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EP1597402B1 - Method for hydrophobing leather and furskins - Google Patents

Method for hydrophobing leather and furskins 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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EP
European Patent Office
Prior art keywords
polysiloxanes
carboxyl group
structural elements
formulation
free
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.)
Expired - Lifetime
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EP04705767.4A
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German (de)
French (fr)
Other versions
EP1597402A1 (en
Inventor
Ralph Lunkwitz
Peter Danisch
Thorsten RÄDLER
Werner Janson
Friedrich Sattler
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Stahl International BV
Original Assignee
Stahl International BV
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Filing date
Publication date
Priority claimed from DE2003106748 external-priority patent/DE10306748A1/en
Priority claimed from DE2003132991 external-priority patent/DE10332991A1/en
Application filed by Stahl International BV filed Critical Stahl International BV
Publication of EP1597402A1 publication Critical patent/EP1597402A1/en
Application granted granted Critical
Publication of EP1597402B1 publication Critical patent/EP1597402B1/en
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

  • 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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  • 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)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Hydrophobierung von Leder und Pelzfellen, dadurch gekennzeichnet, dass man Leder oder Pelzfelle vor, während oder nach der Nachgerbung mit einer oder mehreren Formulierungen behandelt, enthaltend 1 bis 30 Gew.-%, bezogen auf die Formulierung, eines Gemisches von Polysiloxanen, enthaltend
10 bis 90 Gew.-%, bezogen auf das Gemisch, an einem oder mehreren Carboxylgruppen-haltigen Polysiloxanen,
90 bis 10 Gew.-%, bezogen auf das Gemisch, an einem oder mehreren Carboxylgruppen-freien Polysiloxanen,

  • und 3 bis 25 Gew.-%, bezogen auf die Formulierung, mindestens eines Emulgators
  • wobei
  • es sich bei den Carboxylgruppen-haltigen Polysiloxanen um solche Polysiloxane handelt, die Strukturelemente der Formeln I, II und optional III a und III b
    Figure imgb0001
     enthalten, in denen die Variablen wie folgt definiert sind:
    • R1 ist gleich oder verschieden und unabhängig voneinander Wasserstoff, Hydroxyl, C1-C4-Alkyl, C6-C14-Aryl, C1-C4-Alkoxy, Amino, Mono- C1-C4-Alkyl-amino, Di-C1-C4-Alkylamino, oder Z1-A1-COOH;
    • A1 gleich oder verschieden und lineares oder verzweigtes C5-C25-Alkylen,
    • Z1 eine direkte Bindung, Sauerstoff oder eine Amino-, Carbonyl-, Amido- oder Estergruppe bedeutet
      und wobei
    • das oder die Carboxylgruppen-freien Polysiloxane linear oder cyclisch oder verzweigt sind und aus Strukturelementen der Formeln sowie optional IIIa, IIIb und/oder IVa aufgebaut sind,
      Figure imgb0002
       worin R1 gleich oder verschieden und unabhängig voneinander Wasserstoff, Hydroxyl, C1-C4-Alkyl, C6-C14-Aryl, C1-C4-Alkoxy ist, wobei
      • lineare Carboxylgruppen-freie Polysiloxane aus Strukturelementen der Formeln I, IIIa und/ oder IIIb bestehen,
      • cyclische Carboxylgruppen-freie Polysiloxane aus Strukturelementen der Formel I bestehen,
      • verzweigte Carboxylgruppen-freie Polysiloxane aus Strukturelementen der Formeln I, IVa, IIIa und/ oder IIIb bestehen,
The present invention relates to a process for the hydrophobization of leather and fur skins, characterized in that treating leather or fur skins before, during or after the retanning with one or more formulations containing 1 to 30 wt .-%, based on the formulation, one 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 .-%, based on the formulation, of at least one emulsifier
  • in which
  • it is in the carboxyl-containing polysiloxanes are such polysiloxanes, the structural elements of the formulas I, II and optionally III a and III b
    Figure imgb0001
     in which the variables are defined as follows:
    • R 1 is identical or different and independently of one another hydrogen, hydroxyl, C 1 -C 4 -alkyl, C 6 -C 14 -aryl, C 1 -C 4 -alkoxy, amino, mono-C 1 -C 4 -alkyl-amino , Di-C 1 -C 4 -alkylamino, or Z 1 -A 1 -COOH;
    • A 1 is identical or different and linear or branched C 5 -C 25 -alkylene,
    • Z 1 represents a direct bond, oxygen or an amino, carbonyl, amido or ester group
      and where
    • the carboxyl group-free or polysiloxanes are linear or cyclic or branched and are composed of structural elements of the formulas and optionally IIIa, IIIb and / or IVa,
      Figure imgb0002
       wherein R 1 is the same or different and independently of one another hydrogen, hydroxyl, C 1 -C 4 alkyl, C 6 -C 14 aryl, C 1 -C 4 alkoxy, wherein
      • linear carboxyl group-free polysiloxanes consist of structural elements of the formulas I, IIIa and / or IIIb,
      • consist of cyclic carboxyl-free polysiloxanes of structural elements of the formula I,
      • branched carboxyl group-free polysiloxanes consist of structural elements of the formulas I, IVa, IIIa and / or IIIb,

Aus EP 0 213 480 B ist ein Verfahren zur Hydrophobierung von Leder und Pelzfellen bekannt, bei dem man eine wässrige Emulsion eines Silikonöls oder ein wasserfreies Gemisch aus einem Silikonöl und eines Alkanolaminsalzes einer Aminosäure vor, während oder nach der Nachgerbung auf Leder oder Pelze einwirken lässt. Als Polysiloxane sind beispielsweise genannt: Dimethylpolysiloxan, bei dem 3 % der Methylgruppen durch Mercaptopropyl ersetzt sind (Beispiele 1 bis 7), Dimethylpolysiloxan mit einer Viskosität von 80 bis 110 mPa·s, Phenylmethylpolysiloxane mit einer Viskosität von 85 bis 120 mPa·s, sowie Dimethylpolysiloxane mit durchschnittlich 2 bis 10 Carboxylgruppen pro Molekül. Die Gebrauchseigenschaften derartiger Hydrophobierzubereitungen lassen sich jedoch noch verbessern. Auch lassen sich die mit Hilfe der offenbarten Polysiloxane hergestellten Leder in einigen Fällen noch hinsichtlich ihrer Gebrauchseigenschaften verbessern.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. Examples of 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. However, the performance characteristics of such hydrophobing formulations can be improved. In addition, the leathers produced with the aid of the disclosed polysiloxanes can in some cases be improved in terms of their performance properties.

Aus WO 95/22627 ist ein Verfahren zur Hydrophobierung von Leder und Pelzfellen unter Verwendung von carboxylgruppenhaltigen Polysiloxanen in wässriger Emulsion bekannt, bei denen kammartig verzweigte Polysiloxane eingesetzt werden, welche die Formel A haben können:

Figure imgb0003
Out 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:
Figure imgb0003

Dabei können die Struktureinheiten beispielsweise statistisch verteilt sein. Die Variablen sind wie folgt definiert:

  • R ist gleich oder verschieden und unabhängig voneinander Wasserstoff, Hydroxyl, C1-C4-Alkyl, Phenyl, C1-C4-Alkoxy, Amino, Mono- oder Di-C1-C4-Amino,Chlor oder Fluor, wobei an den Kettenenden jeweils auch ein Rest R für die Gruppierung Z-A-COOH stehen kann;
  • A ist eine lineare oder verzweigte C5-C25-Alkylengruppe,
  • Z ist eine direkte Bindung, ein Sauerstoffatom oder eine Amino- Carbonyl-, Amido- oder Estergruppe.
The structural units may be distributed statistically, for example. The variables are defined as follows:
  • R is identical or different and independently of one another hydrogen, hydroxyl, C 1 -C 4 -alkyl, phenyl, C 1 -C 4 -alkoxy, amino, mono- or di-C 1 -C 4 -amino, chlorine or fluorine, where at the chain ends in each case a radical R may stand for the group ZA-COOH;
  • A is a linear or branched C 5 -C 25 -alkylene group,
  • Z is a direct bond, an oxygen atom or an amino carbonyl, amido or ester group.

Pro Molekül sind im Durchschnitt vorzugsweise 2,5 bis 15 Carboxylgruppen vorhanden (Seite 4, Zeile 17).On average, preferably 2.5 to 15 carboxyl groups are present per molecule (page 4, line 17).

Mit Hilfe derartiger kammartiger Polysiloxane behandelte Leder und Pelzfelle weisen im Allgemeinen eine sehr gute Hydrophobie auf.Leather and fur skins treated with the aid of comb-type polysiloxanes generally have a very good hydrophobicity.

Aus WO 98/04748 ist ein Verfahren zum Nachgerben von mit polymeren Gerbstoffen und gegebenenfalls Aldehydgerbstoffen hergestellten Ledern bekannt, die mit Polymergerbstoffen und mit kammartigen Polysiloxanen der oben bezeichneten Formel A behandelt werden.Out 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.

Aus EP-A 1 087 021 ist bekannt, dass Lederbehandlungsmittel, enthaltend eine Kombination aus einem mit Carbonsäure- oder Carbonsäureanhydrid-Gruppen an α,ω-Position substituierte Polysiloxane, wobei die Carboxylgruppen des Polysiloxans in neutralisierter Form vorliegen, mit bestimmten amphiphilen Polymeren, einem Emulgator und einem Öl oder Wachs, als Lederbehandlungsmittel geeignet sind. Mit Hilfe der offenbarten Kombinationsprodukte wurden volle und weiche Leder hergestellt, die gut waschbar waren.Out 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 α, ω-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.

Es wird jedoch beobachtet, dass nach den vorstehend zitierten Schriften erhaltene Leder und Pelzfelle in vielen Fällen eine unerwünscht unegale Färbung aufweisen. Außerdem ist der hohe Preis der kammartig verzweigten Polysiloxane als nachteilig zu betrachten.
Es bestand also die Aufgabe, ein Verfahren zur Herstellung von Leder und Pelzfellen bereitzustellen, welches die oben aufgeführten Nachteile nicht aufweist. Weiterhin bestand die Aufgabe, Leder mit vorteilhaften Anwendungseigenschaften bereit zu stellen. Weiterhin bestand die Aufgabe, neue Formulierungen mit vorteilhaften Anwendungseigenschaften bereit zu stellen.It is observed, however, that leathers and fur skins obtained according to the above-cited documents in many cases have an undesirably unlevered color. In addition, the high price of comb-branched polysiloxanes is to be regarded as disadvantageous.
It was therefore the object to provide a process for the production of leather and fur skins, which does not have the disadvantages listed above. Furthermore, the object was to provide leather with advantageous application properties. Furthermore, the object was to provide new formulations with advantageous application properties.

Demgemäß wurde eingangs definiertes Verfahren gefunden. Erfindungsgemäß behandelt man Leder vor, während oder nach der Nachgerbung mit einer Formulierung.Accordingly, the method defined above has been found. According to the invention, leather is treated before, during or after the retanning with a formulation.

Mindestens eine im erfindungsgemäßen Verfahren eingesetzte Formulierung enthält 1 bis 30 Gew.-%, bevorzugt 5 bis 20, besonders bevorzugt 7 bis 12,5 Gew.-%, bezogen auf das Gewicht der Formulierung, eines Gemisches aus zwei oder mehr Polysiloxanen.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.

10 bis 90 Gew.-%, bezogen auf das Gemisch, der in mindestens einer Formulierung enthaltenen Polysiloxane sind Carboxylgruppen-haltige Polysiloxane, die Strukturelemente der Formeln I, II und optional IIIa und IIIb enthalten.10 to 90% by weight, based on the mixture, of the 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.

Die oben bezeichneten Strukturelemente sind jeweils so angeordnet, dass Si-O-Si-O-Ketten gebildet werden. Die Bildung von Si-Si-Gruppen ist theoretisch möglich, spielt aber in den meisten Fällen eine untergeordnete Rolle.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.

In den Formeln I, II, III a und III b sind die Variablen wie folgt definiert:

  • R1 ist gleich oder verschieden und unabhängig voneinander
  • Wasserstoff,
  • Hydroxyl,
  • C1-C4-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl; insbesondere Methyl;
  • C6-C14-Aryl, beispielsweise Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl, 9-Anthryl, 1-Phenanthryl, 2-Phenanthryl, 3-Phenanthryl, 4-Phenanthryl und 9-Phenanthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl; C1-C4-Alkoxy, wie Methoxy, Ethoxy, n-Propoxy, iso-Propoxy, n-Butoxy, iso-Butoxy, sec.-Butoxy, tert.-Butoxy;
  • Amino,
  • Mono-C1-C4-Alkylamino, beispielsweise -NHCH3, -NHC2H5, -NH(CH2)2CH3, -NH(CH2)3CH3, -NH-CH(CH3)2, NHC(CH3)3;
  • Di-C1-C4-Alkylamino, -N(CH3)2, -N(C2H5)2, -N(CH3)(C2H5), -N[(CH2)2CH3]2, -N(CH3)CH(CH3)2,
  • oder Z1-A1-COOH.
In formulas I, II, III a and III b, the variables are defined as follows:
  • R 1 is the same or different and independent of each other
  • Hydrogen,
  • hydroxyl,
  • C 1 -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 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, more preferably phenyl; C 1 -C 4 alkoxy, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy;
  • amino,
  • 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-C 1 -C 4 -alkylamino, -N (CH 3 ) 2 , -N (C 2 H 5 ) 2 , -N (CH 3 ) (C 2 H 5 ), -N [(CH 2 ) 2 CH 3 ] 2 , -N (CH 3 ) CH (CH 3 ) 2 ,
  • or Z 1 -A 1 -COOH.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind alle R1 gleich und jeweils Methyl.In a preferred embodiment of the present invention, all R 1 are the same and are each methyl.

In einer anderen bevorzugten Ausführungsform sind die Strukturelemente I jeweils gleich, wobei in I jeweils ein R1 gleich Methyl und das andere R1 Phenyl ist.In another preferred embodiment, 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.

In einer Ausführungsform der vorliegenden Erfindung sind die Strukturelemente der Formel III a ausgewählt aus den folgenden Gruppen: Si(CH3)3, Si(CH3)2C6H5, Si(CH3)2OH, Si(CH3)C6H5OH.In one embodiment of the present invention, 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.

A1 gleich oder verschieden und lineares oder verzweigtes C5-C25-Alkylen, unsubstituiert oder substituiert mit einem oder mehreren C1-C4-Alkyl oder Phenyl, beispielsweise -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2)10-, -(CH2)11-, -(CH2)12-, -(CH2)13-, -(CH2)14-, -CH(CH3)-CH2-CH2-CH2-CH(CH3)-,-C(CH3)2-CH2-CH2-CH2-CH(CH3)-; -CH(C6H5)-CH2-CH2-CH2-CH(CH3)-; vorzugsweise -(CH2)8-, -(CH2)9-, -(CH2)10-, -(CH2)11-, -(CH2)12-;
wobei C5-C25-Alkylen durch 1 bis 8 nicht direkt miteinander verbundene O-Atome unterbrochen sein kann.
Z1 bedeutet
eine direkte Bindung,
Sauerstoff
Aminogruppe der Formel -NR2-
Carbonylgruppe,
Amidogruppe der Formel -NR2-CO- oder -CO-NR2- oder
Estergruppe der Formel CO-O oder O-CO;
R2 ist gleich oder verschieden und unabhängig voneinander gewählt aus
Wasserstoff,
C1-C4-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.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 (CH 3 ) -; -CH (C 6 H 5 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -; preferably - (CH 2 ) 8 -, - (CH 2 ) 9 -, - (CH 2 ) 10 -, - (CH 2 ) 11 -, - (CH 2 ) 12 -;
where C 5 -C 25 -alkylene can be interrupted by 1 to 8 not directly connected O atoms.
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.

Polysiloxane, welche die Strukturelemente der allgemeinen Formeln I, II sowie optional III a und/oder III b enthalten, können linear aufgebaut sein oder cyclische oder verzweigte Struktur haben. Verzweigte Polysiloxane, welche die Strukturelemente I, II sowie optional IIIa und/oder III b enthalten, enthalten im Allgemeinen zusätzlich Strukturelemente beispielsweise der Formel IV a oder IV b

Figure imgb0004
in denen die Variablen wie oben stehend definiert sind. Cyclische unverzweigte Polysiloxane, welche die Strukturelemente der allgemeinen Formel I, II enthalten, enthalten üblicherweise keine Strukturelemente der Formeln III a und III b.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
Figure imgb0004
 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.

Die Strukturelemente I, II, optional IV a und IV b können alternierend, blockweise und bevorzugt statistisch in Carboxylgruppen-haltigen Polysiloxanmolekülen verteilt sein.The structural elements I, II, optionally IV a and IV b may be distributed alternately, blockwise and preferably randomly in carboxyl-containing polysiloxane molecules.

In einer Ausführungsform der vorliegenden Erfindung enthalten Carboxylgruppen-haltige Polysiloxane im Bereich von 1 bis 50, bevorzugt 2 bis 25, besonders bevorzugt im Mittel 2,5 bis 15 Carboxylgruppen pro Molekül.In one embodiment of the present invention, 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.

Üblicherweise liegt das Molekulargewicht Mw der erfindungsgemäß eingesetzten Carboxylgruppen-haltigen Polysiloxane mit den Strukturelementen I, II, optional III a, III b, IV a und IV b im Bereich von 5000 g bis 150.000 g/mol, bevorzugt 10000 bis 100.000 g/mol.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 ,

Die Molekulargewichtsbestimmung kann durch dem Fachmann bekannte Methoden durchgeführt werden, beispielsweise durch Lichtstreuungsmethoden oder Viskositätsbestimmungen.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.

In einer Ausführungsform der vorliegenden Erfindung sind alle oder zumindest ein gewisser Anteil, beispielsweise ein Drittel oder die Hälfte, der Carboxylgruppen in den Carboxylgruppen-haltigen Polysiloxanen neutralisiert. Zur Neutralisation eignen sich beispielsweise basische Salze wie Hydroxide oder Carbonate der Alkalimetalle wie beispielsweise Na oder K. Zur Neutralisation eignen sich weiterhin Ammoniak, Alkylamine wie beispielsweise Methylamin, Dimethylamin, Trimethylamin, Ethylamin, Diethylamin, Triethylamin, Ethylendiamin, Alkanolamine wie beispielsweise Ethanol-amin, Diethanolamin, Triethanolamin, N-Methyl-Ethanolamin, N-Methyldiethanolamin oder N-(n- Butyl)-diethanolamin.In one embodiment of the present invention, 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.

Die erfindungsgemäß eingesetzten Gemische enthalten beispielsweise 10 bis 90 Gew.-% Carboxylgruppen-haltiges Polysiloxan, bevorzugt 40 bis 60 Gew.-% und besonders bevorzugt etwa 50 Gew.-% Carboxylgruppen-haltiges Polysiloxan.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.

Die erfindungsgemäß eingesetzten Gemische enthalten weiterhin Polysiloxane, die keine Carboxylgruppen enthalten. Derartige Polysiloxane enthalten Strukturelemente der oben bezeichneten Formeln I, optional III a, III b und IV a, wobei die Variablen wie oben stehend definiert sind, aber R1 nicht gleich Z1 - A1- COOH ist. Bevorzugt sind erfindungsgemäß eingesetzte Carboxylgruppen-freie Polysiloxane aus Strukturelementen der oben bezeichneten Formeln I, optional III a, III b und IV a aufgebaut.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. Preferably, 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.

Besonders bevorzugt eingesetzte Carboxylgruppen-freie Polysiloxane sind Poly(dimethyl)siloxane und Poly(phenylmethyl)siloxane.Particularly preferably used carboxyl-free polysiloxanes are poly (dimethyl) siloxanes and poly (phenylmethyl) siloxanes.

Carboxylgruppen-freie Polysiloxane, welche die Strukturelemente der allgemeinen Formeln I sowie optional III a, III b und IV a enthalten, können linear aufgebaut sein oder cyclische oder verzweigte Struktur haben. Verzweigte Carboxylgruppen-freie Polysiloxane, welche die Strukturelemente I sowie optional III a und/oder III b enthalten, enthalten im Allgemeinen zusätzlich Strukturelemente beispielsweise der Formel IV a. Cyclische unverzweigte Carboxylgruppen-freie Polysiloxane, welche die Strukturelemente der allgemeinen Formel I enthalten, enthalten üblicherweise keine Strukturelemente der Formeln III a und III b.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. Branched carboxyl-free polysiloxanes which contain the structural elements I and optionally III a and / or III b, generally additionally contain structural elements, for example of the formula IV a. 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.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind alle R1 in Carboxylgruppen-freien Polysiloxanen gleich und jeweils Methyl.In a preferred embodiment of the present invention, all R 1 in carboxyl group-free polysiloxanes are the same and are each methyl.

In einer anderen bevorzugten Ausführungsform sind die Strukturelemente I in Carboxylgruppen-freien Polysiloxanen jeweils gleich, wobei in I jeweils ein R1 gleich Methyl und das andere R1 Phenyl ist.In another preferred embodiment, 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.

In einer Ausführungsform der vorliegenden Erfindung sind die Strukturelemente der Formel III a in Carboxylgruppen-freien Polysiloxanen ausgewählt aus den folgenden Gruppen: Si(CH3)3, Si(CH3)2C6H5, Si(CH3)2OH, Si(CH3)C6H5OH.In one embodiment of the present invention, 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.

Üblicherweise liegt das Molekulargewicht Mw der erfindungsgemäß eingesetzten Carboxylgruppen-freien Polysiloxane mit den Strukturelementen I, II, optional III a, III b und IV a im Bereich von 500 g bis 150.000 g/mol, bevorzugt bis 10.000 g/mol.Usually 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.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung wählt man Carboxylgruppen-haltiges und Carboxylgruppen-freies Polysiloxan so aus, dass das Molekulargewicht des Carboxylgruppen-haltigen Polysiloxans höher ist als das Molekulargewicht des Carboxylgruppen-freien Polysiloxans.In a preferred embodiment of the present invention, 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.

Die erfindungsgemäß eingesetzten Gemische enthalten beispielsweise 10 bis 90 Gew.-% Carboxylgruppen-freies Polysiloxan, bevorzugt 40 bis 60 Gew.-% und besonders bevorzugt etwa 50 Gew.-% Carboxylgruppen-freies Polysiloxan.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.

Die erfindungsgemäß eingesetzten Formulierungen enthalten einen oder mehrere Emulgatoren. Bezogen auf die Formulierung, sind beispielsweise 3 bis 25 Gew.-%, bevorzugt 5 bis 20 und besonders bevorzugt 8 bis 18 Gew.-% eines oder mehrerer Emulgatoren.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.

Als Emulgatoren können im Prinzip alle in wässrigen Systemen oberflächenaktiven Verbindungen eingesetzt werden, die nichtionischer, anionischer, kationischer oder auch zwitterionischer Natur sein können.As 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.

Besonders gut geeignete Emulgatoren sind N-acylierte Aminosäurederivate beispielsweise der Formel V

Figure imgb0005
in denen die Variablen wie folgt definiert sind:

  • R3 Wasserstoff,
    C1-C4-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, insbesondere Methyl;
    C6-C14-Aryl, beispielsweise Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl, 9-Anthryl, 1-Phenanthryl, 2-Phenanthryl, 3-Phenanthryl, 4-Phenanthryl und 9-Phenanthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl;
  • R4 C1-C4-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl; insbesondere Methyl;
Particularly suitable emulsifiers are N-acylated amino acid derivatives, for example of the formula V.
Figure imgb0005
 where the variables are defined as follows:
  • R 3 is hydrogen,
    C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, in particular 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, more preferably phenyl;
  • R 4 is C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; especially methyl;

Die Gruppe CO-R5 ist üblicherweise von gesättigten oder ungesättigten Fettsäuren abgeleitet. Unter gesättigten Fettsäuren sind Carbonsäuren mit C9-C20-Alkyl-gruppen zu verstehen, die linear linear oder verzweigt sein können, substituiert oder unsubstituiert. R5 kann beispielsweise sein: n-Nonyl, n-Decyl, n-Dodecyl, n-Tetradecyl, n-Pentadecyl, n-Octadecyl, n-Eicosyl.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-R5 kann von einer ungesättigten Fettsäure mit 9 bis 20 C-Atomen und einer bis 5 C-C-Doppelbindungen abgeleitet sein, wobei die C-C-Doppelbindungen beispielsweise isoliert oder allylisch sein können, beispielsweise der Acylrest der Linolsäure, der Linolensäure, und ganz besonders bevorzugt der Ölsäure.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.

In einer Ausführungsform der vorliegenden Erfindung sind alle oder zumindest ein gewisser Anteil, beispielsweise ein Drittel oder die Hälfte, der Carboxylgruppen in als Emulgatoren eingesetzten N-acylierten Aminosäurederivaten neutralisiert. Zur Neutralisation eignen sich beispielsweise basische Salze wie Hydroxide oder Carbonate der Alkalimetalle wie beispielsweise Na oder K. Zur Neutralisation eignen sich weiterhin Ammoniak, Alkylamine wie beispielsweise Methylamin, Dimethylamin, Trimethylamin, Ethylamin, Diethylamin, Triethylamin, Ethylendiamin, und ganz besonders Alkanolamine wie beispielsweise Ethanolamin, Diethanolamin, Triethanolamin, N-Methyl-Ethanolamin, N-Methyldiethanolamin oder N-(n-Butyl)-diethanolamin.In one embodiment of the present invention, 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. For neutralization are, for example, basic salts such as hydroxides or carbonates of alkali metals such as Na or K. For neutralization are also suitable ammonia, 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.

Als beispielhafte Vertreter für Verbindungen der Formel V seien N-Oleylsarcosin, N-Stearylsarcosin, N-Lauroylsarcosin und N-Isononanoylarcosin sowie die jeweiligen Ethanolammoniumsalze, Diethanolammoniumsalze sowie N-Methyldiethanolammoniumsalze genannt.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.

In einer Ausführungsform der vorliegenden Erfindung setzt man Schwefel-haltigen Emulgator ein.In one embodiment of the present invention, sulfur-containing emulsifier is used.

Als Schwefel-haltige Emulgatoren können im Prinzip alle in wässrigen Systemen oberflächenaktiven Schwefel-haltigen Verbindungen eingesetzt werden, die nichtionischer, anionischer, kationischer oder auch zwitterionischer Natur sein können.As 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.

Besonders gut geeignet sind Verbindungen der Formel VI

Figure imgb0006
in denen die Variablen wie folgt definiert sind:

  • R6, R7 gleich oder vorzugsweise verschieden und gewählt aus
    Wasserstoff,
    C1-C30-Alkyl, verzweigt oder unverzweigt, wie 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-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl, bevorzugt in β-Stellung verzweigte Reste der Formel VI a
    Figure imgb0007
     (CH2CH2O)x-O-R oder [CH(CH3)CH2O)x-O-R, wobei x eine ganze Zahl im Bereich von 1 bis 20 ist,
    C6-C14-Aryl, beispielsweise Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl, 9-Anthryl, 1-Phenanthryl, 2-Phenanthryl, 3-Phenanthryl, 4-Phenanthryl und 9-Phenanthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl;
  • R8 ist gewählt aus C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl und insbesondere Wasserstoff;
  • R9, R10 gleich oder vorzugsweise verschieden und gewählt aus C1-C27-Alkyl, wie 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-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl;
    wobei die Summe der C-Atome von R9 und R10 maximal 30 beträgt.
    Vorzugsweise hat R9 zwei C-Atome mehr als R10; bevorzugt sind beispielsweise die Kombinationen
    R9 = n-Undecyl und R10 = n-Nonyl,
    R9 = n-Dodecyl und R10 = n-Decyl,
    R9 = n-Tridecyl und R10 = n-Undecyl,
    R9 = n-Tetradecyl und R10 = n-Dodecyl,
    R9 = n-Pentadecyl und R10 = n-Tridecyl,
  • R11 ist gewählt aus C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl,
    Phenyl, ortho-Tolyl, meta-Tolyl, para-Tolyl
    und insbesondere Wasserstoff.
Particularly suitable compounds of the formula VI
Figure imgb0006
 where the variables are defined as follows:
  • R 6 , R 7 are the same or preferably different and selected from
    Hydrogen,
    C 1 -C 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 , sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n -Decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, preferably branched in the β-position radicals of the formula VI a
    Figure imgb0007
     (CH 2 CH 2 O) x -OR or [CH (CH 3 ) CH 2 O) x -OR, where x is an integer in the range of 1 to 20,
    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, more preferably phenyl;
  • R 8 is selected from C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and especially hydrogen;
  • R 9 , R 10 is the same or preferably different and selected from C 1 -C 27 -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, iso-heptyl, n Octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl;
    wherein the sum of the C atoms of R 9 and R 10 is at most 30.
    Preferably, R 9 has two C atoms more than R 10 ; For example, the combinations are preferred
    R 9 = n-undecyl and R 10 = n-nonyl,
    R 9 = n-dodecyl and R 10 = n-decyl,
    R 9 = n-tridecyl and R 10 = n-undecyl,
    R 9 = n-tetradecyl and R 10 = n-dodecyl,
    R 9 = n-pentadecyl and R 10 = n-tridecyl,
  • R 11 is selected from C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
    Phenyl, ortho-tolyl, meta-tolyl, para-tolyl
    and especially hydrogen.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist genau einer der Reste R6 und R7 Wasserstoff und der andere Rest gewählt aus C1-C30-Alkyl.In a preferred embodiment of the present invention exactly one of R 6 and R 7 is hydrogen and the other is selected from C 1 -C 30 alkyl.

In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung wählt man ein Gemisch von mehreren Schwefel-haltigen Verbindungen beispielsweise der Formel VI, die sich beispielsweise dadurch unterscheiden können, dass in der ersten Verbindung der Formel VI R6 gleich Wasserstoff und R7 aus C1-C30-Alkyl gewählt wird und in der zweiten R6 gleich Wasserstoff und R7 aus C1-C30-Alkyl gewählt wird.In a particularly preferred embodiment of the present invention, 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.

In einer Ausführungsform der vorliegenden Erfindung sind alle oder zumindest ein gewisser Anteil, beispielsweise ein Drittel oder die Hälfte, der Sulfonylgruppen in als Emulgatoren eingesetzten Schwefel-haltigen Verbindungen neutralisiert. Zur Neutralisation eignen sich beispielsweise basische Salze wie Hydroxide oder Carbonate der Alkalimetalle wie beispielsweise Na oder K. Zur Neutralisation eignen sich weiterhin Ammoniak, Alkylamine wie beispielsweise Methylamin, Dimethylamin, Trimethylamin, Ethylamin, Diethylamin, Triethylamin, Ethylendiamin, und ganz besonders Alkanolamine wie beispielsweise Ethanolamin, Diethanolamin, Triethanolamin, N-Methyl-Ethanolamin, N-Methyldiethanolamin oder N-(n-Butyl)-diethanolamin.In one embodiment of the present invention, 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. For neutralization are also suitable ammonia, 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.

Die Herstellung von Verbindungen der Formel VI ist an sich bekannt und in WO 01/68584 beschrieben. Sie gelingt beispielsweise durch einfache oder doppelte Veresterung von Dicarbonsäureanhydriden der allgemeinen Formel VII

Figure imgb0008
mit entsprechenden Alkoholen, die nicht rein vorliegen müssen, gefolgt von einer Umsetzung mit Disulfit.The preparation of compounds of formula VI is known per se and in WO 01/68584 described. It succeeds, for example, by simple or double esterification of dicarboxylic anhydrides of the general formula VII
Figure imgb0008
 with corresponding alcohols, which need not be pure, followed by a reaction with disulfite.

Man kann anstatt reiner Schwefel-haltiger Verbindungen, beispielsweise Schwefel-haltiger Verbindungen der Formel V, Gemische von verschiedenen Schwefel-haltigen Verbindungen verwenden. Beispielsweise ist es möglich, zur Veresterung das als Oxoöl 135 oder Oxodicköl 135 ( WO 01/68584 ) bekannte Gemisch einzusetzen.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.

In einer Ausführungsform der vorliegenden Erfindung können im erfindungsgemäßen Verfahren eingesetzte Formulierungen bis zu 40 Gew.-%, bevorzugt bis zu 20 Gew.-%, bezogen auf Formulierung, mindestens eines Alkohols der Formel VII

Figure imgb0009
enthalten, wobei in Formel VII die Variablen R9 und R10 wie oben stehend definiert sind.In one embodiment of the present invention, 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
Figure imgb0009
 in formula VII, the variables R 9 and R 10 are as defined above.

In einer Ausführungsform der vorliegenden Erfindung können im erfindungsgemäßen Verfahren eingesetzte Formulierungen bis zu 50 Gew.-%, bevorzugt bis zu 30 Gew.-%, bezogen auf Formulierung, mindestens einer Verbindung der Formel VIII enthalten.In one embodiment of the present invention, 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.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung können im erfindungsgemäßen Verfahren eingesetzte Formulierungen bis zu 40 Gew.-%, besonders bevorzugt bis zu 20 Gew.-% Mischungen enthalten, die mindestens einen Alkohol der allgemeinen Formel VIII umfassen; beispielhaft für derartige Mischungen sei Oxoöl 135 und Oxoöl 13 genannt.In a preferred embodiment of the present invention, 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.

Vorzugsweise ist die bzw. sind die erfindungsgemäß eingesetzten Formulierungen wässrig.Preferably, the or the formulations used according to the invention are aqueous.

In einer Ausführungsform der vorliegenden Erfindung enthält mindestens eine erfindungsgemäß eingesetzte Formulierung mindestens eine weitere hydrophobe Verbindung. Bei mindestens einer weiteren hydrophoben Verbindung handelt es sich dabei um eine Verbindung auf Kohlenstoffbasis, beispielsweise natürliches oder synthetisches Wachs, natives oder synthetisches Öl oder natives oder synthetisches Fett.In one embodiment of the present invention, 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.

Als Beispiele für natürliche Wachse seien Bienenwachs, Korkwachs, Montanwachse oder Carnaúbawachs genannt.Examples of natural waxes are beeswax, cork wax, montan waxes or carnaúba wax.

Als Beispiele für synthetische Wachse seien Polyethylenwachse oder Ethylencopolymerwachse genannt, wie sie beispielsweise durch radikalische Polymerisation von Ethylen oder radikalische Copolymerisation von Ethylen mit beispielsweise (Meth)acrylsäure oder durch Ziegler-Natta-Katalyse erhältlich sind. Weiterhin seien Polyisobutylenwachse genannt. Weiterhin seien Paraffingemische genannt; darunter sind Gemische von Kohlenwasserstoffen zu verstehen, die 12 oder mehr Kohlenstoffatome aufweisen und üblicherweise einen Schmelzpunkt im Bereich von 25 bis 45 °C aufweisen. Derartige Paraffingemische können beispielsweise in Raffinerien oder Crackern anfallen und sind dem Fachmann als Paraffingatsch und Sasolwachse bekannt. Ein weiteres Beispiel für synthetische Wachse sind Montanesterwachse.Examples of 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. Furthermore, polyisobutylene waxes may be mentioned. Furthermore, 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.

Als Beispiele für natürliche Öle seien bei Zimmertemperatur flüssige Triglyceride genannt, beispielsweise Fischöl, Rinderklauenöl, Olivenöl, Baumwollsamenöl, Rizinusöl, Sonnenblumenöl und Erdnussöl genannt.As examples of natural oils are mentioned at room temperature liquid triglycerides, such as fish oil, cattle claw oil, olive oil, cottonseed oil, castor oil, sunflower oil and peanut oil called.

Als Beispiele für synthetische Öle seien Weißöl, Paraffinöl, funktionalisierte Paraffine wie beispielsweise chlorierte oder sulfochlorierte Paraffine oder auch Polyalkylenglykole wie beispielsweise Polyethylenglykol genannt.Examples of synthetic oils include white oil, paraffin oil, functionalized paraffins such as chlorinated or sulfochlorinated paraffins or polyalkylene glycols such as polyethylene glycol.

Als Beispiele für natürliche Fette seien bei Zimmertemperatur feste native Triglyceride genannt wie beispielsweise Lanolin, Schellackwachs sowie deren Gemische.As examples of natural fats, solid native triglycerides, such as, for example, lanolin, shellac wax and mixtures thereof, are mentioned at room temperature.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung handelt es sich bei der weiteren hydrophoben Verbindung um mindestens ein natives Triglycerid.In a preferred embodiment of the present invention, the further hydrophobic compound is at least one native triglyceride.

In einer weiteren bevorzugten Ausführungsform setzt man eine Kombination aus mindestens einem bei Zimmertemperatur festen oder flüssigen nativen Triglycerid sowie einem Paraffingemisch mit einem Schmelzpunkt im Bereich von 25 bis 40°C ein. Das Mengenverhältnis ist an sich unkritisch, geeignet sind Gewichtsverhältnisse natives Triglycerid : Paraffingemisch im Bereich von 10 : 1 bis 1 : 10.In a further preferred embodiment, 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.

Erfindungsgemäß kann man etwa 10 bis 70, bevorzugt 20 bis 40 Gew.-% einer oder mehrerer weiterer hydrophober Verbindungen, bezogen auf die Formulierung, einsetzen.According to the invention, it is possible to use about 10 to 70, preferably 20 to 40,% by weight of one or more further hydrophobic compounds, based on the formulation.

Zur Durchführung des erfindungsgemäßen Verfahrens behandelt man Leder oder Pelzfelle in einer Flotte vor, während oder nach der Nachgerbung mit den erfindungsgemäß eingesetzten Formulierungen. Die erfindungsgemäße Behandlung kann einmal oder wiederholt durchgeführt werden. Die zu behandelnden Leder können nach beliebigen Methoden hergestellt worden sein, beispielsweise durch Mineralgerbung, insbesondere Chromgerbung, oder durch Polymergerbung, Gerbung mit Syntanen, Harzgerbung, Gerbung mit vegetabilen Gerbstoffen oder auch Gerbung mit Kombinationen aus den vorgenannten Gerbstoffen.To carry out the process according to the invention, 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.

In einer Ausführungsform des erfindungsgemäßen Verfahrens wird mindestens eine erfindungsgemäße Formulierung in einer oder mehreren Portionen zu dem zu behandelnden Leder oder den zu behandelnden Pelzen gegeben. Diese Zugabe kann in einer wässrigen Flotte geschehen. Vorzugsweise kann die Flottenlänge 50 bis 2000 Gew.-%, bevorzugt 100 bis 400 Gew.-% betragen, bezogen auf das Falzgewicht der Leder bzw. das Nassgewicht der Pelzfelle.In one embodiment of the method according to the invention, 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.

In einer Ausführungsform des erfindungsgemäßen Verfahrens gibt man die Komponenten Carboxylgruppen-haltiges Polysiloxan, Carboxylgruppen-freies Polysiloxan und Emulgator getrennt zu Leder und/oder Leder und Flotte und stellt die erfindungsgemäße Formulierung in situ her.In one embodiment of the process according to the invention, 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 .

Das erfindungsgemäße Verfahren führt man im Allgemeinen so durch, dass man das zu behandelnde Leder bzw. die zu behandelnden Pelzfelle in geeigneten Gefäßen, beispielsweise in Fässern, insbesondere in drehbaren Fässern mit Einbauten, walkt. Auch andere dem Fachmann bekannte Methoden zur Durchmischung sind möglich.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. Other methods of mixing known to the person skilled in the art are also possible.

Als Temperatur für das erfindungsgemäße Verfahren kann man Temperaturen im Bereich von 20 bis 65°C, bevorzugt 30 bis 60°C wählen.Temperatures in the range from 20 to 65.degree. C., preferably from 30 to 60.degree. C., can be selected as the temperature for the process according to the invention.

Die Druckbedingungen des erfindungsgemäßen Verfahrens sind im Allgemeinen unkritisch. Bevorzugt arbeitet man bei Normaldruck (1 atm), man kann aber auch bei verringertem Druck wie beispielsweise 0,5 bis 0,99 atm oder bei erhöhtem Druck wie beispielsweise 1,01 bis 2 atm arbeiten.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.

Als pH-Wert kann man zu Beginn der erfindungsgemäßen Behandlung pH-Werte im Bereich von 4 bis 8, bevorzugt 4,5 bis 8 einstellen. Am Ende der erfindungsgemäßen Behandlung kann man den pH-Wert durch Zugabe einer Säure, beispielsweise Ameisensäure, auf einen pH-Wert von 3 bis 5 absenken.At the beginning of the treatment according to the invention, pH values in the range from 4 to 8, preferably from 4.5 to 8, can be set as the pH. At the end of the treatment according to the invention, the pH can be lowered to a pH of from 3 to 5 by addition of an acid, for example formic acid.

Die erfindungsgemäße Behandlung ist im Allgemeinen nach einer Zeit von 20 Minuten bis 24 Stunden, bevorzugt 30 Minuten bis 12 Stunden, beendet. Wenn man die Behandlung wiederhol durchführt, so spricht man im Rahmen der vorliegenden Erfindung von erfindungsgemäßen Behandlungsschritten.The treatment according to the invention is generally completed after a time of 20 minutes to 24 hours, preferably 30 minutes to 12 hours. When the treatment is repeated, the treatment steps according to the invention are used in the context of the present invention.

Die Menge der erfindungsgemäß verwendeten Formulierung kann 0,1 bis 20 Gew.-%, insbesondere 0,5 bis 15 Gew.-% betragen, bezogen auf das Falzgewicht der zu behandelnden Leder bzw. das Nassgewicht der zu behandelnden Pelze.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.

Während der erfindungsgemäßen Behandlung kann man der Flotte übliche Lederfarbstoffe zusetzen. Beispielhaft seien saure, substantive oder basische Anilinfarbstoffe in Betracht, die in gerbereiüblichen Mengen eingesetzt werden können.During the treatment according to the invention, it is possible to add to the liquor conventional leather dyes. Examples which may be considered are acidic, substantive or basic aniline dyes which can be used in tannery-customary amounts.

Wünscht man die erfindungsgemäße Behandlung während der Nachgerbung durchzuführen, so kann man mit beliebigen in der Gerberei üblichen Gerbstoffen, beispielsweise Mineralgerbstoffen, insbesondere Chromgerbstoffen, oder Polymergerbstoffen, Syntanen, Harzgerbstoffen, vegetabilen Gerbstoffen oder Kombinationen aus den vorgenannten Gerbstoffen
Während der erfindungsgemäßen Behandlung kann man organische Lösemittel wie beispielsweise Alkohole zusetzen. Vorzugsweise arbeitet man jedoch ohne Zusatz von organischen Lösemitteln.If it is desired to carry out the treatment according to the invention during the retanning, it is possible to use any 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
During the treatment according to the invention, it is possible to add organic solvents such as, for example, alcohols. However, it is preferable to work without the addition of organic solvents.

Die erfindungsgemäße Behandlung kann durch eine Nachbehandlung mit in der Gerberei üblichen Gerbstoffen, beispielsweise Mineralgerbstoffen, insbesondere Chromgerbstoffen, oder mit Polymergerbstoffen, Syntanen, Harzgerbstoffen, vegetabilen Gerbstoffen oder Kombinationen aus den vorgenannten Gerbstoffen ergänzt werden.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.

Im Anschluss an die erfindungsgemäße Behandlung kann man die erfindungsgemäß erhaltenen Leder bzw. Pelzfelle wie gerbereitechnisch üblich aufarbeiten.Following the treatment according to the invention, the leather or fur skins obtained according to the invention can be worked up as usual in the art of tanning.

Ein weiterer Gegenstand der vorliegenden Erfindung sind Leder, hergestellt nach dem erfindungsgemäßen Verfahren. Nach dem erfindungsgemäßen Verfahren hergestellte Leder zeichnen sich durch sehr gute Gebrauchseigenschaften aus, beispielsweise durch sehr gute Hydrophobie, sehr guten Griff und hervorragend egale Färbung.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.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der erfindungsgemäßen Leder zur Herstellung von Bekleidungsstücken, beispielsweise Jacken, Mänteln, Schuhen und insbesondere Stiefeln. Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der erfindungsgemäßen Leder zur Herstellung von Möbeln und Möbelteilen, beispielsweise Ledersofas, Ledersesseln, Armlehnen für Stühle, Sessel oder Sofas oder Bänke. Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der erfindungsgemäßen Leder zur Herstellung von Autoteilen, beispielsweise Autositzen, Teilen von Armaturenbrettern und Innenverkleidungsteilen, beispielsweise in Autotüren.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Pelzfelle, behandelt nach dem erfindungsgemäßen Verfahren.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.

Ein weiterer Gegenstand der vorliegenden Erfindung sind Formulierungen, enthaltend
1 bis 20 Gew.-%, bezogen auf die Formulierung, eines Gemisches von Polysiloxanen, enthaltend
10 bis 90 Gew.-%, bezogen auf das Gemisch, an einem oder mehreren Carboxylgruppen-haltigen Polysiloxanen,
90 bis 10 Gew.-%, bezogen auf das Gemisch, an einem oder mehreren Carboxylgruppen-freien Polysiloxanen,
sowie 3 bis 25 Gew.-%, bevorzugt 5 bis 20 und besonders bevorzugt 8 bis 18 Gew.-%, bezogen auf die Formulierung, mindestens eines Emulgators.
, die dadurch gekennzeichnet sind, dass es sich bei den Carboxylgruppen-haltigen Polysiloxanen um solche Polysiloxane handelt, welche die Strukturelemente der Formeln I, II und optional III a und III b enthalten und dass die Carboxylgruppen-freien Polysiloxane aus Strukturelementen der oben bezeichneten Formeln I sowie optional III a, III b und/oder IV a aufgebaut sind.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.
, characterized in that the 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.

Die Strukturelemente der Formeln I, II, III a und III b sind wie oben stehend definiert.The structural elements of formulas I, II, III a and III b are defined as above.

Die in erfindungsgemäßen Formulierungen enthaltenen Carboxylgruppen-haltigen Polysiloxane können weiterhin Strukturelemente der allgemeinen Formeln IV a und IV b enthalten.The carboxyl-containing polysiloxanes contained in formulations of the invention may further contain structural elements of the general formulas IV a and IV b.

Als Emulgatoren in den erfindungsgemäßen Formulierungen können im Prinzip alle in wässrigen Systemen oberflächenaktiven Verbindungen genannt werden, die nichtionischer, anionischer, kationischer oder auch zwitterionischer Natur sein können.In principle, all surface-active compounds which may be nonionic, anionic, cationic or even zwitterionic in nature may be mentioned as emulsifiers in the formulations according to the invention.

Besonders gut geeignete Emulgatoren sind N-acylierte Aminosäurederivate beispielsweise der Formel V, in denen die Variablen wie oben stehend definiert sind.Particularly suitable emulsifiers are N-acylated amino acid derivatives, for example of the formula V, in which the variables are as defined above.

Andere gut geeignete Emulgatoren sind Schwefel-haltige Emulgatoren.Other suitable emulsifiers are sulfur-containing emulsifiers.

Als Schwefel-haltige Emulgatoren in den erfindungsgemäßen Formulierungen können im Prinzip alle Schwefel-haltigen in wässrigen Systemen oberflächenaktiven Verbindungen genannt werden, die nichtionischer, anionischer, kationischer oder auch zwitterionischer Natur sein können.As 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.

Besonders gut geeignete Emulgatoren sind Schwefel-haltige Verbindungen beispielsweise der Formel VI, in denen die Variablen wie oben stehend definiert sind.Particularly suitable emulsifiers are sulfur-containing compounds, for example of the formula VI, in which the variables are as defined above.

In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei den erfindungsgemäßen Formulierungen um solche Formulierungen, die dadurch gekennzeichnet sind, dass sie 10 bis 70 Gew.-%, bezogen auf die Formulierung, mindestens einer weiteren hydrophoben Verbindung enthalten.In one embodiment of the present invention, 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.

Bei weiteren hydrophoben Verbindungen handelt es sich in einer Ausführungsform der vorliegenden Erfindung um eine Kombination von mindestens einem natürlichen, bei Zimmertemperatur festen oder flüssigen Triglycerid und einem Paraffingemisch.Other 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.

Die erfindungsgemäßen Formulierungen können einen pH-Wert von 7 oder mehr aufweisen. Vorzugsweise weisen sie einen pH-Wert im Bereich von 7 bis maximal 10 auf.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.

Bei den erfindungsgemäßen Formulierungen kann es sich vorzugsweise um wässrige Formulierungen mit einem Feststoffgehalt von bis zu 50 Gew.-% handeln, bezogen auf die gesamte Formulierung.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.

Die erfindungsgemäßen Formulierungen weisen eine sehr gute Lagerstabilität auf. Außerdem lassen sich die erfindungsgemäßen Formulierungen ausgezeichnet im erfindungsgemäßen Verfahren einsetzen.The formulations of the invention have a very good storage stability. In addition, the formulations according to the invention can be used excellently in the process according to the invention.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung der erfindungsgemäßen Formulierungen, im Folgenden auch erfindungsgemäßes Herstellverfahren genannt. Das erfindungsgemäße Herstellungsverfahren lässt sich im Allgemeinen so durchführen, dass man die Komponenten Carboxylgruppen-freies Polysiloxan, Carboxylgruppen-haltiges Polysiloxan und einen oder mehrerer Emulgatoren sowie gegebenenfalls hydrophobe Verbindung oder hydrophobe Verbindungen miteinander mischt. Die Reihenfolge der Zugabe der einzelnen Komponenten ist nicht kritisch. Das kann beispielsweise durch einfaches Verrühren der Komponenten geschehen, beispielsweise mit einem Mixer oder einem Ultra-Thurax-Rührer. In einigen Fällen erfolgt eine weitere Homogenisierung, z.B. mit einem Spalthomogenisator. Besonders lagerstabile erfindungsgemäße Formulierungen erhält man, wenn man eine weitere Homogenisierung durchführt.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. In some cases, 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.

Die Erfindung wird durch Beispiele erläutert.The invention will be illustrated by examples.

1. Herstellung erfindungsgemäßer Formulierungen 1.1 bis 1.4 aus Carboxylgruppen-haltigem Polysiloxan, Carboxylgruppen-freiem Polysiloxan, Emulgator und hydrophoben Stoffen1. Preparation of inventive formulations 1.1 to 1.4 from carboxyl-containing polysiloxane, carboxyl-free polysiloxane, emulsifier and hydrophobic substances

In einem Becherglas wurden bei Zimmertemperatur die unten aufgeführten Komponenten gemäß Tabelle 1 verrührt.At room temperature, the components listed below were stirred in a beaker according to Table 1.

Carboxylgruppen-haltiges Polysiloxan "PS 1": alle R1 sind CH3, A1: -(CH2)10-, Z1: Einfachbindung, kinematische Viskosität v im Bereich 500 - 850 mm2/s, bestimmt bei Zimmertemperatur, Molekulargewicht Mn: 10.000 g/mol, im statistischen Mittel 127 Strukturelemente I und 2 bis 3 Strukturelemente II pro Molekül, Strukturelemente II sind statistisch verteilt.Carboxyl-containing polysiloxane "PS 1": all R 1 are 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, on average 127 Structural elements I and 2 to 3 structural elements II per molecule, structural elements II are randomly distributed.

Carboxylgruppen-freies Polysiloxan "PS 2": alle R1 sind CH3, kinematische Viskosität v von 350 mm2/s, bestimmt bei Zimmertemperatur, Molekulargewicht Mn: 7.500 g/mol.Carboxyl group-free polysiloxane "PS 2": all R 1 are CH 3 , kinematic viscosity v of 350 mm 2 / s, determined at room temperature, molecular weight M n : 7,500 g / mol.

Emulgator: N-Oleylsarcosin als Natriumsalz, kommerziell erhältlich bei
BASF Aktiengesellschaft.Emulsifier: N-Oleyl sarcosine as sodium salt, commercially available at
BASF Aktiengesellschaft.

Natives Triglycerid: Lipodermöl, ein Rinderklauenöl.Native triglyceride: Lipoderm oil, a beef claw oil.

Synthetisches Öl: Paraffingatsch 36/38, kommerziell erhältlich bei Shell und bei Total-Fina.Synthetic Oil: Paraffin gash 36/38, commercially available from Shell and Total-Fina.

Es wurden die erfindungsgemäßen Formulierungen 1.1. bis 1.4 sowie für Vergleichsexperimente die Formulierungen V 1.5 und V 1.6 hergestellt. Die Zusammensetzung der Formulierungen geht aus Tabelle 1 hervor.There were the formulations of the invention 1.1. to 1.4 and for comparative experiments the formulations V 1.5 and V 1.6 prepared. The composition of the formulations is shown in Table 1.

Zur Qualitätskontrolle von den so erhaltenen Emulsionen 10 ml entnommen und mit Wasser auf 100 ml aufgefüllt. Es entstanden über Nacht lagerstabile Emulsionen. Tabelle 1 Komponente 1.1 1.2 1.3 1.4 V 1.5 V 1.6 PS 1 [g] 5,0 5,0 5,0 5,0 10,0 - PS 2 [g] 10,0 5,0 5,0 5,0 - 10,0 N-Oleylsarcosin [g] 12,9 10,0 10,0 17,0 12,9 10,0 Triglycerid [g] 15,3 15,0 10,0 13,0 12,5 17,0 NaOH [g] 1,5 1,3 1,2 2,0 1,5 1,5 Paraffingatsch [g] 15,3 15,0 18,8 8,0 15,3 13,0 Wasser [ml] 45,0 51,3 50,0 50,0 50,0 50,0 pH-Wert 8,5 8,5 8,0 9,0 8,5 8,5 For quality control, remove 10 ml from the emulsions thus obtained and make up to 100 ml with water. It spawned storage-stable emulsions overnight. Table 1 component 1.1 1.2 1.3 1.4 V 1.5 V 1.6 PS 1 [g] 5.0 5.0 5.0 5.0 10.0 - PS 2 [g] 10.0 5.0 5.0 5.0 - 10.0 N-Oleyl sarcosine [g] 12.9 10.0 10.0 17.0 12.9 10.0 Triglyceride [g] 15.3 15.0 10.0 13.0 12.5 17.0 NaOH [g] 1.5 1.3 1.2 2.0 1.5 1.5 Slack wax [g] 15.3 15.0 18.8 8.0 15.3 13.0 Ml water] 45.0 51.3 50.0 50.0 50.0 50.0 PH value 8.5 8.5 8.0 9.0 8.5 8.5

Beispiele 2: Behandlung von LederExamples 2: Treatment of leather Beispiel 2.1 Behandlung von Leder mit den erfindungsgemäßen Formulierungen 1.1Example 2.1 Treatment of leather with the formulations according to the invention 1.1

Es wurde nach der folgenden allgemeinen Rezeptur vorgegangen.The following general recipe was used.

Die Angaben in Gew.-% beziehen sich jeweils auf das Falzgewicht, wenn nicht anders angegeben. Bei allen Operationen wurde das Fass etwa 10 mal pro Minute gedreht, wenn nicht anders angegeben.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.

In einem drehbaren 50-I-Fass mit Einbauten wurden 2,5 kg Chrom-gegerbtes Rindsleder (wet blue) mit einer Falzstärke von 2,5 mm mit 100 Gew.-% Wasser, 3 Gew.-% Natriumformiat und 1 Gew.-% MgO versetzt. Nach 15 Minuten wurden 0,6 Gew.-% NaHCO3 zugegeben und bei 35°C über eine Zeitdauer von 150 Minuten entsäuert, so dass sich ein pH-Wert von 4,8 einstellte.In a rotatable 50 l drum with internals 2.5 kg of chromium-tanned leather (wet blue) with a folding thickness of 2.5 mm with 100 wt .-% water, 3 wt .-% sodium formate and 1 wt. % MgO added. After 15 minutes, 0.6 wt% NaHCO 3 was added and deacidified at 35 ° C over a period of 150 minutes to give a pH of 4.8.

Anschließend wurde das Leder mit 3 Gew.-% mit den folgenden charakteristischen Daten versetzt:
30 Gew.-%ige wässrige, mit NaOH teilneutralisierte Polymerlösung; Homopolymer der Methacrylsäure, Mn ca. 10.000; K-Wert nach Fikentscher: 12, Viskosität der 30 Gew.-% Lösung: 65 mPa·s (DIN EN ISO 3219, 23°C), pH-Wert 5,1.
Es wurde 30 Minuten nachgegerbt.Subsequently, 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.

Im ersten Behandlungsschritt wurde 2 Gew.-% Formulierung 1.1 zugegeben und weitere 30 Minuten gewalkt. Anschließend wurden innerhalb von 10 Minuten 3 Gew.-% des Vegetabilgerbstoffs Mimosaextrakt und 2 Gew.-% des Lederfarbstoffs Luganil® Black NT, kommerziell erhältlich bei BASF Aktiengesellschaft. Außerdem wurden 2 Gew.-% des Harzgerbstoffes Relugan® D, kommerziell erhältlich bei BASF Aktiengesellschaft, 3 Gew.-% des Vegetabilgerbstoffs Chestnut® und 3 Gew.-% des Syntans Basyntan SL® zugegeben, kommerziell erhältlich bei BASF Aktiengesellschaft. Die Behandlung wurde über einen Zeitraum von einer Stunde fortgesetzt.In 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.

Im zweiten Behandlungsschritt wurden weiter 7,5 Gew.-% Formulierung 1.1 zugesetzt und bei einem pH-Wert von 4,7 über 12 Stunden weiter gewalkt.In the second treatment step, a further 7.5% by weight of formulation 1.1 was added and further driven at a pH of 4.7 over 12 hours.

Anschließend wurden 100 Gew.-% Wasser mit einer Temperatur von etwa 70°C zugegeben, so dass sich eine Temperatur von 50°C einstellte, und mit Ameisensäure portionsweise über einen Zeitraum von 80 Minuten ein pH-Wert von 3,6 eingestellt.Subsequently, 100 wt .-% of water at a temperature of about 70 ° C were added, so that a temperature of 50 ° C, and adjusted with formic acid in portions over a period of 80 minutes, a pH of 3.6.

Die Flotte wurde abgelassen, das Leder zweimal mit je 200 Gew.-% Wasser mit einer Temperatur von 40°C gewaschen. Anschließend wurde der Top mit 100 Gew.-% Wasser versetzt und bei einer Temperatur von 40°C mit einer Mischung aus 0,2 Gew.-% Leather Black VM und 0,3 Gew.-% des Lederfarbstoffs Luganil® Black AS, kommerziell erhältlich bei BASF Aktiengesellschaft, sowie 0,2 Gew.-% Ameisensäure bei einem pH-Wert von 3,6 die Topfärbung durchgeführt. Anschließend wurde die Flotte abgelassen, mit 100 Gew.-% Wasser versetzt und mit 3 Gew.-% Cr(III)-Sulfat bei einem pH-Wert von 3,5 behandelt.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.

Schließlich wurde zweimal mit Wasser gewaschen, getrocknet und gerbereiüblich aufgearbeitet. Man erhielt das erfindungsgemäße Leder 3.1.Finally, it was washed twice with water, dried and worked up tanning usual. The leather 3.1 according to the invention was obtained.

Die Eigenschaften der erhaltenen Leder gehen aus Tabelle 2 hervor.The properties of the resulting leathers are shown in Table 2.

Beispiel 2.2Example 2.2

Beispiel 1 wurde wiederholt, jedoch wurde im ersten und im zweiten Behandlungsschritt jeweils Formulierung 1.2 statt 1.1 eingesetzt. Man erhielt das erfindungsgemäße Leder 3.2.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.

Beispiel 2.3Example 2.3

Beispiel 1 wurde wiederholt, jedoch wurde im ersten und im zweiten Behandlungsschritt jeweils Formulierung 1.3 statt 1.1 eingesetzt. Man erhielt das erfindungsgemäße Leder 3.3.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.

Beispiel 2.4Example 2.4

Beispiel 1 wurde wiederholt, jedoch wurde im ersten und im zweiten Behandlungsschritt jeweils Formulierung 1.4 statt 1.1 eingesetzt. Man erhielt das erfindungsgemäße Leder 3.4.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.

Vergleichsbeispiel V 2.5Comparative Example V 2.5

Beispiel 1 wurde wiederholt, jedoch wurde im ersten und im zweiten Behandlungsschritt jeweils Formulierung 1.5 statt 1.1 eingesetzt. Man erhielt die Vergleichs-Lederprobe V 3.5.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.

Vergleichsbeispiel V 2.6Comparative Example V 2.6

Beispiel 1 wurde wiederholt, jedoch wurde im ersten und im zweiten Behandlungsschritt jeweils Formulierung 1.6 statt 1.1 eingesetzt. Man erhielt die Vergleichs-Lederprobe V 3.6. Tabelle 2 Eigenschaften der erfindungsgemäßen Leder und der in den Vergleichsversuchen erhaltenen Leder Leder bzw. Vergleichs-Lederprobe 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 Statische Wasseraufnahme nach 2 Stunden 18 20 19 22 21 27 Färbung 3 3,5 3,5 5,5 4 (Schatten) 4 (Schatten) 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)

Die Maesermessungen wurden mit einem Maesertester nach ASTM D 2099 jeweils als Doppelbestimmungen durchgeführt. Die statische Wasseraufnahme wurde bei 15% Stauchung durchgeführt und in Gew.-% angegeben, bezogen auf das fertige Leder. Die Färbung wurde durch optische Inspektion durch ein Probandenteam beurteilt. Die Bewertungen erfolgte mit Noten wie in der Schule: 1 (sehr gut) bis 6 (ungenügend)The measurements were carried out with a Maesertester according to ASTM D 2099 in each case as duplicate determinations. Static water uptake was performed at 15% compression and reported in weight percent based on the finished leather. Staining was assessed by visual inspection by a panel of volunteers. The ratings were grades as in school: 1 (very good) to 6 (not enough)

4. Herstellung Schwefel-haltiger Emulgatoren4. Preparation of Sulfur-containing Emulsifiers 4.1. Herstellung des Schwefel-haltigen Emulgators E 4.14.1. Preparation of Sulfur-containing Emulsifier E 4.1

In einem 1000-ml-Dreihalskolben, ausgerüstet mit Rührer, Innenthermometer und Rückflusskühler wurden unter Ausschluss von Feuchtigkeit 115 g (0,3 mol) des verzweigten Alkohols der Formel VIII.1

Figure imgb0010
vorgelegt und im Ölbad auf 100°C erwärmt. Unter Rühren wurden dann 29,4 g (0,3 mol) Maleinsäureanhydrid eingetragen und die so erhältliche Mischung 5 Stunden bei 100°C gerührt.In a 1000 ml three-necked flask equipped with stirrer, internal thermometer and reflux condenser, 115 g (0.3 mol) of the branched alcohol of the formula VIII.1
Figure imgb0010
 submitted and heated to 100 ° C in an oil bath. With stirring, 29.4 g (0.3 mol) of maleic anhydride were then added and the resulting mixture was stirred at 100 ° C for 5 hours.

Der so erhältliche Monoester wurde auf 40°C abgekühlt und in 210 ml Wasser eingerührt, durch Zusatz von 17 g (0,21 mol) 50 Gew.-% wässriger NaOH teilneutralisiert und die erhaltene Mischung auf 80°C erwärmt. Danach wurden unter Rühren 28,5 g Natriumdisulfit zugefügt und die Mischung bei 80°C über einen Zeitraum von 6 Stunden weitergerührt. Anschließend wurde auf 40°C abgekühlt.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.

4.2. Herstellung des Schwefel-haltigen Emulgators E 4.24.2. Preparation of Sulfur-containing Emulsifier E 4.2

Es wurde wie oben stehend vorgegangen, jedoch wurde statt 115 g des verzweigten Alkohols VIII.1. 148,9 g (0,3 Äquivalente, berechnet aus der OH-Zahl) Oxodicköl 135 eingesetzt.The procedure was as above, but instead of 115 g of branched alcohol VIII.1. 148.9 g (0.3 equivalent, calculated from the OH number) Oxodicköl 135 used.

5. Herstellung einer erfindungsgemäßen Formulierung 5.1 unter Verwendung von Carboxylgruppen-haltigem Polysiloxan, Carboxylgruppen-freiem Polysiloxan, Schwefel-haltigem Schwefel-haltigem Emulgator E 4.1. und hydrophoben Stoffen5. Preparation of a formulation 5.1 according to the invention using carboxyl-containing polysiloxane, carboxyl group-free polysiloxane, sulfur-containing sulfur-containing emulsifier E 4.1. and hydrophobic substances

In einem Becherglas wurden bei Zimmertemperatur die unten aufgeführten Komponenten gemäß Tabelle 1 mit einem Mixer verrührt.At room temperature, the components listed below were stirred in a beaker in accordance with Table 1 with a mixer.

Carboxylgruppen-haltiges Polysiloxan "PS 1": alle R1 = CH3, A1: -(CH2)10-, Z1: Einfachbindung, kinematische Viskosität v im Bereich 500 - 850 mm2/s, bestimmt bei Zimmertemperatur, Molekulargewicht Mn: 10.000 g/mol, im statistischen Mittel 127 Strukturelemente I und 2 bis 3 Strukturelemente II pro Molekül, Strukturelemente II statistisch verteilt.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.

Carboxylgruppen-freies Polysiloxan "PS 2": alle R1 = CH3, kinematische Viskosität v von 350 mm2/s, bestimmt bei Zimmertemperatur, Molekulargewicht Mn: 7.500 g/mol.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.

Emulgator E 4.1.Emulsifier E 4.1.

  • Natives Triglycerid: Lipodermöl, ein Rinderklauenöl.Native triglyceride: Lipoderm oil, a beef claw oil.
  • Synthetisches Öl: Paraffingatsch 36/38, kommerziell erhältlich bei Shell und bei Total-Fina.Synthetic Oil: Paraffin gash 36/38, commercially available from Shell and Total-Fina.

Anschließend wurde die so erhältliche Mischung mit Hilfe eines Spalthomogenisators SHL 105 der Fa. Brau und Luebbe homogenisiert, wobei ein Druck von 150 bar und eine Temperatur von 50°C gewählt wurde.Subsequently, 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.

Es wurde die erfindungsgemäße Formulierung 5.1 erhalten.
Zur Herstellung der erfindungsgemäßen Formulierungen 5.2 und 5.3 und der Vergleichsformulierungen V 5.4 bis V 5.5 wurde analog vorgegangen, jedoch wurden jeweils Zusammensetzungen gemäß Tabelle 3 gewählt. Die Zusammensetzung der Formulierungen geht aus Tabelle 3 hervor.The formulation 5.1 according to the invention was obtained.
For the preparation of the formulations according to the invention 5.2 and 5.3 and the comparative formulations V 5.4 to V 5.5 was the same procedure, but were respectively Compositions selected according to Table 3. The composition of the formulations is shown in Table 3.

Zur Qualitätskontrolle von den so erhaltenen Emulsionen jeweils 10 ml entnommen und mit Wasser auf 100 ml aufgefüllt. Es entstanden Emulsionen, die über Nacht lagerstabil waren. Tabelle 3 Formulierung 5.1 5.2 5.3 V 5.4 V 5.5 PS 1 [g] 1,0 2,0 0,5 - 4,0 PS 2 [g] 3,0 2,0 3,5 4,0 - Schwefel-haltiger Emulgator E 4.1 [g] 25 25 25 25 25 Oxoöl 135 [g] 17 17 17 17 17 Weißöl [g] 11,5 11,5 11,5 11,5 11,5 Vollentsalztes Wasser [ml] 42,5 42,5 42,5 42,5 42,5 pH-Wert 8,5 8,5 8,5 8,5 8,5 For quality control, remove 10 ml of the emulsions thus obtained and make up to 100 ml with water. Emulsions were formed which were stable in storage overnight. Table 3 formulation 5.1 5.2 5.3 V 5.4 V 5.5 PS 1 [g] 1.0 2.0 0.5 - 4.0 PS 2 [g] 3.0 2.0 3.5 4.0 - Sulfur-containing emulsifier E 4.1 [g] 25 25 25 25 25 Oxo oil 135 [g] 17 17 17 17 17 White oil [g] 11.5 11.5 11.5 11.5 11.5 Demineralized water [ml] 42.5 42.5 42.5 42.5 42.5 PH value 8.5 8.5 8.5 8.5 8.5

Für Beispiel 5.6 wurde Beispiel 5.1 wiederholt, jedoch mit 25 g Schwefel-haltigem Emulgator E 4.2 statt E 4.1.For Example 5.6 Example 5.1 was repeated, but with 25 g of sulfur-containing emulsifier E 4.2 instead of E 4.1.

Beispiele 6: Behandlung von LederExamples 6: Treatment of leather Beispiel 6.1 Behandlung von Leder mit erfindungsgemäßer Formulierung 5.1Example 6.1 Treatment of leather with formulation according to the invention 5.1

Es wurde nach der folgenden allgemeinen Rezeptur vorgegangen.
Die Angaben in Gew.-% beziehen sich jeweils auf das Falzgewicht, wenn nicht anders angegeben. Bei allen Operationen wurde das Fass etwa 10 mal pro Minute gedreht, wenn nicht anders angegeben.The following general recipe was used.
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.

In einem drehbaren 50-I-Fass mit Einbauten wurden 2,5 kg Chrom-gegerbtes Rindsleder (wet blue) mit einer Falzstärke von 2,5 mm mit 100 Gew.-% Wasser, 3 Gew.-% Natriumformiat und 1 Gew.-% MgO versetzt. Nach 15 Minuten wurden 0,6 Gew.-% NaHCO3 zugegeben und bei 35°C über eine Zeitdauer von 150 Minuten entsäuert, so dass sich ein pH-Wert von 4,8 einstellte.In a rotatable 50 l drum with internals 2.5 kg of chromium-tanned leather (wet blue) with a folding thickness of 2.5 mm with 100 wt .-% water, 3 wt .-% sodium formate and 1 wt. % MgO added. After 15 minutes, 0.6 wt% NaHCO 3 was added and deacidified at 35 ° C over a period of 150 minutes to give a pH of 4.8.

Anschließend wurde das Leder mit 3 Gew.-% Polymerisat mit den folgenden charakteristischen Daten versetzt:
30 Gew.-%ige wässrige, mit NaOH teilneutralisierte Polymerlösung; Homopolymer der Methacrylsäure, Mn ca. 10.000; K-Wert nach Fikentscher: 12, Viskosität der 30 Gew.-% Lösung: 65 mPa·s (DIN EN ISO 3219, 23°C), pH-Wert 5,1.Subsequently, 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.

Es wurde 30 Minuten nachgegerbt.It was retanned for 30 minutes.

Im ersten Behandlungsschritt wurde 10 Gew.-% Formulierung 5.1 zugegeben und weitere 30 Minuten gewalkt. Anschließend wurden innerhalb von 10 Minuten 3 Gew.-% des Vegetabilgerbstoffs Mimosaextrakt und 2 Gew.-% des Lederfarbstoffs Luganil® Black NT, kommerziell erhältlich bei BASF Aktiengesellschaft. Außerdem wurden 2 Gew.-% des Harzgerbstoffes Relugan® D, kommerziell erhältlich bei BASF Aktiengesellschaft, 3 Gew.-% des Vegetabilgerbstoffs Chestnut® und 3 Gew.-% des Sulfongerbstoffs aus EP-B 0 459 168 , Beispiel K1 zugegeben. Die Behandlung wurde über einen Zeitraum von einer Stunde fortgesetzt.In the first treatment step, 10% by weight of formulation 5.1 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 sulfone tanning agent were precipitated EP-B 0 459 168 Example K1 added. The treatment continued for a period of one hour.

Im zweiten Behandlungsschritt wurden weitere 7,5 Gew.-% Formulierung 5.1 zugesetzt und bei einem pH-Wert von 4,7 über 12 Stunden weiter gewalkt.In the second treatment step, a further 7.5% by weight of formulation 5.1 were added and further drummed at a pH of 4.7 over 12 hours.

Anschließend wurden 100 Gew.-% Wasser mit einer Temperatur von etwa 70°C zugegeben, so dass sich eine Temperatur von 50°C einstellte, und mit Ameisensäure portionsweise über einen Zeitraum von 80 Minuten ein pH-Wert von 3,6 eingestellt.Subsequently, 100 wt .-% of water at a temperature of about 70 ° C were added, so that a temperature of 50 ° C, and adjusted with formic acid in portions over a period of 80 minutes, a pH of 3.6.

Die Flotte wurde abgelassen, das Leder zweimal mit je 200 Gew.-% Wasser mit einer Temperatur von 40°C gewaschen. Anschließend wurde der Top mit 100 Gew.-% Wasser versetzt und bei einer Temperatur von 40°C mit einer Mischung aus 0,2 Gew.-% Leather Black VM und 0,3 Gew.-% des Lederfarbstoffs Luganil® Black AS, kommerziell erhältlich bei BASF Aktiengesellschaft, sowie 0,2 Gew.-% Ameisensäure bei einem pH-Wert von 3,6 die Topfärbung durchgeführt. Anschließend wurde die Flotte abgelassen, mit 100 Gew.-% Wasser versetzt und mit 3 Gew.-% Cr(III)-Sulfat bei einem pH-Wert von 3,5 behandelt.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.

Schließlich wurde zweimal mit Wasser gewaschen, getrocknet und gerbereiüblich aufgearbeitet. Man erhielt das erfindungsgemäße Leder 6.1.Finally, it was washed twice with water, dried and worked up tanning usual. The leather 6.1 according to the invention was obtained.

Die Eigenschaften der erhaltenen Leder gehen aus Tabelle 4 hervor.The properties of the resulting leathers are shown in Table 4.

Beispiele 6.2, 6.5 und Vergleichsbeispiele V 6.3 bis V 6.4Examples 6.2, 6.5 and Comparative Examples V 6.3 to V 6.4

Beispiel 6.1 wurde wiederholt, jedoch wurde im ersten und im zweiten Behandlungsschritt jeweils Formulierung 5.2 bis 5.3, V 5.4 bzw. V 5.5 statt 5.1 eingesetzt. Man erhielt das erfindungsgemäße Leder 6.2 bis 6.3 bzw. die Vergleichs-Lederproben V 6.4 bzw. V 6.5. Tabelle 4 Eigenschaften der erfindungsgemäßen Leder und der in den Vergleichsversuchen erhaltenen Vergleichs-Lederproben Leder bzw. Vergleichs-Lederprobe 6.1 6.2 6.3 V6.4 V6.5 Eingesetzte Formulierung 5.1 5.2 5.3 V5.4 V5.5 Bally-Penetrometer Wasserdurchtritt nach [min] 120 130 60 40 110 Statische Wasseraufnahme nach 6 29 28 30 34 30 Stunden [Gew.-%] 32 29 32 39 28 Färbung 3 3,5 3 4 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. One received leather 6.2 to 6.3 or the comparative leather samples V 6.4 and V 6.5. 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

Die Maesermessungen und die Wasseraufnahme wurden wie oben stehend durchgeführt. Measurements and water uptake were performed as above.

Claims (15)

  1. Method for hydrophobing leather and furskins, characterised in that leather or furskins are treated before, during or after the retanning process with one or more formulations containing 1 to 30 wt. %, in relation to the formulation, of a mixture of polysiloxanes containing
    10 to 90 wt. %, in relation to the mixture, of one or more carboxyl group-containing polysiloxanes,
    90 to 10 wt. %, in relation to the mixture, of one or more carboxyl group-free polysiloxanes,
    and 3 to 25 wt. % in relation to the formulation of emulsifier,
    wherein
    the carboxyl group-containing polysiloxanes comprise polysiloxanes that contain the structural elements of formulas I, II and optionally IIIa and IIIb
    Figure imgb0016
     the variables of which are defined as follows:
    R1 are equal or different and independently of one another are hydrogen, hydroxyl, C1-C4-alkyl, C6-C14-aryl, C1-C4-alkoxy, amino, mono-C1-C4-alkyl-amino, di-C1-C4-alkylamino or Z1-A1-COOH;
    A1 are equal or different and are a linear or branched C5-C25-alkylene;
    Z1 is a direct bond, oxygen or an amino, carbonyl, amido or ester group and wherein
    the carboxyl group-free polysiloxane(s) are linear or cyclic or branched and are formed of structural elements of formula I and optionally IIIa, IIIb and/or IVa
    Figure imgb0017
     where R1 are equal or different and independently of one another are hydrogen, hydroxyl, C1-C4-alkyl, C6-C14-aryl, C1-C4-alkoxy, wherein
    - linear carboxyl group-free polysiloxanes comprise structural elements of formulas I, IIIa and/or IIIb,
    - cyclic carboxyl group-free polysiloxanes comprise structural elements of formula I,
    - branched carboxyl group-free polysiloxanes comprise structural elements of formulas I, IVa, IIIa and/or IIIb.
  2. Method according to claim 1, characterised in that the formulation contains 10 to 70 wt. % in relation to the formulation of at least one further hydrophobic compound.
  3. Method according to any one of the preceding claims, characterised in that the at least one emulsifier is an N-acylated amino acid.
  4. Method according to any one of claims 1 to 2, characterised in that the at least one emulsifier is a sulphur-comprising emulsifier.
  5. Method according to claim 4, characterised in that the at least one sulphur-containing emulsifier comprises one or more compounds of the general formula VI
    Figure imgb0018
     wherein the variables are defined as follows:
    R6, R7 are equal or different and are selected from hydrogen, C1-C30-alkyl and C6-C14-aryl;
    R8 is C1-C4-alkyl or hydrogen.
  6. Method according to claim 2, characterised in that the further hydrophobic compound comprises a combination of at least one natural triglyceride that is solid or liquid at room temperature and a paraffin mixture.
  7. Method according to any one of the preceding claims, characterised in that the treatment is carried out at a pH value in the range of 4 to 9.
  8. Method according to any one of the preceding claims, characterised in that the treatment is carried out at temperatures in the range of 20 to 65°C.
  9. Leather produced according to a method according to any one of claims 1 to 8.
  10. Use of leather according to claim 9 for producing articles of clothing, furniture or car parts.
  11. Furskin produced according to any one of claims 1 to 8.
  12. Formulation containing
    1 to 20 wt. %, in relation to the formulation, of a mixture of polysiloxanes containing
    10 to 90 wt. %, in relation to the mixture, of one or more carboxyl group-containing polysiloxanes,
    90 to 10 wt. %, in relation to the mixture, of one or more carboxyl group-free polysiloxanes,
    3 to 25 wt. %, in relation to the formulation, of at least one emulsifier,
    wherein the carboxyl group-free polysiloxane(s) are linear or cyclic or branched and are formed of structural elements of formula I and optionally IIIa, IIIb and/or IVa,
    Figure imgb0019
     where R1 are equal or different and independently of one another are hydrogen, hydroxyl, C1-C4-alkyl, C6-C14-aryl, C1-C4-alkoxy, wherein
    - linear carboxyl group-free polysiloxanes comprise structural elements of formulas I, IIIa and/or IIIb,
    - cyclic carboxyl group-free polysiloxanes comprise structural elements of formula I,
    - branched carboxyl group-free polysiloxanes comprise structural elements of formulas I, IVa, IIIa and/or IIIb,
    and wherein the structural elements are arranged such that Si-O-Si-O chains are formed
    and wherein
    carboxyl group-containing polysiloxanes comprise such polysiloxanes that contain the structural elements of formulas I, II and optionally IIIa and IIIb
    Figure imgb0020
     in which the variables are defined as follows:
    R1 are equal or different and independently of one another hydrogen, hydroxyl, C1-C4-alkyl, C6-C14-aryl, C1-C4-alkoxy, amino, mono-C1-C4-alkylamino, di-C1-C4-alkylamino or Z1-A1-COOH;
    A1 are equal or different and linear or branched C5-C25-alkylene;
    Z1 is a direct bond, oxygen or an amino, carbonyl, amido or ester group.
  13. Formulations according to claim 12, characterised in that they contain 10 to 70 wt. % in relation to the formulation of at least one further hydrophobic compound.
  14. Formulations according to any one of claims 12 to 13, characterised in that the further hydrophobic compounds comprise a combination of at least one natural triglyceride that is solid or liquid at room temperature and a paraffin mixture.
  15. Method for preparing formulations according to any one of claims 12 to 146 by mixing the components carboxyl group-free polysiloxane, carboxyl group-containing polysiloxane and one or more emulsifiers.
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DE2003132991 DE10332991A1 (en) 2003-07-18 2003-07-18 Rendering leather and pelts hydrophobic, useful in preparation of e.g. clothes and furniture, by treatment with mixture containing carboxylated and non-carboxylated polysiloxanes
DE10332991 2003-07-18
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