EP1597402A1 - Procede d'impermeabilisation de cuirs et de pelleteries - Google Patents

Procede d'impermeabilisation de cuirs et de pelleteries

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Publication number
EP1597402A1
EP1597402A1 EP04705767A EP04705767A EP1597402A1 EP 1597402 A1 EP1597402 A1 EP 1597402A1 EP 04705767 A EP04705767 A EP 04705767A EP 04705767 A EP04705767 A EP 04705767A EP 1597402 A1 EP1597402 A1 EP 1597402A1
Authority
EP
European Patent Office
Prior art keywords
weight
polysiloxanes
leather
formulation
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP04705767A
Other languages
German (de)
English (en)
Other versions
EP1597402B1 (fr
Inventor
Ralph Lunkwitz
Peter Danisch
Thorsten RÄDLER
Werner Janson
Friedrich Sattler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stahl International BV
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2003106748 external-priority patent/DE10306748A1/de
Priority claimed from DE2003132991 external-priority patent/DE10332991A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1597402A1 publication Critical patent/EP1597402A1/fr
Application granted granted Critical
Publication of EP1597402B1 publication Critical patent/EP1597402B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • 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

  • the present invention relates to a process for the hydrophobization of leather and fur skins, characterized in that leather or fur skins are treated before, during or after retanning with one or more formulations containing 1 to 30% by weight, based on the formulation, of one Mixture of polysiloxanes containing
  • EP 0213480 B discloses a process for the hydrophobization of leather and fur, in which an aqueous emulsion of a silicone oil or an anhydrous mixture of a silicone oil and an alkanolamine salt of an amino acid is allowed to act on leather or furs before, during or after retanning.
  • polysiloxanes examples include dimethylpolysiloxane in which 3% of the methyl groups have been replaced by mercaptopropyl (Examples 1 to 7), dimethylpolysiloxane with a viscosity of 80 to 110 mPa-s, phenylmethylpolysiloxanes with a viscosity of 85 to 120 mPa-s, and Dimethylpolysiloxanes with an average of 2 to 10 carboxyl groups per molecule.
  • the performance properties of such waterproofing preparations can still be improved.
  • the leather produced with the aid of the disclosed polysiloxanes can also be improved in some cases with regard to their useful properties.
  • the structural units can be distributed statistically, for example.
  • the variables are defined as follows:
  • R is the same or different and independently of one another hydrogen, hydroxyl, -CC 4 -alkyl, phenyl, CrC 4 -alkoxy, amino, mono- or di-C C ⁇ amino.Chlor or fluorine, with a residue at the chain ends R can stand for the grouping ZA-COOH;
  • A is a linear or branched C 5 -C 2 5 alkylene group,
  • Z is a direct bond, an oxygen atom or an amino, carbonyl, amido or ester group.
  • WO 98/04748 discloses a process for retanning leather produced with polymeric tanning agents and optionally aldehyde tanning agents, which are treated with polymeric tanning agents and with comb-like polysiloxanes of the formula A described above.
  • leather is treated with a formulation before, during or after retanning.
  • At least one formulation used in the process according to the invention contains 1 to 30% by weight, preferably 5 to 20, particularly preferably 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 polysiloxanes containing carboxyl groups.
  • carboxyl-containing polysiloxanes are those which contain structural elements of the formulas I and II and optionally structural elements III a and / or III b.
  • the structural elements identified above are each arranged in such a way that Si-O-Si-O chains are formed.
  • the formation of Si-Si groups is theoretically possible, but plays a subordinate role in most cases.
  • R 1 is the same or different and independent of each other
  • CrC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; especially methyl;
  • C 6 -C 14 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1 -anthryl, 2-anthryl,
  • 9-anthryl 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
  • CC 4 alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy;
  • Mono-C 1 -C 4 alkylamino for example -NHCH 3 , -NHC 2 H 5 , -NH (CH 2 ) 2 CH 3 , -NH (CH 2 ) 3 CH 3 , -NH-CH (CH 3 ) 2 , NHC (CH 3 ) 3 ; Di-CrOralkylamino, -N (CH 3 ), -N (C 2 H 5 ) 2 , -N (CH 3 ) (C 2 H 5 ), -N [(CH 2 ) 2 CH 3 ] 2,
  • all R 1 are the same and each methyl.
  • the structural elements I are in each case identical, 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.
  • Z 1 means a direct bond
  • R 2 is the same or different and is independently selected from hydrogen
  • G -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 III a and / or III b can have a linear structure or have a cyclic or branched structure.
  • Branched polysiloxanes which contain the structural elements I, II and optionally III a and / or III b generally additionally contain structural elements, for example of the formula IV a or IV b A, / ° OOH
  • Cyclic unbranched polysiloxanes which contain the structural elements of the general formula I, II usually do not contain any structural elements of the formulas III a and III b.
  • the structural elements I, II, optionally IV a and IV b can be distributed alternately, in blocks and preferably randomly in polysiloxane molecules containing carboxyl groups.
  • garboxyl group-containing polysiloxanes contain 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 group-containing polysiloxanes with the structural elements I, II, optionally III a, III b, IV a and IV b is usually in the range from 5000 g to 150,000 g / mol, preferably 10,000 to 100,000 g / mol ,
  • the molecular weight can be determined by methods known to those skilled in the art, for example by light scattering methods or viscosity determinations.
  • all or at least a certain proportion, for example a third or half, of the carboxyl groups in the carboxyl group-containing polysiloxanes are neutralized.
  • basic salts such as hydroxides or carbonates of the alkali metals such as Na or K are suitable for neutralization.
  • Ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylene diamine, alkanolamines such as ethanol are also suitable for neutralization.
  • the mixtures used according to the invention contain, for example, 10 to 90% by weight of polysiloxane containing carboxyl groups, preferably 40 to 60% by weight and particularly preferably about 50% by weight of polysiloxane containing carboxyl groups.
  • the mixtures used according to the invention furthermore contain polysiloxanes which contain no carboxyl groups.
  • Such polysiloxanes generally contain structural elements of the formulas I mentioned above, optionally IM a, III b and IV a, the variables being defined as above, but R 1 is not equal to Z 1 - A 1 - COOH.
  • Carboxyl-free polysiloxanes used according to the invention are preferably constructed from structural elements of the formulas I, optionally III a, IM b and IV a, described above.
  • carboxyl-free polysiloxanes are poly (dimethyl) siloxanes and poly (phenylmethyl) siloxanes.
  • Carboxyl group-free polysiloxanes which contain the structural elements of the general formulas I and optionally IM 1, III b and IV a can 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 do not contain any structural elements of the formulas III a and IM b.
  • all R 1 in carboxyl-free polysiloxanes are the same and are each methyl.
  • the structural elements I in carboxyl group-free polysiloxanes are in each case the same, in which 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-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 carboxyl group-free polysiloxanes used with the structural elements I, II, optionally IM a, III b and IV a is usually in the range from 500 g to 150,000 g / mol, preferably up to 10,000 g / mol.
  • carboxyl group-containing and carboxyl group-free polysiloxane is selected such 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
  • the formulations used according to the invention contain one or more emulsifiers. Based on the formulation, 3 to 25% by weight, preferably 5 to 20 and particularly preferably 8 to 18% by weight, of one or more emulsifiers are, for example.
  • Particularly suitable emulsifiers are N-acylated amino acid derivatives, for example of the formula V.
  • R 3 is hydrogen
  • -C-C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, especially methyl;
  • C 6 -C 1 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1 -anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl; R 4 CC 4 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; especially methyl;
  • the group CO-R 5 is usually derived from saturated or unsaturated fatty acids.
  • Saturated fatty acids are to be understood as carboxylic acids with C 9 -C 20 alkyl groups, which can be linear, linear or branched, substituted or unsubstituted.
  • R 5 can 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 with 9 to 20 C atoms and one to 5 CC double bonds, the CC double bonds being, for example, isolated or allylic, for example the acyl radical of linoleic acid, linolenic acid, and very particularly preferably oleic acid.
  • all or at least a certain proportion, for example a third or half, of the carboxyl groups in N-acylated amino acid derivatives used as emulsifiers are neutralized.
  • basic salts such as hydroxides or carbonates of the alkali metals such as Na or K are suitable for neutralization.
  • Ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylene diamine, and very particularly alkanolamines such as are also suitable for neutralization for example ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyldiethanolamine or N- (n-butyl) diethanolamine.
  • N-stearyl sarcosine, N-lauroylsarcosine and N-isononanoylarcosine as well as the respective ethanol ammonium salts, diethanol ammonium salts and N-methyldiethanol ammonium salts.
  • sulfur-containing emulsifier is used.
  • sulfur-containing compounds which are surface-active in aqueous systems and can be nonionic, anionic, cationic or zwitterionic in nature can be used as sulfur-containing emulsifiers.
  • Compounds of the formula VI are particularly suitable
  • R 6 , R 7 are identical or preferably different and are selected from hydrogen
  • CrC 30 alkyl branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, se ⁇ -
  • C 6 -C 14 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1 -anthryl,
  • R 8 is selected from CrC 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and in particular hydrogen;
  • R 9 , R 10 are identical or preferably different and are selected from dC ⁇ -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, iso-heptyl, n-octyl, n-
  • R 9 preferably has two more C atoms than R 10 ; the combinations are preferred, for example
  • R 11 is selected from C r C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,
  • Phenyl, ortho-tolyl, meta-tolyl, para-tolyl and especially hydrogen are especially hydrogen.
  • radicals R 6 and R7 are hydrogen and the other radical is selected from C t -Cso-alkyl.
  • a mixture of several sulfur-containing compounds for example of the formula VI, is selected, which can differ, for example, in that in the first compound of the formula VI R 6 is hydrogen and R 7 is CrC- 30 - Alkyl is chosen and in the second R 6 is hydrogen and R 7 is selected from -C-C 30 alkyl.
  • all or at least a certain proportion, for example a third or half, of the sulfonyl groups in sulfur-containing compounds used as emulsifiers are neutralized.
  • basic salts such as hydroxides or carbonates of the alkali metals such as Na or K are suitable for neutralization.
  • Ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylene diamine, and very particularly alkanol are also suitable for neutralization.
  • amines such as ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, 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, mixtures of different sulfur-containing compounds can be used.
  • mixtures of different sulfur-containing compounds can be used.
  • formulations used in the process according to the invention can contain up to 40% by weight, preferably up to 20% by weight, based on the formulation, of at least one alcohol of the formula VII
  • formulations used in the process according to the invention can 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 can contain up to 40% by weight, particularly preferably up to 20% by weight, of mixtures which contain at least one alcohol of include general formula VIII; examples of such mixtures include oxo oil 135 and oxo oil 13.
  • the formulations used according to the invention are preferably 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 virgin or synthetic fat.
  • Examples of natural waxes are beeswax, cork wax, montan waxes or cama ⁇ ba wax.
  • Examples of synthetic waxes are polyethylene waxes or ethylene copolymer waxes, as are obtainable, for example, by radical polymerization of ethylene or radical copolymerization of ethylene with, for example, (meth) acrylic acid or by Ziegler-Natta catalysis.
  • Polyisobutylene waxes may also be mentioned.
  • Paraffin mixtures may also be mentioned; are below
  • paraffin mixtures which have 12 or more carbon atoms and usually have a melting point in the range from 25 to 45 ° C.
  • paraffin mixtures can be obtained, for example, in refineries or crackers and are known to those skilled in the art as paraffin gums and sasol waxes.
  • Another example of synthetic waxes are montan ester waxes.
  • natural oils are triglycerides which are liquid at room temperature, for example fish oil, cattle claw oil, olive oil, cottonseed oil, castor oil, sunflower oil and peanut oil.
  • synthetic oils are white oil, paraffin oil, functionalized paraffins such as chlorinated or sulfochlorinated paraffins, or also polyalkylene glycols, for example polyethylene glycol.
  • natural fats are native triglycerides, such as lanolin, shellac wax and mixtures thereof, which are solid at room temperature.
  • the further hydrophobic compound is at least one native triglyceride.
  • a combination of at least one native triglyceride which is solid or liquid at room temperature and a paraffin mixture having a melting point in the range from 25 to 40 ° C. are used.
  • the quantitative ratio is not critical per se; weight ratios of native triglyceride: paraffin mixture in the range from 10: 1 to 1:10 are suitable.
  • about 10 to 70, preferably 20 to 40% by weight of one or more further hydrophobic compounds, based on the formulation, can be used.
  • leather or fur skins are treated in a liquor before, during or after retanning with the formulations used according to the invention.
  • the treatment according to the invention can be carried out once or repeatedly.
  • the leather to be treated can be produced by any method, for example by mineral tanning, in particular chrome tanning, or by polymer tanning, tanning with syntans, resin tanning, tanning with vegetable tanning agents or tanning with combinations of the aforementioned 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 can preferably be 50 to 2000% by weight, preferably 100 to 400% by weight, based on the shaved weight of the leather or the wet weight of the fur skins.
  • the components carboxyl group-containing polysiloxane, carboxyl group-free polysiloxane and emulsifier are added separately to leather and / or leather and liquor and the formulation according to the invention is prepared in situ.
  • the process according to the invention is generally carried out by rolling the leather to be treated or the fur to be treated in 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 printing conditions of the method according to the invention are generally not critical. It is preferred to work at normal pressure (1 atm), but it is also possible to work at reduced pressure, for example 0.5 to 0.99 atm, or at elevated pressure, for example 1.01 to 2 atm.
  • the pH can be set in the range from 4 to 8, preferably 4.5 to 8.
  • the pH can be lowered to a pH of 3 to 5 by adding an acid, for example formic acid.
  • the treatment according to the invention is generally complete after a period of 20 minutes to 24 hours, preferably 30 minutes to 12 hours. If the treatment is carried out repeatedly, one speaks in the context of the present invention of treatment steps according to the invention.
  • the amount of the formulation used according to the invention can be 0.1 to 20% by weight, in particular 0.5 to 15% by weight, based on the shaved weight of the leather to be treated or the wet weight of the fur to be treated.
  • Conventional leather dyes can be added to the liquor during the treatment according to the invention.
  • Examples include acidic, nouns or basic aniline dyes that can be used in tannery-usual amounts.
  • tanning agents customary in tanning for example mineral tanning agents, in particular chrome tanning agents, or polymer tanning agents, syntans, resin tanning agents, vegetable tanning agents or combinations of the aforementioned tanning agents
  • Organic solvents such as alcohols can be added during the treatment according to the invention. However, it is preferred to work without the addition of organic solvents.
  • the treatment according to the invention can be supplemented by post-treatment with tanning agents customary in the tannery, 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 aforementioned tanning agents.
  • tanning agents customary in the tannery 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 aforementioned tanning agents.
  • the leather or fur skins obtained according to the invention can be worked up as usual in terms of preparation technology.
  • the present invention further relates to leather produced by the process according to the invention.
  • Leather produced by the process according to the invention are distinguished by very good usage properties, for example by very good hydrophobicity, very good grip and excellent level coloring.
  • Another object of the present invention is the use of the leather according to the invention for the production of articles of clothing, for example jackets, coats, shoes and in particular boots.
  • Another object of the present invention is the use of the leather according to the invention for the production of furniture and furniture parts, for example 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 car parts, for example 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.
  • the present invention further provides formulations comprising
  • the formulations according to the invention are formulations which are characterized by It is net that the carboxyl-containing polysiloxanes are polysiloxanes which contain the structural elements of the formulas I, II and optionally III a and III b.
  • the carboxyl group-containing polysiloxanes contained in formulations according to the invention can furthermore contain structural elements of the general formulas IV a and IV b.
  • the carboxyl-free polysiloxanes contained in the formulations according to the invention are those polysiloxanes which generally contain structural elements of the formulas I mentioned above and optionally IM a, IM b and IV a, the variables as above are defined standing.
  • Preferred carboxyl group-free polysiloxanes contained in the formulations according to the invention are comprised of structural elements of the formulas I mentioned above and optionally built up IM a, IM b and / or IV a.
  • all emulsifiers in the formulations according to the invention which can be mentioned are all compounds which are surface-active in aqueous systems and which can be nonionic, anionic, cationic or else zwitterionic in nature.
  • Particularly suitable emulsifiers are N-acylated amino acid derivatives, for example of the formula V, in which the variables are defined as above.
  • emulsifiers are sulfur-containing emulsifiers.
  • sulfur-containing emulsifiers in the formulations according to the invention can be all sulfur-containing compounds which are surface-active in aqueous systems and which can be nonionic, anionic, cationic or also zwitterionic in nature.
  • Particularly suitable emulsifiers are sulfur-containing compounds, for example of the formula VI, in which the variables are defined as above.
  • the formulations according to the invention are formulations which are characterized in that they contain 10 to 70% by weight, based on the formulation, of at least one further hydrophobic compound.
  • further hydrophobic compounds are a combination of at least one natural triglyceride which is solid or liquid at room temperature and a paraffin mixture.
  • the formulations according to the invention can have a pH of 7 or more. They preferably have a pH in the range from 7 to a maximum of 10.
  • the formulations according to the invention can preferably be aqueous formulations with a solids content of up to 50% by weight, based on the entire formulation.
  • formulations according to the invention have very good storage stability.
  • formulations according to the invention can be used excellently in the process according to the invention.
  • Another object of the present invention is a process for the preparation of the formulations according to the invention, hereinafter also called the production process according to the invention.
  • the production process according to the invention can generally be carried out by mixing the components carboxyl-free polysiloxane, carboxyl-containing polysiloxane and one or more emulsifiers and, if appropriate, hydrophobic compound or hydrophobic compounds.
  • the order in which the individual components are added is not critical. This can be done, for example, by simply stirring the components together, for example with a mixer or an Ultra-Thurax stirrer. In some cases further homogenization takes place, e.g. with a gap homogenizer. Formulations according to the invention which are particularly stable in storage are obtained if a further homogenization is carried out.
  • Emulsifier N-oleyl sarcosine as sodium salt, commercially available from BASF Aktiengesellschaft.
  • Native triglyceride Lipoderm oil, a bovine claw oil.
  • Synthetic oil Paraffingatsch 36/38, commercially available from Shell and from Total-Fina.
  • the formulations according to the invention 1.1. up to 1.4 as well as formulations V 1.5 and V 1.6 for comparative experiments.
  • the composition of the formulations is shown in Table 1.
  • Example 2.1 Treatment of leather with the formulations 1.1 according to the invention
  • the following general recipe was used.
  • the data in% by weight relate in each case to the fold weight, unless stated otherwise.
  • the barrel was rotated about 10 times a minute unless otherwise stated.
  • the leather was then mixed with 3% by weight with the following characteristic data:
  • the first treatment step 2% by weight of formulation 1.1 was added and drummed for a further 30 minutes. Then 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, were added within 10 minutes. 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. Treatment was continued for one hour.
  • the liquor was drained and the leather was washed twice with 200% by weight of water at a temperature of 40 ° C.
  • the top was then mixed with 100% by weight of water and commercially at a temperature of 40 ° C. with a mixture of 0.2% by weight of Leather Black VM and 0.3% by weight of the leather dye Luganil® Black AS available from BASF Aktiengesellschaft, as well as 0.2% by weight formic acid at pH 3.6.
  • the fleet was then drained off. sen, mixed with 100 wt .-% water and treated with 3 wt .-% Cr (III) sulfate at a pH of 3.5.
  • Example 1 was repeated, but formulation 1.2 instead of 1.1 was used in the first and in the second treatment step.
  • the leather 3.2 according to the invention was obtained.
  • Example 1 was repeated, but formulation 1.3 instead of 1.1 was used in the first and in the second treatment step.
  • the invention was obtained
  • Example 1 was repeated, but formulation 1.4 instead of 1.1 was used in the first and in the second treatment step.
  • the leather 3.4 according to the invention was obtained.
  • Example 1 was repeated, but 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 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.
  • the measurement measurements were carried out with a measurement tester according to ASTM D 2099 as double determinations.
  • the static water absorption was carried out at 15% compression and stated in% by weight, based on the finished leather.
  • the color was assessed by optical inspection by a team of volunteers. The ratings were given as in school: 1 (very good) to 6 (unsatisfactory)
  • the monoester thus obtainable was cooled to 40 ° C. and stirred into 210 ml of water, partially neutralized by adding 17 g (0.21 mol) of 50% by weight aqueous NaOH and the mixture obtained was heated to 80 ° C. Then 28.5 g Sodium disulfite was added and the mixture was further stirred at 80 ° C. for 6 hours. The mixture was then cooled to 40 ° C.
  • Carboxyl group-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, statistical average 127 structural elements I and 2 to 3 structural elements II per molecule, structural elements II statistically distributed.
  • 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.
  • Native triglyceride Lipoderm oil, a bovine claw oil.
  • Synthetic oil Paraffingatsch 36/38, commercially available from Shell and from Total-Fina.
  • the mixture thus obtainable was then homogenized using a SHL 105 gap homogenizer from Brau and Luebbe, a pressure of 150 bar and a temperature of 50 ° C. being selected.
  • Formulation 5.1 according to the invention was obtained.
  • the procedure for preparing the formulations 5.2 and 5.3 according to the invention and the comparative formulations V 5.4 to V 5.5 was analogous, but each Weil selected compositions according to Table 3.
  • the composition of the formulations is shown in Table 3.
  • Example 5.1 was repeated for example 5.6, but with 25 g of sulfur-containing emulsifier E 4.2 instead of E 4.1.
  • the following general recipe was used.
  • the data in% by weight relate in each case to the case weight, unless stated otherwise.
  • the barrel was rotated about 10 times a minute unless otherwise stated.
  • the leather was then mixed with 3% by weight of polymer with the following characteristic data: 30% by weight aqueous polymer solution partially neutralized with NaOH; Homopolymer of methacrylic acid, M n approx. 10,000; K value according to Fikentscher: 12, viscosity of the 30 wt.% Solution: 65 mPa-s (DIN EN ISO 3219, 23 ° C), pH 5.1.
  • the first treatment step 10% by weight of formulation 5.1 was added and drummed for a further 30 minutes. Then 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, were added within 10 minutes. 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 sulfonic tanning agent from EP-B 0459 168, example Kl, were added. Treatment was continued for one hour.
  • the liquor was drained and the leather was washed twice with 200% by weight of water at a temperature of 40 ° C.
  • the top was then mixed with 100% by weight of water and at a temperature of 40 ° C. with a mixture of 0.2% by weight of Leather Black VM and 0.3% by weight of the leather dye Luganil® Black AS , commercially available from BASF Aktiengesellschaft, and 0.2% by weight of formic acid at a pH of 3.6.
  • the liquor was then drained off, mixed 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, formulations 5.2 to 5.3, V 5.4 and V 5.5 were used instead of 5.1.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne un procédé d'imperméabilisation de cuirs et de pelleteries, caractérisé en ce que du cuir ou une pelleterie est traité(e), avant, pendant ou après le processus de tannage, au moyen d'une ou de plusieurs formulation(s) contenant 1 à 30 % en poids, par rapport à la formulation, d'un mélange de polysiloxanes, comprenant : 10 à 90 % en poids, par rapport au mélange, d'un ou plusieurs polysiloxane(s) contenant des groupes carboxyle ; 90 à 10 % en poids, par rapport au mélange, d'un ou plusieurs polysiloxane(s) exempt(s) de groupes carboxyle, et ; 3 à 25 % en poids, par rapport à la formulation, d'au moins un émulsifiant.
EP04705767.4A 2003-02-17 2004-01-28 Procede d'impermeabilisation de cuirs et de pelleteries Expired - Lifetime EP1597402B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
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

Publications (2)

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EP1597402A1 true EP1597402A1 (fr) 2005-11-23
EP1597402B1 EP1597402B1 (fr) 2019-06-26

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US (1) US20060096036A1 (fr)
EP (1) EP1597402B1 (fr)
BR (1) BRPI0406655B1 (fr)
ES (1) ES2743434T3 (fr)
WO (1) WO2004072307A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022154662A1 (fr) 2021-01-18 2022-07-21 Stahl International B.V. Composition et procédé d'imperméabilisation de cuir

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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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Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2004072307A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022154662A1 (fr) 2021-01-18 2022-07-21 Stahl International B.V. Composition et procédé d'imperméabilisation de cuir
NL2027334B1 (en) 2021-01-18 2022-07-25 Stahl Int B V Composition and process for waterproofing leather

Also Published As

Publication number Publication date
ES2743434T3 (es) 2020-02-19
EP1597402B1 (fr) 2019-06-26
US20060096036A1 (en) 2006-05-11
WO2004072307A1 (fr) 2004-08-26
BRPI0406655B1 (pt) 2013-07-16
BRPI0406655A (pt) 2005-12-06

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