EP0648846A2 - Matières de retannage adoucissantes et hydrophobes - Google Patents

Matières de retannage adoucissantes et hydrophobes Download PDF

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Publication number
EP0648846A2
EP0648846A2 EP94115468A EP94115468A EP0648846A2 EP 0648846 A2 EP0648846 A2 EP 0648846A2 EP 94115468 A EP94115468 A EP 94115468A EP 94115468 A EP94115468 A EP 94115468A EP 0648846 A2 EP0648846 A2 EP 0648846A2
Authority
EP
European Patent Office
Prior art keywords
water
minutes
leather
alcohol
liquor
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.)
Granted
Application number
EP94115468A
Other languages
German (de)
English (en)
Other versions
EP0648846B1 (fr
EP0648846A3 (fr
Inventor
Günter Dr. Sackmann
Bruno Dr. Bömer
Joachim Dr. Kochta
Henricus Slaats
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.)
Bayer AG
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Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0648846A2 publication Critical patent/EP0648846A2/fr
Publication of EP0648846A3 publication Critical patent/EP0648846A3/fr
Application granted granted Critical
Publication of EP0648846B1 publication Critical patent/EP0648846B1/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
    • C14C3/22—Chemical tanning by organic agents using polymerisation products

Definitions

  • the invention relates to improved retanning agents for producing soft hydrophobic leather.
  • Retanning means the aftertreatment of pre-tanned (generally chrome-tanned) leather in order to optimize color, levelness, softness, fullness and the behavior against water (hydrophobicity) and to fix tannins.
  • Retanning agents known to date do not meet all of the expectations placed on them because they either insufficiently hydrophobize or adversely affect the feel, the dyeability, the solid grain or the subsequent finishing of the leather.
  • the multitude of desirable properties requires a compromise.
  • Retanning agents are desired which give the leather an optimal hydrophobicity (i.e. make the leather as water-impermeable as possible while maintaining its water vapor permeability), but with a feel, dyeability, solid grain and do not adversely affect the applicability of the subsequent dressing.
  • Preferred monomers c) include, for example, styrene, ⁇ -methylstyrene, p-methylstyrene, vinyl acetate, allyl acetate, isobutyl vinyl ether, allyl alcohol and methallyl alcohol.
  • Terpolymers from a), b) and c) are known; see. e.g. DE-OS 27 01 760. They can be prepared by free-radically initiated polymerization. The polymerization takes place in an organic solvent which is inert under polymerization conditions, in particular in an aromatic solvent such as toluene or xylene
  • Suitable radical formers include, for example, diacyl peroxides such as diacetyl peroxide, dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, peroxy esters such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, alkyl peroxides such as bis- (tert-butyl) doxyperyl peroxybutyl peroxy butyl peroxide Hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, ketone peroxides such as cyclohexanone hydroperoxide, methyl ethyl ketone hydroperoxide, acetylacetone peroxide or azoisobutyrodinitrile.
  • diacyl peroxides such as diacetyl peroxide, dibenzoyl peroxide, di-p-chloro
  • the reaction of the terpolymers A with the alcohols B can take place either directly in the solution of the terpolymers A or after isolation of the solid terpolymers A in bulk, solution or suspension.
  • the reaction can be carried out at temperatures from 60 to 180, preferably 80 to 140 ° C.
  • Primary and secondary alcohols B are preferred. Suitable representatives include, for example, n-hexanol, cyclohexanol, n-octanol, 2-ethylhexanol, n-dodecanol, n-tetradecanol, n-hexadecanol, stearyl alcohol, eicosanol and behenyl alcohol or mixtures thereof.
  • the reaction can be carried out in the absence or presence of an acid catalyst.
  • an acid catalyst Suitable as such are, for example, mineral acids such as sulfuric acid or anhydrous hydrogen chloride, aliphatic and aromatic sulfonic acids such as methanesulfonic acids and p-toluenesulfonic acid, fluorinated aliphatic carboxylic acids such as perfluorobutanoic or -octanoic acid, and acidic ion exchangers.
  • esterification is carried out in the presence of an acidic catalyst, it is advantageous to remove the water of reaction in a water-immiscible organic solvent, such as e.g. Toluene or xylene to work and separate the water of reaction formed azeotropically.
  • the anhydride groups mainly give the half ester, and in the case of acid-catalyzed esterification mixtures of half and diesters of the dicarboxylic acid residues.
  • Base C is added to convert the esterification products obtained into a water-soluble or - dispersible form - preferably as an aqueous solution.
  • Suitable bases C include, for example, alkali metal hydroxides and alcoholates as well as ammonia and primary, secondary and tertiary aliphatic amines with up to 6 carbon atoms per molecule (which can carry up to 1 hydroxyl group per alkyl radical), in particular sodium and potassium hydroxides and ammonia, ethylamine, Propylamine, n-butylamine, diethanolamine, dimethylamine and triethylamine.
  • Base C can be added to the polymer melt or solution or dispersion.
  • the amount of base C is such that at least 20% of the carboxyl groups remaining after the esterification reaction are converted. It is possible to convert all remaining carboxyl groups; however, it can also be advantageous to neutralize only 20 to 80% of the remaining carboxyl groups (in this connection, anhydride groups which have not been converted in the esterification reaction should be formally counted as 2 carboxyl groups).
  • anhydride groups which have not been converted in the esterification reaction should be formally counted as 2 carboxyl groups.
  • the reaction with base C produces aqueous solutions or dispersions which may still contain organic solvents. They can be used directly as such or after removal of the solvent for retanning leather. In particular, they are suitable for everyone from chrome leather (cow, goat, pig, etc.).
  • aqueous solutions or dispersions obtained are preferably used on neutralized wet blue material, i.e. on chrome leather, which has been adjusted to a pH of 4 to 7, preferably 5.5 to 6.5, by means of conventional neutralizing agents (e.g. sodium bicarbonate, formate, etc.) or neutralizing tanning agents.
  • neutralizing agents e.g. sodium bicarbonate, formate, etc.
  • neutralizing tanning agents e.g. sodium bicarbonate, formate, etc.
  • the neutralized wet blue material can possibly be treated with commercially available retanning agents (replacement, white, resin and polymeric tanning agents), vegetable tanning agents and fatliquoring agents. If you want to produce dyed leather, you dye with dyes. In addition, it is also possible to use the solutions or dispersions on purely vegetable-tanned leathers for retanning before dyeing and greasing.
  • aqueous solutions or dispersions obtained can also be used in other stages of retanning, e.g. after treatment with replacement, white or vegetable tannins.
  • the leather retanned according to the invention is notable for a very soft and full grip, as well as good grain strength and grain smoothness, and has a clear pigmentation. Because of their high lightfastness and good thermal resistance to yellowing, they are ideal for producing light-colored leather. In addition, the leather retanned with the dispersions according to the invention show water-repellent properties.
  • aqueous emulsion a solution of 20 g of NaOH in 2300 g of water is added to the solution of the esterified polymer. After toluene has been distilled off under vacuum, a finely divided emulsion of retanning agent II with a solids content of 9.5% by weight is obtained.
  • reaction mixture is introduced into a 2 l three-necked flask with stirring and passing over N2: 178 g toluene 170 g diisobutylene (technical mixture of 75-80% by weight 2,4,4-trimethylpentene-1 and 20-25% by weight 2,4,4-trimethylpentene-2) 102 g maleic anhydride
  • the following solution is pumped into the reaction mixture via a metering pump within 4 hours: 4 g of azoisobutyronitrile 50 g toluene
  • the reaction temperature is increased continuously from 75 to 95.degree. 30 minutes before the end of metering, 6 g of styrene are added to the polymerization solution at once.
  • the retanning agent IV is prepared in a similar manner to the retanning agent III, with the difference that the solution of the terpolymer is reacted with the following mixture: 237 g C12-C18 fatty alcohol mixture 650 g toluene.
  • dispersion IV After a running time of 15 minutes, 1%, based on dry substance, of dispersion IV according to the invention is added as a 20.7% setting and the mixture is left to run for a further 45 minutes.
  • the liquor pH is around 5.2.
  • the resulting leathers are of good fullness and softness and are characterized by excellent grain smoothness.
  • the light fastness is level 5 to 6 (xeno test) and the heat yellowing (24 hours, 120 ° C) is level 3 to 4 (gray scale).
  • dispersion III After a running time of 15 minutes, 1.5%, based on dry substance, of dispersion III according to the invention is added as a 15.7% setting and the mixture is left to run for a further 45 minutes.
  • the liquor pH is around 5.0.
  • the pH is raised to approximately 6.0 by adding 1.5% sodium formate and 0.4% sodium bicarbonate and the liquor is drained after 40 minutes.
  • the dyeing is carried out in 30% in 30% water at 25.degree. C. with the addition of 1.0% of a commercial dyeing aid with 5.0% of a mixture of commercial leather dyes .
  • the resulting leathers are of good fullness and softness and are characterized by excellent smooth scars with fine mill grain.
  • dispersion I according to the invention (see preparation example 1) is added as a 12.7% setting and the mixture is left to run for 30 minutes.
  • the liquor pH is around 5.0.
  • the leathers After draining the liquor, grease in 100% water at 50 ° C, acidified again with formic acid to a pH of 3.9 and draining the liquor again. After rinsing in water at 25 ° C for 10 minutes, the leathers are stretched out in a customary manner, vacuum and hanging-dried, air-conditioned, rolled and vacuum-dried again (1/2 minute at 70 ° C). The resulting leathers are characterized by uniform dyeability with a full, soft feel and good firm grain.
  • the liquor After the liquor has been drained, it is neutralized in 100% water at 40 ° C. with 2% of a commercially available neutralizing tanning agent and 1.5% sodium bicarbonate to a pH of approximately 5.8 over 90 minutes.
  • the leathers are washed in 200% water for 10 minutes at 60 ° C and greased in 100% water at 60 ° C with 7.0% of a commercially available fat mixture.
  • the liquor pH is around 4.5.
  • the leathers are acidified to a pH of approx. 4.0 by adding 0.5% formic acid (85%, 1:10 diluted with water).
  • the leathers are rinsed in the customary manner (water at 20 ° C., 5 minutes), stretched out, vacuum and hanging dried, air-conditioned, stollen, aired, rerolled and again vacuum dried (1/2 minute, 70 ° C.).
  • the resulting gaps have a very high degree of whiteness and are characterized by a soft full grip, with the velor side having a soft, uniform short cut.
  • dispersion III according to the invention from preparation example 3 is added as a 15.7% setting and drummed for 45 minutes.
  • 3% of a commercially available replacement tanning agent is added and 3% dye is added after a running time of 20 minutes. After 40 minutes, the mixture is acidified with 2% formic acid (85%, 1:10 diluted with water) to a pH of approximately 3.8 over 30 minutes.
  • the leathers are rinsed cold and finished in the usual way (dried, milled, splin, etc.).
  • the leathers have a soft, full feel and are characterized by a fine, smooth grain and an even, brilliant color.
  • vegetable-tanned leather is washed in 300% water (based on the shaved weight, like all the following information) at 30 ° C for 10 minutes in the usual way and after draining the liquor in 100% water at 30 ° C with 1 % of a commercial bleach tanning agent bleached for 20 minutes (pH of the liquor: approx. 3.3) and washed with 300% water at 40 ° C.
  • the resulting leathers are soft, of good fullness and have a pleasant slimy grip.

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)
EP94115468A 1993-10-13 1994-09-30 Matières de retannage adoucissantes et hydrophobes Expired - Lifetime EP0648846B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4334796A DE4334796A1 (de) 1993-10-13 1993-10-13 Weichmachende und hydrophobierende Nachgerbstoffe
DE4334796 1993-10-13

Publications (3)

Publication Number Publication Date
EP0648846A2 true EP0648846A2 (fr) 1995-04-19
EP0648846A3 EP0648846A3 (fr) 1995-11-29
EP0648846B1 EP0648846B1 (fr) 1998-12-23

Family

ID=6499990

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94115468A Expired - Lifetime EP0648846B1 (fr) 1993-10-13 1994-09-30 Matières de retannage adoucissantes et hydrophobes

Country Status (4)

Country Link
US (1) US5472741A (fr)
EP (1) EP0648846B1 (fr)
DE (2) DE4334796A1 (fr)
ES (1) ES2126036T3 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19612986A1 (de) 1996-04-01 1997-10-02 Basf Ag Verwendung von Copolymerisaten auf Basis ethylenisch ungesättigter Dicarbonsäuren oder Dicarbonsäureanhydride, niederer Olefine und hydrophober Comonomerer zum Nachgerben, Fetten oder Hydrophobieren von Leder und Pelzfellen
US6248827B1 (en) 1997-12-22 2001-06-19 Bridgestone Corporation Centipede polymers and preparation and application in rubber compositions
US6204354B1 (en) 1998-05-06 2001-03-20 Bridgestone Corporation Soft compounds derived from polypropylene grafted disubstituted ethylene- maleimide copolymers
US6248825B1 (en) 1998-05-06 2001-06-19 Bridgestone Corporation Gels derived from extending grafted centipede polymers and polypropylene
US6207763B1 (en) 1998-06-12 2001-03-27 Bridgestone Corporation Application of disubstituted ethylene-maleimide copolymers in rubber compounds
US6184292B1 (en) 1998-10-05 2001-02-06 Bridgestone Corporation Soft gel polymers for high temperature use
US6133354A (en) * 1998-11-17 2000-10-17 Bridgestone Corporation Copolymers as additives in thermoplastic elastomer gels
US6191217B1 (en) 1998-11-17 2001-02-20 Bridgestone Corporation Gels derived from polypropylene grafted alkyl vinylether-maleimide copolymers
US6395040B1 (en) * 2000-04-28 2002-05-28 Wolverine World Wide, Inc. Process for producing leather
US6384134B1 (en) 2000-06-05 2002-05-07 Bridgestone Corporation Poly(alkenyl-co-maleimide) and maleated polyalkylene grafted with grafting agent, and epoxy polymer
US6476117B1 (en) 2000-06-05 2002-11-05 Bridgestone Corporation Grafted near-gelation polymers having high damping properties
US6350800B1 (en) 2000-06-05 2002-02-26 Bridgestone Corporation Soft polymer gel
US6417259B1 (en) 2000-06-05 2002-07-09 Bridgestone Corporation Polyalkylene grafted centipede polymers
US6353054B1 (en) 2000-07-31 2002-03-05 Bridgestone Corporation Alkenyl-co-maleimide/diene rubber copolymers and applications
US6359064B1 (en) 2000-09-08 2002-03-19 Bridgestone Corporation Compound of polyester and polyalkylene grafted comb polymer
DE10304959A1 (de) * 2003-02-06 2004-08-19 Basf Ag Verfahren zur Herstellung von Leder
US20060288493A1 (en) * 2005-06-24 2006-12-28 Wolverine World Wide, Inc. Process For Producing Leather Footwear Lining
US20060288494A1 (en) * 2005-06-24 2006-12-28 Wolverine World Wide, Inc. Process for producing leather
CN101945904B (zh) 2007-12-28 2014-01-29 株式会社普利司通 包含异丁烯和二烯链节单元的共聚体

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4190687A (en) * 1972-05-09 1980-02-26 Sumitomo Chemical Company, Limited Method for treating leather
IT1035147B (it) * 1974-04-04 1979-10-20 Bayer Ag Procedimento per conciare cuoiocon oligoiuretani idrofili
JPS50136315A (fr) * 1974-04-17 1975-10-29
DE2701760C3 (de) * 1977-01-18 1982-04-01 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Papierleimungsmitteln
DE2840501A1 (de) * 1978-09-18 1980-03-27 Basf Ag Verfahren zur herstellung von copolymerisaten aus maleinsaeureanhydrid und alkenen
DE3304120A1 (de) * 1983-02-08 1984-08-09 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung wasserdichter leder und pelze
DE3529248A1 (de) * 1985-08-16 1987-02-26 Bayer Ag Terpolymerisate
TNSN89128A1 (fr) * 1988-12-02 1991-02-04 Rohn And Haas Company Independance Mall West Traitement du cuir avec des copolymeres amphiphites choisis
DE3931039A1 (de) * 1989-09-16 1991-03-28 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen ungesaettigten estern und ethylenisch ungesaettigten carbonsaeuren zum hydrophobieren von leder und pelzfellen
US5348807A (en) * 1991-02-05 1994-09-20 Rohm And Haas Company Polymeric retan fatliquor for low fogging upholstery leather

Also Published As

Publication number Publication date
DE4334796A1 (de) 1995-04-20
US5472741A (en) 1995-12-05
DE59407529D1 (de) 1999-02-04
EP0648846B1 (fr) 1998-12-23
EP0648846A3 (fr) 1995-11-29
ES2126036T3 (es) 1999-03-16

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