EP0265657B1 - Procédé de tannage du cuir - Google Patents

Procédé de tannage du cuir Download PDF

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Publication number
EP0265657B1
EP0265657B1 EP87113669A EP87113669A EP0265657B1 EP 0265657 B1 EP0265657 B1 EP 0265657B1 EP 87113669 A EP87113669 A EP 87113669A EP 87113669 A EP87113669 A EP 87113669A EP 0265657 B1 EP0265657 B1 EP 0265657B1
Authority
EP
European Patent Office
Prior art keywords
melamine
resin
formaldehyde
leather
tanning
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 - Lifetime
Application number
EP87113669A
Other languages
German (de)
English (en)
Other versions
EP0265657A1 (fr
Inventor
Hermann Becker
Werner Dr. Lotz
Karlfried Dr. Keller
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.)
Hoechst AG
Original Assignee
Hoechst AG
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
Priority claimed from DE19863632638 external-priority patent/DE3632638A1/de
Priority claimed from DE19873711458 external-priority patent/DE3711458A1/de
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT87113669T priority Critical patent/ATE57539T1/de
Publication of EP0265657A1 publication Critical patent/EP0265657A1/fr
Application granted granted Critical
Publication of EP0265657B1 publication Critical patent/EP0265657B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof

Definitions

  • Chrome tanning which has achieved a dominant position in leather production over the past 60 to 80 years, has come under increasing ecological pressure over the past decade due to the high wastewater pollution with chromium (III) salts.
  • chromium (III) salts As a return to the tanning methods with vegetable or animal tanning agents that had been in use for thousands of years before chrome tanning with drastic loss of properties, e.g. If the lightfastness or temperature resistance of the leather had to be paid for, there has been no shortage of attempts to replace chromium (III) salts in tanning with other purely mineral tanning agents such as titanium, zirconium or aluminum salts or by combining them with vegetable tanning agents .
  • Methyl or butyl etherified melamine-formaldehyde resins are also suggested as tannins (Miekeley (see above); Hachihama, Kyogoku, Technol. Repts. Osaka Univ. 6, 397 (1956); CA 52, 10622a (1958)).
  • the leather tanned with butyl etherified melamine-formaldehyde resins was too thin, the leather tanned with methyl etherified melamine-formaldehyde resins were pure white, had excellent lightfastness and fullness, and high alkali resistance, and due to their cationic character showed a good absorption capacity for acid and substantive dyes.
  • these leathers had a very serious deficiency with regard to their tear resistance behavior over time.
  • these leathers tanned with melamine-formaldehyde resins had very good tear resistance.
  • the tear strength decreased sharply and fell to 50% or less of the original value within about four weeks.
  • a resin mixture which consists of 20 to 80% of a melamine-formaldehyde resin and 80 to 20% by weight of an anionically modified melamine-formaldehyde resin is preferred.
  • the melamine resins free from anionic groups are prepared in a known manner by alkaline condensation of melamine with 1.5-6 mol of formaldehyde.
  • the condensation can also be carried out in the presence of plasticizers known for melamine resin condensation, such as mono- and polyhydric alcohols and non-reducing sugars, with partial etherification.
  • plasticizers known for melamine resin condensation, such as mono- and polyhydric alcohols and non-reducing sugars, with partial etherification.
  • additional alcohols e.g. Suitable: methanol, ethanol, glycol, glycerin, sorbitol, other mono- or polyhydric alcohols individually or in mixtures with each other.
  • the amount of these alcohols or sugars is about 0 to 20% by weight of the total solid resin.
  • the melamine resins described here should not contain any anionic groups. Up to 50% by weight of this melamine resin can also be replaced by other aminoplast formers such as guanamine, dicyandiamide or urea.
  • the anionically modified melamine resin used as the second component is produced in the same manner as the unmodified resin described. In the production of this resin, however, at least 0.3 mol, preferably up to 1.5 mol, of an alkali sulfite, alkali hydrogen sulfite or alkali sulfamate are added per mole of melamine, so that the resulting resin bears the corresponding number of sulfo groups and thus anionic Has properties.
  • alkali sulfites or alkali sulfamates are, for example, potassium or sodium sulfites or sulfamates in the form of individual compounds or in Form of mixtures of several alkali sulfites and / or alkali sulfamates used.
  • the hydrogen sulfites can also be taken in the same way.
  • a second aspect of the present invention consists in producing a mixed resin and using it in the method according to the invention.
  • a conventional melamine-formaldehyde resin is produced in one batch with the addition of a correspondingly reduced amount of sulfite or sulfamate.
  • the same melamine resins as described above can be used for such mixed resins.
  • alkali sulfite 0.25 to 0.8 mol of an alkali sulfite, alkali hydrogen sulfite or alkali sulfamate are added per mole of melamine during their preparation, so that the resulting resin carries the corresponding number of sulfo groups and thus has anionic properties.
  • alkali sulfites or alkali sulfamates e.g. Potassium or sodium sulfites
  • hydrogen sulfites or sulfamates are used in the form of individual compounds or in the form of mixtures of several alkali sulfites and / or alkali sulfamates.
  • This partially anionically modified resin is obtained as a liquid solution and can be used directly for tanning in this form.
  • This liquid setting is characterized by improved durability over a similar resin obtained by mixing an unmodified melamine resin with an anionically modified melamine resin.
  • the resin mixtures or mixed resins thus produced are used in the customary manner in the tanning process.
  • soaked, ashed and pickled hides regardless of the animal species, are used in an aqueous liquor at pH values from 7 to 8.5 with 4 to 20%, based on pelt weight, of the resin solutions used according to the invention at temperatures from 30 to 45 ° C in one of the tanneries common in tanneries treated for about 6 to 8 hours.
  • the temperature of the liquor is then raised to up to 50 ° C. and, after a further run time of 1 h, 0.5 to 3%, based on the block weight, of an acid catalyst is added to the bath.
  • Acidic catalysts in particular organic acids which do not damage the skin, such as, for example, formic acid, or acidic salts, such as, for example, ammonium chloride, can be used alone or in a mixture with one another.
  • the leather is then deposited and processed like any other tanned skin material.
  • the process can be carried out successfully on all types of leather, fur and fur.
  • the leather obtained in the process according to the invention have, depending on the process control, shrinking temperatures of 70 to 90 ° C, have a good fullness, are soft to permanent, have very good dyeing properties for dyeing with commercially available anionic dyes due to their predominantly cationic character and because of their also in cross-section white color an excellent basis for the production of pure white leather. They are solid-grain, have a very good light fastness and a similar abrasion behavior, tensile strength and tear behavior like chrome-tanned leather, as well as good self-extinguishing properties after contact with a pilot flame and give freedom any type of aftertreatment customary in leather production, such as retanning, greasing or dressing.
  • the particular advantages of the method according to the invention lie in the environmental friendliness and simplicity of the process.
  • the process saves both the wastewater-polluting pimple before tanning and the neutralization step necessary in the mineral tanning process.
  • the tannery wastewater is not polluted by any environmentally harmful mineral salts.
  • the main advantage of the process according to the invention is that there is no appreciable loss of tear strength when the leather is stored.
  • the pH is 10.6-11.
  • the mixture is heated to 85 ° in about 40 minutes and condensed at this temperature for about 2 hours until it can be diluted with saturated saline at 1: 4 (measured after cooling to 23 ° C.). After cooling to room temperature, 2100 g of a clear, thin resin are obtained; Burn-in content: 47%, viscosity: 14 DIN seconds, pH: 9.6-9.8, density: 1.215, turbidity hardening time: 110-140 minutes, shelf life up to 6 months, no flash point until boiling.
  • Cowhide as is common in the practice of leather production, is soaked, ashed, fleshed, decalcified and pickled.
  • the pH of the nakedness is 7.8 after pickling.
  • the percentages of the further process steps relate to the weight of the beef skin.
  • the nakedness is taken up in a conventional tanning vessel in 50% water at 38 ° C. and mixed with 6% of a 1: 1 mixture of resins A and B, prepared according to Examples 1 and 2, and left to run for 6 hours. Then another 50% water of 55 ° C is added and it is left to run at this temperature for another hour. Then 1% formic acid 85% is added. After a further 30 minutes, the leather is removed from the tanning vessel, deposited overnight and completed after the further process steps, such as folding, greasing, retanning, dyeing, etc., which are customary in leather production.
  • the leather thus obtained has a fine, uniform and firm grain, is well filled, has a smooth, pleasant grip, very good color uniformity and lightfastness and good tear resistance, which, even after 12 weeks of storage, maintains the unchanged high level of immediately after completion of the Leather has a measured initial value, as the table shows.
  • the leathers have good self-extinguishing properties after contact with an ignition flame.
  • the leathers obtained in this way have a very fine, uniform and firm grain, are not very heavily filled, and have a very smooth, pleasant grip.
  • the leather thus obtained is very well filled and stable. They have a uniform, emphatically structured scars and a full, pleasant grip and have very good lightfastness and color uniformity.
  • the tear strength does not quite reach the level of the leather processed according to Examples 4 and 5.
  • the leathers have good self-extinguishing properties after contact with an ignition flame.
  • Cowhide is soaked, ashed, fleshed, descaled and stained, as is common in the practice of leather production.
  • the pH of the nakedness is 8.2 after pickling.
  • the percentages of the further process steps relate to the weight of the beef skin.
  • the pickled nakedness is taken up in a conventional tanning vessel in 50% water at 38 ° C. and mixed with 10% of the mixed condensate (50%) prepared in accordance with Example 3 and left to run for 6 hours.
  • the leather thus obtained has a uniformly fine, firm grain. They are well filled, soft to firm and have a round, full grip. They have high tear resistance values and have very good color levelness and lightfastness. The leathers have good self-extinguishing properties after contact with an ignition flame.

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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)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (7)

1. Procédé de préparation de cuir par tannage, caractérisé en ce qu'on tanne les peaux en tripe avec un mélange de résines ou avec une résine mixte, constitué d'une résine de mélamine-formaldéhyde et d'une résine de mélamine-formaldéhyde à modification anionique.
2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un mélange de 20 à 80% en poids d'une résine de mélamine-formaldéhyde et de 80 à 20% en poids d'une résine de mélamine-formaldéhyde à modification anionique.
3. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des résines de mélamine-formaldéhyde présentant un rapport molaire de la mélamine au formaldéhyde de 1:1,5 à 1:6.
4. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des résines de mélamine-formaldéhyde préparées par addition de 0 à 20% en poids d'un alcool ou d'un sucre non-réducteur.
5. Procédé selon la revendication 1, caractérisé en ce qu'on utilise une résine de mélamine-formaldéhyde à modification anionique partielle, résine qui a été préparée en présence de 0,25 à 0,8 mole d'un sulfite, hydrogénosulfite ou sulfamate de métal alcalin par mole de mélamine.
6. Procédé selon la revendication 1, caractérisé en ce qu'on utilise une résine de mélamine-formaldéhyde à modification anionique, qui a été préparée en présence d'au moins 0,3 mole d'un sulfite, hydrogénosulfite ou sulfamate de métal alcalin par mole de mélamine.
7. Procédé selon la revendication 1, caractérisé en ce qu'on utilise des résines de mélamine-formaldéhyde lors de la préparation desquelles on a remplacé jusqu'à 50% en poids de la mélamine par d'autres substances formant des aminoplastes.
EP87113669A 1986-09-25 1987-09-18 Procédé de tannage du cuir Expired - Lifetime EP0265657B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87113669T ATE57539T1 (de) 1986-09-25 1987-09-18 Verfahren zur gerbung von leder.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3632638 1986-09-25
DE19863632638 DE3632638A1 (de) 1986-09-25 1986-09-25 Verfahren zur gerbung von leder
DE3711458 1987-04-04
DE19873711458 DE3711458A1 (de) 1987-04-04 1987-04-04 Verfahren zur gerbung von leder

Publications (2)

Publication Number Publication Date
EP0265657A1 EP0265657A1 (fr) 1988-05-04
EP0265657B1 true EP0265657B1 (fr) 1990-10-17

Family

ID=25847845

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87113669A Expired - Lifetime EP0265657B1 (fr) 1986-09-25 1987-09-18 Procédé de tannage du cuir

Country Status (7)

Country Link
US (1) US4810252A (fr)
EP (1) EP0265657B1 (fr)
KR (1) KR880004101A (fr)
BR (1) BR8704915A (fr)
DE (1) DE3765616D1 (fr)
ES (1) ES2018807B3 (fr)
PT (1) PT85776B (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4108139A1 (de) * 1991-03-13 1992-09-17 Boehme Chem Fab Kg Verfahren zum gerben von leder und pelzen
US5710239A (en) * 1996-02-29 1998-01-20 Georgia-Pacific Resins, Inc. Water-soluble sulfonated melamine-formaldehyde resins
DE102005008034A1 (de) * 2005-02-22 2006-08-31 Lanxess Deutschland Gmbh Säuregruppenhaltige Kondensationsprodukte
WO2010043680A1 (fr) * 2008-10-17 2010-04-22 Basf Se Procédé de production de cuir
ES2702480T3 (es) 2016-03-10 2019-03-01 Holupelli Consult Gmbh Procedimiento para el mejoramiento de cuero

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2303209A (en) * 1941-03-05 1942-11-24 American Cyanamid Co Leather tanning and finishing
FR974657A (fr) * 1948-11-04 1951-02-23 American Cyanamid Co Perfectionnements à la production de résines amino triazine aldéhydes solubles àl'eau
US3063781A (en) * 1959-10-29 1962-11-13 Nopco Chem Co Method for tanning leather with aminoplasts and compositions therefor
DE3115646A1 (de) * 1981-04-18 1982-11-18 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von wasserloeslichen oder selbstdiespergierenden harzbergstoffen

Also Published As

Publication number Publication date
DE3765616D1 (de) 1990-11-22
BR8704915A (pt) 1988-05-17
PT85776B (pt) 1990-07-31
EP0265657A1 (fr) 1988-05-04
PT85776A (de) 1987-10-01
ES2018807B3 (es) 1991-05-16
US4810252A (en) 1989-03-07
KR880004101A (ko) 1988-06-01

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