WO2013023980A1 - Procédé d'hydrophobisation de substrats contenant des fibres de collagène - Google Patents

Procédé d'hydrophobisation de substrats contenant des fibres de collagène Download PDF

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Publication number
WO2013023980A1
WO2013023980A1 PCT/EP2012/065562 EP2012065562W WO2013023980A1 WO 2013023980 A1 WO2013023980 A1 WO 2013023980A1 EP 2012065562 W EP2012065562 W EP 2012065562W WO 2013023980 A1 WO2013023980 A1 WO 2013023980A1
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groups
water
acid
carbamoylsulfonate
product
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PCT/EP2012/065562
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German (de)
English (en)
Inventor
Jürgen REINERS
Christopher Tysoe
Holger Lütjens
Rafael Grosch
Franz Heinzelmann
Christopher Henzel
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Lanxess Deutschland Gmbh
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Publication of WO2013023980A1 publication Critical patent/WO2013023980A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • 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

Definitions

  • the invention relates to a process for the hydrophobing of collagen fiber-containing substrates which have been tanned with at least one carbamoylsulfonate-containing compound.
  • the object of the present invention was therefore to find a way in which chromium-free tanned collagen fiber-containing substrates, in particular leather or fur skins, can be rendered hydrophobic with satisfactory results which no longer have the abovementioned disadvantages.
  • EP-A 0 690 135 and EP-A 0 814 168 already describe carbamoylsulfonate-containing compounds as tanning agents which are substantially inert to the reaction with water.
  • An aqueous dispersion having a stability sufficient for use in the tanning process is obtained.
  • this process has two serious disadvantages: The reaction of isocyanate with polyether alcohol must be carried out with exclusion of water and preferably without viscosity-lowering solvents and therefore requires technically high-quality and expensive hardware and an additional synthesis step.
  • aqueous compositions containing at least one compound containing carbamoylsulfonate groups and at least one alcohol alkoxylate.
  • collagen fiber-containing substrates for the treatment especially tanning
  • a carbamoylsulfonate group-containing compound according to the invention is in particular the usual animal-derived raw materials, especially hides and skins, for example, Grossviehophute and -file of beef, veal, buffalo, hides and skins of pig , Sheep, goat, reindeer, deer, kangaroo, skins and skins of other small animals such as sable, fox, rabbit, hides of reptiles (eg snakes), fish or birds, as well as split skins (eg crevices, meat split, cleft with hair) and pre-tanned semifinished products (eg wet white) understood.
  • Preferred collagen fiber-containing substrates are preferably leather and fur skins, which in particular have a chromium content of less than 1000 ppm, in particular less than 500 ppm, based on the substrate.
  • the collagen fiber-containing substrates may be associated with keratinic constituents or be free from keratinic constituents.
  • keratinic constituents animal hairs are to be understood in particular.
  • Collagen fiber-containing substrates with associated keratinic constituents are in particular hides and skins in which the keratinic constituents, in particular the animal hairs, are not removed during the work in the water workshop, during the tanning and the subsequent steps in the retanning and completion to the ready-to-use material and not damaged but remain firmly connected to the surface support of the collagen fiber-containing substrate, the so-called dermis.
  • the tanned hides and skins made from this raw material, in which the hair is intact and firmly attached to the dermis, are summarized below under the term fur skins.
  • Collagen fiber-containing substrates without keratinic constituents are in particular hides and skins in which the keratinic constituents, in particular animal hair, were removed in the liming mill in the water workshop and which are used as uncleaved leaves or after splitting as crevices, meat crevices or middle gaps and then during tanning and in the subsequent steps in the retanning and, if necessary, dressing are processed to ready-to-use material.
  • the tanned hides and skins made of this raw material, in which the hair was removed in the water workshop in the so-called limber, are summarized below under the term leather.
  • EP-A-1 647 563 compounds containing carbamoylsulfonate groups are also described for the tanning of sheep skins. However, the method used there is still in need of improvement in terms of process duration and softness and hydrophobicity of the resulting skins.
  • Carbamoylsulfonate-containing compounds (component a) are understood as meaning those having the following structural unit:
  • K + is a cation equivalent
  • Suitable carbamoylsulfonate-containing compounds of component a) are preferably reaction products of at least one organic polyisocyanate and at least one bisulfite and / or disulfite.
  • Suitable organic polyisocyanates are, in particular, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates, as are described, for example, in US Pat. by W. Siefken in Liebigs Annalen der Chemie 562, pages 75 to 136.
  • Preferred polyisocyanates are compounds of the formula Q (NCO) n having a mean
  • n is a number of at least 1, 8, preferably from 1, 8 to 4.2
  • Q is an aliphatic C / j -C ⁇ hydrocarbon radical, a cycloaliphatic Cg-C j 5-hydrocarbon radical or a heterocyclic C2-C 1 2 radical having 1 to 3 heteroatoms from the series
  • diisocyanates Preference is given to using the above diisocyanates.
  • monofunctional aliphatic isocyanates such as, for example, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate or dodecyl isocyanate and / or polyisocyanates having an average NCO functionality of 2.2 to 4.2.
  • the higher-functional polyisocyanates are preferably essentially trimeric 1,6-diisocyanatohexane, trimeric 1,2,3,1- or 1,4-bis (isocyanatomethyl) cyclohexane, trimeric 1, 2-, 1, 3 or 1,4-bis (isocyanatoethyl) cyclohexane, trimeric 1,2-, 1,3- or 1,4-bis (isocyanato-n-propyl) -cyclohexane, trimeric 1-isocyanatopropyl-4-isocyanatomethyl-cyclohexane and isomers or trimeric 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and optionally dimeric 1,6-diisocyanatohexane, dimeric 1,2-, 1, 3- or 1,4-bis (isocyanatomethyl) cyclohexane, dimeric 1, 2-, 1, 3- or 1, 4-bis (isocyanatoethyl
  • polyisocyanates are polyisocyanates prepared by modifying aliphatic or cycloaliphatic diisocyanates with uretdione and / or isocyanurate, urethane and / or allophanate, biuret or oxadiazine structure, as described, for example, in DE-A 1 670 666, DE-A 3 700 209 and DE-A 3 900 053 and in EP-A 336 205 and EP-A 339 396 are described by way of example.
  • Suitable polyisocyanates are e.g. also the ester group-containing polyisocyanates, such.
  • triisocyanates obtainable by reaction of pentaerythritol or trimethylolpropane silyl ethers with isocyanatocaproic acid chloride (compare DE-A 3 743 782).
  • triisocyanates e.g. Tris-isocyanatodicyclohexylmethane to use.
  • the use of monofunctional and of more than difunctional isocyanates in both cases is preferably limited to amounts of not more than 10 mol%, based on all polyisocyanates. However, very particular preference is given to the abovementioned aliphatic, cycloaliphatic and araliphatic diisocyanates.
  • hexamethylene diisocyanate (HDI), diisocyanato-cyclohexane, 1,2-, 1, 3- and 1,4-bis (isocyanatomethyl) cyclohexane and any desired mixtures of isomers, 1, 2, 1, 3 and 1, 4 bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1, 2-, 1, 3- and 1, 4-bis (isocyanato-n-propyl) cyclohexane and any mixtures of these isomers, 2,4'- and 4,4'-diisocyanato-dicyclohexylmethane, 1-isocyanatopropyl-4-isocyanatomethyl-cyclohexane and 1-isomer-1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI).
  • HDI hexamethylene diisocyanate
  • IPDI 1-isomer-1-is
  • bisulfites and / or disulfites are preferably their alkali metal or ammonium salts, in particular the sodium salts of sulfuric or disulfurous acid, i. Sodium hydrogen sulfite (NaHSC> 3) or sodium disulfite (Na2S2Ü5) in question.
  • the other alkali metal and ammonium salts of these acids namely potassium bisulfite, potassium bisulfite, lithium bisulfite, lithium disulfite, ammonium bisulfite, ammonium bisulfite and simple tetraalkylammonium salts of these acids, such as, for example, tetramethylammonium bisulfite, tetraethylammonium bisulfite, etc., can also be used to advantage.
  • the alkali metal salts are very particularly preferred.
  • the salts are preferably used as aqueous solutions with solids contents of 5 to 40 wt .-%.
  • the compounds containing carbamoylsulfonate groups are based on aliphatic polyisocyanates such as ethylacetate, isophorone diisocyanate, bis (isocyanato) cyclohexane, 1,2-, 1,3- and 1,4-bis (Isocyanatomethyl) - cyclohexane and any mixtures of isomers, 1,2-, 1,3- and 1, 4-bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1, 2, 1, 3 and 1, 4 Bis (isocyanato-n-propyl) -cyclohexane and any desired mixtures of these isomers, isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 2,4 'and 4,4'-diisocyanato-dicyclohexylmethane or nonyltriisocyanate, and mixtures
  • the carbamoylsulfonate-containing compounds are particularly preferably based on hexamethylene diisocyanate (HDI), 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) -cyclohexane and mixtures of these isomers.
  • HDI hexamethylene diisocyanate
  • 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) -cyclohexane and mixtures of these isomers.
  • the carbamoylsulfonate group-containing compound used for tanning can be used in liquid form, for example as an aqueous composition or as a particulate solid.
  • aqueous compositions these may be present, for example, as a solution or suspension.
  • a solution is preferred.
  • the dry residue of the aqueous composition i. the total concentration of the ingredients of the aqueous composition, preferably 25 to 50%.
  • a total concentration of the aqueous composition of from 30 to 40% is advantageous, with the proportion of the carbamoylsulfonate group-containing compound in the composition being particularly advantageously from 28 to 35%.
  • the proportion of the carbamoylsulfonate-containing compound decreases in the corresponding ratio according to the proportions of the further additional component, so that the total concentration of the solids in the aqueous solution is preferably not more than 50%.
  • the carbamoylsulfonate-containing compound is used as a particulate solid, which preferably has a melting point of greater than 20 ° C, preferably greater than 60 ° C, in particular greater than 100 ° C.
  • particle is meant, in particular, a material having an average particle size of 0.1 ⁇ to 1000 ⁇ , preferably 1 to 800 ⁇ , in particular 50 to 300 ⁇ , wherein the average value based on the mass (weight average) of all particles
  • the mean particle size can be determined, for example, microscopically, preferably the solid material is in the form of powder or granules, Preferably, the particulate solid material has a residual moisture content of 0 to 10% by weight.
  • the particulate solid material is generally based on any, preferably a spherical or spherical shape-like or derived particle structure Agglomerates of particles of the named forms in the range of the specified particle size in F
  • the particulate solid material contains 1 to 100%, preferably 10 to 100%, more preferably 25 to 100%) of compounds containing carbamoylsulfonate groups.
  • the carbamoylsulfonate group-containing compound used for tanning may contain one or more emulsifiers of component c) or contain no emulsifier.
  • Preferred carbamoylsulfonate-containing compounds contain no emulsifier.
  • Suitable emulsifiers are, for example, cationic, anionic, amphoteric and nonionic surfactants, which are preferably capable of reducing the interfacial tension between an organic and an aqueous phase, so that an oil-in-water emulsion can form.
  • Preferred cationic emulsifiers are quaternary ammonium compounds, for example cetyltrimethylammonium bromide or benzyllauryldimethylammonium chloride.
  • Preferred anionic emulsifiers are soaps, metal soaps, organic soaps such as mono-, di- or triethanolamine oleate, stearate, diethylethanolamine oleate, stearate or 2-amino-2-methylpropane-1-ol stearate, sulfurized compounds such as sodium dodecyl sulfate or Vietnamese red oil and sulfonated compounds such as sodium cetylsulfonate ,
  • Preferred amphoteric emulsifiers are phosphatides such as lecithins, various proteins such as gelatin or casein and the actual amphoteric surfactants.
  • Preferred nonionic emulsifiers are fatty alcohols, such as lauryl, cetyl, stearyl or palmityl alcohol, partial fatty acid esters of polyhydric alcohols with saturated fatty acids, such as glycerol monostearate, pentaerythritol lmono-stearate, ethyl glycerol monostearate, or propylene glycol monostearate, partial fatty acid esters of polyhydric alcohols with unsaturated fatty acids such as glycerol monooleate, pentaerythritol monooleate, furthermore polyoxyethylene esters of fatty acids such as polyoxyethylene stearate, polymerization products of ethylene oxide and propylene oxide onto fatty alcohols such as fatty alcohol polyglycol ethers or fatty acids such as fatty acid ethoxylates.
  • fatty alcohols such as lauryl, cetyl, stearyl or palmityl alcohol
  • nonionic emulsifiers are at least one nonionic, ester group-containing, alkoxylated polyol having an HLB value of at least 1 3 (c1) and / or an alkyl glycoside (c2) and / or a nonionic ester group-free alkoxylated alcohol (c3) , Component cl)
  • the preferred nonionic, ester group-containing, alkoxylated polyols of component cl) have an HLB value of 13 to 19, in particular 14 to 18, wherein the HLB value is determined by the method according to Griffin, W. C: Classification of surface active agents by HLB, J. Soc. Cosmet. Chem. 1, 1949.
  • preferred compounds of component (c1) have a water solubility at 20 ° C. of at least 10 g per liter, in particular at least 20 g per liter.
  • Suitable compounds of component c1) are those which are obtainable in a manner known per se from polyols by alkoxylation and partial esterification of the hydroxyl groups with a carboxylic acid.
  • Suitable starting polyols for example, polyhydric (cyclo) aliphatic alcohols such as glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, derived from mono- or polysaccharides polyols, preferably the molecular weight of 92 to 2000 are used as starter molecules.
  • Particularly preferred starter alcohols are polyols having 3 to 10 hydroxyl groups, in particular glycerol and those having a sorbitan skeleton, in particular 1,4- or 1,5-sorbitan, preferably 1,4-sorbitan.
  • Preferred compounds containing carbamoylsulfonate groups are characterized in that the compound of component c1) used is the reaction product of a polyol with at least one alkylene oxide having 2 to 6 carbon atoms, preferably in an amount of 10 to 60 molar equivalents, based on the Polyol and subsequent reaction with at least one carboxylic acid having 6 to 30 carbon atoms.
  • the polyol used is preferably a polyol selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and mono- and polysaccharide-derived polyols, in particular sorbitol and polyols having a sorbitan skeleton.
  • the compounds of component cl) are particularly preferably partially esterified sorbitan alkoxylates whose hydroxyl groups are esterified before or preferably after the alkoxylation with carboxylic acids having a chain length of 6 to 30 carbon atoms, each hydroxyl group of the base polyol having an independent number of Have alkoxy units and per sorbitan unit on average 10 to 60 alkoxy units are present.
  • the preferred esterified sorbitan alkoxylates have a random distribution of the alkoxy groups.
  • X is a sorbitan radical, in particular a 1,4-sorbitan radical and m is the number 4 with 10 to 60 equivalents, per mole of sorbitan, preferably 10 to 40, more preferably 10 to 30 and most preferably 15 to 25 equivalents of the same or different C2-C6-alkylene oxides, in particular C2- and / or C3-alkylene oxides, preferably ethylene oxide and with
  • reaction with the alkylene oxide is preferably carried out first, followed by the reaction with the carboxylic acid.
  • sorbitan polyoxyethylene monoesters which are alkoxylated with 10-60 moles of ethylene oxide units per sorbitan unit, and preferably have a 1,4-sorbitan skeleton. These preferably correspond to the following structural formulas in which
  • R is an optionally substituted by hydroxyl groups alkyl or alkenyl radical of
  • Is carboxylic acid and m, n, p and q are independent of one another, are statistical values and each represents a number from 0 to 60, with the proviso that the sum of the number of oxyethylene units m + n + p + q of 10 to 60, preferably 18 to 22, in particular 20.
  • alkoxylated sorbitan esters are suitable in which a hydroxyl group of the sorbitan unit, in particular in the formulas given above, is esterified directly with the carboxylic acid, ie in which there is no alkylene oxide unit between the sorbitan unit and the carboxylic acid residue and the three are not acylated Hydroxyl groups are etherified with a correspondingly higher number of alkylene oxide units.
  • Such compounds are obtainable, for example, by first esterifying the sorbitan with a carboxylic acid and subsequently alkoxylating the resulting product, consisting of a mixture of the isomeric monoesters, which may also contain mixtures of the isomeric diesters in the presence of an excess of carboxylic acid.
  • the alkylene oxide used for the alkoxylation of sorbitan is preferably selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. It is also possible that the sorbitan is reacted with various of said alkylene oxides, for example ethylene oxide and propylene oxide, whereby sorbitan-alkoxylates can be obtained, each comprising blocks of several units of an alkylene oxide, for example ethylene oxide, in addition to blocks of several units of another Alkylene oxide, for example propylene oxide having.
  • the sorbitan alkoxylates particularly preferably contain ethylene oxide (EO) units, preferably exclusively. In such a case, the alkylene oxide used is particularly preferably ethylene oxide.
  • sorbitan alkoxylates in which the incorporation of the various alkylene oxides is carried out statistically.
  • the amounts of alkylene oxide used are preferably 10 to 60 moles of alkylene oxide per mole of sorbitan, preferably 10 to 40 moles, more preferably 10 to 30 moles and most preferably 15 to 25 moles.
  • Very preferred alkylene oxide is ethylene oxide.
  • the carboxylic acids suitable for the esterification of the starting polyol, especially the sorbitan alkoxylate are preferably saturated or unsaturated and linear or branched and may optionally be substituted by hydroxyl groups.
  • carboxylic acids may be mentioned as examples: hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, octadecenoic acid (oleic acid), undecenoic acid.
  • decanoic acid undecanoic acid
  • dodecanoic acid lauric acid
  • tetradecanoic acid hexadecanoic acid
  • palmitic acid hexadecanoic acid
  • octadecanoic acid stearic acid
  • Ricinoleic acid very particular preference is given to dodecanoic acid (lauric acid), hexadecanoic acid (palmitic acid) and octadecanoic acid (stearic acid) and octadecenoic acid (oleic acid).
  • sorbitan polyoxyethylene (20) monolaurate for example Polysorbat® 20 or Tween® 20 (Croda Oleochemicals) or Eumulgin® SML 20 (Cognis)
  • sorbitan can be used as compounds of component c1), for example polyoxyethylene (20) monopalmitate (for example polysorbate 40 or Tween® 40 (Croda Oleochemicals)), sorbitan polyoxyethylene (20) monostearate (for example polysorbate 60 or Tween® 60 (Croda Oleochemicals) or Eumulgin® SMS 20 (Cognis)), sorbitan polyoxyethylene ( 20) monooleate (for example Polysorbate 80 or Tween® 80 (Croda Oleochemicals)).
  • polyoxyethylene (20) monopalmitate for example polysorbate 40 or Tween® 40 (Croda Oleochemicals)
  • sorbitan polyoxyethylene (20) monostearate for example polysorbate 60 or Tween® 60 (Croda
  • alkoxylates of mono- and polyglycerol esters are, for example, alkoxylates of mono- and polyglycerol esters.
  • the preparation of such alkoxylated (poly) glycerol esters is carried out either by alkoxylation of glycerol or a polyglycerol and subsequent esterification with a Fatty acid or by esterification of glycerol or polyglycerol with a fatty acid and subsequent alkoxylation.
  • Particularly suitable for the compositions according to the invention are alkoxylates of mono- and polyglycerol esters which have an HLB value of at least 13 and preferably have a water solubility at 20 ° C. of more than 10 g per liter.
  • alkoxylated glycerol esters or polyglycerol esters which have been esterified with more than one carboxylic acid.
  • alkoxylated monoglycerol monoesters are particularly preferred.
  • Suitable for alkoxylation are C 2 to C 6 -alkylene oxides, more preferably ethylene oxide. Preferred is an alkoxylation with 10 to 100 alkylene oxide units, in particular with 20 to 60 alkylene oxide units.
  • the hydroxyl groups of glycerol or of polyglycerol have, independently of one another, on average, a different number of alkylene oxide units.
  • alkoxylates of mono- and polyglycerol esters be particularly suitable alkoxylates of mono- and polyglycerol esters.
  • glycerol monostearate ethoxylates with an average of 15 to 30, in particular with an average of 20 EO units
  • glycerol monooleate ethoxylates with 20 to 40 EO units diglycerol monostearate with 20 to 40 EO units
  • polyglycerol monostearate with 20 to 40 EO units Units castor oil alkoxylates and hydrogenated castor oil alkoxylates, short (hydrogenated) castor oil alkoxylates.
  • the latter are products which are obtainable by alkoxylation of castor oil or hydrogenated castor oil with alkylene oxides, in particular ethylene oxide and propylene oxide, preferred are those containing from 20 to 100 alkylene oxide units per (hydrogenated) castor oil unit, preferably from 20 to 60 Have ethylene oxide units per (hydrogenated) castor oil unit.
  • Corresponding glycerol-based compounds of the components cl) are likewise available as commercial products, for example glycerol monostearate ethoxylate having on average 20 EO units as Cutina® E 24 (Cognis), hydrogenated castor oil ethoxylate having on average 40 EO units as Eumulgin® HRE 40 (Cognis).
  • Component c2) Preferred compounds of component c2) are, for example, alkylmonoglycosides, alkyldiglycosides, alkyltriglycosides and higher homologs, generally referred to herein as alkylglycosides, in particular monoglucosides, diglucosides, triglucosides or higher homologs and mixtures thereof whose hydroxyl groups are partially bonded with Cig alkyl groups are substituted.
  • alkylglycosides in particular monoglucosides, diglucosides, triglucosides or higher homologs and mixtures thereof whose hydroxyl groups are partially bonded with Cig alkyl groups are substituted.
  • DP degree of polymerization
  • alkyl glucosides the alkyl groups of a chain length of 6 to 18 carbon atoms , in particular 6 to 12 C atoms.
  • alkylglucosides whose alkyl groups have a chain length distribution or represent mixtures of alkylglucosides with different alkyl chains.
  • Alkyl glycosides are preferably substances consisting of a single ring of a sugar or a chain of rings of a sugar linked together with glycosidic linkages, the last ring of the glycosidic chain being acetalated with an alcohol.
  • Alkyl glycosides have the following general formula H- (G) w -O-R 'where
  • G represents a glycosidic unit
  • R ' represents the alkyl radical of an alcohol used to form the glycosidic acetal
  • w represents the average degree of polymerization, i. H. the number of linked glycosidic units is and stands for a number from 1 to 5.
  • the value w can be influenced in the synthesis by adjusting the molar ratio of alcohol to saccharide accordingly. By increasing this ratio, alkyl glycosides having a lower average value of w are obtained. Conversely, a higher degree of polymerization is achieved by a low molar ratio of alcohol to saccharide.
  • R ' is an alkyl radical and
  • the compounds are usually present as isomer mixtures.
  • the anomeric carbon atoms (glycosidic C atoms) are present as mixtures of the stereoisomers.
  • the preferred alkyl polyglucosides are mixtures of alkyl monoglucoside, alkyldiglucoside and alkyl triglucoside and optionally alkyl oligoglucoside, which may also contain (poly) glucoses and small amounts of the free alcohol ROH.
  • alkyl polyglucosides are possible, for example, by a direct synthesis starting from sugar with an excess of one or more alcohols.
  • a direct synthesis starting from sugar with an excess of one or more alcohols.
  • one starts from starch which is first reacted with lower alcohols (e.g., methanol, ethanol, butanol) in the presence of an acidic catalyst to form an alkylglucoside having a short chain glycosidic group (e.g., methyl, ethyl, butyl).
  • This intermediate is then reacted under vacuum with the long-chain alcohol R'-OH in the presence of an acid as catalyst by Umacetalmaschine, wherein the equilibrium by distilling off the lower alcohol is shifted.
  • alkyl glucosides are described in WO90 / 001489, US 5576425, DE 69824366 or in a publication by M. Biermann (Henkel KGaA), K. Schmid, P. Schulz in Starch - Horch - Hor, vol. 45 (8), p. 281-288 (1993).
  • alkylglucosides are, in particular, hexylglucoside, octylglucoside, decylglucoside, undecylglucoside, and dodecylglucoside and also their homologs, and the mixture of alkylmono-, di-, tri-, and optionally polyglucoside and mixtures from this series.
  • alkyl glycosides whose sugar moiety is composed of various sugar units.
  • alkyl glycosides which are composed exclusively of glucose units are particularly preferred.
  • the compounds of component c2) are available as commercial products: for example, a Cg-Cio-alkylpolyglucoside having a degree of polymerization (DP) of 1.6 under the trade name Glucopon® 215 CS UP (Cognis) is available.
  • Glucopon® 600 CS UP Cognis
  • Component c3) a Cg-Cio-alkylpolyglucoside having a degree of polymerization (DP) of 1.6 under the trade name Glucopon® 215 CS UP (Cognis) is available.
  • Component c3) Component c3
  • ester group-free alcohol alkoxylates of component c3) polyether alcohols are suitable, which are accessible in a conventional manner by alkoxylation of suitable starter molecules. Such are known, for example, from EP-A-1647563.
  • any mono- or polyhydric alcohols of molecular weight 88 to 438 can be used as starter molecules.
  • alkoxylates of aliphatic alcohols having a chain length of 5 to 30 carbon atoms and 1-25 alkoxy units.
  • chain center means those carbon atoms of the main chain, ie the longest alkyl chain of the radical R, beginning with the carbon atom C # 2, where the numbering starts from the carbon atom (C # 1) which is directly attached to the carbon atom Rest R adjacent oxygen atom is bound, and ending with the carbon atom ⁇ , which is the terminal carbon atom of the main chain, wherein C # 2 and the carbon atom ⁇ -2 are included.
  • C # 1 carbon atom
  • ⁇ which is the terminal carbon atom of the main chain
  • C # 2 and the carbon atom ⁇ -2 are included.
  • To ⁇ ⁇ _2 of the main chain of the radical R is substituted by a C j to C j o -alkyl radical. This is preferred
  • Carbon atom C # 2 of the main chain of the radical R substituted with a C ⁇ - to C j Q-alkyl radical.
  • one or more carbon atoms in the middle of the chain are substituted with two C 1 to C 4 alkyl radicals, that is, one or more carbon atoms in the middle of the chain are quaternary carbon atoms.
  • Particularly preferred is a mixture of alcohol alkoxylates based on 1 to 3 different alcohols ROH, more preferably on 1 or 2 different alcohols ROH.
  • the number of carbon atoms of the radical R may be different and / or the type of branching.
  • the main chain of the alcohols ROH has 1 to 4 branches, provided that the chain length allows more than one branch in the middle of the chain, more preferably 1 to 3, most preferably 2 or 3.
  • These branches are generally independently 1 to 10 carbon atoms, preferably 1 to 6, more preferably 1 to 3
  • Particularly preferred branches are therefore methyl, ethyl, n-propyl or iso-propyl groups.
  • the radical R of the alcohol ROH preferably has 5 to 30 carbon atoms.
  • the main chain comprises 4 to 29 carbon atoms.
  • the radical R has from 6 to 25 carbon atoms, more preferably from 10 to 20. That is, the main chain preferably has 5 to 24 carbon atoms, more preferably 9 to 19. Most preferably, the main chain has 9 to 15 carbon atoms and the others Carbon atoms of the radical R are distributed over one or more branches.
  • Preferred linear alcohols ROH are, for example, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, octadecyl alcohol, octadecenyl alcohol or hexadecenyl alcohol and also their technical mixtures.
  • the alkylene oxide reacted with the branched alcohols ROH to the alcohol alkoxylates used is preferably selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. It is also possible that a single alcohol ROH with various of said alkylene oxides, for. Ethylene oxide and propylene oxide, whereby alcohol alkoxylates each containing blocks of several units of an alkylene oxide, e.g. Ethylene oxide, in addition to blocks of several units of another alkylene oxide, e.g. Propylene oxide.
  • the alcohol alkoxylates used according to the invention particularly preferably comprise ethylene oxide (EO) units, that is to say that the alkylene oxide used is preferably ethylene oxide.
  • EO ethylene oxide
  • alkylene oxides mentioned e.g. Ethylene oxide and propylene oxide
  • the amounts of alkylene oxide used are preferably 1 to 25 moles of alkylene oxide per mole of alcohol, preferably 1 to 20 moles, more preferably 3 to 15 moles and most preferably 5 to 12 moles.
  • the compound containing carbamoylsulfonate groups in a mixture with an emulsifier, in particular one of component c1), c2 and / or c3), preferably component c1) and / or c2), in particular c1).
  • the carbamoylsulfonate group-containing compound is used as an aqueous composition containing
  • the carbamoylsulfonate-containing compound may or may not also contain other additives, for example carboxylic acids of component d) or salts thereof.
  • Suitable compounds of component d) are, in particular, monocarboxylic or polycarboxylic acids, preferably hydroxypolycarboxylic acids. Examples which may be mentioned are: formic acid, acetic acid, oxalic acid, glyoxylic acid, malonic acid, lactic acid, tartaric acid, maleic acid, glutaric acid, phthalic acid, adipic acid, malic acid, succinic acid, citric acid, or polycarboxylic acids such as (co) - polymers of (meth) acrylic acid, maleic acid, crotonic acid or Itaconic acid or derivatives thereof with optionally further monomers such as ethene, propene, styrene, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, especially those having an average molecular weight (weight average MW) of 500 to 100000 g
  • component d) is at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid or adipic acid, in particular at least one hydroxy-polycarboxylic acid, preferably citric acid, tartaric acid or lactic acid or mixtures thereof.
  • component e) is at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid or adipic acid, in particular at least one hydroxy-polycarboxylic acid, preferably citric acid, tartaric acid or lactic acid or mixtures thereof.
  • Preferred further additives of component e) may preferably be auxiliaries, such as fatliquoring agents, dedusting agents, organic tanning agents of component b), buffers and / or fillers, or may not be present.
  • Fatliquoring agents are preferably substances based on biological, mineral or synthetic oils which can be provided with hydrophilic groups in order to improve the usability in water, eg. B. by complete or partial sulfation, sulfitation, carboxylation or phosphating.
  • Suitable fillers are preferably inert inorganic salts and organic polymers in question, for.
  • sulfates such as sodium sulfate or calcium sulfate, talc, silica compounds, starch or lignosulfonates into consideration.
  • Suitable buffers are those which can be adjusted and stabilized by addition in a sufficient amount of a pH range, in particular a pH range of 1 to 5, preferably 2.0 to 3.5.
  • Suitable buffers for this are preferably mixtures of compounds of component d) and their salts in question.
  • Preferred salts are in particular alkali metal salts, preferably sodium or potassium salts.
  • Preferred dedusting agents in the case of a solid, particulate form of the carbamoylsulfonate-containing compound include, for example, alkoxylates of aromatic compounds or polyethers or certain mono- or diesters or certain mono- or diethers.
  • ethoxylates, propoxylates or mixed polyethers based on EO / PO wherein mentioned as aromatic compounds hydroquinone or phenol-styrene, polyethylene glycol having an average molecular weight of 100 to 800, polypropylene glycol having an average molecular weight of 100 to 800, EO / PO mixed polyether having an average molecular weight of 100 to 800, monoalkyl ethers or dialkyl ethers of the abovementioned polyethers, where the alkyl radical may have 1 to 4 carbon atoms, and mono- or dialkyl esters of the abovementioned polyethers with aliphatic carboxylic acids, such as, for example, acetic acid, Propionic acid, maleic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, citric acid.
  • Dustproofing agents based on mineral oil are also suitable. Dust removing agents are preferably used in an amount of 0 to 5.0, preferably
  • the carbamoylsulfonate group-containing compound used contains less than 1% by weight of organic or inorganic tanning agents, preferably less than 0.1% by weight.
  • the carbamoylsulfonate group-containing compound used is substantially free of organic or inorganic tannins, most preferably it is free of organic or inorganic tannins.
  • the carbamoylsulfonate-containing compound used can also be used together with organic tanning agents, in particular those of component b).
  • organic tanning agents in particular those of component b.
  • tanning agent combination 0 to 5 wt .-%, in particular 0 to 2 wt .-% water (residual moisture), in each case based on the material. It is also preferable for such a tanning agent combination to contain less than 1% by weight, preferably less than 0.1% by weight, of inorganic tannins, but essentially free of inorganic tannins, in each case based on the tanning agent composition.
  • the carbamoylsulfonate group-containing compound used can be prepared, for example, as an aqueous composition by mixing components a) and optionally further additives in water.
  • the compound of component a) can also be obtained, for example, by reacting at least one organic polyisocyanate with at least one bisulfite and / or disulfite in an organic or aqueous-organic solvent such as, for example, water / dioxane analogously to the procedure from DE102006056479-A1.
  • a process for preparing the carbamoylsulfonate-containing compounds which comprises reacting at least one organic polyisocyanate with at least one bisulfite and / or disulfite in the presence of water and optionally in the presence of an emulsifier of component c) and optionally in the presence of component d ) and optionally mixed with further additives and then optionally dried, preferably spray-dried.
  • hydrophobic leather and fur skins collagen fiber-containing substrates especially animal skins and skins are used with or without hair.
  • These are first prepared in a manner known to those skilled in the art and as usual in the water workshop.
  • the skins and skins prepared in this way are generally converted into a tanned product by treatment with compounds containing carbamoylsulfonate groups, which preferably has a shrinkage temperature of at least 65 ° C., preferably at least 68 ° C., particularly preferably at least 70 ° C.
  • the shrinkage temperature is determined by methods known to those skilled in the art, for example by heating the tanned intermediate by immersion in a water bath whose temperature is increased at a certain heating rate until the contraction of the material is observed.
  • the temperature reached on contraction is read on the display of the tester (Leather Shrinkage Tester).
  • the shrinkage temperature can also be determined by means of the differential scanning calorimetry (DSC) method known to the person skilled in the art.
  • the entire process for producing hydrophobized leathers and furskins involves various sub-steps, comprising simplified wet-end finishing and finishing of dry leather or fur skins.
  • the wet treatment steps include the Water workshop, tanning and retanning.
  • the water workshop again comprises several pretreatment steps: For the production of leather (hides and skins without hair) these are the steps soft, liming, deliming and stain, for the production of fur skins (skins and skins with hair) these are the steps dirt soft / soft, laundry and degreasing.
  • Subsequent tanning involves the steps of actual tanning, in which the shrinkage temperature of the collagen-containing substrate is increased and the folding.
  • the retanning generally comprises the partial steps of the actual retanning, greasing, dyeing, hydrophobing and fixing.
  • the finished leather (crust) obtained after completion of the work in wet end are finished as usual, for example, stretched out, dried and usually dressed.
  • the dry leather can optionally be provided in the usual manner in finishing with finishes or coatings to adapt the properties of the leather surface to the respective requirements for later use.
  • the fur skins obtained after completion of the work in wet end are completed as usual, for example by drying, cleats, degreasing, combing and ironing the hair coat. If desired, the fur skins can be further treated in order to adapt the properties of the leather surface to the respective requirements for later use.
  • the treatment with carbamoylsulfonate group-containing compounds is generally understood as the actual tanning.
  • the (tanned) material treated in the process according to the invention with the carbamoylsulfonate-containing compound can therefore already be referred to as leather, the so-called wet white.
  • leather the so-called wet white.
  • you can already perform conventional mechanical treatments such as wilting or folding.
  • a ready-to-use leather Crust
  • further treatment steps known per se such as in particular retanning, are required.
  • the process for the tanning of collagen fiber-containing substrates is preferably characterized in that, after the steps of the water workshop, hides pretreated as usual are treated with a compound containing carbamoylsulfonate groups.
  • the collagen fiber-containing substrate not be pickled prior to treatment with a carbamoylsulfonate group-containing compound.
  • a carbamoylsulfonate group-containing compound it is preferred that the collagen fiber-containing substrate not be pickled prior to treatment with a carbamoylsulfonate group-containing compound.
  • Organic reactive tannins in this context are, for example, those with aldehyde functions such as glutaric dialdehyde, glyoxal, succinic dialdehyde, adipic dialdehyde or degraded dialdehyde starch.
  • aldehyde functions such as glutaric dialdehyde, glyoxal, succinic dialdehyde, adipic dialdehyde or degraded dialdehyde starch.
  • organic tanning agents of component b) are not organic reactive tanning agents in the context of the invention.
  • the invention also relates to the use of polysiloxanes for hydrophobicizing collagen fiber-containing substrates, in particular leathers and furskins, which are treated in the presence of carbamoylsulfonate-containing compounds and optionally organic tanning agents, preferably those of component b), but in the absence of mineral or other organic reactive tanning agents have been.
  • the carbamoylsulfonate-containing compound is preferably added to the collagen fiber-containing substrates prepared in the water workshop, in particular skins and hides, at a pH value in the section of the substrate of from pH 5 to pH 10, preferably from pH 7 to pH 10, particularly preferably pH 8 to pH 10, and at a pH in the liquor of pH 5 to 10, preferably pH 6 to pH 9, more preferably pH 6 to pH 8 is added and leaves it for 0.1 to 8 hours, preferably 0.2 to 2 Hours penetrate into the entire cross-section of the substrate and then adds a fixative.
  • fixing agents in the tannery known bases or mixtures thereof are suitable, for example, sodium hydroxide, alkali metal carbonates, Alkalihydrogencarbonate, magnesium oxide, dolomite, tertiary amines, etc., but especially dolomite, magnesium oxide, sodium carbonate and sodium hydroxide solution.
  • the fixation is preferably carried out over a period of 2 to 24 hours, preferably 4 to 12 hours at a pH in the liquor of pH 7 to pH 10, preferably from pH 7.5 to pH 9.0, particularly preferably 7, 8 to 8.8.
  • the temperature in the fixing is preferably 15 to 60 ° C, more preferably 20 to 50 ° C, most preferably 25 to 45 ° C.
  • the appropriately prepared collagen fiber-containing substrates are preferably used in a commercially available tanning drum in an aqueous liquor at a temperature of 10 ° C. to 60 ° C. and a pH of 5 to 10, preferably 7 to 9, with 0.5 to 10%, preferably 1 to 4% of the carbamoylsulfonat phenomenon- containing compound based on pumice weight, wherein a tanned intermediate (leather) having a shrink temperature of at least 65 ° C, preferably at least 68 ° C, especially preferably at least 70 ° C receives.
  • the shrink temperature is determined by the methods known to those skilled in the art, for example by heating the tanned intermediate by immersion in a water bath whose temperature is raised at a certain heating rate until the contraction of the material is observed. The temperature reached on contraction is read on the display of the tester (Leather Shrinkage Tester).
  • the shrinkage temperature can also be determined by means of the differential scanning calorimetry (DSC) method known to the person skilled in the art.
  • the tanned intermediates obtained from the bloom material which are also referred to as wet white due to the light color, are suitable for mechanical further processing by z. B. Wilting, folding or splitting.
  • these intermediates are characterized by a very white, clear and light-fast intrinsic color, which is a clear advantage, for example, compared with glutardialdehyde tanned leathers, especially for the production of white leather.
  • the so-tanned leather can be retanned by other methods, and with well-known steps such as dyeing, greasing, water repellency to soft and airy Crustledem finished with the appropriate shades.
  • the actual tanning essentially serves to stabilize the hides and skins, which thereby become falzbar.
  • Organic tanning agents are, for example, those of component b), which often have more or less extensive filling and softening properties, some of which are dominated by modification in the tannin formulation, such as by addition of resin tanning agents, filling polymer tanning or plasticizing polymer tanning agents Property can be made.
  • all the usual non-tanning fatliquoring agents in the process according to the invention can also be used during the retanning.
  • the working steps of the actual retanning, dyeing and greasing are advantageously carried out in the pH range from 3.5 to 6.0, it being possible to co-use hydrophobicizing agents.
  • the actual hydrophobing is carried out at a pH of 3.5 to 7.0, preferably 3.5 to 6.
  • aluminum salts such as basic aluminum chloride, aluminum formate, titanium or zirconium salts such as zirconium sulfate may be added during the fixing step.
  • non-tanning fatliquoring agents are usually pre-emulsified in aqueous systems and usually contain emulsifiers. Furthermore, such emulsions or dispersions may sometimes contain organic solvents to promote deeper penetration and uniform distribution throughout the leather surface.
  • emulsifiers such as emulsions or dispersions may sometimes contain organic solvents to promote deeper penetration and uniform distribution throughout the leather surface.
  • non-tanning fatliquoring in Nachgerbön these can be used in amounts of up to 80 wt .-%, preferably up to 40 wt .-% solids, based on the shaved weight.
  • the weight ratio of organic tannins of component b) to non-tanning fatliquoring agents is in particular 99: 1 to 20:80, especially 95: 5 to 35:65.
  • the tanning described above can also be carried out with the concomitant use of organic tannins of component b), wherein these can be used or not be co-used.
  • the tanning agents of component b) can be used together with the carbamoylsulfonate group-containing compound or successively.
  • the tanning is followed, preferably by retanning, by treatment with organic tanning agents of component b), preferably with syntans and vegetable tanning agents. During the actual retanning, the desired leather properties are set.
  • organic tanning agents, syntans and vegetable tanning agents are preferably used.
  • polymer retanning agents for example those based on (co) polymers, are advantageously used here, as well as resin grafting agents, dyes, fatliquoring agents and proportionately hydrophobicizing agents.
  • resin grafting agents for example those based on (co) polymers
  • dyes for example those based on (co) polymers
  • fatliquoring agents for example those based on (co) polymers
  • proportionately hydrophobicizing agents are advantageously used here, as well as resin grafting agents, dyes, fatliquoring agents and proportionately hydrophobicizing agents.
  • these agents are used during the retanning in the usual quantities for wet white.
  • the advantage of the tanning process according to the invention is that pimple is no longer required, leather with a wide range of properties is obtained and the folding chips resulting from the mechanical processing do not contain any harmful compounds and can be used in many ways as raw materials, i.a. also for the production of valuable products, which in turn can be used in the leather manufacturing process. This provides a significant contribution to reducing wastes in leather production and simplifying the processing of shavings.
  • the wetted on the basis of Carbamoylsulfonat phenomenon termen compounds wet whites yield white, yellowing resistant, hydrophobized leather and fur skins whose softness is adjusted by the products used in the retanning.
  • the hydrophobized leathers are suitable, for example, for Waterproof shoe upper leather, as they show a very high level of waterproofness under dynamic load in the Bally Penetrometer or Maeser tester.
  • the raw material used is preferably dehydrated, in particular salted and / or air-dried, sheepskin.
  • the treatment of the raw material is usually carried out in a reel, the amounts of the funds used are given, for example, in grams per liter of liquor or in percent by weight, based on the wet weight of the hides and skins.
  • the method is preferably divided into the following steps, wherein the invention is not limited to this described embodiment, but includes any procedure for the treatment of fur skins with carbamoylsulfonate-containing compounds:
  • Step 2) Defoaming, optionally splitting the raw hides Step 3) washing with water in the presence of detergents (surfactants) and brighteners,
  • Step 4) optionally pimples for skin disruption with water, common salt and formic acid, usually in the presence of a bleaching agent, detergent and with the addition of an electrolyte-resistant fatliquoring agent,
  • Step 5 Tanning with compounds containing carbamoylsulfonate groups retanning:
  • Draining, hanging drying, conditioning eg wet with wet sawdust
  • cleats and sanding of the leather side combing the hair coat
  • dry-cleaning degreasing eg with sawdust or if necessary use of special closed equipment and treatment with organic solvents as in a dry cleaning
  • any commercial raw material is suitable and the hides and skins are usually treated in a reel. Most preferably, the hides and skins are first pretreated by a soak, switch, defibering and wash and then thoroughly washed.
  • the inventive method can also be carried out without pimples.
  • the washed hides and skins are treated in an aqueous sodium chloride solution (eg 5 ° Be) with the addition of carboxylic acids at pH 2 to 4 for several hours. Then it will be washed and then de-pipetted and degreased using sodium formate, sodium bicarbonate and surface-active compounds (surfactants), wherein the pH is gradually raised to pH 5 to 10.
  • the pickled material is then used for tanning.
  • the washed hides and skins are used directly for tanning. It is preferred that the skins and hides are not pickled prior to treatment with a carbamoylsulfonate group-containing compound.
  • the progress of the tanning is advantageously followed by measuring the shrinkage temperature of the substrate. If at least a shrinkage temperature of 65 ° C, preferably of at least 68 ° C, more preferably of at least 70 ° C is reached, the pH is lowered, drained the fleet and washed the fur skins.
  • the (tanned) material treated in the process according to the invention with the carbamoylsulfonate-containing compound can therefore already be referred to as wet white.
  • the so-tanned fur skins can then in the retannage (step 6) with
  • organic tanning agents in particular with those of component b), such as syntans, polymeric retanning agents, plasticizing polymer tanning agents,
  • Reservation agents may be added prior to staining if the hair is not to be dyed as well.
  • the dye is advantageously fixed by the addition of cationic auxiliaries after dyeing.
  • the liquor is preferably adjusted to a pH of from 2.5 to 4.5, preferably from 3 to 4, by addition of formic acid, and the fur is washed. 0
  • the retanned fur skins are then usually taken from the reel (step 7). It is drained and dried by hanging. Then the fur skins are dressed and, if necessary, degreased moist in the lautering barrel and dried. The meat side is ground if necessary. Finally, the hair is combed and ironed. It is also possible to treat the fur skins with tools against staining or against static charge, etc., for example, by a spray application of appropriate means.
  • the pretreated in the water workshop hides and skins with hair preferably in a coiler in an aqueous liquor with a fleet length of 300 to 1000%, based on wet weight, at a temperature of 10 ° C to 50 ° C with 0.5 to 10 %, preferably 1 to 5% of at least one compound containing carbamoylsulfonate groups, based on the wet weight of the hides and skins.
  • This gives preferably a tanned intermediate (fur, wet white) with a shrink temperature of at least 65 ° C, preferably at least 68 ° C, particularly preferably at least 70 ° C.
  • the skins and hides pretreated in the water workshop are preferably conditioned in the reel to a pH in the substrate cross section of pH 5 to pH 10, preferably pH 7 to pH 10, particularly preferably pH 8 to pH 10.
  • the carbamoylsulfonate group-containing compound at an initial pH in the substrate cross section of pH 5 to pH 10, preferably pH 7 to pH 10, more preferably pH 8 to pH 10 and an initial pH in the liquor of pH 5 to 10 , preferably pH 6 to pH 9, more preferably pH 6 to pH 8 added and allowed to penetrate 0, 1 to 8 hours, preferably 0.2 to 2 hours in the entire cross section of the substrate and then adds a fixing agent.
  • Suitable fixatives in the tannery known bases or mixtures thereof for example, sodium hydroxide, alkali metal carbonates, Alkalihydrogencarbonate, magnesium oxide, dolomite, tertiary amines, etc., but especially dolomite, magnesium oxide, sodium carbonate and sodium hydroxide.
  • the fixation is preferably carried out over a period of 2 to 24 hours, preferably 4 to 12 hours at a pH in the liquor of pH 7 to pH 10, preferably from pH 7.5 to pH 9.0, particularly preferably 7, 8 to 8.8.
  • the temperature in the fixing is preferably 15 to 60 ° C, more preferably 20 to 50 ° C, most preferably 25 to 45 ° C.
  • Preferred organic tanning agents of component b) are syntans, resin tanning agents, polymeric retanning agents and vegetable tanning agents.
  • the syntans are, for example, at least one condensation product based on
  • Base of means that the condensation product was optionally prepared from other reactants besides A, B and optionally C. Preferably, however, the condensation products in the context of this application are prepared only from A, B and optionally C.
  • sulfonated aromatics are also understood to mean sulfomethylated aromatics.
  • Preferred sulfonated aromatics are: naphthalenesulfonic acids, phenolsulfonic acid, sulfonated ditolyl ethers, 4,4'-dihydroxydiphenylsulfone, sulfonated diphenylmethane, sulfonated diphenyl, sulfonated terphenyl or benzenesulfonic acids, toluenesulfonic acids.
  • Suitable aldehydes and / or ketones are in particular aliphatic, cycloaliphatic and aromatic in question. Preference is given to aliphatic aldehydes, particular preference being given to formaldehyde and other aliphatic aldehydes having 3 to 5 C atoms.
  • urea derivatives for example dimethylolurea, melamine or guanidine can be mentioned.
  • Phenol and phenol derivatives such as, for example, phenolsulfonic acid, are often also linked by simultaneous action of formaldehyde and urea or by dimethylolurea (DE-A 1 113 457).
  • Sulfonation products of aromatic compounds are (according to Ullmann's Encyclopedia of Industrial Chemistry Volume 16 (4th edition) Weinheim 1979, p. 138) usually, without separating the unreacted starting compounds, alone or together with other starting compounds condensed with formaldehyde.
  • a solubilizing group can also be introduced in phenols by sulfomethylating with the simultaneous action of alkali hydrogen sulfite and formaldehyde together with the condensation. This sulfomethylation is described, for example, in DE-A 848 823.
  • condensation products are condensates of ditolyl ether sulfonic acid with 4,4'-dihydroxydiphenylsulfone, and of phenolsulfonic acid with phenol, formaldehyde and urea.
  • condensation products are those which are obtained by condensation of sulfonated and optionally non-sulfonated aromatics with aliphatic aldehydes, preferably formaldehyde, sulfonated aromatics in particular meaning no sulfomethylated aromatics.
  • condensation products are preferably obtained by condensation of sulfonated naphthalene and sulfonated phenol or 4,4'-dihydroxydiphenylsulfone with formaldehyde or by condensation of naphthalenesulfonic acid and formaldehyde or by condensation of sulfonated ditolyl ether, sulfonated phenol with formaldehyde or by condensation of sulfonated phenol, urea, phenol Formaldehyde or by condensation of sulfonated phenol, urea, phenol, sulfonated ditolyl ether with formaldehyde.
  • the condensation product preferably obtained in the condensation preferably has an average degree of condensation of 1 to 150, preferably from 1 to 20, in particular from 1 to 12.
  • organic tanning agents are polycondensates based on dihydroxydiphenylsulfone / naphthalenesulfonic acid and formaldehyde, dihydroxydiphenylsulfone / ditolyl ether sulfonic acid and formaldehyde, dihydroxydiphenylsulfone / phenolsulfonic acid / ditolyl ether sulfonic acid / urea and formaldehyde (commercial tanning agents such as TANIGAN® BN, TANIGAN® PR, TANIGAN® 3LN, TANIGAN ® HO, TANIGAN® UW from Lanxess or mixtures thereof).
  • the organic tanning agents used may contain other additives such as buffers or lignosulfonates.
  • Resin tanning agents are also suitable as organic tanning agents and are preferably polycondensates based on melamine, dicyandiamide, urea, lignin sulfonate or mixtures thereof with formaldehyde or glutardialdehyde.
  • the preferred polymeric retanning agents are high molecular weight water-soluble or water-dispersible products, e.g. B. from the (co) polymerization reaction of unsaturated acids and their derivatives with z. B. filling or greasing effect on leather. Preference is given to (co) polymerization of acrylic and methacrylic acid and their esters.
  • polymeric retanning agents are the polyaspartic acid amides described in WO 97/06279, having a number average molecular weight of from 700 to 30,000, preferably from 1,300 to 16,000, obtainable by reacting
  • polymeric retanning agents are, for example, (co) polymers which are a) structural units of the general formula I
  • R 1 and R 2 are independently hydrogen, optionally substituted alkyl radicals, alkenyl radicals, aralkyl radicals or cycloalkyl radicals represented by O Atoms, N atoms, Si atoms or amide, carbonate, urethane, urea, allophanate, biuret, isocyanurate groups or mixtures thereof may be interrupted and M is H or an alkali ion, an NH 4 ion or a primary, secondary, tertiary or quaternary aliphatic ammonium radical which preferably bears a C 1 -C 22 -alkyl or -hydroxyalkyl group, b) at least 10 mol% to the units of the formula I, structural units of the general formula Ia
  • R 3 is a hydrocarbon radical having C 1 -C 8 -atom atoms, preferably a saturated C 1 -C 6 -alkyl radical, in particular C 1 -C 3 -alkyl radical, and R 4 is hydrogen or has the same meaning as R 3 , and c) polyether radical Contain units with an average molecular weight of 200-6000 g / mol.
  • Vegetable tannins are derived, for example, from vegetable sources tannins from the classes of condensed tannins or hydrolyzable tannins z. As chestnut extract, Mimosa, Tara or Quebracho. Vegetable tanning agents also include those derived from vegetable sources such as algae, fruits, e.g. Rhubarb, olives, plant parts such as leaves, tree bark, roots, wood may optionally be obtained after a chemical or enzymatic modification and / or by extractive methods.
  • the organic tanning agents of component b) are usually in the form of aqueous solutions or aqueous dispersions in amounts of 3 to 100 wt .-%, preferably 10 to 50 wt .-% solids, based on the shaved weight of the leather or based on the wet weight the fur skins, in Nachgerb intimid and in amounts of 0 to 50 wt .-%, preferably 0 to 30% by weight of solid, based on the bladder weight of hides and skins (hairless) or based on the wet weight of hides and skins ( with hair), used in tanning.
  • the hydrophobing can be done in one or more steps.
  • hydrophobizing agent it is particularly advantageous to add a subset of the hydrophobizing agent before or during the addition of organic tanning agents, the actual retanning.
  • the majority of the hydrophobizing agent is preferably used after the actual retanning, optionally together with other fatliquoring agents and / or plasticizing polymers.
  • the hydrophobizing agents are preferably fixed in the customary manner by acidification to, for example, pH 2.5 to 4, preferably with formic acid.
  • salts such as aluminum sulfate, aluminum formate, zirconium sulfate, titanyl sulfate may also be used as auxiliary for fixing.
  • polysiloxanes are suitable as water repellents.
  • Polysiloxanes are here to be understood as meaning relatively high molecular weight (polymeric) oxygen compounds of silicon, which have as repeat units Si-O-Si groupings;
  • the Si atoms contribute to the saturation of the remaining valences hydrogens, heteroatoms such as N, Cl or F or in particular organic radicals, especially methyl groups (polyorganosiloxanes).
  • polysiloxanes as silicones, silicone oils or silicone polymers.
  • a typical example of such a polysiloxane is poly (dimethylsiloxane) of the general formula
  • the polysiloxanes may be free of functional groups or carry functional groups.
  • the designated polysiloxanes carry as functional groups amino groups, hydroxyl groups, mercapto groups, carboxyl groups, phosphonate groups, sulfo groups and / or sulfosuccinic acid monoester groups.
  • Such functional groups improve the emulsifiability of the polysiloxanes in aqueous liquors and improve the binding of the polysiloxanes to the leather fibers.
  • the said functional groups in particular the amino, hydroxyl, mercapto, carboxyl and sulfo groups, are not bonded directly to the main polymer chain but via spacer groups, for example C 2 - to C 40 -alkylene groups.
  • the polysiloxanes generally contain on average from 1 to 10 per molecule of these functional groups. Join sulfo or Carboxyl groups, these are usually in partially or completely neutralized form, ie usually as alkali metal, for example sodium or potassium, or ammonium or amine salts, before.
  • Typical carboxyl group-containing polysiloxanes are described as Lederhydrophobierstoff in general, for example, in EP-B 324 345.
  • the polysiloxanes can also be substituted by hydroxyl groups, alkoxy groups, chlorine atoms and / or fluorine atoms on the Si atoms or on the C atoms of the organic radicals.
  • the carboxyl-functionalized polysiloxanes used are comb-like water-repellent agents in which the carboxyl groups are attached via spacer groups in the form of linear or branched C 2 - to C 10 -alkylene groups which are replaced by up to 8 non-adjacent oxygen atoms or amino groups, carbonyl groups or carboxamide groups are interrupted and may additionally carry up to 5 carboxyl groups or Carbonklamid phenomenon are bound to the polymer backbone, wherein the spacer groups are connected via a direct bond or via an oxygen atom or an amino group, carbonyl group, carboxamide or carboxylic acid ester group with the polymer main chain.
  • Such comb-like carboxyl-functionalized polysiloxanes are described in WO-A 95/22627.
  • carboxyl-containing polysiloxanes are known, for example, from EP-Al 108765, which are characterized in that the polysiloxane chain contains at least one structural unit of the formula (1) and / or at least one structural unit of the formula (2)
  • A is a carboxyl group-containing radical of the formula stands in the
  • R1, R2 and R3 independently represent hydrogen or a monovalent C2-C60 hydrocarbon radical optionally containing one or more nonadjacent ether, imino, amide, urea, urethane, ester or carboxyl groups, and optionally is substituted with one or two carboxyl groups -COOM and / or 1 or 2 hydroxyl groups, and wherein the radical A is at least substituted by a group COOM, wherein
  • M is hydrogen or Na +, K +, Li +, (NH 4 ) +, where R 4 , R 5 and R 6 independently of one another are C 1 -C 18 -alkyl, in particular C 1 -C 4 -alkyl or substituted C 1 -C 18 -alkyl, in particular hydroxyalkyl, or aralkyl, especially benzyl, and wherein Rl to R3 are independently linked via a single bond, a group -COO-, -CO- or -CONH- to the nitrogen atom, and wherein R1 and R2 are not simultaneously H and also are not simultaneously linked to the nitrogen atom via a carbonyl group, D and E independently of one another are a divalent C 2 -C 20 -hydrocarbon radical which may be substituted by hydroxyl or interrupted by nonadjacent O atoms, q is 0 to 3,
  • R is a C 1 to C 12 alkyl radical or a phenyl radical, a is 0 or 1, k is 0 to 50, c is 1 or 2, and n is 10 to 1000, with the proviso that at least one end group of the Formula (3 a) is present in the event that the polysiloxane chain contains only structural units of the formula (2).
  • Bl is an anionic copolymer
  • B2 is polyaspartic acid or a derivative thereof
  • B3 is a paraffin
  • B4 is an isocyanate addition product.
  • the carboxyl groups corresponding to the anhydride groups are not reacted with alcohol and / or amine but are neutralized with a base, - at least 50 mol% of the carboxyl groups are neutralized.
  • the component Bj is present as an aqueous dispersion.
  • copolymers which are prepared by copolymerization of a monomer mixture of 20-90% by weight of a hydrophobic monomer, in particular stearyl methacrylate, hexadecyl methacrylate, eicosanyl methacrylate, dodecyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, and 80-10% by weight of one hydrophilic monomer, in particular methacrylic acid, acrylic acid, maleic anhydride, and 0-30% by weight of another comonomer from the group of styrene, alpha-methylstyrene, diisobutylene.
  • a hydrophobic monomer in particular stearyl methacrylate, hexadecyl methacrylate, eicosanyl methacrylate, dodecyl methacrylate, octyl methacrylate, 2-ethylhexyl methacryl
  • polyacrylate dispersions prepared by free-radical polymerization in the presence of a chain regulator and whose carboxyl groups have been neutralized with a base, wherein the monomer mixture used from 60 to 85 wt .-% stearyl methacrylate or C - 4-methacrylate and 15-40 wt .-% acrylic acid.
  • Dispersions which are prepared by dispersion in the presence of component B3 described below are also preferred.
  • component B3 is in this embodiment in particular
  • the proportion of component B3, based on the active ingredient from B2 + B3, is preferably between 30 and 80 wt .-%, the proportion of solid resin Bj between 20 and 70 wt .-%.
  • Particularly preferred polyacrylate dispersions have an average molecular weight of 2,000 to 50,000 g / mol, preferably 2,000 to 20,000 g / mol.
  • Such dispersions can be prepared, for example, according to EP 579 267, EP 498 634, US Pat. No. 5,348,807.
  • the dispersions of component Bj preferably have a solids content of from 10 to 60% by weight, preferably from 20 to 50% by weight.
  • Suitable polyacrylate dispersions are known per se. Examples of particularly suitable polyacrylate dispersions are the products available from LANXESS
  • a preferred component B2 is a polyaspartic acid derivative having a number average molecular weight of 700 to 30,000, preferably 1,300 to 16,000, obtainable by reacting
  • Suitable components B2 are known per se and described in DE 195 28 782 or EP 842 300.
  • a preferred component B3 is a paraffinic hydrocarbon optionally substituted by
  • Hydroxyl and / or carboxyl groups may be substituted (white oil 285, paraffin oil, paraffin wax, montan wax, carnauba wax, oxidized polyethylene, long-chain fatty alcohols such as Guerbet alcohols, fatty acids, fatty acid esters, phospholipids), wherein the paraffinic hydrocarbon preferably together with the component B j and / or B2 gives a stable dispersion.
  • the components B3 are present as aqueous dispersions.
  • the fixed content of such components B3 is not limited to 0.
  • Dispersions is 5 to 60 wt .-%>, preferably 10 to 35 wt .-%>. It is furthermore particularly preferred to use component B3 together with component B j and B2.
  • the component B3 is preferably added to component B j and / or B2 and converted into a stable dispersion by the application of high shear forces with the aid of customary dispersing machines, dissolvers, homogenizers or ultrasound machines.
  • a preferred component B4 is a reaction product
  • B4-C per equivalent of NCO or latent NCO contained in B4-a) 0.1 to 1.0 mol of cyanamide
  • component B4-d) ammonia or volatile amine as neutralizing agent for the cyanamide groups, wherein the reaction products are free of polyester or polyether groups and free of halogen atoms. It is particularly preferred to use the component B4 as a self-inhibiting emulsifier in admixture with component a) and / or in a mixture with the components to B3 or mixtures thereof. It is very particularly preferred to use component B4 in combination with component a).
  • these mixtures have the following composition:
  • component B4 based on solids content
  • component a) based on active substance / solids content
  • EP-A-757108 EP-A-891430, DE-A-4214150, EP-A-579267 and EP-A-372746.
  • polysiloxanes described as hydrophobizing agents are usually employed as aqueous emulsions or dispersions, in particular as microemulsions or macroemulsions, preferably microemulsions.
  • the hydrophobicizing process according to the invention requires no organic solvents and can be carried out particularly well in many cases if the aqueous emulsion of the polysiloxanes additionally paraffins, which may be solid and / or liquid, for example those having a melting point of up to 100 ° C, paraffin oils or white oils, Mineral oils, natural fats or natural oils, for example fish oil or bone oil, or synthetic or natural waxes, for example polyethylene waxes, polyisobutylene waxes, beeswax or carnauba wax, normally in an amount of up to 90% by weight, in particular up to 50% by weight, especially up to 30 wt .-%, contains.
  • paraffins which may be solid and / or liquid, for example those having a melting point of up to 100 ° C, paraffin oils or white oils, Mineral oils, natural fats or natural oils, for example fish oil or bone oil, or synthetic or natural waxes, for example polyethylene waxes, polyisobutylene waxes,
  • emulsifiers are, in principle, all surface-active compounds of nonionic, anionic, cationic or amphoteric character in aqueous systems which sufficiently emulsify the polysiloxanes and paraffins, paraffin oils, fats, oils and waxes used and do not impair the hydrophobization, but in particular N- (C9- C2o-acyl) amino acids having 2 to 6 carbon atoms in the amino acid parent such as N-oleoylsarcosine, N-stearoylsarcosine, N-lauroylsarcosine or N-isononanoylsarcosine; the latter are mostly in the form of their alkali metal, ammonium or trialkanolamine salts.
  • the polysiloxane emulsion usually contains 3 to 30 wt .-%, in particular 5 to 25 wt .-%, especially 7 to 18 wt .-% emulsifiers, wherein mixtures of said emulsifiers can be used.
  • Such combinations of polysiloxanes and Emulsifiers are described as Lederhydrophobierstoff generally in EP-B 213 480.
  • the emulsifiers mentioned under component c) are also suitable.
  • the described polysiloxane emulsions usually contain from 3 to 90% by weight, in particular from 5 to 60% by weight, in particular from 7 to 40% by weight, of polysiloxanes.
  • the emulsions are normally used in amounts of from 0.1 to 20% by weight, in particular from 0.5 to 15% by weight, based on the shaved weight of the leather or the wet weight of the furs. It may be advisable to dilute the emulsions (concentrates) described in the ratio of 1: 2 to 1: 5 with water and add the working stock in the leather hydrophobing.
  • polysiloxanes are used which are based on microemulsions of polysiloxane-active substances known per se. Suitable microemulsions are known from WO2011 / 042409. Particularly preferred polysiloxanes contain trimethylsiloxy units as end groups and in a chain randomly arranged methyl (N-2-aminoethyl-3-aminopropyl) siloxy units and dimethylsiloxy units, wherein polysiloxane active substances with a content of 0.3 to 1, 0 mmol N / g are preferred.
  • the preparation of microemulsions is known per se to those skilled in the art and is carried out using emulsifiers and co-surfactants.
  • microemulsions based on emulsifiers belonging to the group of alkyl polyglycosides and based on cationic and amphoteric or zwitterionic cosurfactants or surfactants. They are characterized in that they have an improved storage stability compared to macroemulsions because they represent thermodynamically stable mixtures. Suitable microemulsions have a dry residue of 30 to 50 weight percent, the concentration of polysiloxane is 15 to 35 weight percent, based on microemulsion.
  • Very particularly preferred polysiloxane-containing microemulsions are known, for example, from WO 201 1/042409, comprising a) 100 parts by weight of one or more polyorganosiloxanes which have one or more polar Si-C-bonded hydrocarbon radicals, b) from> 50 to 150 parts by weight of a c) 0.1 to 150 parts by weight of one or more cosurfactants selected from the group of amphoteric or zwitterionic surfactants, amine oxide surfactants and cationic surfactants, and d) water.
  • aqueous silicone emulsions are used as hydrophobizing agents in the process according to the invention, comprising
  • the polysiloxanes preferably contain 0.3 to 1.0 mmol N Ig, preferably 0.3 to 0.6 mmol N Ig of amino groups, the ratio of component 2) to 1) is less than 1, and the emulsions have an average particle size d50 of less than 100 nm (laser light scattering).
  • the hydrophobization according to the invention can be carried out in one or more stages.
  • Dyes which can be used simultaneously include, for example, the commonly used acidic, substantive or basic aniline dyes. It is also advantageous to co-use polycarbamoylsulfonate-containing compounds during or after treatment with certain polysiloxanes for hydrophobization. This procedure is particularly advantageous when using polysiloxanes which contain amino groups. By the use of the fixation of the polysiloxanes can be influenced in an advantageous manner and it can be obtained even more hydrophobized leather.
  • the actual hydrophobing according to the invention is generally carried out by walking in a suitable apparatus in a conventional manner, i. at liquor lengths of 50 to 2000%, preferably 100 to 400%, based on the shaved weight of the leather or the wet weight of the fur skins, and at temperatures of 20 to 60 ° C, preferably 35 to 50 ° C, wherein at the beginning the pH values usually between 4.5 and 8.0, preferably 4.8 to 5.5, lie.
  • the hydrophobing is completed in a time of 20 to 240, preferably 30 to 120 minutes.
  • an optionally used emulsifier is usually fixed with acid, preferably formic acid, by adjusting a pH from 3.0 to 5.0, preferably from 3.8 to 4.0.
  • acid preferably formic acid
  • a pH preferably 3.0 to 5.0, preferably from 3.8 to 4.0.
  • the effect of the hydrophobization can be enhanced by an aftertreatment with a ternary, trivalent or tetravalent metal salt, in particular with a basic aluminum chloride, with aluminum sulfate, aluminum formate, titanium sulfate, zirconium sulfate, calcium chloride or magnesium sulfate.
  • salts mentioned expediently, based on the shaved weight of the leather or the wet weight of the fur skins, 0.5 to 5 wt .-%, preferably 1 to 2 wt .-%, is used. Of the indicated salts, basic aluminum chloride, aluminum triformate, titanium and zirconium sulfate are preferred. Many of the as Hydrophobicizing agents described above polysiloxanes require to achieve a good hydrophobizing effect no metal salt fixation.
  • the invention also relates to collagen fiber-containing substrates, in particular leather and fur skins, which have been tanned with at least one carbamoylsulfonate-containing compound and have been rendered hydrophobic with at least one polysiloxane.
  • collagen fiber-containing substrates in particular leather and fur skins, which have been tanned with at least one carbamoylsulfonate-containing compound and have been rendered hydrophobic with at least one polysiloxane.
  • the preferred forms described above also apply here.
  • Example AI Preparation of Polycarbamoyl Sulfonate and Syntan
  • sorbitan polyethylene glycol (20) monododecanoate eg Eumulgin SML 20 (Cognis) or Tween 20 (Croda)
  • HLB 16.7 alkoxylated
  • sodium bisulfite solution NaHS0 3 , 38-40% in water
  • stirring 1 358.3 g of hexamethylene diisocyanate added within 40 minutes
  • the temperature of the reaction mixture is adjusted to 50 ° C.
  • the pH is 5.62.
  • 70.3 g of citric acid (anhydrous) dissolved in 70.3 g of water are added.
  • the mixture is stirred for 1 hour at 50 ° C, the reaction mixture is clear. Then it is cooled to 25 ° C within 2 hours. It is stirred for 1 hour at room temperature (20-23 ° C).
  • the pH of the solution is 4.67.
  • 211.3 g of citric acid (anhydrous) dissolved in 211.3 g of water are added and stirred for 15 minutes. The concentration is adjusted by adding 258.7 g of water. A clear 35.0% solution with a pH of 3.11 is obtained.
  • the batch is filtered.
  • the clear solution has a pH of 4.34.
  • a solution having a solids content of 35.25% by weight and a pH of 2.12 is obtained.
  • a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.20.
  • Example A 2c polycarbamoylsulfonate without syntan
  • To this template are added at 20 ° C 138.6 g of hexamethylene diisocyanate in one portion.
  • the temperature of the reaction mixture is increased to 50 ° C. with dispersion within 60 minutes.
  • 7.8 g of citric acid monohydrate dissolved in 6.5 g of water are added, resulting in a pH of 3.05.
  • the mixture is kept for 1 hour at 50 ° C and then cooled to 25 ° C within 2 hours.
  • the pH of the clear solution is 2.92 at room temperature.
  • 3000 ml of acetone are added to this solution. It is stirred for 2 hours.
  • the precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 93.5%, residual moisture 0.7 wt .-%).
  • a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.4.
  • Example A3 Preparation of a water repellent emulsion
  • the intermediate thus produced is admixed with 12.5 g of caprolactone and 100 g of ethyl acetate at 55 ° C. 0.16 g of zinc octoate and 10 g of ethyl acetate are then added. The mixture is stirred at about 75 ° C.
  • Example A4 Preparation of a Hydrophobizing Microemulsion (according to Example 1, WO 2011/042409)
  • the mixture was acidified to pH 5 with 1.2 g of acetic acid and heated to 70 ° C for 30 minutes. A clear microemulsion was obtained. Neutralization with 2.0 g of a 60% solution of triethanolamine gave a final pH of 8. Then 1.0 g of a 30% solution of parabens in 2-phenoxyethanol was added as a material protection agent. It was an optically clear emulsion having an average particle size of 65 nm (LS), a silicone content of 20 wt .-% and a total solids content of 34.2% by weight, a viscosity of 4.3 mPa * s at 23 ° C. receive. After 5 weeks storage at 40 ° C, the emulsion was unchanged.
  • Example A5 Preparation of a Hydrophobizing Microemulsion (according to Example 2, WO 2011/042409)
  • Example A6 Preparation of a Hydrophobizing Microemulsion (according to Example 3, WO 2011/042409)
  • a slightly opaque emulsion was obtained.
  • the emulsion was acidified to pH 5 with 1.2 g of acetic acid and heated at 60 ° C. for 1 hour to give a microemulsion.
  • the resulting product was an optically clear emulsion having an average particle size of 87 nm (LS), a silicone content of 15% by weight, a total solids content of 33.85% and a viscosity of 8.15 mPa s at 23 ° C.
  • LS average particle size of 87 nm
  • silicone content 15% by weight
  • a total solids content of 33.85%
  • a viscosity of 8.15 mPa s at 23 ° C After 5 weeks at 40 ° C, the emulsion was unchanged. Dilution of the emulsion with a 10% NaCl solution in the ratio 5: 2 showed no change.
  • the emulsion was also stable to pH 8 on neutralization with triethanolamine or a soda solution. In each of these cases, the
  • the amounts of each of the products used are based on the weight of the raw materials or intermediates used.
  • Example B 1A Preparation of Wet White for Upper Shoe Salted cowhides are commercially washed, limed, depilated, fleshed, and split.
  • the pumice material (2.6 mm) is washed with 200% liquor and drained the liquor.
  • the bins are prepared in 100% liquor and 0.2% sodium bisulphite, 0.1% of an ammonium-free decalcifying agent (eg Cismollan DLP, product of LANXESS) and 0.2% of a mixture of dicarboxylic acid derivatives (eg Cismollan DL, product of LANXESS) for 30 minutes at 30 ° C.
  • the fleet is drained.
  • the prepared buff is conditioned for 30 minutes with 50% water, 0.2% sodium bicarbonate and 1% sodium acetate to pH 9.0 and treated with 1.7% of the product from Example AI (powder). After a penetration time of 20 minutes, a further 3.4% of the product from Example AI (powder) are added. During the following 1.5 hours at 40 ° C., the pH is adjusted to 8.1 by adding a total of 0.5% sodium carbonate (diluted 1:10 with water). Then the drum is moved for a further 2 hours at 40 ° C and the shrinkage temperature is measured (pH 7.65, Ts 68 ° C). The drum is moved for 2 hours in automatic mode (10 minutes / hour) and the pH is measured.
  • Comparative Example B 2A Preparation of Wet White for Upper Leather with Glutaric Dialdehyde (GTA) Salted cowhides are commercially washed, limed, depilated, fleshed, and split. The pumice material (2.6 mm) is washed with 200% liquor and drained the liquor. The bins are now delimed in the barrel in 100% liquor and 0.3% sodium bisulfite, 2.5% ammonium chloride, 0.2% formic acid 85% for 30 minutes. Then 0.5% of a Beizenzym (1000 trypsin units) is added and the barrel is agitated for 1 hour. The pH is 8.5. The liquor is drained and the breeze washed for 10 minutes and drained the fleet again.
  • GTA Glutaric Dialdehyde
  • the bins are then mixed with 30% water, 6% sodium chloride, 0.3% of a preservative (eg Preventol WB Plus L, product of LANXESS) 0.5% formic acid 85%, 0.90% sulfuric acid 96% for 70 minutes at 30 ° C moves.
  • a preservative eg Preventol WB Plus L, product of LANXESS
  • 1.00% of a fatliquor e.g., Eureka 975 ES-I
  • the liquor pH is 2.9.
  • 3.0% of an aqueous glutaraldehyde solution GTA, about 24%, pH 1.5-2.5
  • GTA aqueous glutaraldehyde solution
  • the drum is moved for another 2 hours in automatic mode (10 minutes / hour) and the pH is measured (pH 2.9).
  • 1.00% sodium formate is added and after 15 minutes runtime, another 1.00% sodium formate is added, resulting in a pH of 3.6.
  • 1.00% of a neutralizing tanning agent based on aromatic sulfonic acids e.g., TANIGAN PAK, product of LANXESS
  • TANIGAN PAK aromatic sulfonic acids
  • 0.2% sodium bicarbonate is added and agitated for 30 minutes (pH 4.0).
  • 3.0% of a 4,4'-dihydroxydiphenylsulfone based tanning agent e.g., Tanigan HO, product of LANXESS
  • Tanigan HO product of LANXESS
  • the liquor is drained, washed with 200% water and drained again.
  • the Wet White is stored on the box.
  • the shrink temperature is measured again (70 ° C).
  • the leathers can wither without problems and fold to a thickness of 1, 2 mm.
  • Example B 3A Preparation of Wet White for Shoe Upper Leather with Tanning Agents from Example A2a Analogously to Example B 1A, wet white was prepared using 2.1% by weight of the tanning material from Example A2a.
  • Example B 4A Preparation of wet white for shoe upper leather with tannins from example A2b
  • Example B 1A Wet white was prepared analogously to Example B 1A using 2.1%, based on pum weight, of the tanning agent from Example A2b.
  • Example B 5A Preparation of Wet White for Shoe Upper Leather with Tanning Agents from Example A2c Analogously to Example B 1A, wet white was prepared using 2.1%, based on the weight of the body, of Example A2c.
  • the amounts used of the products in the examples under C) refer to the shaved weight.
  • Example C1 Preparation of a hydrophobized shoe upper with silicone from example A3 c h r m m e r, c a p p i n g m i t 2% A I + 2% Z r
  • Example B 1A Folded wet white (thickness 1.3 / 1.4 mm) according to Example B 1A is applied in a tanning drum with a liquor of 120% water (40 ° C.) and 0.5% of a carboxylic acid mixture (eg BLANCOROL CGA, product of LANXESS) Washed for 40 minutes.
  • the fleet has a pH of 4.3 and is drained.
  • a plasticizing polymer tanning agent based on a modified polyamide carboxylic acid eg LEVOTAN LB, product of LANXESS
  • a polycondensate based on aromatic sulfonic acid and phenolic compounds eg TANIGAN VR, product of LANXESS
  • 3.0% of a polyacrylate-based filler polymer tanning material eg, Leukotan 8090, product of Dow Chemical
  • a second hydrophobing step 150% water, 4.0% of a polyacrylate dispersion with long-chain hydrocarbons (eg Lubritan XB, product of Dow Chemical), 4.0% of the hydrophobizing agent according to Example A3, 2.0% of a fatliquoring agent (eg Atlasol WRM, product of Atlas) and 1, 0%> claw oil (30 ° CT) (diluted 1: 5 with water) was added and the barrel was agitated for 60 minutes. Then 0.6% of> formic acid is added. The liquor has a pH of 3.6 after 60 minutes and is drained off.
  • a polyacrylate dispersion with long-chain hydrocarbons eg Lubritan XB, product of Dow Chemical
  • a hydrophobized leather with very good values is obtained in the Bally penetrometer test: Penetration takes place only after more than 8 hours (compression 10%). With the help of the Maeser tester, a first water passage in the water bath was observed after about 35000 buckling.
  • Example C2 Preparation of a hydrophobized shoe upper with silicone from Example A3.
  • Metal-free, capping with Retingan R4-B Folded wet white split leather (thickness 1.6 mm) according to example B1A is applied in a tannery with a liquor of 120% water (40 ° C), and 0.5% of a carboxylic acid mixture (eg BLANCOROL CGA, product of LANXESS) for 60 minutes.
  • the fleet has a pH of 4.4 and is drained.
  • a plasticizing polymer tanning agent based on a modified polyamide carboxylic acid eg LEVOTAN LB, product of LANXESS
  • a polycondensate based on aromatic sulfonic acids and phenolic compounds eg TANIGAN VR, product of LANXESS
  • a polyacrylate-based polymer tanning filler eg, Leukotan 1093, product of Dow Chemical
  • a polyacrylate dispersion with long-chain hydrocarbons eg Lubritan XB, product of Dow Chemical
  • Example C3 Preparation of a hydrophobized shoe upper with silicone from example A3, metal-free, capping with MgSO 4
  • Example C3 the procedure is analogous to Example C2). However, unlike Example C2, 4.0% of magnesium sulfate is added in place of RETINGAN R4-B and agitated for 120 minutes. After draining the fleet and washing, the leather (50 ° C Pasting) dried and staked. There are obtained hydrophobized leather with a pleasantly soft feel.
  • Example C4 Preparation of a hydrophobized shoe upper with silicone from example A3, chromium-free, capping with 2% AI + 2% Zr
  • Folded wet white split leather (thickness 1.8 mm) according to example B1A is washed in a tannery with a liquor of 120% water (40 ° C.), and 0.5% of a carboxylic acid mixture (eg BLANCOROL CGA, product of LANXESS) for 60 minutes , The fleet is drained.
  • a carboxylic acid mixture eg BLANCOROL CGA, product of LANXESS
  • a polyacrylate-based filler polymer tanner eg, Leukotan 8090, product of Dow Chemical
  • a second hydrophobing step 150% water, 4.0% of a polyacrylate dispersion with long-chain hydrocarbons (eg Lubritan XB, product of Dow Chemical), 4.0% of the hydrophobizing agent according to Example A3, 2.0% of a fatliquoring agent (eg Atlasol WRM, product of Atlas) and 1.0% claw oil (30 ° CT) (diluted 1: 5 with water) was added and the barrel was agitated for 60 minutes. Then 0.8% formic acid is added. The liquor has a pH of 3.6 after 20 minutes and is drained off.
  • a polyacrylate dispersion with long-chain hydrocarbons eg Lubritan XB, product of Dow Chemical
  • a fatliquoring agent eg Atlasol WRM, product of Atlas
  • claw oil 30 ° CT
  • so-hydrophobized leathers show a passage of water in the Bally penetrometer test (10%> compression) only after more than 8 hours.
  • the water absorption was 7.4% after 2 hours, after 6 hours 10.2% and after 8 hours 10.8%.
  • Example C5 Preparation of a hydrophobized shoe upper with silicone from example A4, chromium-free, capping with 2% AI + 2% Zr
  • Example C4 The procedure was analogous to Example C4), but in each case instead of the hydrophobizing agent from Example A3, the hydrophobizing agent from Example A4 was used.
  • Example C6 Preparation of a hydrophobized shoe upper with silicone from example A5 without chromium, capping with 2% AI + 2% Zr
  • Example C7) Preparation of a hydrophobized shoe upper with silicone from Example A6 without chromium, capping with 2% AI + 2% Zr
  • Folded Wet White (thickness 1, 8 mm) based on glutaraldehyde tanning according to example B2A is applied in a tannery with a liquor of 120% water (40 ° C.) and 0.5% of a carboxylic acid mixture (eg BLANCOROL CGA, product of LANXESS ) Washed for 60 minutes.
  • the fleet is drained.
  • a plasticizing polymer tanning agent based on a modified polyamide carboxylic acid eg LEVOTAN LB, product of LANXESS
  • a polycondensate based on aromatic sulfonic acids and phenolic compounds eg TANIGAN VR, product of LANXESS
  • 3.0% of a polyacrylate-based filler polymer tanner eg, Leukotan 8090, product of Dow Chemical
  • a second hydrophobing step 150% water, 4.0% of a polyacrylate dispersion with long-chain hydrocarbons (eg Lubritan XB, product of Dow Chemical), 4.0% of the hydrophobizing agent according to Example A3, 2.0% of a fatliquoring agent (eg Atlasol WRM, product of Atlas) and 1.0%> claw oil (30 ° CT) (diluted 1: 5 with water) and the barrel is agitated for 60 minutes. Then 0.8% formic acid is added. The liquor has a pH of 3.6 after 20 minutes and is drained off.
  • a polyacrylate dispersion with long-chain hydrocarbons eg Lubritan XB, product of Dow Chemical
  • a fatliquoring agent eg Atlasol WRM, product of Atlas
  • claw oil 30 ° CT
  • Example C9 Preparation of a hydrophobized shoe upper with wet white B3A and with
  • Example CIO Preparation of a hydrophobized shoe upper with wet white B4A and with
  • Example C4 chromium-free, capping with 2% Al + 2% Zr
  • Example C4A chromium-free, capping with 2% Al + 2% Zr
  • Example Cl1 Preparation of a hydrophobized shoe upper with wet white B5A and with silicone from Example A3
  • Example C4 The procedure was analogous to Example C4), but as a raw material not wet white BIA, but B5A, and each hydrophobing agent from Example A3 was used. In this case too, excellent water resistance and Maesere values of around 40,000 flexes were achieved.
  • the amounts of each of the products used are based on the weight of the raw materials or intermediates used.
  • Example D 1 medical sheepskin, chromium-free In a standard reel, air-dried sheepskin containing 20 l of water per skin and 2.0 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) at 25 ° C backwashed overnight and then defiled.
  • a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) at 25 ° C backwashed overnight and then defiled.
  • a fatty alcohol ethoxylate eg Cismollan AN 90, product of LANXESS
  • the thus prepared skins (3000 g wet weight) are degreased at 35 ° C twice in aqueous liquor with 2.0 g / 1 of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) for every 60 minutes and After draining the fleet thoroughly rinse with warm water.
  • a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) for every 60 minutes and After draining the fleet thoroughly rinse with warm water.
  • the sheepskins are white and dry with a pleasantly soft feel.
  • the sheepskins are hydrophobic and have a greatly reduced static water absorption of less than 30%.
  • Example D 2 medical sheepskin, chromium free
  • Example D 1 was repeated, but 6.2 g / l of the powder product from Example A2a was used instead of the product from Example AI for tanning.
  • Example D1 After 90 minutes, instead of the magnesium oxide used in Example D1, the pH is increased to 8.1 by addition of 0.75 g / l sodium carbonate (diluted 1:10) in three doses and the procedure is continued as in Example D1.
  • the hydrophobizing agent used again is the product from Example A3.
  • the sheepskins have a shrinking temperature of 77 ° C, are white and have a pleasantly soft feel.
  • the static water absorption is less than 30%.
  • Example D 3 medical sheepskin, chromium free
  • Example D 1 was repeated, but 6.2 g / l of the powder product from Example A2b was used instead of the product from Example AI for tanning.
  • Example D1 After 90 minutes, instead of the magnesium oxide used in Example D1, the pH is increased to 8.1 by addition of 0.75 g / l sodium carbonate (diluted 1:10) in three doses and the procedure is continued as in Example D1.
  • Example A4 As a hydrophobing agent, the product of Example A4 is now used in the same dosage.
  • the sheepskins have a shrinking temperature of 75 ° C, are white and have a pleasantly soft feel.
  • the static water absorption is less than 25%.
  • Example D 4 medical sheepskin, chromium free
  • Example D 1 was repeated except that 6.2 g / l of the powder product from Example A2c was used instead of the product from Example AI for tanning.
  • Example D1 After 90 minutes, instead of the magnesium oxide used in Example D1, the pH is increased to 8.1 by addition of 0.75 g / l sodium carbonate (diluted 1:10) in three doses and the procedure is continued as in Example D1.
  • Example A5 As a hydrophobing agent, the product of Example A5 is now used in the same dosage.
  • the sheepskins have a shrinking temperature of 76 ° C, are white and have a pleasantly soft feel.
  • the static water absorption is less than 30%.
  • Example D 5 medical sheepskin, chromium free
  • Example D 1 was repeated and 10 g / l of the product of Example AI were used for tanning.
  • Example D1 After 90 minutes, instead of the magnesium oxide used in Example D1, the pH is increased to 8.1 by addition of 0.75 g / l sodium carbonate (diluted 1:10) in three doses and the procedure is continued as in Example D1.
  • Example A6 As a hydrophobing agent, the product of Example A6 is now used in the same dosage.
  • the sheepskins have a shrinking temperature of 74 ° C, are white and have a pleasantly soft feel.
  • the static water absorption is less than 30%.
  • Example D 6 Sheepskin for decorative purposes, chrome-free (with pimple)
  • the prepared skins (3000 g wet weight, defiled) are diluted at 20 ° C. in an aqueous liquor with 0.2 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) (1: 5) ) Washed for 30 minutes.
  • a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) (1: 5) Washed for 30 minutes.
  • a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone e.g., Tanigan BN, product of LANXESS
  • 15 g / 1 tare 15 g / 1 tare are added.
  • a further 15 g / l of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone eg Tanigan BN, product of LANXESS
  • 20 g / l of a synthetic fatliquoring agent eg Baykanol Licker TSI, product of LANXESS
  • the sheepskins show a shrinkage temperature of 75 ° C and are white. They are water-repellent and have a static water absorption of less than 40%.
  • Example D 7 Sheepskin for decorative purposes, chrome-free (without pimples)
  • Example D 6 Analogously to Example D 6, the prepared skins (3000 g wet weight, defiled) at 20 ° C in an aqueous liquor with 2.0 g / 1 of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) (diluted 1: 5) twice for 60 minutes and degreased. The fleet is drained and it is thoroughly washed.
  • a nonionic emulsifier based on a fatty alcohol ethoxylate eg Cismollan AN 90, product of LANXESS
  • a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone e.g., Tanigan BN, product of LANXESS
  • 15 g / 1 tare 15 g / 1 tare are added.
  • a further 15 g / 1 of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone eg Tanigan BN, product of LANXESS
  • 20 g / 1 of a synthetic fatliquoring agent eg Baykanol Licker TSI, product of LANXESS
  • Example D 8 Sheepskin for decorative purposes, chrome-free (without pimples)
  • Example D 6 Analogously to Example D 6, the prepared skins (8500 g wet weight, uncleaved skins) at 20 ° C in aqueous liquor (5 ° Be) with 2.0 g / 1 of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90 , Product of LANXESS) (diluted 1: 5) twice for 60 minutes and degreased. The fleet is drained and it is thoroughly washed.
  • a nonionic emulsifier based on a fatty alcohol ethoxylate eg Cismollan AN 90 , Product of LANXESS
  • the skins are conditioned in fresh liquor (20 L water) with 2.0 g / l sodium carbonate (diluted 1:10) overnight (pH on average 7.5) and the liquor is drained off.
  • the tanning in fresh liquor (20 L water) is then first pretreated for 30 minutes with 0.1 g / l sodium acetate and 0.1 g / l sodium carbonate (diluted 1:10). Then 15.0 g / l of the powder product of Example AI are added. After 4 hours, add 0.75 g / 1 sodium carbonate (1:10 diluted) in three doses of pH increased to 8.1 and 150 minutes tanned (TS 70 ° C).
  • the sheepskins show a shrinkage temperature of 72 ° C. They are water-repellent and have a static water absorption of less than 40%.
  • Example D 9 Sheepskin for decorative purposes, chrome-free (without pimples, with coloring)

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un procédé d'hydrophobisation de substrats contenant des fibres de collagène et traités avec au moins un composé contenant des groupes carbamoylsulfonate. Ledit procédé est caractérisé en ce que, après avoir traité le substrat contenant des fibres de collagène avec au moins un composé contenant des groupes carbamoylsulfonate, on effectue une hydrophobisation en présence d'au moins un polysiloxane.
PCT/EP2012/065562 2011-08-12 2012-08-09 Procédé d'hydrophobisation de substrats contenant des fibres de collagène WO2013023980A1 (fr)

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EP11177375.0 2011-08-12
EP11177375A EP2557181A1 (fr) 2011-08-12 2011-08-12 Procédé d'hydrophobisation de substrats contenant des fibres de collagène

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WO1998038340A1 (fr) * 1997-02-26 1998-09-03 Bayer Aktiengesellschaft Cuir biodegradable
EP0891430A1 (fr) 1996-04-01 1999-01-20 Basf Aktiengesellschaft Utilisation de copolymerisats a base d'acides dicarboxyliques ou d'anhydrides d'acides dicarboxyliques ethyleniquement insatures, d'olefines inferieures et de comonomeres hydrophobes pour le retannage, la mise en suif et l'impermeabilisation du cuir et des fourrures
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DE69824366T2 (de) 1997-10-30 2005-06-02 Sasol Italy S.P.A. Verfahren zur Synthese von Alkylpolyglucosiden
EP1647563A2 (fr) 2004-10-15 2006-04-19 Lanxess Deutschland GmbH Agents de tannage à base d' isocyanates
DE102006056479A1 (de) 2006-11-28 2008-05-29 Henkel Kgaa Bisulfit-Addukte von Isocyanaten
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DE1113457B (de) 1959-05-27 1961-09-07 Basf Ag Verfahren zur Herstellung lichtechter Kondensationsprodukte durch Umsetzung sulfonierter Phenole mit Harnstoff und Formaldehyd
DE1670666A1 (de) 1966-02-02 1971-07-01 Bayer Ag Verfahren zur Herstellung von Oxadiazinonen mit NCO-Gruppen
DE2308015A1 (de) 1973-02-17 1974-09-12 Bayer Ag Verfahren zur herstellung von polyisocyanaten mit biuretstruktur
EP0213480B1 (fr) 1985-08-21 1989-01-25 BASF Aktiengesellschaft Procédé d'hydrofugation du cuir et des fourrures
DE3700209A1 (de) 1987-01-07 1988-07-21 Bayer Ag Verfahren zur herstellung von polyisocyanaten mit biuretstruktur
DE3743782A1 (de) 1987-12-23 1989-07-13 Bayer Ag Ester-urethan-(meth)-acrylsaeurederivate
EP0324345B1 (fr) 1988-01-12 1992-04-15 BASF Aktiengesellschaft Procédé pour rendre hydrophobes le cuir, les fourrures et les cuirs synthétiques
EP0336205A2 (fr) 1988-04-02 1989-10-11 Bayer Ag Procédé pour la préparation d'isocyanuratepolyisocyanates, les composés obtenus à partir de ce procédé et leur utilisation
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EP1108765A2 (fr) 1999-12-13 2001-06-20 Bayer Ag Hydrophobisation avec des polysiloxanes ayant des groupes carboxyliques
EP1647563A2 (fr) 2004-10-15 2006-04-19 Lanxess Deutschland GmbH Agents de tannage à base d' isocyanates
DE102006056479A1 (de) 2006-11-28 2008-05-29 Henkel Kgaa Bisulfit-Addukte von Isocyanaten
WO2011042409A2 (fr) 2009-10-05 2011-04-14 Momentive Performance Materials Gmbh Émulsions aqueuses de polyorganosiloxanes

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