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EP0163057B1 - Procédé de retannage du cuir ayant subi un tannage minéral ou combiné avec des tannins polymères - Google Patents

Procédé de retannage du cuir ayant subi un tannage minéral ou combiné avec des tannins polymères Download PDF

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Publication number
EP0163057B1
EP0163057B1 EP85103988A EP85103988A EP0163057B1 EP 0163057 B1 EP0163057 B1 EP 0163057B1 EP 85103988 A EP85103988 A EP 85103988A EP 85103988 A EP85103988 A EP 85103988A EP 0163057 B1 EP0163057 B1 EP 0163057B1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylic acid
acid
polymer
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85103988A
Other languages
German (de)
English (en)
Other versions
EP0163057A1 (fr
Inventor
Dolf Dr. Dipl.-Kaufmann Stockhausen
Rudolf Dr. Dipl.-Ing. Nowak
Miroslav Dr. Dipl.-Chem. Chmelir
Manfred Dr. Dipl.-Chem. Kaussen
Kurt Dr. Dipl.-Chem. Dahmen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stockhausen GmbH and Co KG
Original Assignee
Chemische Fabrik Stockhausen GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemische Fabrik Stockhausen GmbH filed Critical Chemische Fabrik Stockhausen GmbH
Priority to AT85103988T priority Critical patent/ATE36174T1/de
Publication of EP0163057A1 publication Critical patent/EP0163057A1/fr
Application granted granted Critical
Publication of EP0163057B1 publication Critical patent/EP0163057B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • 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
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes

Definitions

  • the invention relates to a method for retanning mineral or combined tanned leather with polymer tanning agents.
  • the main tanning of leather is mainly carried out with basic salts of trivalent chromium, aluminum and / or zirconium alone or in combination with synthetic tanning agents.
  • Subsequent retanning preferably serves to improve or modify certain characteristic properties of the leather, which are characterized by terms such as fullness, grain strength, grip, crack, levelness and others. Accordingly, there are significant differences in the target direction between main and retanning.
  • synthetic tanning agents - syntans - are used in retanning, the tanning effect of which can be limited.
  • Typical representatives are low molecular weight (degree of polymerization 1-5) condensation products of formaldehyde with naphthalene and / or phenolsulfonic acids or their alkali salts.
  • EP-A-0151290 (priority: 01/24/84; application date: 12/18/84; publication date: 08/14/85) describes amphoteric condensation products and their use in retanning.
  • the object of the invention is therefore to improve the previously known products used for retanning, in particular with regard to pH sensitivity, electrolyte stability and influencing the dyeing behavior of the leather.
  • the invention relates to a process for retanning mineral or combined tanned leather by treatment with an aqueous solution of water-soluble polymer tanning agent, which is characterized in that polymer tanning agent is composed of polymers of at least one unsaturated monomer containing sulfonic acid groups and, if appropriate, further water-soluble, unsaturated, copolymerizable, not phosphorus-containing monomers are used, with the exception of polymers of 5-100% by weight of vinylsulfonic acid and 0-95% by weight of (meth) acrylic acid and copolymers of 80-90% by weight of (meth) acrylic acid and 20-100% of unsaturated sulfonation products of animal or vegetable oils.
  • polymer tanning agent is composed of polymers of at least one unsaturated monomer containing sulfonic acid groups and, if appropriate, further water-soluble, unsaturated, copolymerizable, not phosphorus-containing monomers are used, with the exception of polymers of 5-100% by
  • Suitable sulfonic group-containing unsaturated monomers for the preparation of the polymer tanning agent according to the invention are preferably those derived from a, ⁇ -unsaturated acids and their derivatives, preferably from (meth) acrylic acid and their derivatives, such as, for example, 2-acrylamido-2-methylpropanesulfonic acid.
  • sulfonic acids are N- (3-sulfopropyl-N- (meth) acrylamidopropyl) -N, N-dimethylammonium betaine or a sulfopropyl- (meth) acrylic acid ester.
  • the sulfone group can also be present as a substituent in a cyclic, preferably aromatic system, while the polymerizable CC double bond is in the side chain of the cyclic system, such as aromatic ⁇ -olefins sulfonated on the ring.
  • a typical example of this is styrene sulfonic acid.
  • the sulfonic acids themselves are suitable, but also their salts, such as the alkali and / or ammonium salts.
  • the polymers according to the invention may also contain further basic units which do not impair the water solubility of the polymer and which are derived from corresponding copolymerizable monomers which do not contain phosphorus.
  • Preferred polymers are copolymers of at least one sulfone group-containing monomer with at least one carboxyl group-containing monomer. These copolymers can in turn contain further basic units derived from other water-soluble, unsaturated monomers.
  • Unsaturated carboxylic acids such as maleic acid as dicarboxylic acid and unsaturated monocarboxylic acids such as (meth) acrylic acid and / or crotonic acid are primarily suitable as monomers containing carboxyl groups.
  • water solubilizers can be added non-impairing copolymerizable monomers (meth) acrylamide or vinyl pyrrolidone.
  • the molecular weight of the polymer tanning agents according to the invention can vary within wide limits. Polymers with molecular weights from 10,000 are suitable. The upper limit of the molecular weight can be, for. B. are at 150000. The molecular weight range of the polymers used is preferably between 20,000 and 100,000, in particular between 25,000 and 50,000.
  • the retanning of the leather is preferably carried out at 0.1-5.0% by weight, based on the shaved weight of the polymeric tanning material with a liquor length of up to 300%, temperatures up to a maximum of 70 ° C. and pH values in the range of at least 2.5 -8.0.
  • Polymer tanning agent from acrylic acid / acrylamide / and 2-acrylamido-2-methylpropanesulfonic acid from acrylic acid / acrylamide / and 2-acrylamido-2-methylpropanesulfonic acid.
  • the monomer solution was then added to the polymerization flask with stirring over a period of about 60 minutes.
  • 1.6 g of hydroxylamine hydrochloride (dissolved in 12 g of water) and 60 g of 45% strength sodium hydroxide solution were metered in proportionally to the monomer solution through further inlet ports.
  • the reaction temperature was kept at 100 ° C. by boiling.
  • the mixture was stirred for a further hour at 100 ° C. and then adjusted to pH 7.4 with sodium hydroxide solution.
  • An approximately 40% solution of a polymer composed of acrylic acid, acrylamide and AMPS with a viscosimetrically determined molar mass of 48,000 g per mol resulted.
  • the polymer tanning agents described in Example 2 were used in the following formulation for cowhide leather, type nappa:
  • the leather treated with the polymer tanning agents according to the invention was distinguished by a deeper coloration than with a commercially available polymer retanning agent produced on the basis of acrylic acid / acylamide.
  • Polymer tanning agent made from acrylic acid, acrylamide and sodium styrene sulfonate
  • the polymer tanning agent obtained was used in accordance with the following recipe:
  • the leather treated according to the invention was significantly softer than the comparative leather worked with a commercially available polymer retanning agent based on acrylic acid / acrylamide copolymer with the same grain strength.
  • the terpolymer has a viscosimetric molecular weight of approximately 30,000 g / mol.
  • the polymer tanning agent described here When used in the formulation in Example 4, the polymer tanning agent described here provided an even higher softness with the same grain strength.
  • the terpolymer described in Example 5 was used in the following formulation for cowhide:
  • the leather produced according to this recipe was dyed deeper than the leather treated with a commercially available polymer retanning agent based on acrylic acid / acrylamide copolymer.
  • the polymer tanning agent described in Example 5 was used and investigated in the following formulation for nappa:
  • the leather treated with the polymer tanning agent according to the invention is dyed deeper and has a higher softness than the leather treated with a commercially available polymer retanning agent based on acrylic acid / acrylamide copolymer.
  • This monomer solution was then, with stirring, over a period of about 60 minutes into the polymerization vessel together with the hydroxylamine solution (1.6 g in 58 ml of water), 7.8 g of hydrogen peroxide (35%) and 56 g of sodium hydroxide solution (45% ) entered.
  • the leather treated with the polymer tanning agent according to the invention showed better grain strength and was dyed deeper than the leather treated with a commercially available polymer retanning agent based on acrylic acid / acrylamide copolymer.
  • Example 1 100 g of water and 1.0 g of hydrogen peroxide (35% strength) were placed in a polymerization flask as described in Example 1 and heated to 90.degree.
  • the monomer solution consisting of 136 g of acrylamide, 65.0 g of sodium styrene sulfate (80%), 94 g of maleic anhydride and 260 g of water, was mixed with the hydroxylamine solution (1.6 g in 58 g of water) within 8 hours, 8 g Hydrogen peroxide and 51.0 g of sodium hydroxide solution (45% strength) are metered into the polymerization flask within 2 hours.
  • the mixture was stirred at 90 ° C. for a further 2 hours and neutralized to pH 7.0 with sodium hydroxide solution.
  • the leather treated with the polymer tanning agent according to the invention showed significantly more color intensity than the leather treated with a commercially available polymer retanning agent based on acrylic acid / acrylamide copolymer.
  • Example 9 100 g of water and 4.0 g of hydrogen peroxide (35% strength) were placed in a polymerization flask as described in Example 1 and heated to 90.degree.
  • the monomer solution consisting of 256 g of acrylamide, 39.1 g of sodium styrene sulfonate (80%) and 260 g of water, was mixed together with the hydroxylamine solution (6.3 g in 78 g of water), 31.2 g of hydrogen peroxide in 2 hours metered the polymerization flask.
  • the reaction temperature was kept at 100 ° C. by boiling. After the polymerization, the mixture was stirred at 90 ° C. for a further 2 hours and neutralized to pH 7.0 with sodium hydroxide solution.
  • the solution obtained in the recipe used in Example 9 gave a leather whose softness, depth of color and brilliance turned out to be significantly better than the leather treated with a commercially available polymer retanning agent based on acrylamide copolymer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Claims (6)

1. Procédé de retannage du cuir ayant subi un tannage minéral ou combiné par traitement avec une solution aqueuse d'un produit tannant polymère soluble dans l'eau, caractérisé en ce qu'à titre de produit tannant polymère, on utilise des polymères d'au moins un monomère insaturé contenant des radicaux acide sulfonique, comme éventuellement aussi d'autres monomères insaturés, solubles dans l'eau, copolymérisables, ne contenant pas de phosphore, à l'exclusion des polymères constitués de 5 à 100% en poids d'acide vinylsulfonique et de 0 à 95% en poids d'acide (méth)acrylique, comme aussi des copolymères constitués de 80 à 90% en poids d'acide (méth)acrylique et de 20 à 10% en poids de produits de sulfuration insaturés d'huiles animales ou végétales.
2. Procédé suivant la revendication 1, caractérisé en ce que l'on utilise, à titre de produit tannant polymère, un polymère composé d'au moins 3% molaires d'unités acide 2-acrylamido-2-méthylpropanesulfonique, N-(3-sulfopropyl-N-(méth)acrylamidopropyl) - N,N - diméthyl - ammonium- bétaïne, ester d'acide sulfopropyl-(méth)acrylique et/ou acide styrènesulfonique, ou leurs sels de métaux alcalins et/ou d'ammonium.
3. Procédé suivant les revendications 1 ou 2, caractérisé en ce que l'on utilise, à titre de monomères supplémentaires, des monomères contenant des radicaux carboxyle, insaturés et/ou du (méth)acrylamide et de la vinylpyrrolidone.
4. Procédé suivant la revendication 3, caractérisé en ce qu'à titre de monomères contenant des radicaux carboxyle, on utilise l'acide maléique, l'acide (méth)acrylique et/ou l'acide crotonique.
5. Procédé suivant la revendication 1 à 4, caractérisé en ce que l'on opère le traitement du cuir tanné avec 0,1 à 5,0% en poids, par rapport au poids au drayage, du produit tannant polymère, à une longueur ou rapport du bain allant jusqu'à 300%, des températures allant jusqu'à un maximum de 70°C et des valeurs de pH fluctuant dans la gamme d'au moins 2,5 jusqu'à 8,0.
6. Procédé suivant les revendications 1 à 5, caractérisé en ce que l'on effectue le retannage en combinaison avec des produits tannants synthétiques ou végétaux.
EP85103988A 1984-04-09 1985-04-02 Procédé de retannage du cuir ayant subi un tannage minéral ou combiné avec des tannins polymères Expired EP0163057B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85103988T ATE36174T1 (de) 1984-04-09 1985-04-02 Verfahren zum nachgerben von mineralisch oder kombiniert gegerbtem leder mit polymergerbstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843413301 DE3413301A1 (de) 1984-04-09 1984-04-09 Verfahren zum nachgerben von mineralisch oder kombiniert gegerbtem leder mit polymergerbstoffen
DE3413301 1984-04-09

Publications (2)

Publication Number Publication Date
EP0163057A1 EP0163057A1 (fr) 1985-12-04
EP0163057B1 true EP0163057B1 (fr) 1988-08-03

Family

ID=6233062

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85103988A Expired EP0163057B1 (fr) 1984-04-09 1985-04-02 Procédé de retannage du cuir ayant subi un tannage minéral ou combiné avec des tannins polymères

Country Status (7)

Country Link
US (1) US4631063A (fr)
EP (1) EP0163057B1 (fr)
AT (1) ATE36174T1 (fr)
CA (1) CA1241155A (fr)
DE (2) DE3413301A1 (fr)
ES (1) ES8607405A1 (fr)
PT (1) PT80236B (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4227974C2 (de) * 1992-08-26 1996-04-18 Stockhausen Chem Fab Gmbh Alkoxygruppenhaltige Copolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung zum Nachgerben von Leder
DE4343993A1 (de) * 1993-12-22 1995-06-29 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Polyhydroxyverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19516957C2 (de) * 1995-05-12 2000-07-13 Stockhausen Chem Fab Gmbh Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung
US5820633A (en) * 1996-09-20 1998-10-13 Lesko; Patricia Marie Method of treating leather with improved retaining agents
US6011104A (en) * 1998-01-20 2000-01-04 Udy; Joseph D. Footware dressings incorporating fluorocarbons
EP1488013A1 (fr) * 2002-03-15 2004-12-22 Basf Aktiengesellschaft Utilisation de polyelectrolytes pour produire du cuir
US7737569B2 (en) * 2006-10-24 2010-06-15 Seadyne Energy Systems, Llc System and method for converting ocean wave energy into electricity
AR081664A1 (es) * 2010-06-30 2012-10-10 Akzo Nobel Chemicals Int Bv Proceso de polimerizacion con formacion in-situ del iniciador
WO2015055730A1 (fr) * 2013-10-16 2015-04-23 Rhodia Operations Agent améliorant l'indice de viscosité de fluides de champs de pétrole dans des conditions difficiles

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3408319A (en) * 1964-12-08 1968-10-29 Rohm & Haas Tanning compositions comprising aqueous solutions of unsaturated acid-unsaturated sulfated oil copolymers
DE1669347A1 (de) * 1967-03-25 1971-05-06 Henkel & Cie Gmbh Verfahren zum Fetten von Leder
FR1533483A (fr) * 1967-06-23 1968-07-19 Basf Ag Procédé de tannage des peaux et cuirs obtenus
US3898037A (en) * 1972-06-01 1975-08-05 Betz Laboratories Acrylamido-sulfonic acid polymers and their use
FR2400587A1 (fr) * 1977-08-19 1979-03-16 Allied Colloids Ltd Perfectionnements aux epaississants de pates d'impression au tamis pour tapis
EP0061420B2 (fr) * 1981-03-06 1992-01-29 Ciba-Geigy Ag Procédé de retannage du cuir avec des oligomères à base acrylique
DE3248019A1 (de) * 1982-12-24 1984-06-28 Cassella Ag, 6000 Frankfurt Wasserloesliche copolymerisate, ihre herstellung und ihre verwendung

Also Published As

Publication number Publication date
DE3413301A1 (de) 1985-10-24
ES8607405A1 (es) 1986-05-16
DE3413301C2 (fr) 1990-08-16
DE3564133D1 (en) 1988-09-08
PT80236B (pt) 1987-10-20
CA1241155A (fr) 1988-08-30
ES542037A0 (es) 1986-05-16
PT80236A (de) 1985-05-01
US4631063A (en) 1986-12-23
ATE36174T1 (de) 1988-08-15
EP0163057A1 (fr) 1985-12-04

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