EP1651781A1 - Procede de production de cuir au moyen de produits de polymerisation - Google Patents

Procede de production de cuir au moyen de produits de polymerisation

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Publication number
EP1651781A1
EP1651781A1 EP04740614A EP04740614A EP1651781A1 EP 1651781 A1 EP1651781 A1 EP 1651781A1 EP 04740614 A EP04740614 A EP 04740614A EP 04740614 A EP04740614 A EP 04740614A EP 1651781 A1 EP1651781 A1 EP 1651781A1
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EP
European Patent Office
Prior art keywords
alkyl
general formula
hydrogen
weight
integer
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EP04740614A
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German (de)
English (en)
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EP1651781B1 (fr
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

  • the present invention relates to a process for the production of leather, characterized in that pelts, pimples or semi-finished products are treated with at least one polymer which can be obtained by copolymerizing
  • R 1 , R 2 , R 3 are identical or different and selected from CC 4 alkyl or hydrogen;
  • R 4 , R 5 are the same or different and are selected from dC 4 alkyl or hydrogen;
  • R 6 selected from hydrogen, SO 3 M, P0 3 M 2 , C Cao-alkyl, CO-H (formyl), CO-d-Cao-alkyl, CO-C 6 -C 14 aryl
  • polymers can be used for pre-tanning, main tanning and retanning.
  • pretanning means that Cr compounds can be dispensed with entirely or at least partially.
  • the choice of polymers can influence the properties of the leather end product.
  • WO 01/96007 discloses water-soluble copolymers which are prepared by copolymerizing (meth) acrylic acid or maleic acid semiesters, an alkyl-capped alkoxylated half ester and optionally a dicarboxylic acid and optionally styrene, and their use as a dispersant for pigments such as, for example, CaCO 3 described.
  • EP-A 0 628085 describes the use of copolymers of maleic anhydride and optionally a second monomer, for example styrene, isobutene or vinyl acetate, the copolymers being reacted with alkoxylated alcohols before use for retanning and filling.
  • a second monomer for example styrene, isobutene or vinyl acetate
  • Copolymers of styrene, methacrylic acid and monopropoxylated allyl alcohol and the use of the copolymers in solvent-based inks are known from US Pat. No. 5,646,225 and US Pat. No. 5,728,777.
  • a process is known from EP-A 0792377 in which the tanning and optionally also the pretanning is carried out by aldehydes or other reactive carbonyl compounds in the presence of polymers, for example maleic anhydride -olefin-styrene terpolymers (variant I).
  • polymers for example maleic anhydride -olefin-styrene terpolymers (variant I).
  • the leathers produced in this way show good lightfastness and heat yellowing stability. However, the tensile strength of the leather produced in this way is not yet satisfactory.
  • the polymers mentioned in the prior art are not yet optimal for treating soft leather in particular.
  • the fullness, grain structure and surface properties of leather produced using the previous methods can be improved.
  • the distribution of the fats used in retanning in the leather cross-section is not yet optimal.
  • the object was therefore to provide an improved process for the production of leather which avoids the above-mentioned weaknesses.
  • ethylenically unsaturated mono- or dicarboxylic acids with 3 to 8 carbon atoms are (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid; acrylic acid is very particularly preferred.
  • anhydrides derived from a mono- or dicarboxylic acid having 3 to 8 carbon atoms are: maleic anhydride, itaconic anhydride, citraconic anhydride, methylene malonic anhydride, preferably itaconic anhydride and maleic anhydride and very particularly preferably maleic anhydride.
  • Mixed anhydrides are also possible, for example the mixed anhydride of (meth) acrylic acid and acetic acid.
  • ⁇ -Methylstyrene is preferably used as (B) and very particularly preferably styrene.
  • R ⁇ R 2 , R 3 the same or different and selected from C r C -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, particularly preferably methyl, or hydrogen
  • R 4 , R 5 are the same or different and are selected from C 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, particularly preferably methyl, or hydrogen
  • R 6 selected from hydrogen, SO 3 M, P0 3 M 2 , and preferably organic radicals such as -CC 30 alkyl, preferably linear or branched, such as methyl, ethyl, n-propyl, iso-propyl, n-buty
  • n-heptyl n-octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl, n-eicosyl; particularly preferably dC-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; CO-H (formyl) or CO-C C 20 alkyl, particularly preferably acetyl, propionyl, n-butyryl, n-stearyl, n-lauryl; CO-C 6 -C 4 -aryl such as ⁇ -naphthoyl, ß-naphthoyl and preferably benzoyl CO-C 6 H 5 , M alkali metal,
  • R 4 and R 5 are each particularly preferably hydrogen.
  • R 1 and R 3 are particularly preferably hydrogen, R 2 is selected from hydrogen or methyl, and y is 1.
  • One or more further monoethylenically unsaturated monomers (D) can optionally be polymerized in.
  • the monomer or monomers (D) which can optionally be copolymerized into the polymers used in the process according to the invention are different from (A).
  • alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether or n-octadecyl vinyl ether ;
  • N-vinyl derivatives of nitrogen-containing aromatic compounds preferably N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 2-vinylpyridine, 4-vinylpyridine, 4-vinylpyridine-N-oxide, N Vinylimidazoline, N-vinyl-2-methylimidazoline,
  • Monomers containing sulfonate, phosphate or phosphonate groups such as, for example, vinylsulfonic acid and vinylphosphonic acid and compounds of the general formula IX, are also suitable
  • phosphate groups, sulfonate groups or phosphonate groups may optionally be present partially or completely in the form of alkali metal salts.
  • R 7 selected from unbranched or branched CrC 10 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso- Pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n- decyl; particularly preferably CC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, and in particular hydrogen;
  • R 8 is selected from unbranched or branched C 1 -C 8 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably CC alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, in particular methyl and in particular hydrogen;
  • R 9 the same or different and CC 22 alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl , n-dodecyl, n-eicosyl; particularly preferred -CC alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl
  • a 1 the same or different and C 2 -C 6 alkylene, for example -CH 2 -, -CH (CH 3 ) -, - (CH 2 ) 2 -, -CH 2 -CH (CH 3 ) -, - (CH 2 ) 3 -, -CH 2 -CH (C 2 H 5 ) -, - (CH 2 ) -, - (CH 2 ) 5 -, - (CH 2 ) 6 -, preferably CC 3 -alkylene; in particular - (CH 2 ) 2 -, -CH 2 -CH (CH 3 ) - and -CH 2 -CH (C 2 H 5 ) -;
  • x is an integer in the range from 2 to 6, preferably 3 to 5;
  • a is an integer in the range from 0 to 6, preferably in the range from 0 to 2;
  • b is an integer in the range from 1 to 40, preferably 1 to 10,
  • n is an integer in the range from 2 to 200, preferably 10 to 40;
  • R 10 , R 11 are the same or different and selected from hydrogen, unbranched or branched CrC 10 alkyl and where unbranched and branched Crdo alkyl is as defined above;
  • R 12 is selected from unbranched or branched CC 10 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl , sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and especially hydrogen or methyl; Phenyl.
  • (meth) acrylamides such as acrylamide, N-methyl acrylamide, N, N-dimethylacrylamide, N-ethyl acrylamide, N-propylacrylamide, N-tert-butylacrylamide, N-tert.- Octylacrylamide, N-undecylacrylamide or the corresponding methacrylamides.
  • N-vinylcarboxamides such as N-vinylformamide, N-vinyl-N-methylfomamide, N-vinyl acetamide or N-vinyl-N-methylacetamide
  • representatives selected by way of example for compounds of the formula IV b are N-vinylpyrrolidone, N-vinyl-4-piperidone and N-vinyl- ⁇ -caprolactam.
  • Compounds of formula VI selected by way of example are (meth) acrylic 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-diethylamino propyl acrylate N, N-diethylaminopropyl methacrylate, 2- (N, N-dimethylamino) ethyl acrylamide, 2- (N, N-dimethylamino) ethyl me
  • the following are very particularly preferably used as 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 monomers (A) to (D) are copolymerized as follows:
  • the polymers used in the process according to the invention can be prepared as follows. It is possible to copolymerize the monomers (A), (B), (C) and, if appropriate, (D) with one another by solution polymerization, precipitation polymerization or preferably solvent-free by bulk polymerization. (A), (B), (C) and optionally (D) can copolymerize in the form of random copolymers or as block copolymers.
  • Pressure and temperature conditions for a copolymerization of (A), (B), (C) and optionally (D) are generally not critical.
  • the temperatures are, for example, in the range from 60 to 200 ° C., preferably 90 to 160 ° C.
  • the pressure is, for example, in the range from 1 to 10 bar, preferably 1 to 3 bar.
  • the reaction times are, for example, 0.5 hours to 12 hours, although shorter and longer reaction times are also conceivable.
  • Suitable solvents are preferably those solvents which are considered inert to anhydrides which are 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 aromatic hydrocarbons mentioned above, n-hexane, petroleum ether or isododecane. Mixtures of aromatic and aliphatic hydrocarbons are also suitable.
  • Polymerization is preferably carried out in the form of bulk polymerization without the addition of organic solvents.
  • R 6 hydrogen
  • Regulators can be used, for example mercaptoethanol or n-dodecyl mercaptan. Suitable amounts are, for example, 0.1 to 6% by weight, based on the mass of all monomers.
  • the copolymerization is advantageously started by initiators, for example peroxides or hydroperoxides.
  • Peroxides or hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl per-maleate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-Chlorobenzoyl peroxide, dicyclohexyl peroxide dicarbonate, exemplified.
  • redox initiators are also suitable, as are azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion-amidine) dihydrochloride and 2,2'-azobis (4-methoxy -2,4-dimethylvaleronitrile).
  • these initiators are used in amounts of 0.1 to 20% by weight, preferably 0.2 to 15% by weight, based on the mass of all monomers.
  • the copolymerization described above gives polymers.
  • the resulting polymers can contain compounds of the general formula I and they can be subjected to purification by conventional methods, for example falling over or extractive removal of unreacted monomers. However, cleaning can be omitted and the copolymers described above used in a mixture with compound I for the production of leather. If a solvent or precipitation medium was used, it is possible to remove it after the copolymerization has ended, for example by distillation.
  • the polydispersity of the polymers described above is generally between 2 and 10, preferably up to 7, but can assume higher values.
  • the K values of the polymers described above are 6 to 100, preferably 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 6 equal to -CO-H (formyl) or -CO-dC 20 -alkyl or -CO- C 6 -C 14 -aryl
  • Particularly preferred anhydrides are acetic anhydride, benzoic anhydride or H-CO-0-COCH 3 .
  • the process according to the invention for the production of leather can be carried out as a process for pretanning or tanning, hereinafter also called the tanning process according to the invention.
  • the tanning process according to the invention is based on the skins of animals, such as cattle, pigs, goats or deer, which are pretreated by conventional methods, the so-called naked ones. It is not essential for the tanning process according to the invention whether the animals have been killed, for example, by slaughtering or have died of natural causes.
  • Conventional pretreatment methods include, for example, liming, descaling, pickling and pickling, as well as mechanical work steps, such as fleshing the skins.
  • the polymers described above can accordingly be used according to the invention in pretanning or tanning.
  • the polymers described above can be used in retanning according to the invention.
  • the tanning process according to the invention is generally carried out by adding one or more of the polymers described above in one portion or in several portions immediately before or 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 rises by about 0.3 to three units while the tanning process according to the invention is being carried out.
  • the pH can also be increased by about 0.3 to three units by adding blunting agents.
  • the tanning process according to the invention is generally carried out at temperatures from 10 to 45 ° C., preferably at 20 to 30 ° C. A duration of 10 minutes to 12 hours has proven useful, and one to three hours are preferred.
  • the tanning process according to the invention can be carried out in any vessels customary in tanning, for example by milling 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 Ullmann's Encyclopedia of Industrial Chemistry, Volume A15 , Pages 259 to 282 and in particular pages 268 ff., 5th edition, (1990), Verlag Chemie Weinheim.
  • the weight ratio of the above-described polymer or hydrolyzed polymer: conventional tanning agent or the sum of the conventional tanning agents is advantageously from 0.01: 1 to . 100: 1.
  • only a few ppm of the conventional tanning agents are added to the polymers or hydrolyzed polymers described above. However, it is particularly advantageous to completely dispense with the addition of conventional tanning agents.
  • the polymers described above are added in one portion or in several portions before or during the pretanning, in a special variant already in the pimple.
  • the process according to the invention for the production of leather can preferably be carried out as a process for retanning leather using the polymers described above, in the following also retanning according to the invention. called procedure.
  • the retanning process according to the invention is based on conventionally tanned semifinished products, that is to say, for example, with chromium tanning agents, mineral tanning agents, polymer tanning agents, aldehydes, syntans or resin tanning agents, semifinished products produced according to the invention as described above.
  • the polymers described above are left to carry out the retanning process according to the invention Act semi-finished products.
  • the retanning process according to the invention can be carried out under otherwise customary conditions.
  • One or more is expediently chosen, i.e. for example 2 to 6 action steps and can rinse with water between the action steps.
  • the temperature in the individual action steps is in each case in the range from 5 to 60 ° C., preferably 20 to 45 ° C.
  • further agents which are usually used during retanning, for example fat licker, polymer tanning agents and fatliquoring agents based on acrylate and / or methacrylate, retanning agents based on resin and vegetable tanning agents, fillers, leather dyes or emulsifiers.
  • a further aspect of the present invention are aqueous dispersions and solutions containing the polymers described above.
  • Dispersions for the purposes of the present invention are understood to mean, for example, emulsions or suspensions of the polymers described above.
  • 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 from 3 to 10 and preferably in the range from 4 to 8.
  • Another 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 the tanning process according to the invention and the retanning process according to the invention.
  • the leathers according to the invention are distinguished by an overall advantageous quality, for example they are particularly soft.
  • the leathers according to the invention contain the polymers described above or the hydrolyzed polymers described above, particularly evenly distributed 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 auto parts.
  • items of clothing include jackets, pants, shoes, belts or braces.
  • Furniture in connection with the present invention includes all such furniture that contains leather components.
  • Seating furniture such as armchairs, chairs and sofas are examples.
  • Car seats are examples of car parts.
  • clothing items containing or made from leathers according to the invention are clothing items containing or made from leathers according to the invention.
  • furniture containing or made from leathers according to the invention are furniture containing or made from leathers according to the invention.
  • Another aspect of the present invention are auto parts containing or made from leathers according to the invention.
  • Another aspect of the present invention are polymers obtainable by copolymerization of
  • R 1 , R 2 , R 3 are the same or different and selected from C 1 -C 4 alkyl or hydrogen;
  • R 4 , R 5 are the same or different and are selected from C r C 4 alkyl or hydrogen;
  • R 13 is selected from hydrogen, SO 3 M, PO 3 M 2 , -CO-H (formyl), -CO-dC 20 -alkyl, -CO-C 6 -C 14 -aryl
  • M alkali metal or NH 4 + or CH 3 n an integer from 3 to 100, y an integer from 0 to 10.
  • polymers according to the invention contain monomers copolymerized in the polymer in the following proportions: (A) 2 to 50 wt .-%, preferably 5 to 30 wt .-% of at least one ethylenically unsaturated mono- or dicarboxylic acid with 3 to 8 carbon atoms or at least one of a mono- or dicarboxylic acid with 3 to 8 carbon atoms derived anhydride,
  • the monomer or monomers (D) which can optionally be copolymerized into the polymers used in the process according to the invention are different from (A).
  • DC 20 alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether or n-octadecyl vinyl ether ;
  • N-vinyl derivatives of nitrogen-containing aromatic compounds preferably N-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, 2-vinylpyridine, 4-vinylpyridine, 4-vinylpyridine-N-oxide, N Vinylimidazoline, N-vinyl-2-methylimidazoline,
  • the polymers according to the invention can be prepared as follows. It is possible to copolymerize the monomers (A), (B), (C) and, if appropriate, (D) with one another by solution polymerization, precipitation polymerization or, preferably, solvent-free by bulk poly-polymerization. (A), (B), (C) and optionally (D) can copolymerize in the form of random copolymers or as block copolymers.
  • Pressure and temperature conditions for a copolymerization of (A), (B) (C) and optionally (D) are generally not critical.
  • the temperatures are, for example, in the range from 60 to 200 ° C., preferably 90 to 160 ° C., the pressure is, for example, in the range from 1 to 10 bar, preferably 1 to 3 bar.
  • reaction times are, for example, 0.5 hours to 12 hours, although shorter and longer reaction times are also conceivable.
  • Suitable solvents are preferably those solvents which are considered inert to anhydrides and are derived from dicarboxylic acids having 3 to 8 carbon atoms, in particular acetone, tetrahydrofuran or 1,4-dioxane.
  • Aromatic and aliphatic hydrocarbons for example toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene or mixtures of one or more of the above-mentioned aromatic hydrocarbons, n-hexane, petroleum ether or are suitable as precipitants
  • Isododecane Mixtures of aromatic and aliphatic hydrocarbons are also suitable.
  • Polymerization is preferably carried out in the form of bulk polymerization without the addition of organic solvents.
  • R 13 hydrogen is selected, it may be advantageous to add certain amounts of water, for example 1 to 30% by weight, based on the mass of all monomers, and thus to prevent the formation of crosslinked copolymers.
  • Regulators can be used, for example mercaptoethanol or n-dodecyl mercaptan. Suitable amounts are, for example, 0.1 to 6% by weight, based on the mass of all monomers.
  • the copolymerization is advantageously started by initiators, for example peroxides or hydroperoxides.
  • Peroxides or hydroperoxides are di-tert.-butyl peroxide, tert.-butyl peroctoate, tert.-butyl perpivalate, tert.-butyl per-2-ethylhexanoate, tert.-butyl permaleilate, tert.-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-Chlorobenzoyl peroxide, dicyclohexyl peroxide dicarbonate, exemplified.
  • redox initiators are also suitable, as are azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion-amidine) dihydrochloride and 2,2'-azobis (4-methoxy -2,4-dimethylvaleronitrile).
  • these initiators are used in amounts of 0.1 to 20% by weight, preferably 0.2 to 15% by weight, based on the mass of all monomers.
  • the copolymerization described above gives polymers according to the invention.
  • the polymers according to the invention can contain compounds of the general formula I a, and the polymers according to the invention can be subjected to cleaning by conventional methods, for example falling over or extractive removal of unreacted monomers. However, cleaning can be omitted and the copolymers described above used 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 the copolymerization has ended, for example by distillation.
  • the polydispersity of the polymers according to the invention is generally between 2 and 10, preferably up to 7, but can assume higher values.
  • the K values of the polymers according to the invention are 6 to 100, preferably 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).
  • the K values of the polymers were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 761-774 (1932) in aqueous solution at 25 ° C. and a polymer concentration of 1% by weight.
  • the reaction mixture thus obtained was then stirred at 150 ° C. for 90 minutes, a clear oil being 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.
  • a 50% by weight thin-viscosity solution of polymer P 3 with a K value of 18 was obtained.
  • the strips were then distributed to separate walk-in drums 1 to 4. Together with 100% by weight of water, the drums 1 to 4 were each at 25-35 ° C. with 1% by weight of a 50% by weight (solids content) aqueous solution dosed by dyes whose solids were composed as follows:
  • the leathers were then washed with 200% by weight of water. Finally, 5% by weight of Lipodermlicker® CMG and 2% by weight of Lipodermlicker® PN were dosed in 100% water at 50 ° C. After a waiting time of 45 minutes, the mixture is acidified with 1% by weight of formic acid.
  • the washed leathers were dried, stabled 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 a statistical acrylic acid-acrylamide copolymer with a K value according to Fikentscher of 70 (1% by weight solution in water), comonomer ratio in mol%: (acrylic acid: acrylamide) 90: 10th
  • the skin of a South German cattle was converted into a wet-white semi-finished product with 1.25% by weight of glutardialdehyde and 3% by weight of the sulfone tanning agent from EP-B 0459 168, example K1 (based on the pimples). After pre-tanning, the pH was 3.9. After withering, the semi-finished products were folded to a thickness of 1.2 mm and cut into strips of approx. 350 g each.
  • the evaluation was based on a grade system like in school from 1 (very good) to 6 (unsatisfactory). Fleet consumption was assessed visually according to the criteria of residual dye (extinction) and turbidity.
  • the furniture leather produced according to the invention had excellent fullness and grain resistance with excellent dye dispersion and fixation. It was also observed that tanning aids were distributed more evenly in the leather by the retanning process according to the invention and the so-called exhaustion was improved; the range of tanning agents, especially dyes, was therefore better used. In addition, the wastewater pollution 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)

Abstract

L'invention concerne un procédé de production de cuir, caractérisé en ce qu'il consiste à traiter des peaux vertes, des peaux picklées ou des semi-produits avec au moins un produit de polymérisation qui peut être obtenu par copolymérisation des éléments suivants: (A) au moins un acide monocarboxylique ou dicarboxylique éthyléniquement insaturé comportant au moins 3 à 8 atomes de carbone, ou au moins un anhydride dérivé d'un acide monocarboxylique ou dicarboxylique comportant au moins 3 à 8 atomes de carbone; (B) au moins un composé vinylaromatique; (C) au moins un éther insaturé alcooxylé de formule générale (I); (D) éventuellement des monomères monoéthyléniquement insaturés supplémentaires. Dans ladite formule (I), les variables sont définies de la manière suivante: R<1>, R<2>, R<3> sont identiques ou différents et sélectionnés entre un groupe alkyle en C1-C4 ou hydrogène; R<4>, R<5> sont respectivement identiques ou différents et sélectionnés entre un groupe alkyle en C1-C4 ou hydrogène; R<6> est sélectionné entre hydrogène, SO3M, PO3M2, C1-C30-alkyle, -CO-H (formyle), CO-C1-C20-alkyle, -CO-C6-C14-aryle; M désigne un métal alcalin ou NH4<+> ou CH3; n représente un nombre entier compris entre 3 et 100; y désigne un nombre entier compris entre 0 et 10.
EP04740614A 2003-07-23 2004-07-03 Procede de production de cuir au moyen de produits de polymerisation Not-in-force EP1651781B1 (fr)

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 (fr) 2003-07-23 2004-07-03 Procede de production de cuir au moyen de produits de polymerisation

Publications (2)

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

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EP04740614A Not-in-force EP1651781B1 (fr) 2003-07-23 2004-07-03 Procede de production de cuir au moyen de produits de polymerisation

Country Status (8)

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

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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
CN101802071B (zh) 2007-09-03 2013-01-16 巴斯夫欧洲公司 含水配制料的制备方法、含水配制料及其用途
EP2190891A1 (fr) * 2007-09-03 2010-06-02 Basf Se Procédé de production de formulations aqueuses, formulations aqueuses et leur utilisation
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

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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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Title
See references of WO2005019480A1 *

Also Published As

Publication number Publication date
US20070107135A1 (en) 2007-05-17
WO2005019480A1 (fr) 2005-03-03
BRPI0412691A (pt) 2006-10-03
DE502004009623D1 (de) 2009-07-30
DE10333749A1 (de) 2005-02-10
AR046512A1 (es) 2005-12-14
ATE434058T1 (de) 2009-07-15
EP1651781B1 (fr) 2009-06-17
CN1826415A (zh) 2006-08-30
CN1826415B (zh) 2010-06-16

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