EP0061420B1 - Procédé de retannage du cuir avec des oligomères à base acrylique - Google Patents

Procédé de retannage du cuir avec des oligomères à base acrylique Download PDF

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Publication number
EP0061420B1
EP0061420B1 EP82810091A EP82810091A EP0061420B1 EP 0061420 B1 EP0061420 B1 EP 0061420B1 EP 82810091 A EP82810091 A EP 82810091A EP 82810091 A EP82810091 A EP 82810091A EP 0061420 B1 EP0061420 B1 EP 0061420B1
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Prior art keywords
parts
leather
oligomer
tanning agent
cooc
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EP82810091A
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German (de)
English (en)
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EP0061420A1 (fr
EP0061420B2 (fr
Inventor
Alain Dr. Lauton
Albert Dr. Würmli
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Novartis AG
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Ciba Geigy AG
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Priority claimed from CH152881A external-priority patent/CH646731A5/de
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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
    • C14C3/28—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/22—Chemical tanning by organic agents using polymerisation products

Definitions

  • the present invention relates to a process for retanning leather with acrylic-based oligomers.
  • polyampholytic acrylic polymers are used as the tanning agent, which (a) acidic carboxyl groups, (b) basic amino groups, (c) a result from z.
  • B. methyl methacrylate and ethyl acrylate can be used, these copolymers and terpolymers have been prepared in the absence of sulfites or hydrogen sulfites.
  • US Pat. No. 3,945,792 describes a process for the aftertreatment of tanned leather with fillers which are prepared from homo- or copolymeric acrylic acids which have been prepared in the absence of sulfites or hydrogen sulfites, e.g. B. consist of a copolymer of acrylic acid and ethyl acrylate, such fillers are mandatory in a mixture with protein glue.
  • FR-A-1 311 602 also discloses a process for retanning leather in which the tanning agent is ammonium or amine salts of polymers of acrylic or methacrylic acid, alkyl esters and, if appropriate, other comonomers, such as, for.
  • the tanning agent is ammonium or amine salts of polymers of acrylic or methacrylic acid, alkyl esters and, if appropriate, other comonomers, such as, for.
  • acrylonitrile or methacrylonitrile which have also been produced in the absence of sulfites or hydrogen sulfites, in particular ammonium salts of copolymers of methacrylic acid and ethyl acrylate can be used.
  • the present invention now relates to a process for retanning chrome-tanned, optionally dyed leather, in which the leather is treated with an aqueous solution containing an acrylic compound as the tanning agent, which is characterized in that an oligomer is used as the tanning agent average molecular weight is at most 14000, the oligomer having been prepared using sulfites or hydrogen sulfites and structural elements of the formulas wherein X, -CN, ⁇ COOR 1 , -OOCR2 or -CONHR 3 , Y 1 ⁇ COOH or ⁇ COOM 2 , Y 2 ⁇ CONH 2 , ⁇ CH 2 OH, -OCH 3 or ⁇ OC 2 H 5 , Z1, Z 2 and Z 3 each represent hydrogen, methyl or ethyl, M, and M 2 each represent an amine, ammonium or alkali metal cation and R 1 , R 2 and R 3 each represent alkyl, hydroxyalkyl or alkoxyalkyl
  • the oligomers which have structural elements of the formulas (1), (2) and (4) are known per se and, for. As described in US-A-3 646 099 as conductive and surface active compounds. Likewise, the oligomers which, in addition to the structural elements (1) and (2) additionally contain the structural element of the formula (3), are known from US-A-2893977 as a component of resin compositions with good adhesive properties.
  • oligomers are prepared in the presence of sulfites or hydrogen sulfites, they have structural elements of the formula (4) in one case and not in the other. Based on analytical studies contain oligomers which, after the end of known production in the presence of sulfites or hydrogen sulfites, by adding strong acids, e.g. As hydrochloric acid, are precipitated from their aqueous solutions, no or only traces of structural elements of the formula (4).
  • strong acids e.g. As hydrochloric acid
  • sulfite or hydrogen sulfite after the preparation of the oligomers in aqueous solution has ended is present exclusively or at least mainly as a mixture component and not as a structural element of the oligomer in the form of the formula (4). Since oligomers reprecipitated with hydrochloric acid, when used as tanning agents, give the same results as non-reprecipitated oligomers, the presence or absence of structural elements of the formula (4) is not a critical feature of the oligomers used according to the invention. For the retanning process according to the invention, however, the oligomers used do not have to be reprecipitated before they are used.
  • An essential feature of the oligomers which can be used according to the invention, in addition to the presence of the structural elements of the formulas (1), (2), if appropriate (3) and if appropriate (4), is the relatively low average molecular weight, which is at most 14,000, in particular 3,000 to 12,000, preferably 3000 to 10,000, in particular 4000 to 9000.
  • These relatively low molecular weights of the oligomers used according to the invention compared to high molecular weight polymers which, for. B. find use in the plastics industry for the production of synthetic fibers are caused by the use of sulfites or hydrogen sulfites in the oligomer production.
  • preferred oligomers indungsgefflessen method f in it are used as a tanning agent, each 2 to 75, preferably 5 to 40, in particular 10 to 25 structural units of formulas (1) and (2) and 0 to 25, preferably 0 to 10, in particular 0 to 5 structural units of the formula (3).
  • oligomers come into consideration which, in addition to the structural elements of the formulas (2), optionally (3) and optionally (4) structural elements of the formula have, wherein X 2 ⁇ CN, ⁇ COOR 4 , ⁇ OOCR 5 or -CONHR 6 , R 4 alkyl, hydroxyalkyl or methoxyalkyl with a total of at most 4 carbon atoms, R 5 methyl or ethyl and R 6 alkyl having 1 to 8 carbon atoms or hydroxyalkyl 1 or 2 carbon atoms, and Z 1 has the meanings given, and in particular structural elements of the formula wherein X 3 is -CN, -COOCH 3 , ⁇ COOC 2 H 5 , -COOC 2 H 4 0H, ⁇ COOC 3 H 6 OH, ⁇ COOC 2 H 4 OCH 3 , ⁇ OOCCH 3 , ⁇ OOCC 2 H 5 , -CONHCH3 , ⁇ CONHC 2 H
  • Structural elements of the formulas have structural elements which are particularly suitable as tanning agents
  • Oligomers which are of primary interest as tanning agents, have structural elements of the formulas
  • the preparation of the known oligomers is carried out according to methods known per se, which, for. B. in US-A-3 646 099 and US-A-2 893 977 by the compounds of the formulas wherein X 1 , Y 1 , -Y 2 , Z 1 , Z 2 and Z 3 each have the meanings given, always in the presence of the compounds of the formulas or wherein M, which has the meanings given, in an aqueous medium and, if appropriate, in the presence of a polymerization catalyst at a maximum of 70 ° C., and at this temperature the aqueous reaction mixture with a base of the formula wherein M 2 has the meanings given, to a pH of 5 to 7.
  • component (5) and then component (6) and optionally (7) are generally used first in order to avoid homopolymerization of the generally more reactive component (6), then small amounts of the monomers initially introduced (e.g.
  • a polymerization catalyst such as azoisobutyronitrile or preferably peroxides, such as benzoyl peroxide or in particular ammonium peroxodisulfate (ie the compound of the formula (NH 4 ) 2 S 2 O 8 ) the aqueous solution of the starting compounds in portions, for. B. added in 8 to 12 portions, or metered in continuously within 5 to 8 hours, an exothermic polymerization reaction starting.
  • the reaction mixture is advantageously cooled in such a way that the temperature does not exceed 70 ° C., in particular 40 ° C.
  • the polymerization is generally complete 4 to 6 hours after the catalyst has been added.
  • the reaction mixture is adjusted to an appropriate pH of about 5 to 7, in particular 6.1 to 6.3, by adding the compound of the formula (10) with cooling so that the temperature indicated above is not exceeded. whereby an aqueous, gel-like solution of the copolymer is obtained.
  • the reaction mixture can, if necessary, for the complete removal of any unpolymerized starting compounds, in particular monomers of formula (5), for 6 to 10 hours under reduced pressure (-10 to -1 bar) at 60 can be kept up to 80 ° C.
  • retanning chrome-tanned leather it is expedient to proceed according to methods known per se by treating the leather with an aqueous solution which contains at least one oligomer of the type specified above, rinsing the tanned material in this way if necessary, and then generally greasing it and dries.
  • a coloring can be carried out before or after the oiling, but preferably before the oiling, provided the leather to be retanned is not already colored.
  • 100 to 200, preferably 150 to 200 parts by weight of water and 2 to 50, in particular 5 to 10 parts by weight, calculated on dry substance, of at least one of the oligomers of the type mentioned are used per 100 parts by weight of leather.
  • Preferred aqueous solutions for carrying out the retanning process preferably contain 1 to 10, in particular 2 to 5, percent by weight of the oligomer as the tanning agent.
  • the leather is treated with the aqueous solution containing the oligomer for 1 to 4 hours at 10 ° C to 50 ° C, preferably 10 ° C to 30 ° C.
  • the dye is expediently used immediately after retanning by adding the dye of the type specified in the tanning liquor, so that in this case the rinse is usually not necessary.
  • the leather is not dyed, it is advantageous to the leather after retanning a short, z. B. 15- to 30-minute rinse with water at 10 ° C to 50 ° C, preferably 10 ° C to 30 ° C.
  • the retanned, optionally dyed leather is then treated with a customary, preferably lightfast, fatliquor based on, for. B. greased sulfonated sperm oil or claw oil.
  • This fat is z. B. at 30 ° C to 80 ° C for about 30 to 90 minutes.
  • a leather is obtained which has excellent lightfastness, a fine, compact, smooth grain and in particular a soft feel. With undyed leather, a very light leather can also be obtained.
  • the strong bleaching effect achieved during retanning is particularly advantageous on uncoloured chrome leather.
  • the oligomers used as tanning agents according to the invention have excellent compatibility with other commercial tanning agents, e.g. B. vegetable tanning agents or synthetic retanning agents, so that the latter can be used together with the oligomers.
  • chrome-tanned leather which can be retanned according to the invention
  • wet blue • leather are particularly suitable, with all types of leather, eg. B. calf, cowhide, goat or sheep leather are considered and the chrome-tanned leather before retanning according to the invention, as usual, with z. B. formates or bicarbonates is neutralized.
  • reaction mixture is kept under reduced pressure and inert nitrogen atmosphere for 2 hours to remove unreacted acrylonitrile fractions.
  • the emulsion is then adjusted to a pH of 6 using 287.3 parts of a 30% strength aqueous sodium hydroxide solution (2.15 mol), the reaction mixture being cooled so that its temperature does not exceed 40.degree elevated.
  • 1,000 parts of a light yellow, gel-like, clear, aqueous solution which contains 34% of an oligomer containing about 15 structural elements of the formula (1.4), about 15 structural elements of the formula (2.2) and Has traces of the structural element of the formula -S0 3 Na.
  • Instructions B The procedure described in Instructions A is followed, but a solution of 185.9 parts of acrylic acid (2.58 mol), 64.7 parts of acrylonitrile (1.22 mol) and 19.8 parts of the 40% sodium bisulfite Solution (0.076 mol) in 69.8 parts of water, which with a total of 19.8 parts of the ammonium peroxodisulfate solution in 10 portions, and after dilution with 96 parts of water, with 344 parts of the sodium hydroxide solution (2.58 mol) is moved.
  • Instructions C The procedure described in Instructions A is followed, but a solution of 185 parts of acrylic acid (2.56 mol), 34 parts of acrylonitrile (0.64 mol) and 55.6 parts of the sodium bisulfite solution (0.214 mol) is used in 257 Parts of water, which are mixed with a total of 10.7 parts of the ammonium peroxodisulfate solution in 10 portions and, after dilution with 116.4 parts of water, with 341.3 parts of the sodium hydroxide solution (2.56 mol).
  • Process D The procedure is as described in instruction A, but a solution of 138.3 parts of acrylic acid (1.92 mol), 127.3 parts of acrylonitrile (2.4 mol), 34.1 parts of acrylamide (0.48 mol ) and 41.6 parts of the sodium bisulfite solution (0.16 mol) in 298.4 parts of water, which together with a total of 11.4 parts of the ammonium peroxodisulfate solution in 10 portions and, after dilution with 92.9 parts of water, 256 parts of the sodium hydroxide solution (1.92 mol) are added.
  • Instructions E The procedure described in Instructions A is followed, but an emulsion of 211 parts of acrylic acid (2.92 mol), 141.5 parts of vinyl acetate (1.64 mol) and 43 parts of the 40% sodium bisulfite solution (0.165 mol) is used. in 80 ml of water, which is dissolved at 50 ° C with a total of 1.5 parts of ammonium peroxodisulfate in 25 ml of water in 10 portions and, after dilution with 155 parts of water, with 320 parts of the sodium hydroxide solution (2.4 mol).
  • reaction mixture 146 parts of a 30% strength aqueous sodium hydroxide solution are then added to the reaction mixture over the course of about 1.5 hours in such a way that the temperature does not rise above 50.degree.
  • the reaction mixture is then heated to the reflux temperature (98-100 ° C.) and kept at the reflux temperature under a reduced pressure of from ⁇ 0.8 to ⁇ 1.0 bar for about 8 hours until a sample of the reaction mixture has less than 100 ppm of unreacted acrylonitrile .
  • the reaction mixture is then cooled to 20 ° C. and adjusted to a pH of 6.1 to 6.3 by adding a total of about 22 parts of a 30% strength aqueous sodium hydroxide solution in portions.
  • About 600 parts of a clear, slightly yellowish solution are obtained, which contains 33 to 34% of an oligomer which has 25 to 30 structural elements each of the formulas (1.4) and (2.2).
  • Instructions G The procedure described in Instructions A is followed, but a solution of 128.4 parts of acrylic acid (1.78 mol), 144.2 parts of methacrylic acid hydroxypropyl ester (1 mol) and 47.4 parts of a 25% strength aqueous potassium hydrogen sulfite solution is used. Solution (0.1 mol) in 100 parts of water with a total of 10 parts of the ammonium peroxodisulfate solution in 10 portions at 60 ° C and, after dilution with 351.5 parts of water, with 218.5 parts of the sodium hydroxide solution (1.63 mol) is added.
  • Instructions H The procedure described in Instructions A is followed, but a solution of 73.6 parts of 2-ethoxyethyl acrylate (0.51 mol), 93.8 parts of acrylic acid (1.30 mol) and 33.6 parts of a 25th %, aqueous potassium hydrogen sulfite solution (0.07 mol) in 60 parts of water, which with 5 parts of the ammonium peroxodisulfate solution in 5 portions at 60 ° C and, after dilution with 565.8 parts of water, with 168, 2 parts of the sodium hydroxide solution (1.26 mol) is added.
  • Procedure 1 The procedure is as given in rule A, but a solution of 130.7 parts of acrylic acid (1.81 mol), 120.3 parts of acrylonitrile (2.26 mol), 26.3 parts of allyl alcohol (0.40 mol ) and 72.6 parts of a 25% aqueous potassium hydrogen sulfite solution (0.15 mol) in 283.5 parts of water, which together with 37.8 parts of an ammonium peroxodisulfate solution in 5 portions and, after dilution with 87 parts Water, with 241.8 parts of the sodium hydroxide solution (1.81 mol) is added.
  • Instructions J The procedure described in Instructions A is followed, but a solution of 133 parts of acrylic acid (1.84 mol), 149.4 parts of methyl acrylate hydroxypropyl ester (1.03 mol) and 49 parts of a 25% strength aqueous potassium hydrogen sulfite solution (0 , 10 mol) in 98.4 parts of water, which with a total of 12.2 parts of the ammonium peroxodisulfate solution in 10 portions at 40 ° C. and, after dilution with 461.7 parts of water, with 96.3 parts of a 30% aqueous ammonia solution (1.7 mol) is added.
  • 100 parts of a chrome-tanned calfskin neutralized in the usual manner are aftertreated with a solution of 200 parts water and 5 parts, calculated on dry substance, of the oligomer according to regulation A for 1 1/2 'hours at 30 ° C.
  • the aftertreated leather is greased as usual with 4 to 6 parts of a lightfast fatliquor based on sulfonated sperm oil and then dried.

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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)

Claims (8)

1. Procédé pour le retannage de cuir tanné au chrome, éventuellement teint, dans lequel on traite le cuir avec une solution aqueuse qui contient en tant que matière tannante un composé acrylique, caractérisé en ce qu'on utilise en tant que matière tannante un oligomère dont la masse moléculaire moyenne est au plus égale à 14 000, l'oligomère ayant été préparé par utilisation de sulfites ou d'hydrogénosulfites, et présentant des éléments structuraux de formules
Figure imgb0027
dans lesquelles X1 est -CN, -COOR,, -OOCR2 ou ―CONHR3, Y1 est ―COOH ou ―COOM2; Y2 est -CONH2, ―CH2OH, -OCH3 ou ―OC2H5 ; Z1, Z2 et Z3 sont chacun l'hydrogène, le radical méthyle ou éthyle ; M1 et M2 sont chacun un cation amine, ammonium ou métal alcalin, et R1, R2 et R3 sont chacun un radical alkyle, hydroxyalkyle ou alcoxyalkyle ayant en tout au plus 8 atomes de carbone, et que le cuir traité est graissé et séché, le cuir traité étant encore éventuellement teint avant ou après le graissage.
2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise en tant que matière tannante un oligomère qui contient 2 à 75 de chacun des éléments structuraux de formules
Figure imgb0028
et 0 à 25 éléments structuraux de formule
Figure imgb0029
dans lesquelles X1, Y1, Y2, Z1, Z2 et Z3 ont chacun signification donnée dans la revendication 1.
3. Procédé selon la revendication 1, caractérisé en ce qu'on utilise en tant que matière tannante un oligomère contenant des éléments structuraux de formules
Figure imgb0030
dans lesquelles X2 est -CN, ―COOR4, ―OOCR5 ou ―CONHR6 ; R4 est un radical alkyle, hydroxyalkyle ou méthoxyalkyle ayant en tout au plus 4 atomes de carbone ; R5 est le radical méthyle ou éthyle, et R6 est un radical alkyle ayant de 1 à 8 atomes de carbone ou hydroxyalkyle ayant 1 ou 2 atomes de carbone, et M1, Y1, Y2, Z1, Z2 et Z3 ont chacun les significations données dans la revendication 1.
4. Procédé selon la revendication 3, caractérisé en ce qu'on utilise en tant que matière tannante un oligomère contenant des éléments structuraux de formules
Figure imgb0031
dans lesquelles X3 est -CN, ―COOCH3, ―COOC2H5, ―COOC2H4OH. ―COOC3H6OH, ―COOC2H4O-CH3, -OOCCH3, -OOCC2H5, ―CONHCH3, ―CONHC2H5, -CONHCH20H, ―CONHC3H7 ou -CONHC3HI7 et M1, Y1, Y2, Z1, Z2 et Z3 ont chacun les significations données dans la revendication 1.
5. Procédé selon la revendication 4, caractérisé en ce qu'on utilise en tant que matière tannante un oligomère contenant des éléments structuraux de formules
Figure imgb0032
dans lesquelles X4 est ―CN, ―COOCH3, ―COOC2H5, ―COOC2H4OH, ―COOC3H6OH, ―OOCCH3, -OOCC2H5, ―CONHCH3, ―CONHC2H5, ―CONHO3H7 et ―CONHC8H17; Y3 est -COOH ou ―COOM4 ; Y4 est -CONH2, ―CH2OH ou ―OCH3 ; M3 et M4 sont chacun un cation sodium, potassium ou ammonium, et Z4, Z5 et Z6 sont chacun l'hydrogène ou le radical méthyle.
6. Procédé selon la revendication 5, caractérisé en ce qu'on utilise en tant que matière tannante un oligomère qui contient des éléments structuraux de formules
Figure imgb0033
7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce qu'on utilise en tant que matière tannante sur 100 parties en poids de cuir, 2 à 50 parties en poids, sur la base de l'extrait sec, de l'oligomère.
8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que le cuir est traité pendant 1 à 4 heures à 10 à 50 °C par la solution aqueuse contenant l'oligomère en tant que matière tannante, et que le cuir ainsi traité ou bien est rincé, graissé et séché, ou bien est teint, graissé et séché.
EP82810091A 1981-03-06 1982-03-01 Procédé de retannage du cuir avec des oligomères à base acrylique Expired - Lifetime EP0061420B2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH1528/81 1981-03-06
CH152881A CH646731A5 (en) 1981-03-06 1981-03-06 Process for retanning chrome-tanned leather with sulphite-containing acrylic oligomers
CH820181 1981-12-22
CH8201/81 1981-12-22

Publications (3)

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EP0061420A1 EP0061420A1 (fr) 1982-09-29
EP0061420B1 true EP0061420B1 (fr) 1985-10-30
EP0061420B2 EP0061420B2 (fr) 1992-01-29

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US (1) US4439201A (fr)
EP (1) EP0061420B2 (fr)
AR (1) AR243557A1 (fr)
CA (1) CA1192703A (fr)
DE (1) DE3267088D1 (fr)
ES (1) ES510160A0 (fr)

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US5348807A (en) * 1991-02-05 1994-09-20 Rohm And Haas Company Polymeric retan fatliquor for low fogging upholstery leather
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
DE4242076A1 (de) * 1992-12-14 1994-06-16 Roehm Gmbh Gerbmittel und Gerbverfahren
GB2275481B (en) * 1993-02-18 1996-06-12 Sandoz Ltd Re-tanning process
US5428117A (en) * 1993-10-18 1995-06-27 Interface, Inc. Treatment for imparting stain resistance to polyamide substrates and resulting stain resistant materials
US5820633A (en) * 1996-09-20 1998-10-13 Lesko; Patricia Marie Method of treating leather with improved retaining agents
CN104328229B (zh) * 2014-10-27 2016-09-14 浙江理工大学 一种针对皮质文物大豆油加脂剂的制备方法
CN104313204A (zh) * 2014-10-27 2015-01-28 浙江理工大学 一种用超声波技术针对硬化皮革文物加脂剂的制备方法
PT3257955T (pt) 2016-06-13 2022-11-28 Tfl Ledertechnik Gmbh Processo de pré-curtimento ou recurtimento de couro utilizando carboximetilcelulose e seus sais

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AR243557A1 (es) 1993-08-31
EP0061420A1 (fr) 1982-09-29
DE3267088D1 (en) 1985-12-05
ES8302784A1 (es) 1983-02-01
ES510160A0 (es) 1983-02-01
CA1192703A (fr) 1985-09-03
US4439201A (en) 1984-03-27
EP0061420B2 (fr) 1992-01-29

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