EP1651781B1 - Verfahren zur herstellung von leder unter verwendung von polymerisaten - Google Patents

Verfahren zur herstellung von leder unter verwendung von polymerisaten Download PDF

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Publication number
EP1651781B1
EP1651781B1 EP04740614A EP04740614A EP1651781B1 EP 1651781 B1 EP1651781 B1 EP 1651781B1 EP 04740614 A EP04740614 A EP 04740614A EP 04740614 A EP04740614 A EP 04740614A EP 1651781 B1 EP1651781 B1 EP 1651781B1
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EP
European Patent Office
Prior art keywords
alkyl
formula
hydrogen
butyl
weight
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EP04740614A
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German (de)
English (en)
French (fr)
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EP1651781A1 (de
Inventor
Stephan Hüffer
Gerhard Wolf
Matthias KLÜGLEIN
Stefan Becker
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BASF SE
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BASF SE
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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

  • polymers can be used in pre-treatment, main- and retanning. In many cases, the use of polymers in the pre-tanning process makes it possible to dispense entirely or at least partially with Cr compounds.
  • the choice of polymers can affect the properties of the final leather product. For the choice of polymers different proposals are made in the literature.
  • Water-soluble copolymers are known, which are prepared by copolymerization of (meth) acrylic acid or of maleic monoesters, an alkyl-capped alkoxylated half ester and optionally a dicarboxylic acid and optionally styrene, and their use as dispersants for pigments such as CaCO 3 is described.
  • EP-A 0 628 085 describes the use of copolymers of maleic anhydride and optionally a second monomer, for example styrene, isobutene or vinyl acetate, the copolymers being reacted before use with retanning and filling with alkoxylated alcohols.
  • a second monomer for example styrene, isobutene or vinyl acetate
  • EP-A 0 792 377 a process is known in which the tanning and optionally also the pretanning by aldehydes or other reactive carbonyl compounds in the presence of polymers, for example maleic anhydride- ⁇ -olefin-styrene terpolymers (variant I) is carried out.
  • polymers for example maleic anhydride- ⁇ -olefin-styrene terpolymers (variant I) is carried out.
  • the leathers thus produced show good light fastness and heat yellowing stability. However, the tear strength of the leathers thus produced is not yet satisfactory.
  • the polymers mentioned in the prior art are not yet optimal for the treatment of especially soft leathers.
  • the leathers produced by the previous methods can be improved in their fullness, their grain texture and the surface properties.
  • the distribution of the fats used in the retanning in the leather cross section is not optimal.
  • R 4 and R 5 are each hydrogen.
  • R 1 and R 3 are hydrogen, R 2 is selected from hydrogen or methyl, and y is 1.
  • Exemplary selected compounds of formula III are (meth) acrylamides such as acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-undecylacrylamide or the corresponding methacrylamides.
  • Exemplary selected compounds of the formula IV a are N-vinylcarboxamides such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide or N-vinyl-N-methylacetamide;
  • Examples of selected representatives of compounds of formula IV b are N-vinylpyrrolidone, N-vinyl-4-piperidone and N-vinyl- ⁇ -caprolactam.
  • Exemplary selected compounds of formula VI are (meth) acrylic acid esters and amides such as N, N-dialkylaminoalkyl (meth) acrylates or N, N-dialkylaminoalkyl (meth) -acrylamides; Examples are N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl acrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl acrylate, N, N-diethylaminopropyl methacrylate, 2- (N, N-Dimethylamino) ethylacrylamide, 2- (N, N-dimethylamino) ethylmethacrylamide,
  • Exemplary selected compounds of formula VII are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate or vinyl laurate.
  • monomer (D) methyl acrylate, methyl methacrylate, acrylamide, vinyl n-butyl ether, vinyl isobutyl ether, N-vinylformamide, N-vinylpyrrolidone, 1-vinylimidazole, 4-vinylpyridine, vinylphosphonic acid, vinylsulfonic acid.
  • the preparation of the polymers used in the process according to the invention can be carried out as follows. It is possible to copolymerize the monomers (A), (B), (C) and optionally (D) by solution polymerization, precipitation polymerization or, preferably, solvent-free by bulk polymerization. In this case, (A), (B), (C) and optionally (D) may copolymerize in the form of random copolymers or as block copolymers.
  • Pressure and temperature conditions for copolymerization of (A), (B), (C) and optionally (D) are generally not critical.
  • the temperatures are for example in the range of 60 to 200 ° C, preferably 90 to 160 ° C, the pressure is for example in the range of 1 to 10 bar, preferably 1 to 3 bar.
  • Suitable solvents are preferably those solvents which are considered inert to anhydrides derived from dicarboxylic acids having 3 to 8 carbon atoms, in particular acetone, tetrahydrofuran or 1,4-dioxane.
  • Suitable precipitants are aromatic and aliphatic hydrocarbons, for example toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene or mixtures of one or more of the abovementioned aromatic hydrocarbons, n-hexane, petroleum ether or isododecane. Also mixtures of aromatic and aliphatic hydrocarbons are suitable.
  • R 6 hydrogen
  • regulators for example mercaptoethanol or n-dodecylmercaptan. Suitable amounts are, for example, 0.1 to 6 wt .-%, based on the mass of all monomers.
  • the copolymerization is advantageously started by initiators, for example peroxides or hydroperoxides.
  • Suitable peroxides or hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permalate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-butyl peroxide. Chlorobenzoyl peroxide, Dicyclohexylperoxiddicarbonat, exemplified.
  • redox initiators is also suitable, as well as azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride and 2,2'-azobis (4-methoxy-2,4 dimethylvaleronitrile).
  • these initiators are used in amounts of 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-%, calculated on the mass of all monomers.
  • the copolymerization described above gives polymers.
  • the resulting polymers may contain compounds of general formula I and may be subjected to purification by conventional methods, for example reprecipitation or extractive removal of unreacted monomers. But you can omit the cleaning and use the copolymers described above in admixture with compound I for the production of leather. If a solvent or precipitant was used, it is possible to remove this after completion of the copolymerization, for example by distillation.
  • the polydispersity of the polymers described above is generally between 2 and 10, preferably up to 7, but may assume higher values.
  • the K values of the polymers described above are from 6 to 100, preferably from 10 to 60 (measured according to H. Fikentscher at 25 ° C. in, for example, water or tetrahydrofuran and a polymer concentration of 1% by weight).
  • R 6 is -CO-H (formyl), or -CO-C 1 -C 20 -alkyl or-CO-C 6 -C 14 aryl display, so it is advantageous to from the corresponding derivative in which R 6 is Hydrogen from, for example, it reacts with mixed anhydrides or symmetrical anhydrides.
  • Particularly preferred anhydrides are acetic anhydride, benzoic anhydride or H-CO-O-COCH 3 .
  • the process according to the invention for the production of leather can be carried out as a process for pretanning or tanning, in the following also called tanning process according to the invention.
  • the tanning process according to the invention is based on hides pretreated by conventional methods from animals such as, for example, cattle, pigs, goats or deer, the so-called pelts. It is not essential for the tanning process according to the invention, whether the animals were killed, for example, by slaughtering or have died of natural causes.
  • Conventional methods of pre-treatment include, for example, liming, deliming, pickling and pimpling, as well as mechanical operations such as skinning the hides.
  • the polymers described above can accordingly be used according to the invention in the pretanning or tanning.
  • the polymers described above can be used according to the invention in the retanning.
  • the tanning process according to the invention is generally carried out by adding one or more polymers described above in one portion or in several portions immediately before or else during the tanning step.
  • the tanning process according to the invention is preferably carried out at a pH of 2.5 to 4, it being frequently observed that the pH increases by about 0.3 to three units during the performance of the tanning process according to the invention. It is also possible to increase the pH by about 0.3 to three units by adding blunting agents.
  • the tanning process according to the invention is generally carried out at temperatures of 10 to 45 °, preferably at 20 to 30 ° C. Has proven useful a duration of 10 minutes to 12 hours, preferably one to three hours.
  • the tanning process according to the invention can be carried out in any conventional tanning vessel, for example by walking in barrels or in rotated drums.
  • the polymers described above are used together with one or more conventional tanning agents, for example with chrome tanning agents, mineral tanning agents, syntans, polymer tanning agents or vegetable tanning agents, as described, for example, in US Pat Ullmann's Encyclopedia of Industrial Chemistry, Vol. A15, pages 259 to 282 and in particular page 268 ff., 5th edition, (1990), Verlag Chemie Weinheim.
  • the weight ratio of the above-described polymers or hydrolyzed polymer: conventional tanning agent or sum of the conventional tanning agents is advantageously from 0.01: 1 to 100: 1.
  • the above-described polymers are added in one portion or in several portions before or during pre-tanning, in a particular variant already in pimples.
  • the retanning process according to the invention is based on conventionally tanned semifinished products, ie semifinished products tanned, for example, with chromium tanning agents, mineral tannins, polymer tanning agents, aldehydes, syntans or resin tanning agents, or semifinished products produced according to the invention.
  • the above-described polymers are allowed to act on semi-finished products.
  • the retanning process according to the invention can be carried out under otherwise customary conditions. It is convenient to choose one or more, i. For example, 2 to 6 action steps and can rinse between the interaction steps with water.
  • the temperature in the individual reaction steps is in each case in the range from 5 to 60.degree. C., preferably from 20 to 45.degree.
  • further agents customarily used during the retanning for example fatliquors, polymer tanning agents and acrylate- and / or methacrylate-based fatliquoring agents, retanning agents based on resin and vegetable tanning agents, fillers, leather dyes or emulsifiers.
  • aqueous dispersions and solutions containing the polymers described above are aqueous dispersions and solutions containing the polymers described above.
  • dispersions are to be understood as meaning, for example, emulsions or suspensions of the above-described polymers.
  • the aqueous dispersions according to the invention and the aqueous solutions according to the invention usually contain from 20 to 50% by weight of the polymers according to the invention.
  • Their pH is usually in the range of 3 to 10, and preferably in the range of 4 to 8.
  • a further aspect of the present invention is leather produced by the tanning process according to the invention or the retanning process according to the invention or by a combination of inventive tanning process and retanning process according to the invention.
  • the leathers of the invention are characterized by an overall advantageous quality, for example, they are particularly soft.
  • the leathers according to the invention comprise the above-described polymers or the hydrolyzed polymers described above, distributed particularly uniformly over the cross-section.
  • Another aspect of the present invention is the use of the leather according to the invention for the production of clothing, furniture or car parts.
  • garments are, for example, jackets, trousers, shoes, belts or suspenders.
  • furniture is to be understood as meaning all furniture which contains leather components. Examples include seating, such as armchairs, chairs, sofas.
  • Car parts are exemplified by car seats.
  • Another aspect of the present invention are garments comprising or made of leathers of the invention.
  • Another aspect of the present invention is furniture comprising or made of leathers according to the invention.
  • Another aspect of the present invention are car parts containing or made from leathers of the invention.
  • the preparation of the polymers according to the invention can be carried out as follows. It is possible to copolymerize the monomers (A), (B), (C ') and optionally (D) by solution polymerization, precipitation polymerization or, preferably, solvent-free by Massepoly-ization with each other. In this case, (A), (B), (C ') and optionally (D) may copolymerize in the form of random copolymers or as block copolymers.
  • Pressure and temperature conditions for copolymerization of (A), (B) (C ') and optionally (D) are generally not critical.
  • the temperatures are for example in the range of 60 to 200 ° C, preferably 90 to 160 ° C, the pressure is for example in the range of 1 to 10 bar, preferably 1 to 3 bar.
  • reaction times are, for example, 0.5 hours to 12 hours in question, although shorter and longer reaction times are conceivable.
  • Suitable solvents are preferably those solvents which are considered inert to anhydrides derived from dicarboxylic acids having 3 to 8 carbon atoms, in particular acetone, tetrahydrofuran or 1,4-dioxane.
  • Suitable precipitants are aromatic and aliphatic hydrocarbons, for example toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene or mixtures of one or more of the abovementioned aromatic hydrocarbons, n-hexane, petroleum ether or isododecane. Also mixtures of aromatic and aliphatic hydrocarbons are suitable.
  • R 13 hydrogen
  • regulators for example mercaptoethanol or n-dodecylmercaptan. Suitable amounts are, for example, 0.1 to 6 wt .-%, based on the mass of all monomers.
  • the copolymerization is advantageously started by initiators, for example peroxides or hydroperoxides.
  • Suitable peroxides or hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permaleinate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-butyl peroxide. Chlorobenzoyl peroxide, Dicyclohexylperoxiddicarbonat, exemplified.
  • redox initiators is also suitable, as well as azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride and 2,2'-azobis (4-methoxy-2,4 dimethylvaleronitrile).
  • these initiators are used in amounts of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight, calculated on the mass of all monomers.
  • the copolymerization described above gives inventive polymers.
  • the polymers according to the invention may contain compounds of the general formula Ia, and the polymers according to the invention may be subjected to purification by conventional methods, for example reprecipitation or extractive removal of unreacted monomers. But you can omit the cleaning and use the copolymers described above in a mixture with compound I a for the production of leather. If a solvent or precipitant has been used, it is possible to remove it after completion of the copolymerization, for example by distillation.
  • the polydispersity of the polymers according to the invention is generally between 2 and 10, preferably up to 7, but may assume higher values.
  • the K values of the polymers according to the invention are from 6 to 100, preferably from 10 to 60 (measured according to H. Fikentscher at 25 ° C. in, for example, water or tetrahydrofuran and a polymer concentration of 1% by weight).
  • derivatives with R 13 as CO-H (formyl) or CO-C 1 -C 20 -alkyl
  • the polymers according to the invention or the aqueous dispersions according to the invention can be used particularly well for leather production under the conditions described above.
  • the K values of the polymers were determined by H. Fikentscher, Cellulosic Chemistry, Vol. 13, 58-64 and 761-774 (1932 ) in aqueous solution at 25 ° C and a polymer concentration of 1 wt .-%.
  • the reaction mixture thus obtained was then stirred for 90 minutes at 150 ° C, whereby a clear oil was formed.
  • the oil was taken up in 670 ml of water and adjusted to pH 6-7 with a 25% by weight sodium hydroxide solution.
  • % by weight refers to the shaved weight unless otherwise specified.
  • the washed leathers were dried, staked and evaluated according to the test criteria set out in Table 3.
  • the rating was based on a grading system from 1 (very good) to 5 (poor).
  • Polymer V 1 was an acrylic acid acrylamide random copolymer having a Fikentscher K value of 70 (1 wt% solution in water), comonomer ratio in mol%: (acrylic acid: acrylamide) 90:10.
  • the skin of a Southern German cattle was (with respect to the Pickelblête) 1.25 wt .-% glutaric dialdehyde and 3 wt .-% of the sulfone tonic from EP-B 0 459 168
  • Example K1 converted into a wet-white semi-finished product. After pre-tanning, the pH was 3.9.
  • the semi-finished products were folded after wilting to a thickness of 1.2 mm and cut into strips of about 350 g each.
  • the furniture leathers produced according to the invention had excellent fullness and grain firmness with excellent dye dispersion and fixation. Furthermore, it has been observed that by means of the retanning process according to the invention tanning auxiliaries have been distributed more uniformly in the leather and the so-called wastage has been improved; the range of tannery additives, in particular the dyes, has thus been better utilized. In addition, the wastewater load could be reduced accordingly.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
EP04740614A 2003-07-23 2004-07-03 Verfahren zur herstellung von leder unter verwendung von polymerisaten Expired - Lifetime EP1651781B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10333749A DE10333749A1 (de) 2003-07-23 2003-07-23 Verfahren zur Herstellung von Leder unter Verwendung von Polymerisaten
PCT/EP2004/007270 WO2005019480A1 (de) 2003-07-23 2004-07-03 Verfahren zur herstellung von leder unter verwendung von polymerisaten

Publications (2)

Publication Number Publication Date
EP1651781A1 EP1651781A1 (de) 2006-05-03
EP1651781B1 true EP1651781B1 (de) 2009-06-17

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EP04740614A Expired - Lifetime EP1651781B1 (de) 2003-07-23 2004-07-03 Verfahren zur herstellung von leder unter verwendung von polymerisaten

Country Status (8)

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US (1) US20070107135A1 (pt)
EP (1) EP1651781B1 (pt)
CN (1) CN1826415B (pt)
AR (1) AR046512A1 (pt)
AT (1) ATE434058T1 (pt)
BR (1) BRPI0412691A (pt)
DE (2) DE10333749A1 (pt)
WO (1) WO2005019480A1 (pt)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004031158A1 (de) * 2004-06-28 2006-01-19 Basf Ag Verwendung von Ethergruppen enthaltenden Polymeren als Lösungsvermittler
CN100396795C (zh) * 2007-01-25 2008-06-25 陕西科技大学 一种填充发泡型皮革复鞣剂的制备方法
PT2190913E (pt) 2007-09-03 2015-10-20 Basf Se Processo para a produção de formulações aquosas, formulações aquosas e a sua utilização
BRPI0816186A2 (pt) * 2007-09-03 2015-04-14 Basf Se Processo para a preparação der formulações aquosas, formulações aquosas, uso de formulações aquosas, processo para a produção de couro, couro, copolímero,e, misturas
US8419948B2 (en) * 2009-11-22 2013-04-16 United Laboratories International, Llc Wastewater treatment
CN101831024A (zh) * 2010-05-15 2010-09-15 甘肃宏良皮业股份有限公司 一种聚合物复鞣加脂剂的制备方法及复鞣加脂剂
CN116536460B (zh) * 2023-05-10 2024-05-24 四川大学 一种基于折射率相匹配原理制备透明皮革的方法

Family Cites Families (8)

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DE4018873A1 (de) * 1990-06-13 1991-12-19 Basf Ag Verwendung von kondensaten auf basis von arylsulfonsaeuren und formaldehyd als dispergiermittel
DE4236556A1 (de) * 1992-10-29 1994-05-05 Stockhausen Chem Fab Gmbh Verfahren zur Weichmachung/Fettung von Ledern und Pelzen
DE4328817A1 (de) * 1993-08-27 1995-03-02 Basf Ag Wasserlösliche, Carboxylgruppen enthaltende Copolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung als Scaleinhibitor
US5646225A (en) * 1996-05-13 1997-07-08 Arco Chemical Technology, L.P. Water-reducible resins for coatings and inks
DE19815946A1 (de) * 1998-04-09 1999-10-14 Basf Ag N-Vinyleinheiten enthaltende polymere Gerbstoffe
DE19941423A1 (de) * 1999-08-30 2001-03-01 Stockhausen Chem Fab Gmbh Polymerzusammensetzung und ein Verfahren zu dessen Herstellung
CN1151276C (zh) * 2000-09-19 2004-05-26 中国科学院成都有机化学研究所 含醛皮革复鞣剂的制备方法
US7552605B2 (en) * 2002-10-15 2009-06-30 Seton Company Natural grain leather

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Publication number Publication date
BRPI0412691A (pt) 2006-10-03
CN1826415A (zh) 2006-08-30
CN1826415B (zh) 2010-06-16
AR046512A1 (es) 2005-12-14
US20070107135A1 (en) 2007-05-17
ATE434058T1 (de) 2009-07-15
EP1651781A1 (de) 2006-05-03
WO2005019480A1 (de) 2005-03-03
DE502004009623D1 (de) 2009-07-30
DE10333749A1 (de) 2005-02-10

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