EP1597402B1 - Procede d'impermeabilisation de cuirs et de pelleteries - Google Patents

Procede d'impermeabilisation de cuirs et de pelleteries Download PDF

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Publication number
EP1597402B1
EP1597402B1 EP04705767.4A EP04705767A EP1597402B1 EP 1597402 B1 EP1597402 B1 EP 1597402B1 EP 04705767 A EP04705767 A EP 04705767A EP 1597402 B1 EP1597402 B1 EP 1597402B1
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Prior art keywords
polysiloxanes
carboxyl group
structural elements
formulation
free
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German (de)
English (en)
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EP1597402A1 (fr
Inventor
Ralph Lunkwitz
Peter Danisch
Thorsten RÄDLER
Werner Janson
Friedrich Sattler
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Stahl International BV
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Stahl International BV
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Priority claimed from DE2003106748 external-priority patent/DE10306748A1/de
Priority claimed from DE2003132991 external-priority patent/DE10332991A1/de
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    • 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • Out EP 0 213 480 B is a process for the hydrophobization of leather and fur skins is known, which is an aqueous emulsion of a silicone oil or an anhydrous mixture of a silicone oil and an alkanolamine salt of an amino acid before, during or after retanning to leather or furs act.
  • polysiloxanes which are mentioned are: dimethylpolysiloxane in which 3% of the methyl groups are replaced by mercaptopropyl (Examples 1 to 7), dimethylpolysiloxane having a viscosity of 80 to 110 mPa ⁇ s, phenylmethylpolysiloxanes having a viscosity of 85 to 120 mPa ⁇ s, and Dimethylpolysiloxanes having on average 2 to 10 carboxyl groups per molecule.
  • the performance characteristics of such hydrophobing formulations can be improved.
  • the leathers produced with the aid of the disclosed polysiloxanes can in some cases be improved in terms of their performance properties.
  • WO 95/22627 is a process for the hydrophobization of leather and fur skins using carboxyl group-containing polysiloxanes in aqueous emulsion are known in which comb-branched polysiloxanes are used, which may have the formula A:
  • WO 98/04748 discloses a process for retanning leathers made with polymeric tanning agents and optionally aldehyde tanning agents which are treated with polymer tanning agents and with comb-like polysiloxanes of formula A above.
  • EP-A 1 087 021 It is known that leather treatment compositions containing a combination of a polysiloxanes substituted with carboxylic acid or carboxylic anhydride groups at ⁇ , ⁇ -position, wherein the carboxyl groups of the polysiloxane are present in neutralized form, with certain amphiphilic polymers, an emulsifier and an oil or wax, are suitable as leather treatment agents. With the help of revealed full and soft leathers that were well washable.
  • leather is treated before, during or after the retanning with a formulation.
  • At least one formulation used in the process according to the invention contains from 1 to 30% by weight, preferably from 5 to 20, particularly preferably from 7 to 12.5% by weight, based on the weight of the formulation, of a mixture of two or more polysiloxanes.
  • polysiloxanes contained in at least one formulation are carboxyl-containing polysiloxanes which contain structural elements of the formulas I, II and optionally IIIa and IIIb.
  • the above-described structural elements are each arranged so that Si-O-Si-O chains are formed.
  • the formation of Si-Si groups is theoretically possible, but plays a minor role in most cases.
  • all R 1 are the same and are each methyl.
  • the structural elements I are the same in each case, where in each case one R 1 is methyl and the other R 1 is phenyl.
  • the structural elements of the formula III a are selected from the following groups: Si (CH 3 ) 3 , Si (CH 3 ) 2 C 6 H 5 , Si (CH 3 ) 2 OH, Si (CH 3 ) C 6 H 5 OH.
  • a 1 is identical or different and linear or branched C 5 -C 25 -alkylene, unsubstituted or substituted by one or more C 1 -C 4 -alkyl or phenyl, for example - (CH 2 ) 5 -, - (CH 2 ) 6 - , - (CH 2 ) 7 -, - (CH 2 ) 8 -, - (CH 2 ) 9 -, - (CH 2 ) 10 -, - (CH 2 ) 11 -, - (CH 2 ) 12 -, - (CH 2 ) 13 -, - (CH 2 ) 14 -, -CH (CH 3 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -, - C (CH 3 ) 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -; -CH (C 6 H 5 ) -CH 2 -CH 2 -
  • Z 1 means a direct bond, oxygen Amino group of the formula -NR 2 - carbonyl group, Amido group of the formula -NR 2 -CO- or -CO-NR 2 - or Ester group of the formula CO-O or O-CO;
  • R 2 is the same or different and selected independently of one another Hydrogen, C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.
  • Polysiloxanes which contain the structural elements of the general formulas I, II and optionally IIIa and / or IIIb may have a linear structure or have a cyclic or branched structure.
  • Branched polysiloxanes which contain the structural elements I, II and optionally IIIa and / or IIIb generally additionally contain structural elements of the formula IVa or IVb, for example in which the variables are defined as above.
  • Cyclic unbranched polysiloxanes which contain the structural elements of the general formula I, II usually contain no structural elements of the formulas III a and III b.
  • the structural elements I, II, optionally IV a and IV b may be distributed alternately, blockwise and preferably randomly in carboxyl-containing polysiloxane molecules.
  • carboxyl group-containing polysiloxanes in the range from 1 to 50, preferably 2 to 25, particularly preferably on average 2.5 to 15 carboxyl groups per molecule.
  • the molecular weight M w of the carboxyl-containing polysiloxanes used according to the invention with the structural elements I, II, optionally IIIa, IIIb, IVa and IVb is usually in the range from 5000 g to 150,000 g / mol, preferably from 10,000 to 100,000 g / mol ,
  • the molecular weight determination can be carried out by methods known to the person skilled in the art, for example by light scattering methods or viscosity determinations.
  • all or at least a certain proportion, for example one third or one-half, of the carboxyl groups in the carboxyl group-containing polysiloxanes are neutralized.
  • Suitable for neutralization For example, basic salts such as hydroxides or carbonates of alkali metals such as Na or K.
  • Further suitable for neutralization are ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, alkanolamines such as ethanolamine, diethanolamine, triethanolamine, N-methyl-ethanolamine, N-methyldiethanolamine or N- (n-butyl) -diethanolamine.
  • the mixtures used according to the invention contain, for example, 10 to 90% by weight of carboxyl-containing polysiloxane, preferably 40 to 60% by weight and more preferably about 50% by weight of carboxyl-containing polysiloxane.
  • the mixtures used according to the invention furthermore contain polysiloxanes which contain no carboxyl groups.
  • Such polysiloxanes contain structural elements of the above-identified formulas I, optionally III a, III b and IV a, where the variables are as defined above, but R 1 is not equal to Z 1 -A 1 -COOH.
  • carboxyl group-free polysiloxanes used according to the invention are composed of structural elements of the above-described formulas I, optionally III a, III b and IV a.
  • carboxyl-free polysiloxanes are poly (dimethyl) siloxanes and poly (phenylmethyl) siloxanes.
  • Carboxyl-free polysiloxanes which contain the structural elements of the general formulas I and optionally III a, III b and IV a may have a linear structure or have a cyclic or branched structure.
  • Cyclic unbranched carboxyl group-free polysiloxanes which contain the structural elements of the general formula I usually contain no structural elements of the formulas III a and III b.
  • all R 1 in carboxyl group-free polysiloxanes are the same and are each methyl.
  • the structural elements I in carboxyl group-free polysiloxanes are the same in each case, wherein in each case one R 1 is methyl and the other R 1 is phenyl.
  • the structural elements of the formula III a in carboxyl group-free polysiloxanes are selected from the following groups: Si (CH 3 ) 3 , Si (CH 3 ) 2 C 6 H 5 , Si (CH 3 ) 2 OH, Si (CH 3 ) C 6 H 5 OH.
  • the molecular weight M w of the inventively used carboxyl group-free polysiloxanes having the structural units I, II, optionally III a, III b and IV a in the range of 500 g to 150,000 g / mol, preferably up to 10,000 g / mol.
  • carboxyl group-containing and carboxyl group-free polysiloxane are selected so that the molecular weight of the carboxyl group-containing polysiloxane is higher than the molecular weight of the carboxyl group-free polysiloxane.
  • the mixtures used according to the invention contain, for example, 10 to 90% by weight of carboxyl-free polysiloxane, preferably 40 to 60% by weight and more preferably about 50% by weight of carboxyl-free polysiloxane.
  • the formulations used according to the invention contain one or more emulsifiers. Based on the formulation, for example, 3 to 25 wt .-%, preferably 5 to 20 and particularly preferably 8 to 18 wt .-% of one or more emulsifiers.
  • emulsifiers it is possible in principle to use all compounds which are surface-active in aqueous systems and may be nonionic, anionic, cationic or even zwitterionic in nature.
  • the group CO-R 5 is usually derived from saturated or unsaturated fatty acids.
  • Saturated fatty acids are to be understood as meaning carboxylic acids having C 9 -C 20 -alkyl groups which may be linear or branched, substituted or unsubstituted.
  • R 5 may be, for example: n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-octadecyl, n-eicosyl.
  • CO-R 5 can be derived from an unsaturated fatty acid having 9 to 20 C atoms and one to 5 CC double bonds, wherein the CC double bonds can be, for example, isolated or allylic, for example the acyl residue of linoleic acid, linolenic acid, and more particularly preferably the oleic acid.
  • all or at least a certain proportion, for example one third or one-half, of the carboxyl groups in N-acylated amino acid derivatives used as emulsifiers is neutralized.
  • neutralization are, for example, basic salts such as hydroxides or carbonates of alkali metals such as Na or K.
  • alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and especially alkanolamines such as ethanolamine , Diethanolamine, triethanolamine, N-methyl-ethanolamine, N-methyldiethanolamine or N- (n-butyl) -diethanolamine.
  • Exemplary representatives of compounds of the formula V are N-oleylsarcosine, N-stearylsarcosine, N-lauroylsarcosine and N-isononanoylarcosine and also the respective ethanolammonium salts, diethanolammonium salts and N-methyldiethanolammonium salts.
  • sulfur-containing emulsifier is used.
  • sulfur-containing emulsifiers it is possible in principle to use all sulfur-containing compounds which are surface-active in aqueous systems and which may be nonionic, anionic, cationic or even zwitterionic in nature.
  • R 6 and R 7 are hydrogen and the other is selected from C 1 -C 30 alkyl.
  • a mixture of a plurality of sulfur-containing compounds, for example of the formula VI which may differ, for example, in that in the first compound of the formula VI R 6 is hydrogen and R 7 is C 1 -C 30 alkyl is selected and in the second R 6 is hydrogen and R 7 is selected from C 1 -C 30 alkyl.
  • all or at least a certain proportion, for example a third or half, of the sulfonyl groups are neutralized in sulfur-containing compounds used as emulsifiers.
  • Suitable neutralizing agents are, for example, basic salts such as hydroxides or carbonates of the alkali metals such as Na or K.
  • alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine
  • alkanolamines such as ethanolamine, diethanolamine, triethanolamine, N-methyl-ethanolamine, N-methyldiethanolamine or N- (n-butyl) -diethanolamine.
  • sulfur-containing compounds of the formula V instead of pure sulfur-containing compounds, for example sulfur-containing compounds of the formula V, it is possible to use mixtures of various sulfur-containing compounds. For example, it is possible to esterify as Oxoöl 135 or Oxodicköl 135 ( WO 01/68584 ) use known mixture.
  • formulations used in the process according to the invention may contain up to 40% by weight, preferably up to 20% by weight, based on formulation, of at least one alcohol of the formula VII in formula VII, the variables R 9 and R 10 are as defined above.
  • formulations used in the process according to the invention may contain up to 50% by weight, preferably up to 30% by weight, based on the formulation, of at least one compound of the formula VIII.
  • formulations used in the process according to the invention may contain up to 40% by weight, particularly preferably up to 20% by weight, of mixtures which contain at least one alcohol of the include general formula VIII; oxo oil 135 and oxo oil 13 may be mentioned as examples of such mixtures.
  • the or the formulations used according to the invention are aqueous.
  • At least one formulation used according to the invention contains at least one further hydrophobic compound.
  • At least one other hydrophobic compound is a carbon-based compound, for example, natural or synthetic wax, virgin or synthetic oil, or native or synthetic fat.
  • Examples of natural waxes are beeswax, cork wax, montan waxes or carna ⁇ ba wax.
  • synthetic waxes are polyethylene waxes or ethylene copolymer waxes, as obtainable, for example, by free-radical polymerization of ethylene or free-radical copolymerization of ethylene with, for example, (meth) acrylic acid or by Ziegler-Natta catalysis.
  • polyisobutylene waxes may be mentioned.
  • paraffin mixtures These are understood as meaning mixtures of hydrocarbons which have 12 or more carbon atoms and usually have a melting point in the range from 25 to 45 ° C. Such paraffin mixtures can be obtained, for example, in refineries or crackers and are known to those skilled in the art as slack wax and Sasol waxes.
  • Another example of synthetic waxes are montan ester waxes.
  • liquid triglycerides such as fish oil, cattle claw oil, olive oil, cottonseed oil, castor oil, sunflower oil and peanut oil called.
  • synthetic oils examples include white oil, paraffin oil, functionalized paraffins such as chlorinated or sulfochlorinated paraffins or polyalkylene glycols such as polyethylene glycol.
  • solid native triglycerides such as, for example, lanolin, shellac wax and mixtures thereof, are mentioned at room temperature.
  • the further hydrophobic compound is at least one native triglyceride.
  • a combination of at least one native or liquid native triglyceride at room temperature and a paraffin mixture having a melting point in the range of 25 to 40 ° C is used.
  • the quantitative ratio is not critical per se; suitable weight ratios are native triglyceride: paraffin mixture in the range from 10: 1 to 1:10.
  • leather or fur skins are treated in a liquor before, during or after the retanning with the formulations used according to the invention.
  • the treatment according to the invention can be carried out once or repeatedly.
  • the leathers to be treated may have been prepared by any desired methods, for example by mineral tanning, in particular chrome tanning, or by polymer tanning, tanning with syntans, tanning of the resin, tanning with vegetable tannins or else tanning with combinations of the abovementioned tanning agents.
  • At least one formulation according to the invention is added in one or more portions to the leather or furs to be treated. This addition can be done in an aqueous liquor.
  • the liquor length may preferably be from 50 to 2000% by weight, preferably from 100 to 400% by weight, based on the shaved weight of the leather or the wet weight of the fur skins.
  • the components carboxyl-containing polysiloxane, carboxyl group-free polysiloxane and emulsifier are added separately to leather and / or leather and liquor and produces the formulation according to the invention in situ .
  • the process according to the invention is generally carried out by passing the leather to be treated or the furskins to be treated into suitable vessels, for example in barrels, in particular in rotatable barrels with internals.
  • suitable vessels for example in barrels, in particular in rotatable barrels with internals.
  • Other methods of mixing known to the person skilled in the art are also possible.
  • the pressure conditions of the process according to the invention are generally not critical. Preference is given to working at atmospheric pressure (1 atm), but it is also possible to work at reduced pressure such as 0.5 to 0.99 atm or at elevated pressure such as 1.01 to 2 atm.
  • pH values in the range from 4 to 8, preferably from 4.5 to 8, can be set as the pH.
  • the pH can be lowered to a pH of from 3 to 5 by addition of an acid, for example formic acid.
  • the treatment according to the invention is generally completed after a time of 20 minutes to 24 hours, preferably 30 minutes to 12 hours.
  • the treatment steps according to the invention are used in the context of the present invention.
  • the amount of the formulation used according to the invention may be from 0.1 to 20% by weight, in particular from 0.5 to 15% by weight, based on the shaved weight of the leathers to be treated or the wet weight of the furs to be treated.
  • tanning agents customary in tanning for example mineral tanning agents, in particular chrome tanning agents or polymeric tanning agents, syntans, resin tanning agents, vegetable tanning agents or combinations of the abovementioned tanning agents
  • organic solvents such as, for example, alcohols.
  • the treatment according to the invention can be supplemented by an aftertreatment with tanning agents customary in tanning, for example mineral tanning agents, in particular chrome tanning agents, or with polymer tanning agents, syntans, resin tanning agents, vegetable tanning agents or combinations of the abovementioned tanning agents.
  • tanning agents customary in tanning for example mineral tanning agents, in particular chrome tanning agents, or with polymer tanning agents, syntans, resin tanning agents, vegetable tanning agents or combinations of the abovementioned tanning agents.
  • the leather or fur skins obtained according to the invention can be worked up as usual in the art of tanning.
  • Another object of the present invention are leather, prepared by the method according to the invention.
  • leathers produced by the process according to the invention are distinguished by very good performance properties, for example by very good hydrophobicity, very good feel and excellent level dyeing.
  • Another object of the present invention is the use of the leather according to the invention for the production of garments, such as jackets, coats, shoes and especially boots.
  • Another object of the present invention is the use of leather according to the invention for the production of furniture and furniture parts, such as leather sofas, leather armchairs, armrests for chairs, armchairs or sofas or benches.
  • Another object of the present invention is the use of the leather according to the invention for the production of auto parts, such as car seats, parts of dashboards and interior trim parts, for example in car doors.
  • Another object of the present invention are fur skins treated by the method according to the invention.
  • Another object of the present invention are formulations containing 1 to 20 wt .-%, based on the formulation, of a mixture of polysiloxanes containing From 10 to 90% by weight, based on the mixture, of one or more carboxyl-containing polysiloxanes, From 90 to 10% by weight, based on the mixture, of one or more carboxyl group-free polysiloxanes, and 3 to 25 wt .-%, preferably 5 to 20 and particularly preferably 8 to 18 wt .-%, based on the formulation, of at least one emulsifier.
  • carboxyl-containing polysiloxanes are those polysiloxanes which contain the structural elements of the formulas I, II and optionally III a and III b contained and that the carboxyl-free polysiloxanes from structural elements of the above-mentioned formulas I and optionally III a, III b and / or IV a are constructed.
  • the carboxyl-containing polysiloxanes contained in formulations of the invention may further contain structural elements of the general formulas IV a and IV b.
  • Particularly suitable emulsifiers are N-acylated amino acid derivatives, for example of the formula V, in which the variables are as defined above.
  • Suitable emulsifiers are sulfur-containing emulsifiers.
  • sulfur-containing emulsifiers in the formulations according to the invention it is possible in principle to mention all sulfur-containing compounds which are surface-active in aqueous systems and which may be nonionic, anionic, cationic or even zwitterionic in nature.
  • Particularly suitable emulsifiers are sulfur-containing compounds, for example of the formula VI, in which the variables are as defined above.
  • the formulations according to the invention are those formulations which are characterized in that they contain from 10 to 70% by weight, based on the formulation, of at least one further hydrophobic compound.
  • hydrophobic compounds in one embodiment of the present invention are a combination of at least one natural room temperature solid or liquid triglyceride and a paraffin mixture.
  • the formulations according to the invention may have a pH of 7 or more. Preferably, they have a pH in the range of 7 to a maximum of 10.
  • the formulations according to the invention may preferably be aqueous formulations having a solids content of up to 50% by weight, based on the total formulation.
  • the formulations of the invention have a very good storage stability.
  • the formulations according to the invention can be used excellently in the process according to the invention.
  • a further subject of the present invention is a process for the preparation of the formulations according to the invention, also referred to below as preparation process according to the invention.
  • the preparation process according to the invention can generally be carried out by mixing together the components carboxyl-free polysiloxane, carboxyl-containing polysiloxane and one or more emulsifiers and optionally hydrophobic compound or hydrophobic compounds.
  • the order of addition of the individual components is not critical. This can be done for example by simply stirring the components, for example with a mixer or an Ultra Thurax stirrer.
  • further homogenization e.g. with a split homogenizer.
  • Particularly storage-stable formulations according to the invention are obtained if a further homogenization is carried out.
  • inventive formulations 1.1 to 1.4 from carboxyl-containing polysiloxane, carboxyl-free polysiloxane, emulsifier and hydrophobic substances
  • Emulsifier N-Oleyl sarcosine as sodium salt, commercially available at BASF Aktiengesellschaft.
  • Native triglyceride Lipoderm oil, a beef claw oil.
  • Synthetic Oil Paraffin gash 36/38, commercially available from Shell and Total-Fina.
  • Example 2.1 Treatment of leather with the formulations according to the invention 1.1
  • the data in% by weight are based on the shaved weight, unless stated otherwise. In all operations, the barrel was rotated about 10 times per minute unless otherwise stated.
  • the leather was added at 3% by weight with the following characteristic data: 30% by weight aqueous, partially neutralized with NaOH polymer solution; Homopolymer of methacrylic acid, M n about 10,000; K value according to Fikentscher: 12, viscosity of the 30% by weight solution: 65 mPa.s (DIN EN ISO 3219, 23 ° C.), pH 5.1. It was retanned for 30 minutes.
  • the first treatment step 2% by weight of formulation 1.1 was added and drumming for a further 30 minutes. Then, within 10 minutes, 3% by weight of the vegetable tanning agent mimosa extract and 2% by weight of the leather dye Luganil® Black NT, commercially available from BASF Aktiengesellschaft. In addition, 2% by weight of the resin tanning agent Relugan® D, commercially available from BASF Aktiengesellschaft, 3% by weight of the vegetable tanning agent Chestnut® and 3% by weight of the syntans Basyntan SL® were added, commercially available from BASF Aktiengesellschaft. The treatment continued for a period of one hour.
  • the liquor was drained, the leather washed twice with 200 wt .-% water at a temperature of 40 ° C. Subsequently, the top was mixed with 100 wt .-% water and at a temperature of 40 ° C with a mixture of 0.2 wt .-% Leather Black VM and 0.3 wt .-% of the leather dye Luganil® Black AS, commercial Available from BASF Aktiengesellschaft, and 0.2 wt .-% of formic acid at a pH of 3.6, the pot color carried out. Then the fleet was drained, added with 100 wt .-% water and treated with 3 wt .-% Cr (III) sulfate at a pH of 3.5.
  • the leather 3.1 according to the invention was obtained.
  • Example 1 was repeated, but in each case formulation 1.2 was used instead of 1.1 in the first and in the second treatment step.
  • the leather 3.2 according to the invention was obtained.
  • Example 1 was repeated, but in each case formulation 1.3 was used instead of 1.1 in the first and in the second treatment step.
  • the leather 3.3 according to the invention was obtained.
  • Example 1 was repeated, but in each case formulation 1.4 instead of 1.1 was used in the first and in the second treatment step.
  • the leather 3.4 of the invention was obtained.
  • Example 1 was repeated, but in each case formulation 1.5 instead of 1.1 was used in the first and in the second treatment step.
  • the comparative leather sample V 3.5 was obtained.
  • Example 1 was repeated, but in each case formulation 1.6 instead of 1.1 was used in the first and in the second treatment step.
  • the comparative leather sample V 3.6 was obtained.
  • Table 2 Properties of the leathers of the invention and the leather obtained in the comparative experiments leather or comparative leather sample 3.1 3.2 3.3 3.4 V 3.5 V 3.6 Maesertest 18,000 15,000 15,000 15,000 7600 400 26,000 12,000 17,000 18,000 8700 700 Static water absorption after 2 hours 18 20 19 22 21 27 coloring 3 3.5 3.5 5.5 4 (shadow) 4 (shadow)
  • the monoester thus obtained was cooled to 40 ° C and stirred into 210 ml of water, partially neutralized by the addition of 17 g (0.21 mol) of 50 wt .-% aqueous NaOH and the mixture was heated to 80 ° C. Thereafter, with stirring, 28.5 g Sodium disulfite added and the mixture stirred at 80 ° C for a period of 6 hours. It was then cooled to 40 ° C.
  • Carboxyl-containing polysiloxane "PS 1": all R 1 CH 3 , A 1 : - (CH 2 ) 10 -, Z 1 : single bond, kinematic viscosity v in the range 500-850 mm 2 / s, determined at room temperature, molecular weight M n: 10,000 g / mol, randomly distributed in the statistical average, 127 structural elements I and 2 to 3 structural elements per molecule II, structural elements II.
  • Carboxyl-free polysiloxane "PS 2": all R 1 CH 3 , kinematic viscosity v of 350 mm 2 / s, determined at room temperature, molecular weight M n : 7,500 g / mol.
  • Emulsifier E 4.1 Emulsifier E 4.1.
  • the mixture thus obtained was homogenized using a gap homogenizer SHL 105 from. Brau and Luebbe, with a pressure of 150 bar and a temperature of 50 ° C was selected.
  • the formulation 5.1 according to the invention was obtained.
  • Example 5.1 was repeated, but with 25 g of sulfur-containing emulsifier E 4.2 instead of E 4.1.
  • Example 6.1 Treatment of leather with formulation according to the invention 5.1
  • the leather was treated with 3% by weight of polymer having the following characteristic data: 30% by weight aqueous, partially neutralized with NaOH polymer solution; Homopolymer of methacrylic acid, M n about 10,000; K value according to Fikentscher: 12, viscosity of the 30% by weight solution: 65 mPa.s (DIN EN ISO 3219, 23 ° C.), pH 5.1.
  • the liquor was drained, the leather washed twice with 200 wt .-% water at a temperature of 40 ° C. Subsequently, the top was mixed with 100 wt .-% water and at a temperature of 40 ° C with a mixture of 0.2 wt .-% Leather Black VM and 0.3 wt .-% of the leather dye Luganil® Black AS, commercial Available from BASF Aktiengesellschaft, and 0.2 wt .-% of formic acid at a pH of 3.6, the pot color carried out. The liquor was then drained off, admixed with 100% by weight of water and treated with 3% by weight of Cr (III) sulfate at a pH of 3.5.
  • Example 6.1 was repeated, but in the first and in the second treatment step in each case formulation 5.2 to 5.3, V 5.4 or V 5.5 instead of 5.1 was used.
  • Table 4 Properties of the leathers of the invention and the comparative leather samples obtained in the comparative experiments leather or comparative leather sample 6.1 6.2 6.3 V6.4 V6.5 Used formulation 5.1 5.2 5.3 V5.4 V5.5 Bally penetrometer water passage to [min] 120 130 60 40 110 Static water uptake after 6 29 28 30 34 30 Hours [weight%] 32 29 32 39 28 coloring 3 3.5 3 4 5

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  • Oil, Petroleum & Natural Gas (AREA)
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Claims (15)

  1. Procédé d'imperméabilisation de cuirs et de fourrures, caractérisé en ce que l'on traite les cuirs ou les fourrures avant, pendant ou après le retannage avec une ou plusieurs formulations contenant 1 à 30 % en poids, par rapport à la formulation, d'un mélange de polysiloxanes contenant
    10 à 90 % en poids, par rapport au mélange, d'un ou plusieurs polysiloxanes contenant des groupes carboxyle,
    90 à 10 % en poids, par rapport au mélange, d'un ou plusieurs polysiloxanes sans groupes carboxyle,
    et 3 à 25 % en poids, par rapport à la formulation, d'au moins un émulsifiant
    où
    les polysiloxanes contenant des groupes carboxyle sont des polysiloxanes qui contiennent des éléments structuraux des formules I, II et éventuellement III a et III b
    Figure imgb0021
     dans lesquels les variables sont définies comme suit :
    R1 est identique ou différent et représente indépendamment les uns des autres l'hydrogène, hydroxyle, C1-C4-alkyle, C6-C14-aryle, C1-C4-alcoxy, amino, mono-C1-C4-alkyl-amino, Di-C1-C4-alkylamino ou Z1-A1-COOH ;
    A1 identique ou différent et représente C5-C25-alkylène linéaire ou ramifié,
    Z1 représente une liaison directe, l'oxygène ou un groupe amino, carbonyle, amido ou ester
    et où
    le ou les polysiloxanes sans groupes carboxyle sont linéaires ou cycliques ou ramifiés et sont construits à partir d'éléments structuraux des formules I et éventuellement IIIa, IIIb et/ou IVa,
    Figure imgb0022
     où
    R1 est identique ou différent et représente indépendamment les uns des autres l'hydrogène, hydroxyle, C1-C4-alkyle, C6-C14-aryle, C1-C4-alcoxy,
    où
    - les polysiloxanes sans groupes carboxyle linéaires consistent en éléments structuraux des formules I, IIIa et/ou IIIb,
    - les polysiloxanes sans groupes carboxyle cycliques consistent en éléments structuraux de formule I,
    - les polysiloxanes sans groupes carboxyle ramifiés consistent en éléments structuraux des formules I, IVa, IIIa et/ou IIIb.
  2. Procédé selon la revendication 1, caractérisé en ce que la formulation contient 10 à 70 % en poids, par rapport à la formulation, d'au moins un autre composé hydrophobe.
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que le au moins un émulsifiant est un acide aminé N-acylé.
  4. Procédé selon l'une des revendications 1 à 2, caractérisé en ce que le au moins un émulsifiant est un émulsifiant contenant du soufre.
  5. Procédé selon la revendication 4, caractérisé en ce que le au moins un émulsifiant contenant du soufre est un ou plusieurs composés de formule générale VI
    Figure imgb0023
     où les variables sont définies comme suit
    R6, R7 sont identiques ou différents et sont choisis parmi l'hydrogène, C1-C30-alkyle et C6-C14-aryle
    R8 est C1-C4-alkyle ou l'hydrogène.
  6. Procédé selon la revendication 2, caractérisé en ce que l'autre composé hydrophobe est une combinaison d'au moins un triglycéride naturel solide ou liquide à la température ambiante et d'un mélange de paraffines.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on réalise le traitement à des pH dans le domaine de 4 à 9.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'on réalise le traitement à des températures dans le domaine de 20 à 65°C.
  9. Cuirs, produits selon un procédé selon l'une des revendications 1 à 8.
  10. Utilisation de cuirs selon la revendication 9 pour la production de pièces d'habillement, de meubles et de pièces d'automobiles.
  11. Fourrures, produites selon l'une des revendications 1 à 8.
  12. Formulations, contenant
    1 à 20 % en poids, par rapport à la formulation, d'un mélange de polysiloxanes consistant en
    10 à 90 % en poids, par rapport au mélange, d'un ou plusieurs polysiloxanes contenant des groupes carboxyle,
    90 à 10 % en poids, par rapport au mélange, d'un ou plusieurs polysiloxanes sans groupes carboxyle,
    3 à 25 % en poids, par rapport à la formulation, d'au moins un émulsifiant
    où
    le ou les polysiloxanes sans groupes carboxyle sont linéaires ou cycliques ou ramifiés et sont construits à partir d'éléments structuraux des formules I et éventuellement IIIa, IIIb et/ou IVa,
    Figure imgb0024
     où
    R1 est identique ou différent et représente indépendamment les uns des autres l'hydrogène, hydroxyle, C1-C4-alkyle, C6-C14-aryle, C1-C4-alcoxy,
    où
    - les polysiloxanes sans groupes carboxyle linéaires consistent en éléments structuraux des formules I, IIIa et/ou IIIb,
    - les polysiloxanes sans groupes carboxyle cycliques consistent en éléments structuraux de formule I,
    - les polysiloxanes sans groupes carboxyle ramifiés consistent en éléments structuraux des formules I, IVa, IIIa et/ou IIIb,
    et où les éléments structuraux sont disposés de telle manière que des chaînes Si-O-Si-O- sont formées
    et où
    les polysiloxanes contenant des groupes carboxyle sont des polysiloxanes qui contiennent des éléments structuraux des formules I, II et éventuellement III a et III b
    Figure imgb0025
     dans lesquels les variables sont définies comme suit :
    R1 est identique ou différent et représente indépendamment les uns des autres l'hydrogène, hydroxyle, C1-C4-alkyle, C6-C14-aryle, C1-C4-alcoxy, amino, mono-C1-C4-alkyl-amino, Di-C1-C4-alkylamino ou Z1-A1-COOH ;
    A1 identique ou différent et représente C5-C25-alkylène linéaire ou ramifié,
    Z1 représente une liaison directe, l'oxygène ou un groupe amino, carbonyle, amido ou ester.
  13. Formulations selon la revendication 12, caractérisées en ce qu'elles contiennent 10 à 70 % en poids, par rapport à la formulation, d'au moins un autre composé hydrophobe.
  14. Formulations selon l'une des revendications 12 à 13, caractérisées en ce que les autres composés hydrophobes sont une combinaison d'au moins un triglycéride naturel solide ou liquide à la température ambiante et d'un mélange de paraffines.
  15. Procédé de production de formulations selon l'une des revendications 12 à 146 par mélange des composants polysiloxane sans groupes carboxyle, polysiloxane contenant des groupes carboxyle et un ou plusieurs émulsifiants.
EP04705767.4A 2003-02-17 2004-01-28 Procede d'impermeabilisation de cuirs et de pelleteries Expired - Lifetime EP1597402B1 (fr)

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DE2003106748 DE10306748A1 (de) 2003-02-17 2003-02-17 Verfahren zur Hydrophobierung von Leder und Pelzfellen
DE10306748 2003-02-17
DE2003132991 DE10332991A1 (de) 2003-07-18 2003-07-18 Verfahren zur Hydrophobierung von Leder und Pelzfellen
DE10332991 2003-07-18
PCT/EP2004/000706 WO2004072307A1 (fr) 2003-02-17 2004-01-28 Procede d'impermeabilisation de cuirs et de pelleteries

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WO2008022918A2 (fr) 2006-08-23 2008-02-28 Basf Se Composés et leur utilisation pour la fabrication de cuir et en tant qu'agents de dispersion
NL2027334B1 (en) 2021-01-18 2022-07-25 Stahl Int B V Composition and process for waterproofing leather

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4311626A (en) * 1980-09-25 1982-01-19 Toray Silicone Company, Ltd. Silicone compositions for the treatment of fibers

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DE4402029A1 (de) * 1994-01-25 1995-07-27 Basf Ag Wäßrige Lösungen oder Dispersionen von Copolymerisaten
DE4404890A1 (de) * 1994-02-16 1995-08-17 Basf Ag Verfahren zum Hydrophobieren von Leder und Pelzfellen mit kammartig carboxylfunktionalisierten Polysiloxanen
DE4415062B4 (de) * 1994-04-29 2004-04-01 Stockhausen Gmbh & Co. Kg Mittel und Verfahren zur Hydrophobierung von Ledern und Pelzen
DE19629986A1 (de) * 1996-07-25 1998-01-29 Basf Ag Verfahren zum Hydrophobieren von mit Polymergerbstoffen gegerbten Ledern und Pelzfellen
DE19646916C1 (de) * 1996-11-13 1998-04-23 Basf Ag Verwendung von Carboxyamid-Polysiloxanen zur Hydrophobierung von Materialien faseriger Struktur und Verfahren zur Durchführung
EP1087021B1 (fr) * 1999-09-18 2003-08-06 Trumpler GmbH & Co. Chemische Fabrik Agent de traitement du cuir

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4311626A (en) * 1980-09-25 1982-01-19 Toray Silicone Company, Ltd. Silicone compositions for the treatment of fibers

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US20060096036A1 (en) 2006-05-11
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BRPI0406655B1 (pt) 2013-07-16
BRPI0406655A (pt) 2005-12-06

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