US3909193A - Tanning formulations - Google Patents

Tanning formulations Download PDF

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Publication number
US3909193A
US3909193A US345506A US34550673A US3909193A US 3909193 A US3909193 A US 3909193A US 345506 A US345506 A US 345506A US 34550673 A US34550673 A US 34550673A US 3909193 A US3909193 A US 3909193A
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United States
Prior art keywords
tanning
parts
formulations
formaldehyde
dialdehyde
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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
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US345506A
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English (en)
Inventor
Hans Erdmann
Franz Friedrich Miller
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BASF SE
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BASF SE
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Publication date
Priority claimed from DE19722215948 external-priority patent/DE2215948C3/de
Priority claimed from DE19722227598 external-priority patent/DE2227598C3/de
Priority claimed from DE19722243826 external-priority patent/DE2243826C3/de
Application filed by BASF SE filed Critical BASF SE
Application granted granted Critical
Publication of US3909193A publication Critical patent/US3909193A/en
Anticipated expiration legal-status Critical
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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

Definitions

  • ABSTRACT Tanning formulations containing a reaction product of a dialdehyde, which may be totally acetalized, with formaldehyde.
  • This invention relates to novel tanning formulations based on reaction products of emf-dialdehydes with formaldehyde.
  • the invention also relates to tanning and retanning with the novel tanning formulations.
  • One tanning agent which has been used for many years is formaldehyde.
  • leathers tanned with formaldehyde are pure white and have a shrink temperature of from 9092C when tanning is carried out at pl-ls of from seven to eight.
  • it suffers from the disadvantage that the fullness, softness, flexibility and tensile strength of the resulting leathers are not satisfactory in all respects.
  • dialdehyde is a particularlysuitable tanning agent.
  • This patent describes a number of advantages of the leather resulting from tanning with this compound. Particular stress is laid on the distinct improvement in softness and flexibility, the high shrink temperature of about 88C at relatively low pHs (4.0) and the excellent tensile strength. These specific properties have made the dialdehydes somewhat superior to formaldehyde.
  • tanning with, say, glutaraldehyde alone has hitherto been suitable mainly when darker leathers are required or when chromium tanning is carried out simultaneously, where the color of the chromium is applied to the leather and thus masks any yellowing which might occur.
  • a further object is to provide formulations which give approximately the same optimum results as achieved with dialdehydes as regards softness, fullness, tensile strength and shrink resistance.
  • Yet another object of the invention is to provide formulations of the kind mentioned which give optimum results when used in conjunction with mineral or vegetable tannages.
  • tanning formulations containing at least one reaction product of one molar portion of a C w,m'-dialdehyde, or an amount of a mixture of w,w-dialdehydes of from 2 to 8 carbon atoms equivalent to one molar portion, and from 4 to 6 molar portions of formaldehyde.
  • the formulations of the invention are simple to produce, conveniently by mixing commercial aqueous solutions of dialdehyde, usually containing from 25 to 50% dialdehyde, with usually 30 to 40% w/w formaldehyde (formal in) solutions and heating the combined solutions to from to 95C and preferably to about C for from 30 to 60 minutes.
  • the reaction proceeds best at pHs near the neutral point, preferably from pH 5 to 7.
  • the pH may be conveniently adjusted with aqueous alkaline solutions such as caustic soda, caustic potash or sodium carbonate solution.
  • a preferred method permits a pH of about 6.5.
  • a particularly favorable tanning formulation is produced when the reaction is carried out in the presence of from 5 to 20% by weight, based on w,w'-dialdehydes used, of at least one tertiary alkanolamine having from 2 to 4 carbon atoms per alkanol group.
  • tanning agents are produced when the w,w-dialdehydes used in the reaction of the invention are not the simple w,w-dialdehydes but complete acetals thereof.
  • Particularly suitable acetals are obtained when the alcohols used for the purpose are those having from 1 to 10 carbon atoms.
  • the preparation may be carried out in the presence of the above tertiary alkanolamines.
  • tanning When tanning is carried out with such preferred tanning agents, it is possible to achieve excellent results on leathers, the tanning of which takes a long time, without there being any risk of a weakening in the tanning action and thus of incomplete penetration.
  • the two last-named modifications are mainly suitable for work on furs.
  • the temperatures may be maintained at the required values by cooling of the reaction mixture in known manner. It is particularly important to maintain the above molar ratio of m,w"dialdehyde or dialdehyde mixture or appropriate acetal to formaldehyde at from 1:4 to 1:6 in order to achieve the object of the invention, since at higher formaldehyde contents the tanning properties characteristic of dialdehydes progressively disappear, whilst at lower formaldehyde contents it is no longer possible to eliminate yellowing completely;
  • Suitable w,w'-dialdehydes for use in the invention are generally all w,m'-dialdehydes or mixtures thereof provided the dialdehydes contain from 2 to 8 carbon atoms and saturated aliphatic CC bonds where they are aldehydes of more than 3 carbon atoms.
  • suitable representatives are glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, pimelaldehyde and sebacaldehyde.
  • Industrially preferred representatives are succinaldehyde, glutaraldehyde, adipaldehyde and glyoxal, of which glutaraldehyde and glyoxal are the most important.
  • the alcohol components may be alcohols of from 1 to 10 carbon atoms
  • preferred alcohols for this purpose are methanol, ethanol and propanol, of which methanol is the preferred compound. In this case, care must be taken to ensure that acetalation proceeds to completion.
  • the formulations are prepared using such acetals, the results are much better, since it has been found that the stability of the formulations may be considerably improved by the use of said acetals.
  • the pl-ls selected are conveniently between 6.5 and 10 and preferably they are maintained at from Preferred alkanolamines for use in the present invention are, in particular, triethanolamine, tri-npropanolamine, tri-isopropanolamine and tri-nbutanolamine.
  • alkanolamines are alkaline-reacting substances.
  • the pHs which are favorable for 1 our process are not just near the neutral point or in the region of slight acidity, as generally required by the invention, but are in the above-mentioned pH ranges,
  • the alkanolamines are added to the reaction mixture conveniently in percentages of from to 20% w/w, based on the w,w'-dialdehyde or corresponding acetal used, preferably in amounts of from 8 to 12%.
  • the tanning formulations of the invention may be used alone and constitute excellent tanning agents, pretanning agents and post-tanning agents for hide and skins (also referred to below as pelts) or for finished leathers,
  • Tanning with our novel formulations may be simply carried out, for example, by weakly pickling the pelt material for approx. one hour with 0.6% of formic acid, 5% of common salt and 80% of water, these percentages being based on the weight of the pelt material,
  • tanning When tanning is carried out with formulations of the invention based on completely acetalized dialdehydes, it is advantageous to add reducing agents such as sodium dithionite or sodium bisulfite to the tanning liquors toward the end of tanning in order to destroy any excess tanning agent.
  • reducing agents such as sodium dithionite or sodium bisulfite
  • Tanning with the formulations of the invention and in particular with the formulations prepared in the preferred manner provides leathers and furs of excellent whiteness and fully equal to leathers tanned with glutaraldehyde alone as regards their other properties such as softness of handle, shrinkage temperature and tensile strength.
  • this type of tanning may be carried out with formulations which have been prepared in the presence or tertiary alkanolamines.
  • Blending is conveniently effected so that the chromium, aluminum or zirconium tanning salt is added in such a quantity that 2 moles of metal ions is present per liter of combined formulation.
  • Other mineral tanning agents, synthetic tanning agents and/or vegetable tanning agents which may be used and their optimum proportions are known in the art and therefore require no further explanation in this specification.
  • the formulations of the invention may be used to particular advantage in pretanning operations but above all in post-tanning processes and also together with the tanning agents used in the main tanning operation, in which latter case the conditions of working are adjusted to meet the demands of the main tanning component. It is convenient to use the same concentrations of formulation of the invention when used in combination with other tanning agents in tanning operations, pretanning operations and post-tanning processes, based on the weight of the pelt or fur being tanned.
  • EXAMPLE 1 250 parts of 50% glutaraldehyde are mixed with 750 parts of 30% formaldehyde and the mixture is adjusted to pH 6.5 with soda solution and heated to 90C with reflux cooling. An exothermic reaction commences. The heat of reaction is removed by cooling so that the solution does not exceed 90C. The temperature is maintained at 90C for 30 minutes, whereupon the sothe product are then added and the-liquor isagitated for 3 hours, parts of a fat-liquor for furs being'added in the final hour. The fur ispure white and its shrinkage temperature is 88C. The skins .are then finished off in the usual manner. A
  • the finished solution is used for tanning calfskin as follows:
  • calfskin 100 parts of calfskin is pickled with a solution of 80 parts of water, 0.6 part of formic acid and 5 parts of sodium chloride. After 1 hour, 15 parts of the product is added to this solution, which is drummed for 1 hour, the liquor then being adjusted to pH 6.5 to 7.0 by the addition of 1.5 parts of sodium bicarbonate, whereupon the reaction is allowed to continue for a further 2 hours.
  • the leather is white and has a shrinkage temperature of 86C. The leather is then rinsed, fatliquored and finished off as usual.
  • EXAMPLE 3 145 parts of 40% glyoxal are mixed with 400 parts of 30% formaldehyde and the mixture is adjusted to pH 6.5 with soda solution and then heated to 90C under reflux. A weak exothermic reaction begins. The mixture is held at 90C for 1 hour and then cooled.
  • the finished solution may be used for tanning as described in Examples 1 and 2.
  • EXAMPLE 4 The tanning formulation described in Example 1 is mixed with a solution containing 600 parts of a 33% basic chromium(lll) sulfate (equivalent to 2 moles of chromium) in 1 liter, mixing being effected at a ratio by volume of 1:1. The resulting solution is used for tanning, in which pickling, tanning and neutralizing of the pelt material is carried out as for conventional chrome tanning.
  • EXAMPLE 5 The tanning formulation described in Example 2 is mixed with a solution containing 452 parts of a 66% basic aluminum chloride (equivalent to 2 moles of aluminum) in 1 liter, mixing being effected in a ratio by volume of 2:1. This solution is used for tanning, the pickling, tanning and neutralizing of the pelt material being carried out as for conventional aluminum tanning.
  • This mixture isthen neutralized by adding 1.6 parts by weight of sodaor 7.6 parts by volume of a 2M soda solution, whereupon 400 parts of 30% formaldehyde are added and the pH of the mixture is readjusted to from 6 to 7 and preferably to 6.5 by this addition of acid or soda as required.
  • This mixture is heated at C for 30 minutes and then cooled to 25C.
  • the fur is pure white and-the leather is very soft and shows good handle.
  • the shrinkage temperature is 80C.
  • calfskin 100 parts of calfskin is treated in a pickling bath consisting of 0.6 part of formic acid, 5 parts of sodium chloride and 80 parts of water, for 1 hour. There are then added 20 parts of the tanning composition to said pickling bath, which is agitated for 2 hours. There are then added 2 parts of sodium dithionite followed by agitation for 15 minutes. To the bath there are then added 50 parts of an 83.3% basic aluminum chloride solution (containing 2 moles of aluminum per liter) and 0.2 part of chromium formate. After a tanning period of from .3 to 4 hours, the bath is neutralized to pH 5.5 to 5.8
  • the leathers are then horsed up overnight.
  • the skins are then rinsed, fat-liquored and tinished off as usual.
  • the resulting leathers are pure white, very soft and shows good handle.
  • the shrinkage temperature is C.
  • EXAMPLE 8 200 parts of 50% glutardialdehyde are mixed with 400 parts of 30% formaldehyde and the mixture is adjusted to pH 8.0 by the addition of triethanolamine, for which purpose about 10 parts of amine are necessary. The mixture is heated at 90C for 2 hours and then cooled.
  • the fur is pure white and the leather is very soft and shows good handle.
  • the shrinkage temperature is 85C.
  • aqueous solution for from 30 to 120 minutes at 80 to 95C and at a pH of from 6.5 to 10 in the presence of from 5 to 20% by weight, based on said dialdehyde of at least one trialkanol amine having from 2 to 4 carbon atoms in each alkanol group.

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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)
US345506A 1972-04-01 1973-03-28 Tanning formulations Expired - Lifetime US3909193A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19722215948 DE2215948C3 (de) 1972-04-01 1972-04-01 Wäßrige Gerbstoff-Formulierungen und Verfahren zum Gerben, Vor- oder Nachgerben mit den Formulierungen
DE19722227598 DE2227598C3 (de) 1972-06-07 Wäßrige Gerbstoff-Formulierungen
DE19722243826 DE2243826C3 (de) 1972-09-07 1972-09-07 Wäßrige Gerbstoff-Formulierungen

Publications (1)

Publication Number Publication Date
US3909193A true US3909193A (en) 1975-09-30

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US (1) US3909193A (enrdf_load_stackoverflow)
JP (1) JPS5343561B2 (enrdf_load_stackoverflow)
AR (1) AR196921A1 (enrdf_load_stackoverflow)
AT (1) AT324524B (enrdf_load_stackoverflow)
CA (1) CA1021108A (enrdf_load_stackoverflow)
DD (1) DD107486A5 (enrdf_load_stackoverflow)
ES (1) ES413222A1 (enrdf_load_stackoverflow)
FR (1) FR2178927B1 (enrdf_load_stackoverflow)
GB (1) GB1423438A (enrdf_load_stackoverflow)
IT (1) IT980038B (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4270912A (en) * 1979-06-26 1981-06-02 Seton Company Stabilized tanning composition comprising a reaction product of (a) polyaldehyde (b) secondary amine and (c) an alcohol and method
US4285689A (en) * 1979-06-26 1981-08-25 Seton Company Leather tanning composition and method
US4327997A (en) * 1980-08-11 1982-05-04 Rohm And Haas Company Chrome utilization in chrome tanning
US5360453A (en) * 1992-01-28 1994-11-01 Ciba-Geigy Corporation Process for pickling and pretanning raw hides
USRE34986E (en) * 1988-04-02 1995-07-04 Schill & Seilacher Gmbh & Co. Tanning agent formulation for manufacture of semifinished leather products
US6251414B1 (en) 1992-01-28 2001-06-26 Tfl Ledertechnik Gmbh & Co. Kg Aqueous formulation for pretanning raw hides
RU2198223C1 (ru) * 2002-04-16 2003-02-10 Федеральное государственное унитарное предприятие Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ получения металлсодержащего синтетического дубителя
CN108884500A (zh) * 2016-04-06 2018-11-23 德瑞皮革科技有限公司 用于基于醛类鞣制剂的缩醛进行鞣制的组合物和方法
US20190309379A1 (en) * 2016-04-06 2019-10-10 Tfl Ledertechnik Gmbh Tanning composition and method based on an acetal of an aldehydic tanning agent

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2129162C1 (ru) * 1998-07-23 1999-04-20 Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ получения синтетического дубителя "биотан"
RU2156305C1 (ru) * 1999-12-09 2000-09-20 Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ получения синтетического дубителя для светлых кож
RU2188871C1 (ru) * 2001-12-14 2002-09-10 ОАО "Научно-исследовательский институт меховой промышленности" Состав для дубления меховых шкурок
RU2255112C1 (ru) * 2004-06-30 2005-06-27 ОАО "Научно-исследовательский институт меховой промышленности" Способ обработки меховых шкурок

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2516284A (en) * 1949-08-31 1950-07-25 Adolph H Winheim Impregnating a dialdehyde tanned hide with a resin of urea, formaldehyde, and a primary amine
US2851329A (en) * 1955-11-18 1958-09-09 Seligsberger Ludwig Process of tanning with malonaldehyde or succinaldehyde and optionally mineral tanning agent and leather produced thereby
US2941859A (en) * 1959-04-08 1960-06-21 Martin L Fein Tanning with glutaraldehyde
US2971814A (en) * 1957-12-23 1961-02-14 Seligsberger Ludwig Tanning with alkaline glyoxal
US3080281A (en) * 1959-07-24 1963-03-05 Shell Oil Co Hydroxy-containing hemi-acetals, their preparation and use
US3166074A (en) * 1963-05-29 1965-01-19 Ethicon Inc Aldehyde, chrome and polyhydric alcohol tanned collagen articles and their production
US3812246A (en) * 1970-12-24 1974-05-21 Oreal Cosmetic skin coloring compositions cosmetic skin coloring compositions containing aminatedypsilon-dialdehydes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2516284A (en) * 1949-08-31 1950-07-25 Adolph H Winheim Impregnating a dialdehyde tanned hide with a resin of urea, formaldehyde, and a primary amine
US2851329A (en) * 1955-11-18 1958-09-09 Seligsberger Ludwig Process of tanning with malonaldehyde or succinaldehyde and optionally mineral tanning agent and leather produced thereby
US2971814A (en) * 1957-12-23 1961-02-14 Seligsberger Ludwig Tanning with alkaline glyoxal
US2941859A (en) * 1959-04-08 1960-06-21 Martin L Fein Tanning with glutaraldehyde
US3080281A (en) * 1959-07-24 1963-03-05 Shell Oil Co Hydroxy-containing hemi-acetals, their preparation and use
US3166074A (en) * 1963-05-29 1965-01-19 Ethicon Inc Aldehyde, chrome and polyhydric alcohol tanned collagen articles and their production
US3812246A (en) * 1970-12-24 1974-05-21 Oreal Cosmetic skin coloring compositions cosmetic skin coloring compositions containing aminatedypsilon-dialdehydes

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4270912A (en) * 1979-06-26 1981-06-02 Seton Company Stabilized tanning composition comprising a reaction product of (a) polyaldehyde (b) secondary amine and (c) an alcohol and method
US4285689A (en) * 1979-06-26 1981-08-25 Seton Company Leather tanning composition and method
US4327997A (en) * 1980-08-11 1982-05-04 Rohm And Haas Company Chrome utilization in chrome tanning
USRE34986E (en) * 1988-04-02 1995-07-04 Schill & Seilacher Gmbh & Co. Tanning agent formulation for manufacture of semifinished leather products
US5360453A (en) * 1992-01-28 1994-11-01 Ciba-Geigy Corporation Process for pickling and pretanning raw hides
US6251414B1 (en) 1992-01-28 2001-06-26 Tfl Ledertechnik Gmbh & Co. Kg Aqueous formulation for pretanning raw hides
RU2198223C1 (ru) * 2002-04-16 2003-02-10 Федеральное государственное унитарное предприятие Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ получения металлсодержащего синтетического дубителя
CN108884500A (zh) * 2016-04-06 2018-11-23 德瑞皮革科技有限公司 用于基于醛类鞣制剂的缩醛进行鞣制的组合物和方法
US20190106758A1 (en) * 2016-04-06 2019-04-11 Tfl Ledertechnik Gmbh Tanning composition and method based on an acetal of an aldehydic tanning agent
US20190309379A1 (en) * 2016-04-06 2019-10-10 Tfl Ledertechnik Gmbh Tanning composition and method based on an acetal of an aldehydic tanning agent
US10604813B2 (en) * 2016-04-06 2020-03-31 Tfl Ledertechnik Gmbh Tanning composition and method based on an acetal of an aldehydic tanning agent
US10815542B2 (en) * 2016-04-06 2020-10-27 Tfl Ledertechnik Gmbh Tanning composition and method based on an acetal of an aldehydic tanning agent
CN108884500B (zh) * 2016-04-06 2022-08-19 德瑞皮革科技有限公司 用于基于醛类鞣制剂的缩醛进行鞣制的组合物和方法

Also Published As

Publication number Publication date
GB1423438A (en) 1976-02-04
AT324524B (de) 1975-09-10
ES413222A1 (es) 1976-04-16
AR196921A1 (es) 1974-02-28
FR2178927A1 (enrdf_load_stackoverflow) 1973-11-16
CA1021108A (en) 1977-11-22
JPS5343561B2 (enrdf_load_stackoverflow) 1978-11-21
FR2178927B1 (enrdf_load_stackoverflow) 1976-09-10
IT980038B (it) 1974-09-30
JPS4913301A (enrdf_load_stackoverflow) 1974-02-05
DD107486A5 (enrdf_load_stackoverflow) 1974-08-05

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