amount such that 20 to 70 g of solid are applied per square meter of leather surface and the material is dried at 60 to 80 ° C within a few minutes. The primer dispersion can also be applied in several steps, each interrupted by intermediate drying.

Anschliessend bringt man in üblicher Weise in Mengen von 10 bis 30 g Feststoff pro qm Leder die Dispersion für die abschliessende Appretur auf. Man trocknet zunächst bei 60 bis 80° C, bügelt bei 140 bis 170° C und bügelt gegebenenfalls bei 80 bis 100° C unter vermindertem Druck hydraulisch nach.The dispersion for the final finish is then applied in a customary manner in amounts of 10 to 30 g of solid per square meter of leather. It is first dried at 60 to 80 ° C, ironed at 140 to 170 ° C and optionally ironed at 80 to 100 ° C under reduced pressure.

Bei der Grundierung können selbstverständliche handelsübliche Pigmentpräparationen und/ oder Farbstoffe in der Grundierung- und Appreturdispersion verwendet werden. Hierbei gibt man zweckmässigerweise 1 bis 5 g Pigmentpräparation und/oder handelsüblichen Farbstoff - bezogen auf 10g der in den Dispersionen enthaltenen Feststoffe zu.Of course, commercially available pigment preparations and / or dyes can be used in the primer and finish dispersion for the primer. It is advantageous to add 1 to 5 g of pigment preparation and / or commercial dye - based on 10 g of the solids present in the dispersions.

Insbesondere sei noch darauf hingewiesen, dass zur Erzielung guter Gebrauchsechtheiten ein gründliches Zwischentrocknen des grundierten und mit der Appretur versehenen Leders vorteilhaft ist. Besonders günstig wirkt sich ausserdem ein heisses Abbügeln der getrockneten Appretur aus.In particular, it should also be pointed out that in order to achieve good fastness to use, thorough drying of the primed and finished leather is advantageous. Hot ironing of the dried finish also has a particularly favorable effect.

Unter gründlichem Trocknen ist z. B. das Trocknen in einem üblichen Trockenkanal bei einer Temperatur von 50 bis 90° C, vorzugsweise 60 bis 80° C, bei einer Verweilzeit von 1 bis 5, vorzugsweise 2 bis 3 min, zu verstehen. Unter heissem Abbügeln soll verstanden werden, dass z. B. das Leder bei einer Temperatur von 90 bis 180° C, vorzugsweise bei 120 bis 170° C, mit einer üblichen Durchlaufbügelmaschine gebügelt wird.With thorough drying z. B. drying in a conventional drying tunnel at a temperature of 50 to 90 ° C, preferably 60 to 80 ° C, with a residence time of 1 to 5, preferably 2 to 3 minutes, to understand. Hot ironing should be understood to mean that e.g. B. the leather is ironed at a temperature of 90 to 180 ° C, preferably at 120 to 170 ° C, with a conventional continuous ironing machine.

Die folgenden Beispiele erläutern die Erfindung. Teile sind Gewichtsteile.The following examples illustrate the invention. Parts are parts by weight.

Beispiele:Examples:

Folgende Dispersionen wurden eingesetzt:

  • 1. Beispiele für wässerige Dispersionen eines Copolymerisats a aus:
    Figure imgb0001
    Figure imgb0002
    Das Copolymerisat a4 eignet sich insbesondere in Mischungen mit einem Copolymerisat gemäss a1 bis a3.
  • 2. Beispiele für wässerige Dispersionen eines Copolymerisats b aus:
    Figure imgb0003
  • 3. Beispiele für wässerige Dispersionen eines Copolymerisats c aus:
    Figure imgb0004
    Figure imgb0005
    Anwendungsbeispiele
The following dispersions were used:
  • 1. Examples of aqueous dispersions of a copolymer from:
    Figure imgb0001
    Figure imgb0002
    The copolymer a4 is particularly suitable in mixtures with a copolymer according to a1 to a3.
  • 2. Examples of aqueous dispersions of a copolymer b from:
    Figure imgb0003
  • 3. Examples of aqueous dispersions of a copolymer c from:
    Figure imgb0004
    Figure imgb0005
    Examples of use

Beispiel 4:Example 4: Grundierdispersion:Primer dispersion:

Figure imgb0006
Figure imgb0006

Beispiel 5:Example 5: Grundierdispersion:Primer dispersion:

Figure imgb0007
Figure imgb0007

Beispiel 6:Example 6: Grundierdisaersion:Primer version:

Figure imgb0008
Figure imgb0008

Beispiel 7:Example 7: Appreturdispersion:Finishing dispersion:

Figure imgb0009
Figure imgb0009

Anwendungsbeispiele auf LederApplication examples on leather Beispiel I:Example I:

Vollnarbiges Rindleder wurde mit zwei Spritzaufträgen folgender Zubereitung mit Hilfe der Druckluftpistole qrundiert:

Figure imgb0010
Full-grain cowhide was primed with two spray orders of the following preparation using the compressed air gun:
Figure imgb0010

Das so besprühte Leder wurde nach jedem Spritzauftrag bei 70° C getrocknet und nach dem ersten Spritzauftrag bei 70° C und 50 bar zwischengebügelt. Auftrasgsmenge: 45 g Feststoffe/m2.The leather sprayed in this way was dried at 70 ° C. after each spray application and ironed in at 70 ° C. and 50 bar after the first spray application. Application rate: 45 g solids / m 2 .

Das so grundierte Leder wurde anschliessend mit einer Zubereitung folgender Zusammensetzung appretiert:

Figure imgb0011
The leather primed in this way was then finished with a preparation of the following composition:
Figure imgb0011

Die Zubereitung wurde mittels Druckluftpistole mit zwei Spritzaufträgen aufgesprüht, bei 70° C zwischen- und schlussgetrocknet, danach bei 170° C auf der Durchlaufbügelmaschine gebügelt. Das dabei erhaltene Leder besitzt die für ein Schuhoberleder gewünschten sensorischen Eigenschaften (Griff, Glanz, etc.) und erfüllt ebenfalls die in der Praxis geforderten Echtheiten, wie z.B. Wasserfestigkeit, Elastizität und Aminfestigkeit.The preparation was sprayed on by means of a compressed air gun with two spraying jobs, intermediate and final drying at 70 ° C, then ironed at 170 ° C on the continuous ironing machine. The leather obtained has the sensory properties desired for a shoe upper leather (feel, gloss, etc.) and also fulfills the fastness properties required in practice, e.g. Water resistance, elasticity and amine resistance.

Beispiel II:Example II:

Rindnappaleder für Bekleidungszwecke wurde mit folgender grundierungszubereitung beschichtet:

Figure imgb0012
Cowhide nappa leather for clothing was coated with the following primer preparation:
Figure imgb0012

Das so behandelte Leder wurde nach jedem der drei Spritzaufträge bei 70° C zwischengetrocknet.The leather treated in this way was intermediate dried at 70 ° C. after each of the three spray applications.

Danach wurde das Leder mit nachfolgender Appreturzubereitung besprüht:

Figure imgb0013
The leather was then sprayed with the following finish preparation:
Figure imgb0013

Auftragsmenge bei zwei Spritzaufträgen mit Zwischentrocknen und Schlusstrocknen bei 70° C: 35 g Feststoff/m2. Danach wurde das Leder bei 125°C auf der Durchlaufbügelpresse und anschliessend bei 90° C auf der hydraulischen Presse abgebügelt.Application quantity for two spray applications with intermediate drying and final drying at 70 ° C: 35 g solid / m 2 . The leather was then ironed off at 125 ° C on the continuous press and then at 90 ° C on the hydraulic press.

Das erhaltene Leder zeigte sämtliche für Bekleidungszwecke erforderliche Eigenschaften, wie z.B. Griff, Abriebfestigkeit oder Wasserechtheit.The leather obtained showed all the properties required for clothing, such as Handle, abrasion resistance or waterfastness.

Beispiel III:Example III

Rindleder für Polsterzwecke wurde in ähnlicher Weise mit einer Grundiermischung folgender Zusammensetzung beschichtet (Auftragsmenge:

Figure imgb0014
Cowhide for upholstery purposes was similarly coated with a primer mixture of the following composition (order quantity:
Figure imgb0014

Von dieser Mischung wurden zwei Spritzaufträge aufgetragen, das Leder danach bei 80° C getrocknet, bei 80° C zwischengebügelt, nochmals zwei Spritzaufträge gegeben und bei 70° C nachgetrocknet.Two spray applications were applied from this mixture, the leather was then dried at 80 ° C., ironed at 80 ° C., two further spray applications were applied and the mixture was subsequently dried at 70 ° C.

Danach wurde folgende Appreturzubereitung aufgespritzt:

Figure imgb0015
The following finish preparation was then sprayed on:
Figure imgb0015

Zwei Spritzaufträge (Druckluftpistole), jeweils getrocknet bei 70° C, gebügelt bei 150° C (Durchlaufbügelmaschine) und nachgebügelt bei 90° C auf der hydraulischen Bügelmaschine.Two spraying jobs (compressed air gun), each dried at 70 ° C, ironed at 150 ° C (continuous ironing machine) and ironed at 90 ° C on the hydraulic ironing machine.

Das somit erhaltene Leder weist alle für Polstermöbelleder erwünschten Eigenschaften, wie z. B. Reibwerte, Elastizität, Lichtechtheit, Scheuerfestigkeit, Aminfestigkeit und Heissbügelechtheit, auf.The leather thus obtained has all the properties desired for upholstered leather, such as. B. coefficients of friction, elasticity, light fastness, abrasion resistance, amine resistance and hot iron fastness.

Beispiel lV:Example IV:

Geschliffene Rindleder für Schuhe Grundmischung:

Figure imgb0016
Ground cowhide for shoes basic mix:
Figure imgb0016

Das Leder wurde mit dieser Grundiermischung mit dem Pfüschbrett einmal beschichtet, danach bei 70° C getrocknet, bei 70° C gebügelt, nochmals geplüscht und mit jeweiligem Zwischentrocknen bei 70° C mit zwei Spritzaufträgen (Luftdruckpistole) besprüht. Auftragsmenge: 80 g Feststoff/m2.The leather was coated once with this primer mixture with the puddle board, then dried at 70 ° C, ironed at 70 ° C, plushed again and with intermediate drying sprayed at 70 ° C with two spray jobs (air pressure gun). Application quantity: 80 g solid / m 2 .

Das grundierte Leder wurde anschliessend mit folgender Appreturzubereitung beschichtet:

Figure imgb0017
Auftragsmenge: 30 g/m 2.The primed leather was then coated with the following finish:
Figure imgb0017
 Application quantity: 30 g / m 2 .

Diese Zubereitung wurde mittels Druckluftpistole mit zwei Spritzaufträgen aufgetragen, bei 70° C getrocknet und bei 100°C auf der Durchlaufbügelmaschine gebügelt. Das hierbei erhaltene Leder besitzt die für Schuhoberleder gewünschten Eigenschaften. Es ist lichtecht, aminbeständig, wasserfest und besitzt ein genügende Elastizität.This preparation was applied using a compressed air gun with two spraying jobs, dried at 70 ° C and ironed at 100 ° C on the continuous ironing machine. The leather obtained has the properties desired for upper leather. It is lightfast, amine-resistant, waterproof and has sufficient elasticity.

Beispiel V:Example V

Vollnarbiges Rindleder wurde mit zwei Spritzaufträgen mit jeweiliger Zwischentrocknung bei 70° C und anschliessendem Bügeln bei 70° C mit folgender Zubereitung so lange behandelt, bis 50 g Polymerisat pro m2 Leder aufgebracht waren :

Figure imgb0018
Full-grain cowhide was treated with two spray jobs, each with intermediate drying at 70 ° C and then ironed at 70 ° C, with the following preparation until 50 g of polymer per m 2 of leather had been applied:
Figure imgb0018

Das grundierte Leder wurde anschliessend mit einer Zubereitung folgender Zusammensetzung appretiert:

Figure imgb0019
The primed leather was then finished with a preparation of the following composition:
Figure imgb0019

Das erhaltene Leder ist wasserfest und mechanisch beanspruchbar, ohne dass die Appretur abblättert.The leather obtained is waterproof and mechanically stressable without the finish peeling off.

Beispiel VI:Example VI:

Es wurde gemäss den Angaben in Beispiel V gearbeitet (Rindleder für Bekleidungszwecke), wobei jedoch diesmal bei der Grundierung (40 g/m2):

Figure imgb0020
The procedure was as described in Example V (cowhide for clothing), but this time with the primer (40 g / m2):
Figure imgb0020

Das erhaltene Leder zeigte sämtliche für Bekleidungszwecke erwünschte Eigenschaften bezüglich Griff, Abriebfestigkeit und Wasserechtheit.The leather obtained showed all the properties desired for clothing purposes in terms of grip, abrasion resistance and waterfastness.

Beispiel VII:Example VII:

Ziegenleder wurde in ähnlicher Weise mit einer Mischung aus (30 g/m2)Goat leather was similarly made with a mixture of (30 g / m 2 )

Figure imgb0021
Figure imgb0021

Das erhaltene Leder weist alle Eigenschaften auf, die bei Handtaschen und Aktenmappen erwünscht sind.The leather obtained has all the properties that are desired for handbags and briefcases.

Die Beispiele V, VI und VII wurden wiederholt, jedoch anstelle der genannten Grundierungs- und Appreturdispersion folgende Dispersionen eingesetzt:

  • Grundierungsdispersion mit a2, a4 und b5 sowie a1, a4 und b4 und den übrigen Bestandteilen gemäss Beispiel 6 sowie Appreturdispersion mit c2, c3 und d (Vergleich) mit den übrigen Bestandteilen gemäss Beispiel 7.
Examples V, VI and VII were repeated, but the following dispersions were used instead of the primer and finishing dispersion mentioned:
  • Primer dispersion with a2, a4 and b5 as well as a1, a4 and b4 and the other ingredients according to example 6 and a finishing dispersion with c2, c3 and d (comparison) with the other ingredients according to example 7.

Die Ergebnisse sind im wesentlichen dieselben, wobei im Falle der Anwendung der Dispersion b4 in der Grundierungsdispersion die Leder hinsichtlich ihrer Elastizität weniger befriedigen (etwas hart), was auf den hohen Gehalt an Vinylidenchlorid zurückzuführen ist. Bei der Verwendung der Dispersion d (Vergleich) in der Beschichtungsdispersion (kein Vernetzer anwesend) erhält man Leder mit deutlich geringerer Wasserechtheit.The results are essentially the same, but when the dispersion b4 is used in the primer dispersion, the leather is less satisfactory in terms of elasticity (somewhat hard), which is due to the high vinylidene chloride content. When using dispersion d (comparison) in the coating dispersion (no crosslinking agent present), leather with significantly lower water fastness is obtained.

Claims (1)

  1. A process for finishing leather or a synthetic leather replacement material by applying a bottoming based on an aqueous acrylic resin dispersion, drying the coating and then applying a season containing an aqueous styrene/acrylate dispersion, wherein the dispersion used in the bottoming procedure comprises one or more copolymers (a) which contain, as copolymerized units, from 30 to 85% by weight of a C2-C6-alkyl acrylate or methacrylate, from 1 to 8% by weight of a carboxyl-containing monomer and from 7 to 65% by weight of one or more monomers, which are copolymerizable with the above monomers, from the group comprising acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinyl acetate and styrene, the percentages being based on the copolymer, and a copolymer (b) which contains, as copolymerized units, from 50 to 90% by weight of vinylidene chloride, from 10 to 50% by weight of a C2-C4-alkyl acrylate or methacrylate and from 1 to 5% by weight of N-methylolacrylamide or -methacrylamide which carries a group capable of crosslinking the copolymer, with or without from 1 to 5% by weight of acrylamide or methacrylamide, the percentages being based on the copolymer, or the composition contains, in dispersed form, from 50 to 90% by weight of vinyl chloride and from 10 to 50% by weight of a C1 -C4-alkyl acrylate or methacrylate as well as from 0 to 5% by weight of acrylamide or methacrylamide in a ratio a to b of from 2:1 to 5:1, and the season used is a dispersion which contains a divalent metal ion and, in dispersed form, a copolymer (c) which contains, as copolymerized units, from 20 to 40% by weight of styrene, from 50 to 75% by weight of one or more C1 -C6-alkyl acrylate or methacrylates, from 1 to 10% by weight of acrylic acid or mehtacrylic acid and from 1 to 5% by weight of N-methylolacrylamide or -methacrylamide which carries a group capable of crosslinking the copolymer, the percentages being based on the copolymer.
EP83107140A 1982-07-28 1983-07-21 Process for finishing leather or leather substitutes Expired EP0100493B1 (en)

Priority Applications (1)

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AT83107140T ATE17023T1 (en) 1982-07-28 1983-07-21 PROCESS FOR TRIMMING LEATHER OR SYNTHETIC LEATHER REPLACEMENT.

Applications Claiming Priority (4)

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DE19823228128 DE3228128A1 (en) 1982-07-28 1982-07-28 Method for dressing leather or synthetic leather replacement material
DE3228128 1982-07-28
DE19833307431 DE3307431A1 (en) 1983-03-03 1983-03-03 Process for the dressing of leather or synthetic leather replacement material
DE3307431 1983-03-03

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EP0100493B1 true EP0100493B1 (en) 1985-12-18

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DE3736475A1 (en) * 1987-10-28 1989-05-11 Basf Ag METHOD FOR MAKING LEATHER
AU717402B2 (en) * 1995-09-15 2000-03-23 Rohm And Haas Company Method for coating leather
US6080209A (en) * 1996-03-26 2000-06-27 Basf Aktiengesellschaft Stable colorant compositions
US5723182A (en) * 1996-08-27 1998-03-03 Rohm And Haas Company Method for coating leather
AUPO216396A0 (en) 1996-09-06 1996-10-03 Ici Australia Operations Proprietary Limited Stain resistant water-borne paint
US20040245490A1 (en) * 2001-09-28 2004-12-09 Holger Schopke Top coating composition for leather
US6849682B2 (en) * 2002-09-30 2005-02-01 Omnova Solutions Inc. VOC containment coating, methods and articles
DE102004032766A1 (en) * 2004-07-06 2006-02-09 Röhm GmbH & Co. KG Concentrated aqueous methacrylamide solution with the addition of methacrylic acid
KR102407460B1 (en) * 2015-12-18 2022-06-13 롬 앤드 하아스 컴패니 Retanning of chrome-free leather fabric

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