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
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/02—Material containing basic nitrogen
  • D06P3/04—Material containing basic nitrogen containing amide groups
  • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
  • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes

Definitions

• the invention relates to a process for dyeing a collagen fiber-containing substrate treated with a carbamoylsulfonate group-containing compound.
• the coloring of chrome-tanned leather has long been known, for example US-A-5085167 .
• the coloring of chromium-free tanned leathers for example of vegetable or glutardialdehyde tanned leathers (wet white)
• vegetable or glutardialdehyde tanned leather still have problems in terms of their brilliance, fürstärb sadness, levity and uniform coloring of meat side and grain side.
• the object of the present invention was to find a method by which chromium-free tanned collagen fiber-containing substrates, in particular leather or fur skins, can be dyed with satisfactory results and have improvements in the abovementioned properties.
• the invention therefore relates to a process for dyeing collagen fiber-containing substrates treated with at least one carbamoylsulfonate-containing compound, which comprises subsequently dyeing the thus treated collagen fiber-containing substrate with at least one anionic dye.
• EP-A-1647563 are known aqueous compositions containing at least one carbamoylsulfonate group-containing compound and at least one alcohol alkoxylate.
• Under collagen fiber-containing substrates for the treatment, in particular tanning, with a carbamoylsulfonate-containing compound in the context of the invention is in particular the usual raw materials derived from animals, especially hides and skins, for example, large cattle hides and skins of beef, veal, buffalo, hides and skins of pork, sheep, goat, reindeer, deer, kangaroo, hides 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 hairs ) and pre-tanned semifinished products (eg wet white).
• hides and skins for example, large cattle hides and skins of beef, veal, buffalo, hides and skins of pork, sheep, goat, reindeer, deer, kangaroo, hides and skins of other small animals such as sable, fox, rabbit, hides of reptile
• 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. These also have disadvantages in the dyeing.
• Collagen fiber-containing substrates without keratinic constituents are in particular hides and skins in which the keratinic constituents, in particular animal hairs, have been removed in the liming mill in the water workshop and which are used as un-split blossoms or after splitting as crevices, meat crevices or center 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 from this raw material, where the hair was removed in the water workshop in the so-called limber, are summarized below under the term leather.
• Carbamoylsulfonate-containing compounds (component a) are understood as meaning those having the following structural unit: -NH-CO-S0 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), Düsocyanato-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 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 ).
• 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 tetramethylammonium bisulfite, tetraethylammonium bisulfite, etc., may also be used to advantage Solutions with solids contents of 5 to 40 wt .-% used.
• the compounds containing carbamoylsulfonate groups are based on aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanato) cyclohexane, 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane and also any desired 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 triis
• 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 aqueous compositions, 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 is 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 is 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 cl) 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.
• 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.
• a sorbitan of the formula X- (OH) m wherein X is a sorbitan radical, in particular a 1,4-sorbitan radical, and m stands for the number 4
• X is a sorbitan radical, in particular a 1,4-sorbitan radical
• m stands for the number 4
• 10 to 60 equivalents, per mole of sorbitan preferably 10 to 40, particularly preferably 10 to 30 and very particularly preferably 15 to 25 equivalents of identical or different C 2 -C 6 -alkylene oxides, in particular C 2 - and / or C 3 -alkylene oxides, preferably ethylene oxide and with 1 to 3, preferably 0.8 to 1.2 equivalents, based on the sorbitan, of an aliphatic, optionally unsaturated carboxylic acid, preferably having a chain length of 6 to 30 carbon atoms, which is unsubstituted or substituted by hydroxy groups, preferably straight-chain, in made in any order.
• 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 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), octadecanoic acid (stearic acid) and ricinoleic acid are particularly preferred.
• 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 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)
• 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, 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.
• glycerol-based compounds of the components cl) 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 group of 5 to 30 carbon atoms having a main chain of 4 to 29 carbon atoms branched in the middle of the chain with at least one C 1 -C 10 alkyl group; 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 by two C 1 to C 10 alkyl radicals, ie 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 carbon atoms. Accordingly, particularly preferred branches are 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.
• carbamoylsulfonate-containing compound in a mixture with an emulsifier, in particular one of the component c1), c2) and / or c3), preferably the component c1) and / or c2), in particular c1).
• the carbamoylsulfonate-containing compound may, in addition to the preferred emulsifiers and other additives such as carboxylic acids of component d) or salts thereof, contain or do not contain.
• 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, in particular those having an average molecular weight (weight average MW) of 500 to 100,000 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, 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, in particular the carbamoylsulfonate-containing compound used is essentially free of organic or inorganic tannins, most preferably it is free of inorganic tannins.
• tanning agent combination it is preferred that it is less than 1% by weight of inorganic tanning agents, preferably less than 0.1% by weight, but substantially free of inorganic tannins, each 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 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 of producing dyed leathers and furskins involves various sub-steps, including simplifying the wet-finishing steps and the finishing of the dry leather or fur skins.
• the wet treatment steps again 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 tanning, in which the shrinkage temperature of the collagen-containing substrate is increased and folding is enabled.
• the retanning generally comprises the partial steps of the actual retanning, greasing, dyeing, optionally 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 retanning takes place in the presence of less than 1% by weight of inorganic tanning agents, preferably less than 0.1% by weight, based on the amount of retanning agent used, in particular the post-tanning steps are carried out in the absence of inorganic tanning agents like chrome tanning agents.
• 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 substrate to be tinted collagen fiber in particular the hides and skins, in particular of the pollen material, in which the collagen fiber-containing substrate with the aid of strong acids and salt, preferably with a mixture containing formic acid and / or sulfuric acid in the presence of sodium chloride is treated in which the pH of the aqueous tanning liquor is set to 2 to 3.5.
• the treatment with a compound containing carbamoylsulfonate groups 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 anionic dyes for dyeing collagen fiber-containing substrates, in particular tanned hides and skins, i. Leather and furskins which have been 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 is preferably added to the collagen fiber-containing substrates in the water workshop, in particular hides and skins, at a pH in the section of the substrate of 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, especially preferably pH 6 to pH 8 is 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.
• 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 carbamoylsulfonat phenomenon inconveniencen compound, based on blast weight, wherein a tanned intermediate (leather) having a shrink temperature of at least 65 ° C, preferably at least 68 ° C, more preferably at least 70 ° C receives.
• a tanned intermediate (leather) having a shrink temperature of at least 65 ° C, preferably at least 68 ° C, more 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 finished with known steps such as dyeing, greasing and given 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. It is also possible to additionally perform a pot dyeing with anionic dyes before fixation.
• 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 compound containing carbamoylsulfonate groups 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 method is preferably divided into the following steps, wherein the invention is not limited to this described Aus colihrungsform, but includes any procedure for the treatment of fur skins with Carbamoylsulfonat phenomenon-containing compounds:
• 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 (e.g., 5 ° Be) with the addition of carboxylic acids at pH 2 to 4 for several hours. It is then washed and then de-pipetted and degreased by means of sodium formate, sodium bicarbonate and surface-active compounds (surfactants), the pH being 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.
• the tanned fur skins can then be retanned (step 6)
• 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 dyeing process according to the invention can also be used with certain furskins, preferably with sheepskins for medical purposes or for direct skin contact.
• 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) having a shrink temperature of at least 65 ° C, preferably at least 68 ° C, more 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.
• Dyeing is preferably carried out by treating a collagen fiber-containing substrate which has been treated with at least one carbamoylsulfonate-containing compound in an aqueous liquor containing at least one anionic dye before, during or after the actual retanning. After tanning and folding, very white wet white substrates are obtained, which can be used for the subsequent steps.
• the pH is lowered to 3 to 4, then washed and then in the presence of fatliquoring, dyeing auxiliaries and anionic dyes, which are preferably used in diluted form, at 15 to 70 ° C and pH 3 to 4 im Stained for 1 to 3 hours, then acidified to a pH of 2.5 to 4, optionally treated with further concentrated anionic dye (pot color),
• the anionic dye is preferably used in an amount of 0.05 to 5%, based on shaved weight (leather) or based on wet weight (fur skins)
• a pot dyeing preferably 0.01 to 1.5% of anionic dye, based on shaved weight (leather) or based on wet weight (fur skins) is used.
• the anionic dyes can be used as aqueous solutions, suspensions or in solid form as powders or granules. These may contain other auxiliary agents, such as organic solvents, stabilizers, dyeing auxiliaries or other customary additives.
• the wet white tanned based on Carbamoylsulfonat phenomenon termed compounds yield white, yellowing resistant, leather and fur skins whose softness is adjusted by the products used in the retanning.
• the dyed leather and fur skins of the process according to the invention have extremely brilliant colorations, a very good through-coloring, a high levelness of the dyeing and also show a uniform coloring of the meat and scar sides.
• the dyed leather meets the authenticity requirements, for example, shoe upper leather, furniture leather and car leather
• the dyed fur skins meet the authenticity requirements, for example, for applications in the medical field, for clothing and for decorative purposes.
• 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 Ullmanns Encyklopadie der ischen Chemie 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 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 are also those which are made vegetable sources such as algae, fruits, such as rhubarb, olives, plant parts such as leaves, tree bark, roots, wood may optionally be obtained by 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 anionic dyes can also be used simultaneously together with a fatliquoring agent and optionally hydrophobing agent.
• Suitable hydrophobizing agents are, for example, polysiloxanes, preferably aqueous emulsions of polysiloxanes.
• the hydrophobing is usually carried out by milling 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 between 4.8 and 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 chromium sulfate, with aluminum sulfate, aluminum formate, zirconium sulfate, titanium sulfate, calcium chloride or magnesium sulfate.
• a basic chromium sulfate with aluminum sulfate, aluminum formate, zirconium sulfate, titanium sulfate, calcium chloride or magnesium sulfate.
• a basic chromium sulfate with aluminum sulfate, aluminum formate, zirconium sulfate, titanium sulfate, calcium chloride or magnesium sulfate.
• a basic chromium sulfate with aluminum sulfate, aluminum formate, zirconium sulfate, titanium sulfate, calcium chloride or magnesium sulfate.
• 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 dyed with at least one anionic dye.
• carbamoylsulfonate-containing compound and dyed with at least one anionic dye.
• Example A1 particulate polycarbamoyl sulfonate with emulsifier and organic tanning agent
• 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 Particulate polycarbamoylsulfonate with HDI, without emulsifier
• 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.
• To this solution is added 3000 ml of acetone. 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 90.3%, residual moisture 0.5 wt .-%).
• a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.20.
• Example A 2b Particulate polycarbamoylsulfonate with CHDI, without emulsifier
• 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 1.75 g of powder in 5 ml of water is clear and has a pH of 2.60.
• Example A 2c Particulate polycarbamoylsulfonate with HDI, without emulsifier
• 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.
• a solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.4.
• 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 cuvettes 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 acids (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 e.g., Preventol U-Tec G, product on LANXESS
• a preservative e.g., Preventol U-Tec G, product on LANXESS
• the pH is reduced to 4.3 with 0.3% formic acid (85%, 1:10 diluted). You move the barrel for 1.5 hours. Then the fleet is drained. The wet white leathers 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 added 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 30 ° C pickled. 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, 3.00% of an aqueous glutaraldehyde solution (GTA, about 24%, pH 1.5 to 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
• a fatliquor e.g., Eureka 975 ES-I
• GTA aqueous glutaraldehy
• 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 eg TANIGAN PAK, product of LANXESS
• a neutralizing tanning agent based on aromatic sulfonic acids eg TANIGAN PAK, product of LANXESS
• the barrel is agitated for 20 minutes, the pH is 3.75.
• 0.2% sodium bicarbonate is added and agitated for 30 minutes (pH 4.0).
• Now be 3.0 % of a 4,4'-dihydroxydiphenylsulfone based tanning agent eg 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 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 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 1A Wet white was prepared analogously to Example B 1A using 2.1%, based on pum weight, of the tanning agent from Example A2c.
• Example C1 Preparation of a retanned leather with wet white from example B1A
• Folded wet white (thickness 1.3 / 1.4 mm) from example B 1A is applied in a tannery with a liquor of 300% water (40 ° C.) and 0.2% of a fatty alcohol alkoxylate (eg CISMOLLAN AN 90, product of LANXESS ) (Diluted 1: 5) for 10 minutes.
• the fleet has a pH of 4.3 and is drained.
• 50% water (30 ° C) 3.0% of an organic tanning agent (eg TANIGAN RFS, product of LANXESS), 1.5% sodium formate and 3% of a Lickers (eg Baykanol Licker SL, product of LANXESS) (1 : 8 diluted) added.
• an organic tanning agent eg TANIGAN RFS, product of LANXESS
• Lickers eg Baykanol Licker SL, product of LANXESS
• the barrel is moved for 30 minutes, the fleet has a pH of 4.8. Then 3.0% of a softening polymer tanning agent based on a modified polyamide carboxylic acid (eg LEVOTAN LB, product of LANXESS) (diluted 1: 3 with water) and after 10 minutes 5.0% of a polycondensate based on aromatic sulfonic acid and phenolic compounds (eg TANIGAN BN, product of LANXESS) and 8.0% of an adjuvant (eg Granofin TA, product of Clariant).
• a softening polymer tanning agent based on a modified polyamide carboxylic acid eg LEVOTAN LB, product of LANXESS
• an adjuvant eg Granofin TA, product of Clariant
• a lickers e.g., BAYKANOL Licker SL, product of LANXESS
• a lickers e.g., BAYKANOL Licker SL, product of LANXESS
• diluted 1: 8 50% water (20 ° C) and 3.0% of a lickers (e.g., BAYKANOL Licker SL, product of LANXESS) (diluted 1: 8) are added and tumbled for 60 minutes.
• a naphthalenesulfonic acid condensate eg TANIGAN PR, product of LANXESS
• 3.0% of an anionic dye BAYGENAL Black TDE, (CI Acid Black 210), product of LANXESS
• Example C2 Preparation of a retanned leather with wet white from Example B 1A
• Folded wet white (thickness 1.3 / 1.4 mm) from example B 1A is applied in a tannery with a liquor of 300% water (40 ° C.) and 0.2% of a fatty alcohol alkoxylate (eg CISMOLLAN AN 90, product of LANXESS ) (Diluted 1: 5) for 10 minutes.
• the fleet has a pH of 4.3 and is drained.
• 50% water (30 ° C) 3.0% of a neutralization tanning agent (eg TANIGAN PAK, product of LANXESS), 1.5% sodium formate and 3% of a Lickers (eg BAYKANOL Licker SIS, product of LANXESS) (1: 8 diluted) was added.
• a neutralization tanning agent eg TANIGAN PAK, product of LANXESS
• Lickers eg BAYKANOL Licker SIS, product of LANXESS
• the barrel is moved for 30 minutes, the fleet has a pH of 5.5. Then 3.0% of a softening polymer tanning agent based on a modified polyamide carboxylic acid (eg LEVOTAN LB, product of LANXESS) (diluted 1: 3 with water) and after 10 minutes 5.0% of a polycondensate based on aromatic sulfonic acid and phenolic compounds (eg TANIGAN BN, product of LANXESS) and 8.0% of an adjuvant (eg Granofin TA, product of Clariant).
• a softening polymer tanning agent based on a modified polyamide carboxylic acid eg LEVOTAN LB, product of LANXESS
• an adjuvant eg Granofin TA, product of Clariant
• a lickers e.g., BAYKANOL Licker SL, product of LANXESS
• a lickers e.g., BAYKANOL Licker SL, product of LANXESS
• diluted 1: 8 50% water (20 ° C) and 3.0% of a lickers (e.g., BAYKANOL Licker SL, product of LANXESS) (diluted 1: 8) are added and tumbled for 60 minutes.
• a naphthalenesulfonic acid condensate eg TANIGAN PR, product of LANXESS
• 3.0% of an anionic dye BAYGENAL Yellow 4GL, (CI Acid Yellow 79), product of LANXESS
• Example C3 Preparation of a retanned leather with wet white from example B3A
• Example C2 was repeated except that the wet white from Example B3A was used and used as the anionic dye BAYGENAL Red GX (Acid Red 374). This gives a soft, full, no matter colored red leather with good color and high color brilliance.
• BAYGENAL Red GX Acid Red 374.
• Example C4 Preparation of a retanned leather with wet white from example B4A
• Example C2 was repeated except that the wet white from Example B4A was used and used as the anionic dye BAYGENAL Brown CGG New (Acid Brown 83). This gives a soft, full, no matter colored brown leather with good color and high color brilliance.
• Example C5 Preparation of a retanned leather with wet white from example B5A
• Example C2 was repeated except that the wet white from example B5A was used and used as the anionic dye BAYGENAL Brown CGG New (Acid Brown 83). This gives a soft, full, no matter colored brown leather with good color and high color brilliance.
• Example C6 Comparative Example / Preparation of a retanned leather with wet white from example B2A (GTA)
• Example C2 was repeated except that the GTA-based wet white from Example B2A was used and used as the anionic dye BAYGENAL Yellow 4GL (C.I. Acid Yellow 79). This gives a soft, less full, dull yellow leather with insufficient coloring. The leather undergoes a color shift to a dirty yellow during storage. The leather thus has significant disadvantages over the inventive example C2.

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Citations (21)

• 2011
  • 2011-08-12 EP EP11177377A patent/EP2557224A1/fr not_active Withdrawn
• 2012
  • 2012-08-09 WO PCT/EP2012/065561 patent/WO2013023979A1/fr active Application Filing
  • 2012-08-13 AR ARP120102962 patent/AR087526A1/es not_active Application Discontinuation

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