Classifications

• • C—CHEMISTRY; METALLURGY
  • C14—SKINS; HIDES; PELTS; LEATHER
  • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
  • C14C3/00—Tanning; Compositions for tanning
  • C14C3/02—Chemical tanning
  • C14C3/08—Chemical tanning by organic agents
• • 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-1647563 are known aqueous compositions containing at least one carbamoylsulfonate group-containing compound and at least one alcohol alkoxylate.
• 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, skins and hides 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 reproduction and finishing to the ready-to-use material and are 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 skins and skins in which the keratinic constituents, in particular animal hairs, were removed in the liming mill in the water workshop and which were used as un-split blossoms or after splitting as crevices, meat crevices or middle crevices 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.
• Carbamoylsulfonat phenomenon brave compounds 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: -NH-CO-SO 3 - K + where 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 used, for example, by W. Siefken in Liebig's Annalen der Chemie 562, pages 75 to 136 to be discribed.
• Preferred polyisocyanates are compounds of the formula Q (NCO) n having an average molecular weight below 800, wherein n is a number of at least 1.8, preferably from 1.8 to 4.2, Q is an aliphatic C 4 -C 12 hydrocarbon radical, a cycloaliphatic C 6 -C 15 -hydrocarbon radical or a heterocyclic C 2 -C 12 radical having 1 to 3 heteroatoms from the series oxygen, sulfur, nitrogen, for example (i) diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6 Hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 2-isocyanatomethyl-1,8-octamethylene diisocyanate, 1,3-diisocyanato-cyclobutane, 1-isocyanato-2-isocyanatomethyl-cyclopentane, 1,3- and 1,4-diisocyanato-cycl
• Particularly preferred polyisocyanates are those having a molecular weight of less than 400 g / mol with NCO groups attached to aliphatics or cycloaliphatic compounds, for example 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 1,5-diisocyanato-2, 2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane (TMHI), 1,3- and 1,4-diisocyanatohexane, 1,3- and 1,4-diisocyanato cyclohexane (CHDI) and any mixtures of these isomers, 1-isocyanato-2-isocyanatomethyl-cyclopentane, 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) -cyclohexane and any desired mixtures of isomers, 1,2 -, 1,3- and 1,4
• 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 composed of trimeric 1,6-diisocyanatohexane, trimeric 1,2-, 1,3- 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 (isocyana
• 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 US Pat DE-A 1 670 666 .
• DE-A 3 700 209 and DE-A 3 900 053 and in the EP-A 336,205 and EP-A 339 396 are described by way of example.
• Suitable polyisocyanates are, for example, the polyisocyanates containing ester groups, such as, for example, the tetrakis or triisocyanates obtainable by reaction of pentaerythritol or trimethylolpropane silyl ethers with isocyanatocaproic acid chloride (cf. DE-A 3 743 782 ).
• ester groups such as, for example, the tetrakis or triisocyanates obtainable by reaction of pentaerythritol or trimethylolpropane silyl ethers with isocyanatocaproic acid chloride (cf. DE-A 3 743 782 ).
• triisocyanates such as tris-isocyanatodicyclohexylmethane.
• 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.
• aliphatic, cycloaliphatic and araliphatic diisocyanates Particularly preferred are 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 isomers and 1-isocyanato-3,3,5-trimethyl
• Preferred bisulfites and / or disulfites are their alkali metal or ammonium salts, in particular the sodium salts of sulfurous or disulfurous acid, ie sodium bisulfite (NaHSO 3 ) or sodium disulfite (Na 2 S 2 O 5 ).
• 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 carbamoylsulfonate-containing compounds based on aliphatic polyisocyanates such as hexamethylene diisocyanate, 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 desired mixtures of these isomers, 1,2-, 1,3- and 1,4-bis (isocyanato-n-propyl) Cyclohexane and any mixtures of these isomers, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 2,4 'and 4,4'-diisocyanato-dicyclohexylmethane or nonyl triisocyanate and
• 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 group-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 in particular a material having an average particle size of 0.1 .mu.m to 1000 .mu.m, preferably 1 to 800 .mu.m, in particular 50 to 300 microns, wherein the average value based on the mass (weight average) of all particles.
• Other means can be calculated by analytical methods and vice versa.
• the average particle size can be determined, for example, microscopically.
• the solid material is present as powder or granules.
• the particulate solid material has a residual moisture of 0 to 10 wt .-%, in particular 0 to 5 wt .-%, particularly preferably 0 to 2 wt .-%, based on the material.
• the particulate solid material is usually based on any, preferably a spherical or spherical shape-like or derived particle structure. There are also agglomerates of particles from the mentioned forms in the range of the specified particle size in question.
• the particulate solid material contains 1 to 100%, preferably 10 to 100%, most 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 monostearate, ethylene glycol 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 with 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
• partial fatty acid esters of polyhydric alcohols with saturated fatty acids
• nonionic emulsifiers are at least one nonionic, ester group-containing, alkoxylated polyol having an HLB value of at least 13 (c1) and / or an alkyl glycoside (c2) and / or a nonionic ester group-free alkoxylated alcohol (c3).
• the preferred nonionic, ester group-containing, alkoxylated polyols of component c1) have an HLB value of from 13 to 19, in particular from 14 to 18, the HLB value being determined by the method Griffin, WC: 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.
• Preferred 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 carbamoylsulfonate group-containing compounds 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 c1) 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.
• 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.
• 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 with various of the above alkylene oxides, e.g. Ethylene oxide and propylene oxide, to obtain sorbitan 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. Particularly preferably, the sorbitan alkoxylates contain ethylene oxide (EO) units, preferably exclusively. In such a case, the alkylene oxide used is particularly preferably ethylene oxide.
• EO 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.
• the following 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
• Further preferred compounds of component c1) 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.
• Particularly preferred are alkoxylated monoglycerol monoesters.
• Suitable for alkoxylation are C 2 to C 6 alkylene oxides, particularly preferably ethylene oxide, preference is given to 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, especially 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 components c1) are likewise available as commercial products, for example glycerol monostearate ethoxylate with an average of 20 EO units as Cutina® E 24 (Cognis), hydrogenated castor oil ethoxylate with an average of 40 EO units as Eumulgin® HRE 40 (Cognis).
• alkyl monoglycosides, alkyl diglycosides, alkyl triglycosides and higher homologs generally referred to herein as alkyl glycosides, in particular monoglucosides, diglucosides, triglucosides, or higher homologues and mixtures thereof, whose hydroxyl groups partially with C 6 -C 18 Alkyl groups are substituted.
• alkylglucosides whose alkyl groups have a chain length of 6 to 18 carbon atoms , in particular 6 to 12 C atoms.
• Suitable are alkyl glycosides in which w is a number from 1 to 5 and R 'is the radical of a linear or branched aliphatic alcohol having 6 to 30 carbon atoms. These products are known per se and commercially available.
• 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.
• 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 proportions of the free alcohol R'OH.
• alkyl polyglucosides are possible, for example, by a direct synthesis starting from sugar with an excess of one or more alcohols.
• starch is used which is first reacted with lower alcohols (eg methanol, ethanol, butanol) in the presence of an acidic catalyst to give an alkylglucoside having a short-chain glycosidic group (eg methyl, ethyl, butyl).
• This intermediate is then reacted under vacuum with the long-chain alcohol R'-OH in the presence of an acid as a catalyst by transacetalization, the equilibrium being shifted by distilling off the lower alcohol.
• 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 C 8 -C 10 -alkyl polyglucoside having a degree of polymerization (DP) of 1.6 is available under the trade name Glucopon® 215 CS UP (Cognis). A C 12 -C 16 -alkylpolyglucoside with a DP of 1.4 is available, for example, under the trade name Glucopon® 600 CS UP (Cognis).
• 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.
• suitable starter molecules such are for example EP-A-1647563 known.
• 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.
• linear or branched, saturated or unsaturated alcohol alkoxylates which are obtained by reacting at least one alcohol ROH with n moles of at least one alkylene oxide per mole of alcohol ROH, wherein R is an alkyl radical having 5 to 30 carbon atoms, which has a main chain having 4 to 29 carbon atoms, which is branched in the middle of the chain with at least one C 1 -C 10 alkyl radical, the alkylene oxide has 2 to 6 carbon atoms and where n is a value from 1 to 25.
• 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, the numbering starting 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.
• the carbon atom C # 2 of the main chain of the radical R is preferably substituted by a C 1 - to C 10 -alkyl radical.
• one or more carbon atoms in the middle of the chain are substituted with two C 1 to C 10 alkyl radicals, ie that 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. Since the group R preferably has at least one branch with at least one carbon atom, the main chain comprises 4 to 29 carbon atoms. Preferably, 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, e.g. 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-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 its derivatives 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.
• 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 tannins, 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.
• tanning agent combination 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 the components a) and optionally further additives in water.
• the compound of component a) can also be prepared, 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 DE102006056479-A1 to be obtained.
• an organic or aqueous-organic solvent such as, for example, water / dioxane analogously to the procedure DE102006056479-A1 to be obtained.
• the skins and skins prepared in this way are generally converted into a tanned product by treatment with carbamoylsulfonate-containing compounds, 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
• 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, Ausgereckt, dried and usually staked.
• 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 is not pickled prior to treatment with a carbamoylsulfonate group-containing compound.
• a treatment step of the collagen fiber-containing substrate to be tanned, in particular the hides and skins in which the collagen fiber-containing substrate is treated with strong acids and salt, preferably with a mixture containing formic acid and / or sulfuric acid in the presence of sodium chloride, at which the pH the aqueous tanning liquor is set to 2 to 3.5.
• the treatment with a carbamoylsulfonate group-containing compound and in particular also all subsequent steps of the process according to the invention are preferably carried out in the absence of mineral or other organic reactive tanning agents other than compounds containing carbamoylsulfonate groups.
• 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 organically reactive tanning agents in the context of the invention.
• the invention also relates to the use of polysiloxanes for hydrophobing collagen fiber-containing substrates, in particular tanned hides and skins, i. leather and furskins treated in the absence of mineral or other organic reactive tanning agents other than carbamoylsulfonate group-containing compounds and optionally in the presence of organic tanning agents, preferably those of component b).
• the carbamoylsulfonate-containing compound at a pH in the section of the substrate from pH 5 to pH 10, preferably from pH 7 to pH 10, particularly preferably from 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.
• 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 float 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 correspondingly prepared collagen fiber-containing substrates are preferably in a commercial Gerbkraft in 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 carbamoylsulfonate-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.
• so-tanned leather can be retanned by other methods, and with well-known steps such as dyeing, greasing, water repellency soft and airy crust leather 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 simultaneously more or less extensive filling and softening properties, in some cases by modification in the tannin formulation, such as the addition of resin tanning agents, filling polymer tanning or plasticizing polymer tanning agents, to the dominant characteristic can be made.
• modification in the tannin formulation such as the addition of resin tanning agents, filling polymer tanning or plasticizing polymer tanning agents, to the dominant characteristic 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 hydrophobization 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.
• non-tanning fatliquoring When co-use of non-tanning fatliquoring in Nachgerbitz 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 in succession.
• the tanning is followed, preferably by retanning, by treatment with organic tanning agents of component b), preferably with syntans and vegetable tanning agents.
• organic tanning agents, syntans and vegetable tanning agents are preferably used.
• polymeric retanning agents for example those based on (co) polymers, as well as resin tanning agents, dyes, fatliquoring agents and proportionately hydrophobicizing agents, are advantageously used here.
• 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.
• 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 by means of 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 hides and skins 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.
• 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.
• 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 struck, 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 for 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.
• condensation product was optionally prepared from other reactants besides A, B and optionally C.
• condensation products in the context of this application are preferably prepared only from A, B and, if appropriate, 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.
• Suitable non-sulfonated aromatics are, for example, phenol, cresol or dihydroxydiphenylsulfone, dihydroxydiphenylmethane, ditolyl ether, dihydroxyditolyl ether, dihydroxyditolylsulfone, hydroxybenzoic acid.
• urea derivatives for example dimethylolurea, melamine or guanidine can be mentioned.
• Phenol and phenol derivatives such as phenolsulfonic acid, are often linked by the 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) in general . 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 eg in DE-A 848 823 described.
• 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).
• 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.
• 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 the Nachgerb intimid and in amounts of 0 to 50 wt .-%, preferably 0 to 30 wt .-% solids, based on the bladder weight of hides and skins (without hair) 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. 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). Often called such polysiloxanes as silicones, silicone oils or silicone polymers.
• a typical example of such a polysiloxane is poly (dimethylsiloxane) of the general formula (CH 3 ) 3 Si-O- [Si (CH 3 ) 2 -O] x -Si (CH 3 ) 3
• 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 functional groups mentioned, in particular the amino, hydroxyl, mercapto, carboxyl and sulfo groups, are preferably not attached directly to the polymer main chain but via spacer groups, for example C 2 -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 generally used as leather water repellents, for example in US Pat EP-B 324 345 described.
• 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.
• comb-type carboxyl-functionalized polysiloxanes are used as hydrophobizing agents in which the carboxyl groups are interrupted via spacer groups in the form of linear or branched C 2 -C 40 -alkylene groups which are interrupted by up to 8 non-adjacent oxygen atoms or amino groups, carbonyl groups or carboxamide groups and additionally may carry up to 5 carboxyl groups or carboxamide groups attached to the polymer backbone, the spacer groups being linked to the polymer backbone via a direct bond or via an oxygen atom or an amino group, carbonyl group, carboxylic acid amide group or carboxylic acid ester group.
• Such comb-like carboxyl-functionalized polysiloxanes are in the WO-A 95/22627 described.
• copolymers prepared by copolymerizing a monomer mixture of 20-90% by weight of a hydrophobic monomer, especially stearyl methacrylate, hexadecyl methacrylate, eicosanyl methacrylate, dodecyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, and 80-10% by weight of a 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 especially stearyl methacrylate, hexadecyl methacrylate, eicosanyl methacrylate, dodecyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, and
• polyacrylate dispersions prepared by 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 .-% of stearyl methacrylate or C 17.4- methacrylate and 15-40% by weight of acrylic acid.
• Dispersions which are prepared by dispersion in the presence of component B 3 described below are also preferred.
• component B 3 especially white oil or a liquid C 14 -C 17 paraffin oil or a wax melting at 30-40 ° C. is particularly preferred in this embodiment.
• the proportion of component B 3 based on the active ingredient of B 1 + B 3 , is preferably between 30 and 80 wt .-%, the proportion of solid resin B 1 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 may, for example, be EP 579,267 . EP 498 634 . U.S. Patent 5,348,807 getting produced.
• the dispersions of component B 1 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 the Lubritan ® / Leukotan ® series (Dow Chemical), especially Lubritan ® WP, Leukotan ® NS3, Lubritan ® XB, Lubritan ® AS, Lubritan ® SP.
• Suitable components B2 are known per se and in the DE 195 28 782 respectively. EP 842 300 described.
• a preferred component B 3 is a paraffinic hydrocarbon which may optionally be substituted by hydroxyl and / or carboxyl groups (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 1 and / or B 2 gives a stable dispersion.
• the components B 3 are present as aqueous dispersions.
• the solids content of such dispersions is 5 to 60 wt .-%, preferably 10 to 35 wt .-%. It is furthermore particularly preferred to use component B 3 together with component B 1 and B 2 .
• component B 3 is preferably added to component B 1 and / or B 2 and converted into a stable dispersion by using high shear forces with the aid of customary dispersing machines, dissolvers, homogenizers or ultrasound machines.
• component B 4 as a self-inhibiting emulsifier in admixture with component a) and / or in a mixture with the components B 1 to B 3 or mixtures thereof.
• component B 4 in combination with component a).
• EP-A-757 108 It can also be used, for example, in EP-A-757 108 .
• EP-A-891430 DE-A-4214150 .
• EP-A-579267 and EP-A-372 746 described means are used.
• 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, 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 all 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, for example fish oil or bone oil, or synthetic or natural waxes, for example polyethylene waxes, polyisobutylene waxes, bees
• emulsifiers are, in principle, all surface-active compounds in aqueous systems of nonionic, anionic, cationic or amphoteric character, which sufficiently emulsify the polysiloxanes and paraffins, paraffin oils, fats, oils and waxes used and does not impair the hydrophobization, but in particular N- (C 9 -C 20 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 generally used as leather water repellents in the EP-B 213 480 described.
• the emulsifiers mentioned under component c) are also suitable.
• the described polysiloxane emulsions usually contain 3 to 90 wt .-%, in particular 5 to 60 wt .-%, especially 7 to 40 wt .-% 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 known. 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 which belong 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, for example, from WO 2011/042409 known, comprising a) 100 parts by weight of one or more polyorganosiloxanes having one or more polar Si-C-bonded hydrocarbon radicals, b) from> 50 to 150 parts by weight of one or more alkyl polyglucosides, c) 0.1 to 150 parts by weight of one or more Co Surfactants selected from the group of amphoteric or zwitterionic surfactants, amine oxide surfactants and cationic surfactants, and d) water.
• the hydrophobization according to the invention can be carried out in one or more stages.
• dyes which can be used simultaneously for example, the commonly used acidic, substantive or basic aniline dyes come into consideration.
• 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 45 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.
• 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.
• 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.
• 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.
• the salts mentioned expediently, based on the shaved weight of the leather or the wet weight of the fur skins, 0.5
• 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.
• 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.
• Example A 2a Polycarbamoylsulfonate without syntan
• 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.
• the temperature of the reaction mixture is 3 hours after addition of the isocyanate 60 ° C. After a reaction time of 3.5 hours, the organic phase has disappeared. It is then cooled in 1.5 hours to 40 ° C, while further dispersed at 15000 revolutions per minute. After a total reaction time of 5 hours, the mixture is filtered and mixed with a solution of 28.3 g of citric acid monohydrate in 23.4 g of water, resulting in a pH of 2.58. A 35.0% solution with a pH of 2.58 is obtained.
• a solution of 326.5 g of water, 461.7 g of sodium bisulfite solution (NaHSO 3 , 38-40% in water) and 9.8 g of an adduct of 2 moles of citric acid and 1 mole of hexamethylene diisocyanate obtained by drying the aqueous solution, Dispersion at 12000 revolutions per minute).
• 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. After reaching 50 ° C., 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.
• Example A3 Preparation of a water repellent emulsion
• 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 wt .-%, a viscosity of 4.3 mPa * s at 23 ° C. receive. After 5 weeks storage at 40 ° C, the emulsion was unchanged. Dilution with a 10% NaCl solution in the ratio 5: 2 showed no change. The emulsion was also stable against dilution with a 10% soda solution.
• Example A5 Preparation of a Hydrophobizing Microemulsion (according to Example 2, WO 2011/042409)
• the mixture was acidified to pH 5 with 1.3 g of acetic acid. A clear microemulsion was obtained. Neutralization with 2.0 g of a 60% triethanolamine solution gave a final pH of 8. Finally, 1.0 g of a 30% solution of parabens in 2-phenoxyethanol was added as a material protection agent.
• the product obtained was an optically clear emulsion having an average particle size of 66 nm (LS), a silicone content of 20% by weight, a total solids content of 38.9%. After 5 weeks at 40 ° C, the emulsion was unchanged. The dilution of the emulsion with 10% NaCl solution in the ratio 5: 2 showed no change. The emulsion was also stable when diluted with a 10% soda solution.
• 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 amounts of each of the products used are based on the weight of the raw materials or intermediates used.
• Salted cowhides are washed commercially, limed, depilated, fleshed, and split.
• the pumice material (2.6 mm) is washed with 200% liquor and drained the liquor.
• the pots are casked in 100% liquor and 0.2% sodium bisulfite, 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 pelt 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 A1 (powder). After a penetration time of 20 minutes, a further 3.4% of the product from Example A1 (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 cask is moved for 2 hours in automatic mode (10 minutes / hour) and the pH is measured.
• a preservative eg Preventol U-Tec G, product on LANXESS
• the pH is reduced to 4.3 with 0.3% formic acid (85%, 1: 1 of 0).
• the fleet is drained.
• the wet white leather are washed and 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.
• Salted cowhides are washed commercially, limed, depilated, fleshed, and split.
• the pumice material (2.6 mm) is washed with 200% liquor and drained the liquor.
• the pods 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.
• 0.5% of a Beizenzym 1000 trypsin units
• the pH is 8.5.
• the fleet is drained and the pelts washed for 10 minutes and drained the fleet again.
• the pots are now filled 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. Then 1.00% of a fatliquor (e.g., Eureka 975 ES-I) is added and agitated for 3 hours. The liquor pH is 2.9. Subsequently, 3.0% of an aqueous glutaraldehyde solution (GTA, about 24%, pH 1.5-2.5) are added and pre-tanned for 2 hours. The drum is moved for another 2 hours in automatic mode (10 minutes / hour) and the pH is measured (pH 2.9).
• a preservative eg Preventol WB Plus L, product of LANXESS
• 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 tannins from Example A2a
• 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 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 tannins from example A2c
• 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 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 without chromium, capping with 2% A1 + 2% Zr
• 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 polyacrylate-based filler polymer tanning material eg, Leukotan 1093, product of Dow Chemical
• a polyacrylate-based filler polymer tanning material eg, Leukotan 1093, product of Dow Chemical
• the liquor has a pH of 4.4 and is further reduced to pH with 1.2% formic acid (diluted 1:10 with water) Acidified 3.9. After stirring for 30 minutes in a barrel, the liquor is drained and the leather washed.
• 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% 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 fatliquoring agent eg Atlasol WRM, product of Atlas
• claw oil 30 ° CT
• 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 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 has a pH of 4.4 and is drained.
• a carboxylic acid mixture eg BLANCOROL CGA, product of LANXESS
• a polyacrylate-based filler polymer tanner eg, Leukotan 1093, product of Dow Chemical
• Polyacrylate-based polymer tanning material e.g., Leukotan 1093, product of Dow Chemical
• diluted 1: 3 with water was added and agitated for 30 minutes. After adding 100% water (45 ° C) and 1.0% formic acid (diluted 1:10 with water) is stirred for 20 minutes. Then it is further acidified to pH 3.95 with 1.2% formic acid (diluted 1:10 with water). After stirring for 30 minutes in a barrel, the liquor is drained and the leather washed.
• 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% 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 fatliquoring agent eg Atlasol WRM, product of Atlas
• claw oil 30 ° CT
• Example C3 Preparation of a hydrophobized shoe upper with silicone from example A3, metal-free, capping with MgSO4
• Example C3 the procedure is analogous to Example C2). However, unlike Example C2), 4.0% 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% Al + 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 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) 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
• the so-hydrophobized leathers in the Bally penetrometer test (10% compression) show water penetration 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% Al + 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% Al + 2% Zr
• Example C7) Preparation of a hydrophobized shoe upper with silicone from Example A6 without chromium, capping with 2% Al + 2% Zr
• Folded wet white (thickness 1.8 mm) based on glutaraldehyde tanning according to example B2A 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 60 minutes. The fleet is drained.
• a carboxylic acid mixture eg BLANCOROL CGA, product of LANXESS
• 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) 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
• the so-hydrophobized leathers show water penetration after 6 hours in the Bally penetrometer test (10% compression). The water absorption was 9.3% after 2 hours, after 3 hours 10.7% and after 6 hours 13.6%.
• Example C9 Preparation of a hydrophobized shoe upper with wet white B3A and with silicone from Example A3
• Example C4 The procedure was analogous to Example C4), but as a raw material not wet white B1A, but B3A, and each hydrophobizing agent from Example A3 was used. In this case too, excellent water resistance and Maeser values of about 31,000 flexes were achieved.
• Example C10 Preparation of a hydrophobized shoe upper with wet white B4A and with silicone from example A3
• Example C4 The procedure was analogous to Example C4), but as a raw material not wet white B1A, but B4A, and in each case hydrophobing agent from Example A3 was used. In this case too, excellent water resistance and Maeser values of about 38,000 flexes were achieved.
• Example C11 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 B1A, but B5A, and each hydrophobizing agent from Example A3 was used. In this case too, excellent water resistance and Maeser values of approximately 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
• 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 except that instead of the product from Example A1 for tanning, 6.2 g / l of the powder product from Example A2a were used.
• 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 except that instead of the product from Example A1 for tanning, 6.2 g / l of the powder product from Example A2b were used.
• 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 instead of the product from Example A1 for tanning, 6.2 g / l of the powder product from Example A2c were used.
• 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 D1 was repeated and 10 g / l of the product of Example A1 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.
• the tanning is in fresh liquor (10 L water) with 3 g / l sodium bicarbonate and 1 g / l sodium acetate for 30 minutes deacidified (pH on average 6.9). Then add 0.9 g / l of sodium carbonate (diluted 1:10) in 2 portions and condition the skins for 1 hour (pH on average 7.9).
• a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone e.g., Tanigan BN, product of LANXESS
• 15 g / L of 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 / l 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 / L of 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 74 ° C. They are water-repellent and have a static water absorption of less than 40%.
• 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 ° Bé) with 2.0 g / l 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 (1:10 diluted) 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 A1 is added. After 4 hours, add 0.75 g / l sodium carbonate (1:10 diluted) in three doses of pH increased to 8.1 and 150 minutes tanned (TS 70 ° C). The next morning (pH of the flask 7.3) 0.25 g / l of a preservative (eg Preventol U-TEC G, product of LANXESS) is added. After 15 minutes, 3 portions of 1.0 g / l formic acid (1:10) are adjusted to pH 6.5 at intervals of 15 minutes. After 90 minutes, the liquor is drained and washed. Foaming is not observed during tanning.
• a preservative eg Preventol U-TEC G, product of LANXESS
• 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)
• a pH of 3.4 is set with 2 g / l of formic acid (1:10) and after 30 minutes the liquor is drained off. Then in fresh liquor (10 l of water) with 1 g / l of a cationic dyeing aftertreatment agent is fixed for 30 minutes. The fleet is then drained, it is thoroughly washed and finished the fur skins commercially.
• the sheepskins show a uniform dark brown color and a shrinking temperature of 73 ° C.

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