TW201326401A - Process for dyeing collagen fibre substrates - Google Patents

Abstract

A process for dyeing collagen fibre substrates treated with at least one carbamoylsulphonate compound, which is characterized in that the collagen fibre substrate thus treated is subsequently dyed with at least one anionic dye, the carbamoylsulphonate compound being a reaction product formed from at least one organic polyisocyanate and at least one bisulphite and/or disulphite, characterized in that the organic polyisocyanate has a molecular weight of less than 400 g/mol and NCO groups attached to aliphatics or cycloaliphatics.

Description

Method for dyeing a collagen fiber substrate

The present invention relates to a method for dyeing a collagen fiber substrate treated with an amine formamidine sulfonate compound.

The dyeing of chrome tanned leather has been known for a long time, for example from US-A-5085167. Dyeing of chrome-free tanned leather, such as vegetable tanned or glutaraldehyde tanned leather (wet white), is also known. However, it is disadvantageous that the leather of the vegetable tanning or glutaraldehyde tanning has problems in terms of brightness, complete penetration of the dye, flatness, uniform dyeing on the flesh side and the grain side. It is also important to meet the additional requirements of individual leather products in terms of visual and sensory properties, such as softness, grain smoothness and fullness.

According to WO 2010/130311, the use of organic, reactive, dichloro-based An alternative tanning process for bismuth formulations of compounds which are amine functionalized aryl sulfonic acids and trichloros. The reaction was obtained. Even if this gives a wet white with a low yellowness, the above characteristics of wet white and the above characteristics of subsequent dyeing still need improvement.

The problem addressed by the present invention is to find a method by which even a chrome-free collagen fiber substrate, in particular leather or fur, can be dyed and obtain satisfactory results and improvements in the properties mentioned. .

It has now surprisingly been found that collagen fiber substrates which have been treated with an amine-mercapto sulfonate compound and which are dyed with an anionic dye have a significant advantage over other tanned leathers in terms of the properties mentioned. This problem can be solved.

The invention therefore relates to a method for dyeing a collagen fibrous substrate treated with at least one amine-mercapto sulfonate compound, characterized in that the collagen fibrous substrate thus treated is subsequently subjected to at least one anionic dye Performing dyeing, the amine mercaptosulfonate compound is a reaction product formed from at least one organic polyisocyanate and at least one bisulfite and/or disulphite, characterized in that the organic Polyisocyanates have a molecular weight of less than 400 g/mol with NCO groups attached to aliphatic or alicyclic groups, especially 1,4-diisocyanatobutane, 1,6-diisocyanate Hexane (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diiso Cyanyl hexane (TMHI), 1,3- and 1,4-diisocyanatohexane, 1,3- and 1,4-diisocyanatocyclohexane (CHDI), and also Any desired mixture of isomers, 1-isocyanato-2-isocyanatomethylcyclopentane, 1,2-, 1,3- and 1,4-bis(isocyanato) Methyl)cyclohexane and also any desired blend of such isomers 1,2-, 1,3- and 1,4-bis(isocyanatoethyl)cyclohexane and also any desired mixture of such isomers, 1,2-, 1, 3- and 1,4-bis(isocyanato-n-propyl)cyclohexane and also any desired mixture of such isomers, 1-isocyanatopropyl-4-isocyanato Methylcyclohexane and isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-isocyanato-1 -Methyl-4-isocyanatomethylcyclohexane (IMCI), 2,4'- and 4,4'-diisocyanatobicyclohexylmethane (H ₁₂ MDI) and isomers , dimeryl diisocyanate (DDI), bis(isocyanatomethyl)-bicyclo[2.2.1]heptane (NBDI), bis(isocyanatomethyl)tricyclo[5.2 .1.0 ^2,6 ]decane (TCDDI) and isomers, and any desired mixtures of such diisocyanates, and benzoyl diisocyanate having the formula

EP-A 0 690 135, WO 98/38340 and EP-A 0 814 168 describe amine mercapto sulfonate compounds which are useful as hydrazine formulations which are substantially inert to the reaction with water. An aqueous dispersion with sufficient stability is obtained for use in the tanning process. However, this method has two serious drawbacks:

- The reaction of the isocyanate with the polyether alcohol must be carried out in the absence of water and preferably no solvent which inhibits the viscosity, and therefore requires a high-tech and high-priced hardware with an additional synthesis step.

The reaction of the polyether alcohol with the isocyanate consumes a part of the functionality of the isocyanate and thus reduces the tanning properties of the product.

EP-A-1 647 563 discloses aqueous compositions comprising at least one amine mercapto sulfonate compound and at least one alcohol alkoxylate.

For the purposes of the present invention, collagen fiber substrates for use in the treatment, in particular tantalum, of the treatment with the amine formamidine sulfonate compound are more particularly conventional animal-derived materials, especially raw hides and raw hides, such as cowhide, small Cowhide, buffalo, pigskin, sheepskin, goatskin, reindeer skin, deer skin, kangaroo skin, skins from other small animals such as black crickets, foxes, rabbits, skins from reptiles (such as snakes), fish or birds. There are also split skins (eg, bare skin splits, flesh cuts, hair cuts) and pre-tanning intermediates (eg wet white).

The collagen fiber substrate may be combined with a keratin component or may be free of keratin components. The keratin component is more specifically animal hair.

Collagen fibrous substrates with attached keratin components are more particularly hides and skins, wherein keratin components, especially animal hair, are in the process of beamhouse operation, in tanning and subsequent retanning steps And there is also a sheet-like bottom that remains untreated and not damaged during the final treatment to become a usable material, but remains firmly attached to the collagen fiber substrate (the leather hide). The tanned raw hides and raw hides produced from this raw material, in which the hair is intact and firmly attached to the leather, are included in the term fur below. They also have a number of disadvantages in dyeing.

The collagen fiber substrate having no keratin component is more specifically the following raw hides and raw hides, wherein the keratin component, especially the animal hair, is removed by lime treatment in the liming operation, and is used as an unsplit skin. Or used as a skin split, flesh cut or central split after splitting, and then processed during the tanning process and subsequent retanning steps and optionally also finished until ready for use s material. Raw hides and raw hides tanning from such raw materials, in which the lime treatment of the hair in the liming operation is removed, are included below in the term leather. They also have a number of disadvantages in dyeing.

Preferred collagen fibrous substrates are preferably leathers and pelts based on the substrate, in particular having a chromium content of less than 1000 ppm and especially less than 500 ppm.

The amine mercapto sulfonate compound (component a) is a compound comprising the following structural unit: -NH-CO-SO ₃ ^- K ⁺ wherein K ⁺ is a cationic equivalent. Preferred are organic polyisocyanates having an NCO functionality of from 1.8 to 2.5.

It is preferred to use the above diisocyanate. However, it is also possible to use monofunctional aliphatic isocyanates such as, for example, butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate or dodecyl isocyanate and/or Or a polyisocyanate having from 2.2 to 4.2 average NCO functionality.

The high functionality polyisocyanate is preferably a mixture of polyisocyanates consisting essentially of: trimeric 1,6-diisocyanatohexane, trimerized 1,2-, 1,3- or 1, 4-bis(isocyanatomethyl)cyclohexane, trimerized 1,2-, 1,3- or 1,4-bis(isocyanatoethyl)cyclohexane, trimerized 1,2-, 1,3- or 1,4-bis(isocyanato-n-propyl)cyclohexane, trimerized 1-isocyanatopropyl-4-isocyanatomethylcyclohexane Alkane and isomer, or trimerized 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and optionally dimerized 1,6-di Isocyanate hexane, dimerized 1,2-, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, dimerized 1,2-, 1,3- or 1,4-Bis(isocyanatoethyl)cyclohexane, dimerized 1,2-, 1,3- or 1,4-bis(isocyanato-n-propyl)cyclohexane, dimerization 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, or dimerized 1-isocyanato-3,3,5-trimethyl-5-iso Cyanate methylcyclohexane and correspondingly higher homologues, including trimeric isocyanate groups and optional isocyanate diester groups and having an NCO content of from 19 wt% to 24 wt%, such as Obtained by conventional catalytic trimerization and by formation of the following trimeric isocyanate: 1,6-diisocyanatohexane, 1,2-, 1,3- or 1,4-double (iso) Cyanate methyl)cyclohexane, 1,2-, 1,3- or 1,4-bis(isocyanatoethyl)cyclohexane, 1,2-, 1,3- or 1,4 -double( Cyanyl n-propyl)cyclohexane, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 1-isocyanato-3,3,5-tri Methyl-5-isocyanatomethylcyclohexane, and preferably has an (average) NCO functionality of from 3.2 to 4.2.

The use of monofunctional and more than difunctional isocyanates is preferably limited in each case to no more than 10 mol% based on the total polyisocyanate.

However, the above aliphatic, alicyclic and arylaliphatic diisocyanates are very particularly preferred. Particularly preferred is hexamethylene diisocyanide Acid esters (HDI), diisocyanate cyclohexane, 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane and also such isomers Any desired mixture, 1,2-, 1,3- and 1,4-bis(isocyanatoethyl)cyclohexane and also any desired mixture of such isomers, 1, 2 -, 1,3- and 1,4-bis(isocyanato-n-propyl)cyclohexane and also any desired mixtures of such isomers, 2,4'- and 4,4'- Diisocyanate dicyclohexylmethane, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, and 1-isocyanato-3,3,5-tri Methyl-5-isocyanatomethylcyclohexane (IPDI). Of the last mentioned groups, particularly preferred are hexamethylene diisocyanate (HDI), 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane and There is also a mixture of such isomers.

The bisulfite and/or metabisulfite is preferably an alkali metal or ammonium salt thereof, especially a sodium salt of sulfurous acid or a sodium salt of disulphurous acid, namely sodium hydrogen sulfite, respectively. (NaHSO ₃ ) and sodium metabisulfite (Na ₂ S ₂ O ₅ ).

It is also advantageous to use other alkali metal and ammonium salts of the acids, that is, potassium hydrogen sulfite, potassium metabisulfite, lithium hydrogen sulfite, lithium metabisulfite, ammonium hydrogen sulfite, partial bismuth. Ammonium sulfate and also simple tetraalkylammonium salts of such acids, such as tetramethylammonium hydrogensulfite, tetramethylammonium metasulfite, and the like. For the purpose of hindrance, the salts are preferably used in the form of an aqueous solution having a solid content of from 5 wt% to 40 wt%.

In a preferred embodiment of the invention, the amine mercaptosulfonate group-containing compound is based on an aliphatic polyisocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanate) Base Alkane, 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane and also any desired mixture of such isomers, 1,2-, 1, 3- and 1,4-bis(isocyanatoethyl)cyclohexane and also any desired mixtures of such isomers, 1,2-, 1,3- and 1,4-double ( Isocyanato-n-propyl)cyclohexane and also any desired mixture of such isomers, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers , 2,4'- and 4,4'-diisocyanatodicyclohexylmethane or decyl isocyanate and also mixtures thereof, but especially hexamethylene diisocyanate, 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane and also any desired mixtures of such isomers, 1,2-, 1,3- and 1,4- Bis(isocyanatoethyl)cyclohexane and also any desired mixture of such isomers, 1,2-, 1,3- and 1,4-bis(isocyanato-n-propyl) Cyclohexane and also any desired mixture of such isomers and /isophorone diisocyanate, or more preferably hexamethylene diisocyanate, isophorone diisocyanate, 1,3-double ( Isocyanide Acid methyl)cyclohexane and 2,4'- and 4,4'-diisocyanatodicyclohexylmethane. In the last mentioned group, very preferred amine formamidine hexamethylene diisocyanate (HDI), 1,2-, 1,3- and 1,4-bis(isocyanatomethyl) Cyclohexane and also any desired mixture of such isomers, which contain a compound of the amine mercaptosulfonate group in a particular portion.

Form of bismuth preparation

The amine mercaptosulfonate compound for tanning can be used in liquid form, for example, as an aqueous solution or as a particulate solid material.

The aqueous composition can be, for example, in the form of a solution or in the form of a suspension. The solution is preferred.

The dry residue of the aqueous composition, i.e., the total concentration of the components of the aqueous composition, is preferably from 25% to 50%. A total concentration of 30% to 40% is particularly advantageous for the aqueous composition, and the proportion of the amine mercaptosulfonate compound in the composition is particularly preferably in the range of from 28% to 35%.

When other added materials are used, it is preferred to reduce the proportion of the amine methiosulfonate compound in an appropriate ratio in relation to the ratio of the additionally added component, so that the total concentration of solids in the aqueous solution is preferably It is no more than 50%.

It is similarly preferred to use an amine formamyl sulfonate compound in the form of a particulate solid material, preferably having a solids content above 20 ° C, preferably above 60 ° C, especially above 100 ° C. Melting point.

The "particle" more specifically represents a material having an average particle diameter of from 0.1 μm to 1000 μm, preferably from 1 to 800 μm and especially from 50 to 300 μm, and this average value is the weight average of all the particles. Other averages (volume averages) can be calculated from this by analytical methods and vice versa. The average particle diameter can be determined, for example, by a microscope. This solid material is preferably in the form of a powder or pellet.

The particulate solid material preferably has a residual moisture content of from 0 to 10 wt%, especially from 0 to 5 wt%, and more preferably from 0 to 2 wt%, based on the material. The particulate solid material is generally based on any desired particle structure, preferably a spherical or similar sphere Or the structure derived from it. It is also possible to have particle agglomerates of the shape from a specific particle size range.

The particulate solid material comprises from 1% to 100%, preferably from 10% to 100%, and more preferably from 25% to 100% of the amine mercaptosulfonate compound.

Very particularly preferred are the amine mercapto sulfonate compounds and their preparations using component d) and optionally component e), which do not comprise an emulsifier and have a pH below 4.5 based on a 35% aqueous solution. It is especially preferred to use an amine formamyl sulfonate compound in the form of a particulate solid for tanning.

Emulsifier

The amine mercapto sulfonate compound for tanning may comprise one or more emulsifiers of component c) or may not comprise any emulsifiers. Preferred amine mercapto sulfonate compounds do not contain any emulsifiers. Useful emulsifiers include, for example, cationic, anionic, amphoteric, or nonionic surfactants which are preferably capable of reducing the interfacial tension between the organic phase and the aqueous phase to enable formation of an oil-in-water emulsion.

Preferred cationic emulsifiers are quaternary ammonium compounds such as cetyltrimethylammonium bromide or benzyl lauryl dimethyl ammonium chloride.

Preferred anionic emulsifiers are soaps, metal soaps, organic soaps such as mono-, di- or triethanolamine oleate or stearate, diethylethanolamine oleate or stearate or 2-amine Alkyl-2-methylpropan-1-ol stearate, a sulfurized compound such as sodium lauryl sulfate or turkey red oil, and a sulfonated compound such as sodium hexadecanosulfonate.

Preferred amphoteric emulsifiers are phospholipids such as lecithin, various proteins such as gelatin, casein, and true amphoteric surfactants.

Preferred nonionic emulsifiers are fatty alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol or palmitol, partial fatty acid esters of polyhydric alcohols with saturated fatty acids such as glyceryl monostearate, neopentyl monostearate Alcohol esters, ethylene glycol monostearate, or propylene glycol monostearate, partial fatty acid esters of polyhydric alcohols with unsaturated fatty acids such as glycerol monooleate, neopentyl glycol monooleate, and fatty acids Polyoxyethylene esters such as polyoxyethylene stearate, addition polymerization products of ethylene oxide and propylene oxide to fatty alcohols, such as fatty alcohol polyglycol ethers; or fatty acids such as ethoxylated fatty acids.

Particularly preferred nonionic emulsifiers are at least one nonionic, ester-containing, alkoxylated polyol (c1) and/or an alkyl glycoside (c2) having an HLB value of at least 13 and/or A nonionic, ester-free, alkoxylated alcohol (c3).

Component c1)

Preferred nonionic, alkoxylated, ester group-containing polyols of component c1) have an HLB value of from 13 to 19, and especially from 14 to 18, which is by Griffin, WC: surface The active agents were determined by the method of Classification of surface active agents by HLB, J. Soc. Cosmet. Chem. 1, 1949. It is preferred for component c1) that the compound also has a water solubility of at least 10 g/liter, and especially at least 20 g/liter at 20 °C.

Preferred compounds of component c1) are obtainable in a conventional manner from the polyol by alkoxylation and partial esterification of a hydroxyl group with a carboxylic acid. suitable The starting polyols include, for example, poly (cyclo) fatty alcohols such as glycerol, trimethylolpropane, neopentyl alcohol, dipentaerythritol, mono- or polysaccharide-derived polyols, preferably It has a molecular weight in the range from 92 to 2000. Particularly preferred starter alcohols are polyols having from 3 to 10 hydroxyl groups, especially glycerol and those having a sorbitan core structure, especially having a 1,4- or 1,5-dehydration Sorbitol, and preferably 1,4-sorbitan.

Preferred amine mercapto sulfonate compounds are characterized in that the compound of component c1) used at the same time is a polyol and at least one alkylene oxide having 2 to 6 carbon atoms (preferably based on a polyol) It is a reaction product of 10 to 60 mol equivalents and subsequently with at least one carboxylic acid having 6 to 30 carbon atoms. The polyol used is preferably from the group consisting of glycerol, trimethylolpropanol, pentaerythritol, dipentaerythritol and polyols derived from mono- and polysaccharides, especially sorbus Sugar alcohols, as well as polyols having a sorbitan core structure.

It is especially preferred that the compound of component c1) is a partially esterified sorbitan alkoxylate having a hydroxyl group having a chain length of from 6 to 30 carbon atoms before, or preferably after, alkoxylation. Carboxylation of the carboxylic acid, in which case each hydroxyl group of the parent polyol may exhibit an alkoxy unit number independent of each other, and an average of from 10 to 60 alkoxy units per sorbitan unit . Preferred esterified sorbitan alkoxylates include randomly distributed alkoxy groups.

The partially esterified, alkoxylated sorbitan derivative is preferably prepared by reacting a sorbitan having the following chemical formula: X-(OH) _m wherein X is dehydrated sorbus a sugar alcohol group, especially a 1,4-sorbitan group, and m represents a number 4, and is 10 to 60 equivalents, preferably 10 to 40 equivalents, more preferably 10 to 10 moles per mole of sorbitan. 30 and most preferably 15 to 25 equivalents of the same or different C ₂ -C ₆ alkylene oxides, especially C ₂ - and/or C ₃ -alkylene oxides, preferably ethylene oxide, and Based on the sorbitan 1 to 3, preferably 0.8 to 1.2 equivalents of an aliphatic, optionally unsaturated carboxylic acid, preferably having a chain length of 6 to 30 carbon atoms, the carboxylic acid It is unsubstituted or substituted by a hydroxy group, and is preferably linear, in any desired order. Preferably, this reaction with alkylene oxide is carried out prior to the reaction with the carboxylic acid.

Preferably, the sorbitan polyoxyethylene monoester has from 10 to 60 mol of ethylene oxide unit per sorbitan unit, and preferably has a 1,4-sorbitan core structure. Alkyl oxidation is carried out.

They are preferably in accordance with the following structural formula, wherein R represents an optionally hydroxy-substituted alkyl or alkenyl group of the carboxylic acid, and m, n, p and q are each independently a statistical value, and in the range from 0 to 60, the premise is that the oxyethylene unit The sum of the numbers of m+n+p+q is in the range from 10 to 60, preferably from 18 to 22 and especially 20.

The corresponding alkoxylated sorbitan diesters and mixtures thereof are likewise suitable.

It is furthermore possible to use alkoxylated sorbitan esters in which a hydroxyl group of the sorbitan unit, in particular in the formula indicated above, is directly esterified with a carboxylic acid, ie in a sorbitan unit There is no alkylene oxide unit between the carboxylic acid groups and the three undeuterated hydroxyl groups are etherified with correspondingly more alkylene oxide units. Such compounds are obtainable, for example, by first esterifying sorbitan with a carboxylic acid and then alkoxylating the resulting product, which product consists of a mixture of isomeric monoesters in excess of carboxylic acid In this case, the mixture may also comprise a mixture of isomeric diesters.

The alkylene oxide used for alkoxylating sorbitan is preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. It is also possible here to react sorbitan with the various alkylene oxides mentioned, such as ethylene oxide and propylene oxide, of which sorbitan alkoxylates are obtainable, except that they each comprise one In addition to the block composed of a plurality of units of an alkylene oxide (e.g., propylene oxide), a block composed of a plurality of units of another alkylene oxide (e.g., ethylene oxide) is included. It is especially advantageous that the sorbitan alkoxylate comprises (preferably only) an ethylene oxide (EO) unit. In this case, the alkylene oxide used is particularly preferred as ethylene oxide.

It is also possible to react a sorbitan with the various alkylene oxides mentioned, such as ethylene oxide and propylene oxide, to obtain sorbitan in which the different oxyalkylenes are randomly incorporated. Alcohol alkoxylation Things. The amount of alkylene oxide to be used is preferably in the range of from 10 to 60 mol per mol of sorbitan, preferably in the range of from 10 to 40 mol, and even more preferably from 10 to 30. Within the range of mol, and most preferred are alkylene oxides ranging from 15 to 25 mol. A completely preferred alkylene oxide-based ethylene oxide.

The carboxylic acid suitable for esterifying the starting polyol, in particular the alkoxylate of the sorbitan, is preferably saturated or unsaturated, linear or branched, and optionally substituted by a hydroxy group. . By way of example, the following carboxylic acids may be mentioned: caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid. , palmitic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, octadecenoic acid (oleic acid), undecylenic acid. Particularly preferred are capric acid, undecanoic acid, dodecanoic acid (lauric acid), myristic acid, palmitic acid (palmitic acid), octadecanoic acid (stearic acid) and ricinoleic acid. Very particularly preferred are dodecanoic acid (lauric acid), palmitic acid (palmitic acid) and octadecanoic acid (stearic acid) and octadecenoic acid (oleic acid).

Compounds useful as component c1) include, for example, commercially available products such as sorbitan polyoxyethylene (20) monolauryl ester (e.g., Polysorbat® 20 or Tween® 20 (Croda Oleochemicals) or Eumulgin® SML 20 ( Cognis), sorbitan polyoxyethylene (20) monopalmitate (eg Polysorbat® 40 or Tween® 40 (Croda Oleochemicals), sorbitan polyoxyethylene (20) monostearate (eg Polysorbat® 60) Or Tween® 60 (Croda Oleochemicals) or Eumulgin® SMS 20Cognis), dehydration Sorbitol polyoxyethylene (20) monooleate (eg Polysorbat® 80 or Tween® 80 (Croda Oleochemicals)).

Other preferred compounds of component c1) are, for example, mono- and polyglycerol alkoxides. Such alkoxylated (poly)glycerides are alkoxylated by glycerol or polyglycerol and subsequently esterified with fatty acids, or esterified with fatty acids by glycerol or polyglycerol and subsequent alkoxy groups Prepared by chemical. The compositions according to the invention suitably employ, in particular, alkoxides of esters of mono- and polyglycerol esters having an HLB value of at least 13 and preferably having a water solubility of greater than 10 g/liter at 20 ° C. . It is also possible to use alkoxylated glycerides or polyglycerides which are esterified using more than one carboxylic acid. Alkoxylated monoglyceride systems are especially preferred.

The C ₂ to C ₆ alkylene oxide is suitable for use in alkoxylation, more preferably ethylene oxide. Preferred is alkoxylation with from 10 to 100 alkylene oxide units, especially from 20 to 60 alkylene oxide units. The hydroxyl groups of glycerol or polyglycerol typically each independently exhibit a different number of alkylene oxide units.

As a particularly suitable alkoxylate of mono- and polyglycerol esters, mention may be made, by way of example, of glycerol monostearate ethoxylates having an average of from 15 to 30, and in particular an average of 20 EO units, a glycerol monooleate ethoxylate having 20 to 40 EO units, a diglycerin monostearate having 20 to 40 EO units, a polyglyceryl monostearate having 20 to 40 EO units, Castor oil alkoxylate and hydrogenated castor oil alkoxylate, abbreviated as: (hydrogenated) castor oil alkoxylate Alkide. The latter are obtainable by alkoxylated castor oil or hydrogenated castor oil with alkylene oxides (especially ethylene oxide and propylene oxide), and preferably each of them (hydrogenated) castor oil The unit comprises from 20 to 100 alkylene oxide units, preferably each of the (hydrogenated) castor oil units comprises from 20 to 60 ethylene oxide units.

The corresponding, glycerol-based compounds of component c1) are likewise commercially available, for example glycerol monostearate ethoxylates having an average of 20 EO units, such as Cutina® E 24 (Cognis), with 40 Hydrogenated castor oil ethoxylates of EO units, such as Eumulgin® HRE 40 (Cognis).

Component c2)

Preferred compounds of component c2) are, for example, alkyl monoglycosides, alkyl diglucosides, alkyl triglycosides and higher homologs, which in this context generally refer to alkyl glycosides, especially monoglucosides, diclofenac A glycoside, a triglucoside or higher homologue and mixtures thereof, the hydroxy moiety of which is substituted by a C ₆ -C ₁₈ alkyl group. Preferred are mixtures of mono-, di- and triglucosides having a C ₆ -C ₁₈ alkyl group and having a degree of polymerization (DP) of from 1 to 5 and higher homologs. Particularly preferred are alkyl glucosides whose alkyl groups have a chain length of from 6 to 18 carbon atoms, especially from 6 to 12 carbon atoms. More preferably, the alkyl group has a chain length distribution of alkyl glucoside or a mixture of components of alkyl glucosides having different alkyl chains.

The alkyl glycoside is preferably a material consisting of a single ring of sugars or a chain of one chain of sugars interconnected by glycosidic bonds, wherein the last ring of the glycosidic chain is acetalized with an alcohol. The alkyl glycoside has the general formula: H-(G) _w -O-R' wherein G represents a glycoside unit, R' represents an alkyl group of an alcohol used to form a glycoside acetal, and W represents an average degree of polymerization, ie, The number of linked glycoside units and is a number from 1 to 5.

In a suitable alkyl glycoside, w represents a number from 1 to 5, and R' represents a group of a linear or branched aliphatic alcohol having 6 to 30 carbon atoms. These products are known per se and are commercially available. The value of w can be influenced by appropriately adjusting the molar ratio of the alcohol to the saccharide during the synthesis. Increasing this ratio gives an alkyl glycoside with a lower average w value. In contrast, higher degrees of polymerization are obtained by lower alcohol to sugar molar ratios.

Examples are structures in which R' represents an alkyl group and v employs an alkyl glucoside having a value from 1 to 4:

The compounds are generally in the form of a mixture of isomeric forms. In particular, a mulleled carbon atom (the carbon atom of a glycoside) will exist as a mixture of stereoisomers.

Preferred alkyl polyglucosides consist of a mixture of alkyl monoglucosides, alkyl diglucosides and alkyl triglucosides with or without alkyl oligoglucosides, starting with the oligoglucoside The molar ratio of the material will vary and will vary with the conditions of the process, possibly still containing (poly) glucose and a small portion of the free alcohol R'OH.

Alkyl polyglucosides are obtained, for example, by direct synthesis from a sugar with an excess of one or more alcohols. Another way of synthesizing is starting from starch, in the initial step in the presence of an acid catalyst, the starch is reacted with a lower alcohol (eg methanol, ethanol, butanol) to form a short chain glycoside group (eg methyl, ethyl) , butyl) alkyl glucoside. This intermediate is reacted in the subsequent step with a long-chain alcohol R'-OH by transacetalization in the presence of an acid as a catalyst under vacuum, wherein the equilibrium is shifted by distilling off the lower alcohol. . The preparation of alkyl glucosides is described, for example, in WO 90/001489, US Pat. No. 5,576,425, DE 69,824,366 or in M. Biermann (Henkel KGaA), K. Schmid, P. Schulz in Starch-Stärke, p. 281-288 (1993). Description of the paper.

Particularly preferred alkyl glucosides include, in particular, hexyl glucoside, octyl glucoside, decyl glucoside, undecyl glucoside and dodecyl glucoside and also their homologs and with or without alkyl groups A mixture of an alkyl monoglucoside, an alkyl diglucoside, an alkyl triglucoside of a polyglucoside, and mixtures thereof.

Alkyl glycosides in which a sugar residue is composed of different sugar units are also suitable. Particularly preferred, however, are alkyl glycosides composed solely of glucose units.

The compound of component c2) is commercially available, wherein, for example, a C ₈ -C ₁₀ alkyl polyglucoside having a polymer of 1.6 (DP = degree of polymerization) is available under the trade name Glucopon® 215 CS UP (Cognis) of. Having a DP 1.4 C ₁₂ -C ₁₆ alkyl polyglucosides, for example, Glucopon® 600 CS UP (Cognis) available under the trade name.

Component c3)

Preferred nonionic, ester-free alcohol alkoxylates of component c3) are suitably polyether alcohols obtainable by alkoxylation of suitable starter molecules in a conventional manner. They are known, for example, from EP-A-1647563. These polyether alcohols can be prepared using any desired mono- or polyhydric alcohol having a molecular weight of 88 to 438 as a starting molecule.

It is particularly preferred to consider a fatty alcohol alkoxylate having a chain length of 5 to 30 carbon atoms and 1 to 25 alkoxy units.

It is preferred to use a linear or branched, saturated or unsaturated alcohol alkoxide which is obtainable by reacting at least one alcohol ROH with at least one alkylene oxide per molol ROH. Wherein R is an alkyl moiety having 5 to 30 carbon atoms, having a main chain of 4 to 29 carbon atoms, and having at least one C ₁ to C ₁₀ alkyl branch attached to the middle of the chain; The alkylene oxide has 2 to 6 carbon atoms, and the n series is from 1 to 25.

For the purposes of the present invention, the middle of the chain is understood to mean the carbon atoms of the main chain, i.e. from the C#2 carbon atom on the longest alkyl chain in the R moiety, from the direct connection to the oxygen adjacent to the R moiety. The carbon atom on the atom (C#1) begins to number and ends with a carbon atom ω, where ω is the terminal carbon atom of the main chain and includes C#2 and the carbon atom ω-2. The carbon atom C which means that the main chain, R portion # 2, C # 3, ... to at least one substituted with an alkyl _{moiety. 1} C to ₁₀ C in the Cω-2. Desirably, the carbon atom C#2 of the main chain of the R moiety substituted with a C1 to C10 alkyl moiety. However, it is similarly possible to replace one or more carbon atoms in the middle of the chain with two C1 to C10 alkyl moieties, i.e. one or more carbon atoms in the middle of the chain are quaternary carbon atoms.

Particularly preferred are mixtures based on 1 to 3 different alcohol ROHs, more preferably based on 1 or 2 different alcohol ROH alcohol alkoxylates. The number of carbon atoms in the R moiety can be different and/or branched.

When the chain length allows for more than one branch point in the middle of the chain, the main chain of the alcohol ROH preferably has from 1 to 4 branches, more preferably from 1 to 3, most preferably 2 or 3. The branches generally have independently from 1 to 10 carbon atoms, preferably from 1 to 6, and more preferably from 1 to 3 carbon atoms. Particularly preferred branches are accordingly methyl, ethyl, n-propyl or isopropyl groups.

The R moiety of the alcohol ROH preferably has from 5 to 30 carbon atoms. Since the R moiety preferably has at least one branch with at least one carbon atom, the backbone comprises from 4 to 29 carbon atoms. The R moiety preferably has 6 to 25 carbon atoms and more preferably has 10 to 20 One. That is, the main chain preferably has 5 to 24 carbon atoms, and more preferably 9 to 19 carbon atoms. Very particularly preferred is that the backbone has from 9 to 15 carbon atoms and the remaining carbon atoms of the R moiety are distributed over one or more branches.

Preferred linear alcohol ROHs include, for example, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, dodecanol, tridecyl alcohol, tetradecanol, pentadecyl alcohol, cetyl alcohol, ten Octadecanol, octadecenyl or cetyl alcohol, and also industrial grade mixtures thereof.

The alkylene oxide used to react with the branched alcohol ROH to form an alcohol alkoxylate is preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. It is also possible to react a single alcohol ROH with the various alkylene oxides (e.g., ethylene oxide and propylene oxide), in which case it is possible to obtain alcohol alkoxylates, each of which includes an epoxy removal A block of two or more units of another alkylene oxide (e.g., ethylene oxide) other than the block of two or more units of an alkane (e.g., propylene oxide). It is especially preferred that the alcohol alkoxylate used in accordance with the invention comprises an ethylene oxide (EO) unit, that is, the alkylene oxide used is preferably ethylene oxide.

It is also possible to obtain an alcohol alkoxy group in which various alkylene oxides are randomly combined under conditions in which a single alcohol ROH is reacted with various alkylene oxides mentioned, such as ethylene oxide and propylene oxide. Compound. The amount of the alkylene oxide to be used is preferably from 1 to 25 mol, more preferably from 1 to 20 mol, even more preferably from 3 to 15 mol and most preferably from 5 to 12 mol per molol. Alkylene oxide.

It is especially preferred to use an amine mesoyl sulfonate compound, in particular one of the components c1), c2), and/or c3), preferably component c1) and/or in a mixture with an emulsifier. C2), especially c1).

The amine mercapto sulfonate compound is preferably used as an aqueous composition containing: -5 wt% to 50 wt%, especially 10 wt% to 40 wt% of component a) aminomethylsulfonylsulfonate The acid ester compound, and -0.05 wt% to 5 wt%, especially 0.1 wt% to 2 wt% of component c), in particular component c1), are all based on the composition.

Other added substances

The amine mercaptosulfonate compound may comprise, or in other cases not comprise, other additional substances, such as the carboxylic acids of component d) or salts thereof, in addition to the preferred emulsifiers.

Component d)

Suitable compounds of component d) are especially mono- or polycarboxylic acids, preferably hydroxypolycarboxylic acids. Suitable examples include: 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 (meth)acrylic acid, maleic acid, crotonic acid or itaconic acid or derivatives thereof and optionally further monomers such as ethylene, propylene, styrene, hydroxyethyl methacrylate, methyl a (co)polymer of hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, especially having 500 to 100 000 g/mol, especially 500 to 30 000 g /mol average molar mass (weight average Mw).

Particularly preferred for use as component d) is at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid, or adipic acid, especially at least one hydroxypolycarboxylic acid, preferably citric acid. , tartaric acid or lactic acid or a mixture thereof.

Component e)

By means of the preferred additional substances of component e), it is preferred to include or not to include auxiliaries such as milk fatliquors, dustproofs, organic bismuth formulations, component b), buffers and/or fillers. Agent.

The milky fatliquor is preferably a bio-based, mineral or synthetic oil-based substance which may have a hydrophilic group such as by full or partial sulphatization, sulphitization (sulphitization) ), carboxylation or phosphating to increase their utility in water.

Possible fillers are preferably inert inorganic salts and also organic polymers such as sulphates such as sodium sulphate or calcium sulphate, talc, cerium oxide compounds, starch or lignosulfonates.

Suitable buffering agents are those which, when added in a sufficient amount, are capable of setting and stabilizing the pH range, especially from 1 to 5, preferably from 2.0 to 3.5. Buffers suitable for this are preferably mixtures of the compounds of component d) and their salts. Preferred salts are especially alkali metal salts, preferably sodium or potassium salts.

In the case of an amine methyl sulfonate compound in the form of solid particles, preferred dusting agents include, for example, alkoxylates of aryl compounds, or polyethers, or certain monoesters or diesters, or certain Ether or diether. specific Examples are: ethoxylates, propoxylates, or mixed polyethers based on EO-PO, wherein as the aromatic compound there may be mentioned hydroquinone or phenol-styrene, having an average molar mass of from 100 to 800. Polyethylene glycol, polypropylene glycol having an average molar mass of 100 to 800, EO-PO mixed polyether having an average molar mass of 100 to 800, monoalkyl ether or dialkyl ether of the above polyether a group wherein the alkyl moiety may have from 1 to 4 carbon atoms, and also a mono- or dialkyl ester of the above polyether with an aliphatic carboxylic acid such as acetic acid, propionic acid, maleic acid, succinic acid, Fumaric acid, glutaric acid, adipic acid, citric acid. Mineral oil based dusting agents are also suitable. The dustproofing agent is preferably used in an amount of from 0 to 5.0%, more preferably from 0.05% to 2.0%, based on the solid material according to the present invention.

In a likewise preferred embodiment, the amine mercapto sulfonate compound used comprises less than 1 wt% of an organic or inorganic hydrazine formulation, preferably less than about 0.1 wt%. More specifically, the amine mercaptosulfonate compound used is substantially free of organic or inorganic hydrazine formulations, and optimally it does not contain an inorganic hydrazine formulation.

In another embodiment, the amine mercapto sulfonate compound used can also be used with organic hydrazine formulations, especially those of component b). Particularly preferred of this type of composition in the form of a particulate solid material comprises from -10 wt% to 90 wt%, especially from 30 wt% to 70 wt% of the group of amine-containing mercaptosulfonate groups. a compound of a), -10 wt% to 90 wt%, especially 30 wt% to 70 wt% of component b), and -0 to 5 wt%, especially 0 to 2 wt% of water (residual moisture), all based on Material meter.

Such an antimony formulation combination is also preferably comprised of less than 1 wt% of an inorganic antimony formulation, and more preferably less than 0.1 wt%, but is substantially free of inorganic antimony formulations, all based on the tanning formulation composition.

Making a composition comprising an amine methyl sulfonate group

The amine mercaptosulfonate compound used is obtained, for example, by mixing component a) with optionally other additives in water as an aqueous composition.

The compound of component a) is, for example, by reacting at least one organic polyisocyanate with at least one bisulfite and/or metabisulfite in an organic or water-organic solvent (eg water-two The reaction in alkane) can also be obtained, for example analogously to the procedure of DE 10 2006 056 479-A1.

Preference is given to the following process for the production of amine-mercapto sulfonate compounds, wherein at least one organic substance is present in the presence of water and optionally the emulsifier of component c) and optionally component d) The polyisocyanate is reacted with at least one of bisulfite and/or metabisulfite, and optionally with other additional materials and then optionally dried (preferably spray dried).

method

The raw materials for the production of dyed leather and fur are collagen fibrous substrates, especially animal hides and raw hides with or without hair. First of all They are prepared as usual in the ash room in a conventional manner. The hide and the raw material skin thus prepared are generally converted into a tanning product by treatment with an amine mercaptosulfonate compound, preferably having at least 65 ° C, preferably at least 68 ° C, and more preferably. It is a shrinkage temperature of at least 70 °C. The shrinkage temperature is determined by methods known to those skilled in the art, for example by immersing the tanning intermediate product in a water bath, and raising the temperature of the water bath at a certain heating rate until the material is observed. shrink. The temperature at the point of contraction is read from the display of the leather shrink tester. The shrinkage temperature can also be determined using a differential scanning calorimetry (DSC) known to those skilled in the art.

The overall operation of producing dyed leather and fur includes a number of additional steps, which are grouped for the sake of simplicity into a wet end step and a finished leather or fur finish. The wet end operation further includes an ash inter-operation; a tannage; and retanning. The liming operation further includes a plurality of pretreatment steps: a soaking, liming treatment, deliming and softening steps to produce leather (green and raw skin without hair); and dipping/pre-soaking, The steps of washing and degreasing to produce fur (skin and raw skin with hair). Subsequent tanning includes the actual tanning steps used to increase the shrinkage temperature of the collagen-containing substrate and allow for shaving. Retanning generally includes actual retanning, milky fatliquoring, staining, optional hydrophobization, and immobilization. The crust leather obtained at the completion of the wet end operation is finally treated as usual, for example by flattening, drying and usual softening. In addition, the dried leather can optionally be finished with a finishing agent or other coating in a conventional manner, such that the leather table The characteristics of the face can be optimized for specific requirements in later use. The fur obtained upon completion of the wet end operation is subjected to final treatment as usual, for example by drying, softening, degreasing, combing and ironing the hair covering. The fur can optionally be further post-treated such that the characteristics of the leather surface can be optimized for specific requirements in later use.

The treatment with an amine mercaptosulfonate compound is generally understood to be actual tanning.

Thus, a material treated with an amine mercaptosulfonate compound (tanned) may be referred to as leather, i.e., wet white, in the process of the present invention. The leather obtained in tanning can therefore be subjected to conventional mechanical treatments such as samming or shaving. However, the production of ready-to-use leather (blank), which can optionally be finished, requires additional known processing steps, such as retanning.

Preferably, in the process of the present invention, treatment with an aminoformylsulfonate compound (tanning) is followed by an additional retanning step, more specifically including the use of an organic hydrazine formulation (preferably having components) b)) actual retanning, dyeing, optional milky fatliquoring and hydrophobization, and fixation.

In a similarly preferred embodiment, the retanning is carried out in the presence of less than 1 wt%, preferably less than 0.1 wt%, of the inorganic hydrazine formulation based on the amount of retanning agent used, more specifically The retanning step is carried out in the absence of an inorganic hydrazine preparation such as a chrome tanning preparation.

The method of tanning collagen fiber substrates (especially raw hides and raw hides) is preferably characterized in that the hides pretreated in the liming compartment are treated with an amine sulfonate compound in a usual manner.

It is preferred for the collagen fibrous substrate not to be pickled prior to treatment with the amine amylsulfonate compound. Immersion acid is a processing step in which a collagen fiber substrate to be tanning, especially a rawhide and a raw material skin, more specifically a bare skin material, is treated with a strong acid and a salt, preferably in the presence of sodium chloride. The mixture of formic acid and/or sulfuric acid, the pH of the aqueous tanning bath is adjusted to a range from 2 to 3.5. A particular advantage of the method according to the invention over the known method is therefore that wet whitening can be produced without the need for impregnation. This makes it possible to save the manufacturer additional operations and possibly also avoid contamination of the effluent with high salt loading.

Treatment with an amine-mercapto sulfonate compound and more particularly all subsequent steps of the process according to the invention are preferably in the absence of minerals or other organic reactive oximes other than the amine sulfonate compound In the case of the formulation.

In this context, organic reactive hydrazine preparations are, for example, those having aldehyde functional groups, such as glutaraldehyde, glyoxal, succinaldehyde, adipaldehyde or degraded dialdehyde starch.

The organic hydrazine formulation of component b) is not an organic reactive hydrazine formulation for the purposes of the present invention.

The invention further relates to the use of anionic dyes for dyeing collagen fibre substrates, in particular tanned hides and skins (ie leathers and furs) in the presence of amine-mercaptosulfonate compounds and optionally organic Treatment with bismuth preparations (preferably component b), but without the presence of mineral or other organic reactive hydrazine preparations.

Preferably, the collagen fiber substrate pretreated in the ash chamber, in particular the hide and the skin, is mixed with the amine sulfonate compound at a pH of the substrate region ranging from pH 5 to pH 10. Preferably, it is from pH 7 to pH 10, and more preferably from pH 8 to pH 10, and the pH of the bath is in the range from pH 5 to 10, preferably from pH 6 to pH 9. More preferably, from pH 6 to pH 8, the mixture is allowed to penetrate into the entire cross section of the substrate in 0.1 to 8 hours, and preferably 0.2 to 2 hours, and then a fixing agent is added. Useful fixing agents include any of the bases known per se in tanning or mixtures thereof, such as aqueous sodium hydroxide, alkali metal carbonates, alkali metal hydrogencarbonates, magnesium oxide, dolomite, tertiary amines, etc., but Preferred are dolomite, magnesia, sodium carbonate and aqueous sodium hydroxide. The immobilization is preferably in the bath pH range from pH 7 to pH 10, preferably from pH 7.5 to pH 9.0, and more preferably from 7.8 to 8.8 from 2 to 24 hours and more preferably From 4 to 12 hours. The fixing temperature is preferably in the range from 15 ° C to 60 ° C, more preferably in the range from 20 ° C to 50 ° C, and more preferably in the range from 25 ° C to 45 ° C.

A suitably pretreated collagen fibrous substrate, especially an ash-pretreated depiled hide and raw hide (naked skin), is preferably in an aqueous bath at 10 ° C in a commercially available tanning drum. At a temperature of 60 ° C and a pH of 5 to 10, preferably 7 to 9, an amine-methyl sulfonate compound is 0.5% to 10%, preferably 1% to 4%, based on the weight of the bare skin. Processing to obtain a tanned intermediate product (leather) having at least 65 ° C, preferably at least 68 ° C and more preferably at least Shrinkage temperature of 70 ° C. The shrinkage temperature is determined by methods known to those skilled in the art, for example by immersing the tanning intermediate product in a water bath, and raising the temperature of the water bath at a certain heating rate until the material is observed. shrink. The temperature at the point of contraction is read from the display of the leather shrink tester. The shrinkage temperature can also be determined using a differential scanning calorimetry (DSC) known to those skilled in the art.

It is also possible to slow or interrupt the tanning by acidification to a pH ranging from pH 3 to pH 6, and preferably from pH 3.5 to pH 5.5, or by addition of ammonia or a primary or secondary amine. Base compound. This is especially advantageous when excessive astringency in the bath is to be avoided and it is desirable to partially deactivate the tincture. These additional measures are suitable for influencing the tanning operation in an advantageous manner.

It is very particularly advantageous to permeate the amine formamyl sulfonate compound by selecting a lower initial bath pH of 6 to 8 and adjust the fixing step to a pH range from 7.8 to 8.8 and by increasing the temperature to The method of the present invention is operated up to 60 °C.

The tanning intermediates obtained from the bare skin material are light colored and are therefore also referred to as wet white, which are used for further mechanical treatment by, for example, regaining, shaving or dissection. Moreover, these intermediate products are unique in that they are significantly white, clear, and resistant to light, and this is a significant advantage over leathers made with glutaraldehyde, such as, in particular, for the production of white leather.

The tanned leather can be retanning using a further process and finally processed into a gentle crust having a corresponding hue using conventional operations such as dyeing, milky fatliquoring and optionally hydrophobization.

The actual tanning must be used to stabilize the hides and raw hides, otherwise they will not be shaved. Subsequent retanning with organic bismuth preparations, especially those of component b), completes the tanning process and serves to adjust and enhance its properties in order to obtain leather useful for different leather articles.

It is generally convenient to retort the leather while it is retanning, and to use a suitable creamy fatliquor for this purpose. Examples of organic bismuth formulations are those of component b), which often also have some filling and softening properties which, in some cases, can be tailored to their main characteristics by changing the bismuth formulation, for example By adding a resin type bismuth preparation, a filled polymer hydrazine preparation or a softening polymer retanning agent. In principle, however, any conventional non-tanning milk fatliquor can be used in the process of the invention between the retanning steps. The actual retanning, dyeing and milky fatliquoring operation is advantageously carried out in a pH range from 3.5 to 6.0, whether or not a certain proportion of hydrophobizing agent is included. It is also possible to additionally perform a top dyeing operation with an anionic dye before fixing.

Preferably thereafter, the actual hydrophobization is carried out at a pH of from 3.5 to 7.0, preferably from 3.5 to 6. Finally, the hydrophobized leather is fixed by acidification to a pH of between 2.5 and 4.0, preferably between 2.5 and 3.5, washing and final treatment in a conventional manner, for example by horsing, flattening Vacuum drying and suspension drying soft. When a particularly high degree of hydrophobicity is required, an aluminium salt can be added during the fixing step, such as basic aluminum chloride, aluminum formate, titanium or zirconium salts, such as zirconium sulfate.

The non-tanning milk fatliquors mentioned are generally pre-emulsified in aqueous systems and for this purpose comprise emulsifiers as a whole. Such emulsions or dispersions may sometimes further comprise an organic solvent to promote deeper penetration and uniform distribution throughout the leather surface.

When non-tanned milk fatliquors are used in the retanning step, they can be used in an amount of up to 80% by weight, preferably up to 40% by weight, based on the weight of the shaved solids. The proportion of the organic bismuth preparation of component b) to the non-tanning milk fatliquor is in particular in the range from 99:1 to 20:80, and in particular in the range from 95:5 to 35:65.

The above-mentioned tanning can also be carried out by using the organic hydrazine preparation of the component b) in combination, in which case the hydrazine preparations may be used together or not in common. The hydrazine formulation of component b) can be used together with the amine mercapto sulfonate compound or sequentially.

Preferably, after tanning, retanning by treatment with the organic bismuth formulation of component b), preferably using synthetic tanning agents and plant sputum preparations. The actual retanning is used to set the desired leather properties. Advantageously, it is again preferred to use an organic guanidine formulation, a synthetic bismuth agent and a plant bismuth formulation. It is also advantageous to use polymeric retanning agents, such as (co)polymer based retanning agents, as well as resin type bismuth formulations, dyes, milk fatliquors, and also certain proportions of hydrophobizing agents. Preferably, the agents are used in retanning in conventional amounts for wet white.

The tanning process of the present invention is advantageous because no pickling is required any more; leather having a broad spectrum of properties is obtained; and the shaved material produced during mechanical handling does not contain harmful compounds and can be widely used as a raw material, Included for the manufacture of useful products, which in turn are used in tanning operations. This has made a significant contribution to reducing waste in tanning and simplifying the recovery of shaved material.

The wet white based on the amine mercapto sulfonate compound results in a white, anti-yellowing, bright and fully dyed leather or fur, optionally comprising hydrophobized leather or fur, the softness of which is achieved by Set the product used in the reclamation.

For the pre-warming of the fur, the hair removal effect is of course omitted.

Collagen fiber substrates with attached keratin components, especially hides and skins with hair, can have very different processing steps leading to a final fur in which the iso-keratin components, especially hair, are retained. The processing steps for producing the base of the sheepskin will now be described in simplified form by way of example.

The starting materials used preferably comprise dehydrated, especially salted and/or air-dried sheepskin. The processing of the raw materials is typically carried out in a reel beck wherein the amount of reagent is based on the wet weight of the hide and the raw hide, for example, in grams per liter of bath or by weight.

Preferably, the process is decomposed into the following steps, although the invention is not limited to this particular example described, but includes any method for treating fur with an amine-mercaptosulfonate compound: Immersion room: Step 1) soaking/pre-soaking in water in the presence of a softening aid or cleaning agent (surfactant), step 2) de-meating, optionally splitting the hide, step 3) in the cleaning agent ( Washing with water in the presence of a surfactant) and a brightening agent, step 4) optionally pickling the acid to open the hide with water, sodium chloride and formic acid, usually in the presence of a bleaching agent, a cleaning agent and adding an electrolyte resistant Milky fatliquor, tanning: Step 5) Tanning with an amine sulfonate compound, retanning: Step 6a) Actual retanning, milky fatliquoring, optionally dyeing with an organic hydrazine formulation, step 6b Dyeing and optionally hydrophobization, step 7) drying and final treatment of the raw material skin: drainage, suspension drying, conditioning (for example with moist sawdust), softening, and side grinding of the leather, combing the hair The cover layer is then dried and purified (degreased, for example with sawdust or optionally using a special sealing device and treated with an organic solvent, such as in a chemical dry cleaned garment), combed and ironed the hair covering.

Any commercially available materials are suitable and the hides and skins are typically treated in a roll. Particularly good for raw hides and raw hides It is first pretreated by pre-soaking, soaking, removing meat and washing and then completely washing.

The process of the invention can also be carried out without pickling. When pickling is used, the washed hides and raw hides are treated in the presence of a carboxylic acid in the presence of a carboxylic acid at pH 2 to 4 in an aqueous solution of sodium chloride (e.g., 5 ° Bé) for several hours. Subsequent washing and subsequent deliming and degreasing with sodium formate, sodium bicarbonate and surfactant, the pH is gradually increased to a range of pH 5 to 10. The pickled material is subsequently used for tanning.

When the pickling is not used, the washed hides and raw hides are used directly for tanning. It is preferred for the hide and the raw material skin to be free of pickling prior to treatment with the amine amylsulfonate compound.

The tanning process is advantageously tracked by measuring the shrinkage temperature of the substrate. When a shrinkage temperature of at least 65 ° C, preferably at least 68 ° C, and more preferably at least 70 ° C is reached, the pH is lowered, the bath drops and the fur is washed.

Thus, materials treated with an amidomethyl sulfonate compound (tanned) may be referred to as wet white fur in the process of the present invention.

The tanned fur can be subsequently retanning (step 6) using 6a-1 organic bismuth preparations, especially those of component b), such as synthetic tanning agents, polymeric retanning agents, softening polymer tanning agents, 6a-2 milky fatliquor, and 6a-3 dye 6b) and optionally a hydrophobizing agent.

If the hair is also not required to be dyed, the tolerant can be added prior to dyeing. After dyeing, the dye is advantageously fixed by the addition of a cationic auxiliary.

The dyeing method according to the invention can also be applied in the case of certain furs, preferably sheepskins for medical purposes or direct skin contact.

Upon completion of the retanning step (step 6), it is preferred to adjust the bath with formic acid to a pH ranging from 2.5 to 4.5, preferably 3 to 4, and to clean the fur.

The retapped fur is then typically removed from the roll (step 7). They are drained and suspended in suspension. Thereafter, the fur is softened and optionally wet degreased and dried in a sawdust drum. Preferably, the flesh side is subjected to a burst. The hair is finally combed and ironed. It is also possible to treat the fur with an adjuvant to control the soil or to control static buildup, etc., for example by spraying a suitable reagent.

The individual steps of the method will now be described in detail.

The ash-treated pre-treated hairy hides and raw hides are preferably at a temperature of from 10 ° C to 50 ° C in an aqueous bath having a bath-to-liquid ratio of 300% to 1000% based on wet weight in the coil. Next, the wet weight of the hide and the raw material skin is tanned with 0.5% to 10%, preferably 1% to 5%, of at least one amine sulfonate compound. It is preferred to provide a tanning intermediate (wet white fur) having a shrinkage temperature of at least 65 ° C, preferably at least 68 ° C, and more preferably at least 70 ° C.

Preferably, the ash pretreated skin and the raw material skin are adjusted in the roll to have a pH from 5 to pH 10, preferably from pH 7 to pH 10, in the cross section of the substrate. It is the pH from pH 8 to pH 10. The addition of the amine formamidine sulfonate compound at a pH from pH 5 to pH 10, preferably from pH 7 to pH 10, and more preferably from pH 8 to pH 10, at the initial pH of the substrate cross section, And the pH of the initial bath is in the range from pH 5 to 10, preferably from pH 6 to pH 9, and more preferably from pH 6 to pH 8, so as to be from 0.1 to 8 hours and preferably It is allowed to penetrate into the entire cross section of the substrate in 0.2 to 2 hours, and then a fixing agent is added. Useful fixing agents include any of the bases known per se in tanning or mixtures thereof, such as aqueous sodium hydroxide, alkali metal carbonates, alkali metal hydrogencarbonates, magnesium oxide, dolomite, tertiary amines, etc., but Preferred are dolomite, magnesia, sodium carbonate and aqueous sodium hydroxide. The fixation is preferably carried out in a bath pH range from pH 7 to pH 10, preferably from pH 7.5 to pH 9.0, and more preferably from 7.8 to 8.8 from 2 to 24 hours and more preferably. It is from 4 to 12 hours. The fixing temperature is preferably in the range from 15 ° C to 60 ° C, more preferably in the range from 20 ° C to 50 ° C, and more preferably in the range from 25 ° C to 45 ° C.

The tanning reaction of the collagen fiber substrate releases bisulfite, resulting in a decrease in the pH of the bath. It is particularly advantageous to maintain the pH within the range specified above during the tanning process by the addition of a fixing agent. After the completion of the infiltration, it is sufficient to add 2 to 3 parts of the fixing agent as a whole to set the preferred one. pH range. The covalent attachment of the amine formamyl sulfonate compound to the collagen fiber substrate is accomplished by treatment with a fixative.

Preferably, the dyeing is carried out by treating the collagen fibrous substrate which has been treated with at least one amine mesylate compound in an aqueous bath comprising at least one anionic dye before, during or after the actual retanning . After tanning and shaving, very white wet whites are obtained as substrates and they can be used in subsequent steps.

After the actual retanning, the pH is preferably reduced to 3 to 4, followed by washing and subsequent dyeing in the presence of a milk fatliquor, a dyeing aid and an anionic dye, preferably in diluted form. For use, it is carried out at 15 ° C to 70 ° C and at pH 3 to 4 for 1 to 3 hours, then acidified to a pH of 2.5 to 4 and optionally treated with a further concentrated anionic dye (top dyeing).

The anionic dye is preferably used in an amount of from 0.05% to 5%, based on the weight after shaving (leather) or on the basis of wet weight (fur).

In the case of tops dyeing, it is preferred to use 0.01% to 1.5% anionic dye based on the weight after shaving (leather) or based on wet weight (fur).

The anionic dyes can be used as a powder or granules in aqueous solutions or suspensions or in solid form. They may include other auxiliaries such as organic solvents, stabilizers, dyeing auxiliaries or other conventional additives.

Examples of preferred anionic dyes include the following: acid black 2, acid black 52, acid black 71, acid black 84, acid black 107, acid black 173, acid black 194, acid black 210, acid black 220, acid black 234 , Acid Blue 25, Acid Blue 90, Acid Blue 113, Acid Blue 158, Acid Blue 193, Acid Blue 284, Acid Blue 349, Acid Brown 75, Acid Brown 83, Acid Brown 161, Acid Brown 194, Acid Brown 282, Acid Brown 298, sour brown 311, sour brown 314, sour brown 322, sour brown 324, sour brown 349, sour brown 355, sour brown 365, sour brown 413, sour brown 414, sour brown 425, sour brown 431, sour brown 432, Acid Brown 434, Acid Brown 452, Acid Brown 75, Acid Brown 97, Acid Brown Mixed, Acid Green 26, Acid Green 68, Acid Green 104, Acid Green 111, Lime 33, Lime 61, Lime 74, Lime 142, lime 56, acid red 119, acid red 131, acid red 374, acid red 414, acid red 425, acid red 434, acid red 97, acid purple 48, acid yellow 42, acid yellow 49, acid yellow 79, Acid Yellow 99, Acid Yellow 194, Acid Yellow 232, Direct Black 168 and/or Direct Blue 59 or a mixture thereof.

Particularly preferred are dyes which do not contain any transition metals.

The wet white tanned based on the amine mercaptosulfonate compound produces white, anti-yellowing leather and fur, the softness of which is determined by the product used in the retanning. The dyed leather and fur according to the method of the invention have exceptionally bright colours, very good dye penetration and high dye uniformity, and also exhibit uniform coloration of the flesh and grain. The dyed leather satisfies the fastness requirements such as applied to upper leather, furniture leather, and automotive leather; the dyed fur satisfies the fastness requirements such as applied in the medical field, clothing articles, and decorative purposes.

Preferred organic tanning agents of component b) include synthetic tanning agents, resin tanning agents, polymeric retanning agents, and also vegetable tanning agents.

Synthetic tanning agents include, for example, at least one aromatic compound which is sulfonated based on the condensation product A) below. B) an aldehyde and/or a ketone, and optionally C) one or more compounds selected from the group of aromatic compounds of non-sulfonated, urea and urea derivatives.

"Based on" is understood to mean that such condensation products are optionally prepared from A, B and optionally other reactants other than C. However, in the context of this case, such condensation products are preferably prepared only from A, B and optionally C.

Sulfonated aromatic compounds also include sulfomethylated aromatic compounds in the context of the present disclosure. Preferred sulfonated aromatic compounds are: naphthalenesulfonic acid, phenolsulfonic acid, sulfonated xylene ether, 4,4'-dihydroxydiphenylphosphonium, sulfonated diphenylmethane, sulfonated biphenyl, sulfonate Combine triphenyl or benzenesulfonic acid, toluenesulfonic acid.

Useful aldehydes and/or ketones include, inter alia, aliphatic, cycloaliphatic and also aromatic. Preferred are aliphatic aldehydes, more preferably formaldehyde, and other aliphatic aldehydes having 3 to 5 carbon atoms are useful.

Useful non-sulfonated aromatic compounds include, for example, phenol, cresol or dihydroxydiphenylhydrazine, dihydroxydiphenylmethane, xylyl ether, dihydroxydimethylphenyl ether, dihydroxydimethylphenylhydrazine, hydroxybenzoic acid .

Useful urea derivatives include, for example, dimethylolurea, melamine or guanidine.

Phenol and phenol derivatives such as, for example, benzenesulfonic acid are usually also linked by simultaneous reaction with formaldehyde and urea or by dimethylol urea (DE-A 1 113 457). Sulfonated products of aromatic compounds as a whole (according to Ullmanns Encyklopaedie der technischen Chemie Volume 16 (4th edition) Weinheim 1979, p. 138) is condensed with formaldehyde alone or with other starting compounds without removing the unconverted starting compound. In the case of phenol, it is also possible to introduce a solubilizing group by sulfomethylation together with condensation under the simultaneous action of an alkali metal hydrogensulfite and formaldehyde. This sulfomethylation is described, for example, in DE-A 848 823.

Further preferred condensation products are condensates of xylyl ether sulfonic acid with 4,4'-dihydroxydiphenyl hydrazine, phenolsulfonic acid and phenol, formaldehyde and urea.

Particularly preferred condensation products are obtained by condensation of a sulfonated and optionally non-sulfonated aromatic compound with a fatty aldehyde, preferably formaldehyde, although the meaning of the sulfonated aromatic compound is more specifically not Includes sulfomethylated aromatics.

The condensation products are preferably condensed by sulfonated naphthalene and sulfonated phenol or 4,4'-dihydroxydiphenylanthracene with formaldehyde, or by condensation of naphthalenesulfonic acid with formaldehyde, or by Condensation of sulfonated xylyl ether, sulfonated phenol with formaldehyde, or condensation of sulfonated phenol, urea, phenol with formaldehyde, or by sulfonated phenol, urea, phenol, sulfonated xylene The condensation of a base ether with formaldehyde is obtained.

The condensation product which is preferentially obtained in the condensation preferably has an average degree of condensation in the range from 1 to 150, preferably in the range from 1 to 20 and especially from 1 to 12. .

Preferred are naphthalenesulfonic acid, xylyl ethersulfonic acid, phenolsulfonic acid, dihydroxydiphenylphosphonium and phenol, and also combinations of such materials A product of the condensation of formaldehyde, glyoxal or glutaraldehyde and optionally a urea or urea derivative.

A similarly suitable organic hydrazine formulation is based on dihydroxydiphenyl hydrazine/naphthalene sulfonic acid and formaldehyde, dihydroxydiphenyl hydrazine/xylyl ether and formaldehyde, dihydroxydiphenyl hydrazine/phenol sulfonic acid/xylyl Ether sulfonic acid/urea and formaldehyde (a commercially available hydrazine formulation such as, for example, TANINI® BN from LANXESS, TANIGAN® PR, TANIGAN® 3LN, TANIGAN® HO, TANIGAN® UW or mixtures thereof).

The organic tanning agents used, especially synthetic tanning agents, may additionally comprise additional additives such as buffers or lignosulfonates.

Similarly, resin tanning agents can be considered as organic antimony preparations, and they are preferably based on polycondensation of melamine, dicyandiamide, urea, lignosulfonate or a mixture thereof with formaldehyde or glutaraldehyde. Things.

Preferred polymer retanning agents are high molecular weight water-soluble or water-dispersible products, for example (co)polymerization from unsaturated acids and their derivatives, having, for example, filling or milky fatliquoring on leather effect. Preferred are (co)polymerized products of acrylic acid and methacrylic acid and esters thereof.

Other polymeric retanning agents are polyasparagine described in WO 97/06279 which have a number average molecular weight of from 700 to 30,000, preferably from 1300 to 16 000, by allowing the following in the presence of water The reaction can be carried out to obtain A. a polysuccinimide having a number average molecular weight of 500 to 10,000, preferably 500 to 6000 and especially 1000 to 4000, and B. amber succinimide based on polysuccinimide A The monomer is from 5 mol% to 90 mol%, preferably from 20 mol% to 80 mol%, of a primary or secondary amine, the nitrogen substituent of which contains from 1 to 60, preferably from 1 to 36 carbon atoms and May be interrupted by a fluorine atom, a hydroxyl group, an amine group and/or an organic oxime moiety and/or interrupted by an oxygen atom, an ester group, a guanylamino group, a ureido group, or a urethane group, wherein at least 2.5 mol%, Preferably at least 15 mol%, and especially at least 30 mol% of the nitrogen substituent of the amine comprises at least 12 carbon atoms, and optionally C. (i) C ₁ -C ₁₈ -monocarboxylic acid and/or a derivative of a C ₂ -C ₁₀ -dicarboxylic acid and/or (ii) a monoisocyanate, a diisocyanate or an epichlorohydrin (reacting with an amine and/or a hydroxyl group on a nitrogen substitute of the reaction product of A and B) And, (must) D. 95 mol% to 10 mol%, preferably 80 mol% to 20 mol% of the ring-opening base.

Thus, the preferred polyasparagine of WO 97/06279 should also be considered to be incorporated herein.

Other polymeric retanning agents are, for example, (co)polymers comprising a) a plurality of structural units of the formula I Where W represents a trivalent moiety from the following group (moiety) Wherein ^* represents the orientation for binding the W moiety in Formula I, and Z represents a -OH, -O ^- M ⁺ or -NR ¹ R ² moiety, wherein R ¹ and R ² independently of each other represent hydrogen, optionally substituted An alkyl moiety, an alkenyl moiety, an aralkyl moiety, or a cycloalkyl moiety which may be an oxygen atom, a nitrogen atom, a halogen atom or a decylamine, a carbonate, a urethane, a urea, a ureidocarboxylic acid The ester, biuret or trimer isocyanate group, or mixtures thereof are interrupted, and M ⁺ represents H ⁺ or an alkali metal ion, NH ₄ ⁺ ion or preferably C ₁ -C ₂₂ -alkyl or C ₁ -C a primary, secondary, tertiary or tertiary aliphatic ammonium moiety of ₂₂ -hydroxyalkyl, b) at least 10 mol% of the structural units of formula I, having a plurality of structural units of formula Ia Wherein R ³ represents a hydrocarbon moiety having a C ₁ - C ₆₀ atom, preferably a saturated C ₁ -C ₆₀ -alkyl moiety, especially a C ₈ -C ₃₀ -alkyl moiety, and R ⁴ represents hydrogen or has a R ^{3 has the} same meaning and c) a polyether unit having an average molecular weight of from 200 to 6000 g/mol.

Vegetable tinctures are, for example, those obtained from plant sources and belonging to the class of condensed or hydrolyzable elixirs, such as chestnut extract, mimosa, tara or quebracho. Vegetable tanning agents also include those obtained from plant sources such as algae, fruits such as rhubarb, olives, parts of plants such as leaves, bark, roots, wood optionally chemically/enzymatically modified and/or by extraction methods. Those who are.

In the retanning step, the organic hydrazine preparation of component b) is typically used in the form of an aqueous solution or an aqueous dispersion in an amount of from 3 wt% to 100 wt%, preferably from 10 wt% to 50 wt%. , based on the weight of the leather after shaving or the wet weight based on the fur; and in the tanning, the amount is 0 to 50 wt%, preferably 0 to 30 wt%, based on the bare skin weight of the raw hide and the raw material skin (none Hair) or wet weight (with hair) based on raw hides and raw hides.

Anionic dyes can also be used in conjunction with a fatliquor and optionally a hydrophobizing agent.

Suitable hydrophobizing agents are, for example, polyoxyalkylenes, preferably aqueous emulsions of polyoxyalkylene.

Hydrophobization is generally carried out by grinding in a conventional manner in a suitable apparatus, i.e., the weight of the leather or the wet weight of the fur based on shaving is from 50% to 2000%, preferably from 100% to 400%. The bath ratio is at a temperature of from 20 ° C to 60 ° C, preferably from 35 ° C to 50 ° C, wherein the pH is generally between 4.5 and 8.0, preferably between 4.8 and 5.5. Hydrophobization generally takes from 20 to 240 minutes and preferably from 30 to 120 minutes.

Upon completion of the hydrophobization, the optional co-emulsifier is typically immobilized with an acid, preferably formic acid, by adjusting the pH to 3.0 to 5.0 and preferably from 3.8 to 4.0.

Hydrophobization can be amplified by post-treatment with di-, tri- or tetravalent metal salts conventionally used for tanning, especially with basic chromium sulphate, aluminum sulphate, aluminum formate, zirconium sulphate, titanium sulphate, chlorine Calcium or sulfur Magnesium acid. It is advantageous to use from about 0.5 wt% to 5 wt%, and preferably from 1 wt% to 2 wt% of the salts mentioned, based on the weight of the shaved leather or the wet weight of the fur. Among the salts, basic aluminum chloride, aluminum triacetate, titanium sulfate, and zirconium sulfate are preferred. As the hydrophobizing agent, many of the above polyoxyalkylenes do not require metal salt fixation to provide a good hydrophobizing effect.

The invention also provides collagen fibrous substrates, especially leather and fur, which are tanning with at least one amine mercaptosulfonate compound and dyed with at least one anionic dye. The above preferred forms are also applicable here respectively.

Example A) Manufacturing Example Example A1: Granule polyamine sulfonyl sulfonate with emulsifier and organic hydrazine formulation

(HLB 16.7) sorbitan polyethylene glycol (20) monododecyl ester (eg Eumulgin) alkoxylated from 95.5 g of a total of 20 ethylene oxide units per sorbitan unit SML 20 (Cogins) or Tween 20 (Croda) in a solution of 3199.5 g water and 4524.8 g sodium bisulfite solution (NaHSO ₃ , 38-40% in water) at 25 ° C and a pH of 4.36 1358.3 g of hexamethylene diisocyanate was added over a period of 40 minutes with stirring, during which time the temperature of the reaction mixture was adjusted to 50 °C. The pH system is 5.62. Then, 70.3 g of citric acid (anhydrous) dissolved in 70.3 g of water was added.

The reaction mixture was then stirred at 50 ° C for more than 1 hour during which time the reaction mixture became clear. It was then cooled to 25 ° C over a 2 hour period. It was then stirred at room temperature (20-23 ° C) for an additional hour. The pH of the solution was 4.67. Then, 211.3 g of citric acid (anhydrous) dissolved in 211.3 g of water was added and stirred for 15 minutes. The concentration was adjusted by adding 258.7 g of water to obtain a clear, 35.0% solution having a pH of 3.11.

5000 g of 35% of the above amine carbamate sulfonate compound solution and 5000 g of 50% sulfonated xylyl ether and 4,4'-dihydroxydiphenylfluorene-based methylene bridged aroma The aqueous solution of the polycondensate was pumped into a spray dryer equipped with a disk atomizer and the inlet temperature was adjusted to 165 °C. The outlet temperature is between 70 ° C and 80 ° C. No baked goods were found in the dryer. A substantially white finely divided powder having an overall density of 562 g per 1000 ml was obtained with a dry residue of 99.27% (Mettler IR dryer HR 73 P, 120 ° C, standard dry, to constant weight). The dust-free powder obtained has a particle diameter of 5.0 μm to 300 μm. It dissolves quickly in water without clumping. A solution of 5 g of powder in 50 ml of water has a pH of 3.40.

Example A 2a: Granule polyamine-mercaptosulfonate with HDI, no emulsifier

Add hexamethylene diisocyanate to 391.4 g of water and 527.6 g of sodium bisulfite solution (NaHSO ₃ , 38% to 40% in water) at 23 ° C while operating the disperser at 15,000 per minute. The mixture was dispersed by disrotating, the disperser being based on the rotor stator principle (from the Ultraturrax assembly of IKA). Starting from the addition of the isocyanate, the temperature of the reaction mixture was raised to 60 ° C over a period of 60 minutes. The pH system was initially 3.02 and rose to pH 5.84 during the course of the reaction. A cloudy solution formed after a reaction time of 180 minutes. The speed was reduced to 12,000 rpm and the solution was cooled to 34 °C over 2 hours. The batch was filtered. The clarified solution had a pH of 4.34 and was mixed with 28.3 g of citric acid monohydrate dissolved in 23.4 g of water to obtain a solution having a solids content of 35.25 wt% and a pH of 2.12. This solution was mixed with 3000 ml of acetone. The mixture was then stirred for 2 hours. The precipitated white solid was filtered off with suction, washed with acetone and dried to a constant weight (yield: 90.3%, residual moisture content: 0.5 wt%) in vacuo at 20 °C.

A solution of 1.75 g of powder in 5 ml of water was clear and had a pH of 2.20.

Example A 2b: Granule polyamine sulfonate having CHDI and no emulsifier

Adding 191.8 g of bis(isocyanatomethyl)cyclohexane (isomeric) to 431.8 g of water and 554.1 g of sodium hydrogen sulfite solution (NaHSO ₃ , 38% to 40% in water) at 20 ° C The mixture or exactly 1,4- and 1,3-isomers, while dispersing the mixture at 15,000 rpm by using a disperser based on the rotor stator principle (Ultraturrax assembly from IKA) . After 2 hours, the setting of the dispersion assembly was increased to 18,000 rpm. After another 30 minutes, the speed is increased to 20,000 rpm. After the addition of the isocyanate for 3 hours, the temperature of the reaction mixture was 60 °C. After a reaction time of 3.5 hours, the organic phase disappeared. It was then cooled at 40 ° C for 1.5 hours while continuing to disperse at 15,000 rpm. After a total reaction time of 5 hours, the batch was filtered and mixed with a solution of 28.3 g of citric acid monohydrate in 23.4 g of water to obtain a pH of 2.58 and a 35.0% strength solution having a pH of 2.58.

This solution was mixed with 3000 ml of acetone at room temperature. The mixture was then stirred for 2 hours. The precipitated white solid was filtered off with suction, washed with acetone and dried to a constant weight (yield: 80.5%, residual moisture content: 0.9 wt%) in vacuo at 20 °C.

A solution of 1.75 g of powder in 5 ml of water was clear and had a pH of 2.60.

Example A 2c: Granule polyamine-mercaptosulfonate with HDI, no emulsifier

Adduct from 326.5 g of water, 461.7 g of sodium bisulfite solution (NaHSO ₃ , 38% to 40% in water) and 9.8 g of 2 mol of citric acid and 1 mol of hexamethylene diisocyanate (drying) The aqueous solution was obtained afterwards, and the solution was prepared by dispersing at 12,000 rpm. The initial filler was mixed at one time with 138.6 g of hexamethylene diisocyanate at 20 °C. The temperature of the reaction mixture was raised to 50 ° C over 60 minutes under dispersion. At 50 ° C, 7.8 g of citric acid monohydrate dissolved in 6.5 g of water was added, resulting in a pH of 3.05. This batch was then kept at 50 ° C for 1 hour and then cooled to 25 ° C in 2 hours. The pH of the clear solution was 2.92 at room temperature. A 23.6 g portion of citric acid monohydrate dissolved in 19.5 g of water was added. The solids concentration was adjusted by adding 26.4 g of water to obtain a clear, 35.0% strength solution having a pH of 2.30.

This solution was mixed with 3000 ml of acetone at room temperature. The mixture was then stirred for 2 hours. The precipitated white solid was filtered off with suction, washed with acetone and dried to a constant weight (yield: 93.5%, residual moisture content: 0.7 wt%) in vacuo at 20 °C.

A solution of 1.75 g of powder in 5 ml of water was clear and had a pH of 2.4.

B) Use example (wet white production)

The amount of a particular product used, such as the commercial product provided, is based on the weight of the raw or intermediate product used.

B 1A: Production of wet white with the bismuth preparation from Example A1

The salted cowhide is washed, limed, depilated, de-sliced and sectioned in a commercial manner. The bare skin material (2.6 mm) was washed with a 200% bath and drained. For pre-deashing, the bare skin is in a drum with 100% bath and 0.2% sodium bisulfite, 0.1% amine-free deashing agent (eg Cistollan DLP from LANXESS) and 0.2% The carboxylic acid mixture (for example, Canceollan DL from LANXESS) was stirred at 30 ° C for 30 hours. The bath was dropped. Then for further deashing, 30% water, 0.2% sodium hydrogen sulfite and also 0.1% amine-free deashing agent (for example Canceollan DLP from LANXESS) and 0.2% carboxylic acid mixture (eg The product Canceollan DL from LANXESS was added and the drum was stirred at 30 ° C for 1 hour. At pH 7.7, add 1% The softening enzyme (for example, Levazyme AF from LANXESS) and 0.1% of a fatty alcohol ethoxylate-based degreaser (such as Cismollan AN 90) are then stirred for a further 45 minutes. The bath was then dropped and the pelt was washed twice. (The amount of products used below is based on the bare skin weight.)

The prepared pelts were adjusted with 50% water, 0.2% sodium hydrogencarbonate and 1% sodium acetate for 30 minutes to pH 9.0, and mixed with 1.7% of the product (powder) from Example A1. After a penetration time of 20 minutes, another 3.4% of the product (powder) from Example A1 was added. A total of 0.5% sodium carbonate (diluted 1:10 with water) was added over the next 1.5 hours at 40 °C to adjust the pH to 8.1. Then, the drum was stirred at 40 ° C for 2 hours and the shrinkage temperature (pH 7.65, Ts 68 ° C) was measured. The drum was stirred for another 2 hours (10 minutes/hour) in the automatic mode, and the pH was measured. Then, 0.2% preservative (for example, Preventol U-Tec G from LANXESS) was added and the pH was lowered to 4.3 with 0.3% formic acid (85%, diluted 1:10). The drum was stirred for 1.5 hours. The bath was then dropped. The wet white leather is washed and horse-drawn. Re-measure the shrinkage temperature (70 ° C). These leathers are easy to squeeze and cut to 1.2 mm.

B 2A: Comparative Example: Production of wet white with GTA

The salted cowhide is washed, limed, depilated, de-sliced and sectioned in a commercial manner. The cortical material (2.6 mm) was washed with a 200% bath and drained. The pelts were then de-ashed in a drum in a 100% bath and 0.3% sodium bisulfite, 2.5% ammonium chloride, 0.2% formic acid (85%) for 30 minutes. Then add 0.5% softening enzyme (1000 trypsin unit (tryps.units)) and the drum was stirred for 1 hour. The pH system is 8.5. The bath was dropped and the rind was washed for 10 minutes and the bath was again dripped. (The amount of products used below is based on the bare skin weight.)

The bare skin is then treated with 30% water, 6% sodium chloride, 0.3% preservative (eg, Preventol WB Plus L from LANXESS), 0.5% formic acid (85%), 0.90% at 30 °C. The sulfonic acid (96%) was pickled for 70 minutes. Then, a 1.00% milk fatliquor (for example, Eureka 975 ES-I) was added, followed by stirring for 3 hours. The bath pH was 2.9. Then, 3.00% aqueous glutaraldehyde solution (GTA, about 24% strength, pH 1.5 to 2.5) was added for 2 hours of pre-twisting. The drum was stirred for another 2 hours (10 minutes/hour) in the automatic mode, and the pH (pH 2.9) was measured.

For neutralization, 1.00% sodium formate was added and after a 15 minute run time, 1.00% sodium formate was added to give a pH of 3.6. After an execution time of 30 minutes, a 1.00% neutralization oxime formulation based on aromatic sulfonic acid (for example the product TANIGAN PAK from LANXESS) was added. The drum was stirred for 20 minutes and the pH was 3.75. Then, 0.2% sodium hydrogencarbonate was added, followed by stirring for 30 minutes (pH 4.0). Then, 3.0% of a 4,4'-dihydroxydiphenylfluorene-based hydrazine preparation (for example, Tanigan HO from LANXESS) was added and the drum was stirred for 1 hour.

Subsequent drainage, washing with 200% water and draining again. Will be wet white horse. Re-measure the shrinkage temperature (70 ° C). These leathers are easy to squeeze and cut to 1.2 mm.

B 3A: Production of wet white with the bismuth preparation from Example A2a

Example B 1A was repeated, using a bismuth formulation from Example A2a based on a skin weight of 2.1% to produce wet white.

B 4A: Production of wet white with the bismuth preparation from Example A2b

Example B 1A was repeated, using a bismuth formulation from Example A2b based on a skin weight of 2.1% to produce wet white.

B 5A: Production of wet white with the bismuth preparation from Example A2c

Example B 1A was repeated, using a bismuth formulation from Example A2c based on a skin weight of 2.1% to produce wet white.

C) Dyeing examples

(The amount of products used below is based on the weight of the leather after shaving.)

Example C: Production of retanning leather with wet white from Example B1A

The shaved white (thickness 1.3/1.4 mm) from Example B 1A was used with 300% water (40 ° C) and 0.2% fatty alcohol ethoxylate (eg CIS MOLLAN AN 90 from LANXESS) The bath formed by dilution (1:5) was washed in a tanning drum for 10 minutes. The bath had a pH of 4.3 and dripped. Then add 50% water (30 ° C), 3.0% organic bismuth preparation (such as TANIGA RFS from LANXESS), 1.5% sodium formate and 3% milk fatliquor (such as Baykanol Licker from LANXESS) SL) (diluted 1:8). The drum was stirred for 30 minutes and the bath had a pH of 4.8. Then add a 3.0% softening polymer oxime formulation based on modified polyamidocarboxylic acid (eg LEVOTAN LB from LANXESS) (diluted 1:3 with water) and add 5.0% aromatic sulphur after 10 minutes Aggregation of acid and phenolic compounds Shrinkage (eg TANIGA BN from LANXESS) and 8.0% auxiliaries (eg Granofin TA from Clariant).

After 30 minutes (pH 4.6), 5.0% of a polycondensate based on aromatic sulfonic acid and phenol compound (for example, TANIGA BN from LANXESS) and 8.0% of vegetable mash preparation (Mimosa) were added, followed by stirring 150 minute. At this time, the pH was 4.4.

Then 50% warm water (50 ° C) was added and the drum was heated to 50 °C. After 10 minutes, a 3.0% milk fatliquor (for example, BAYKANOL Licker SL from LANXESS) (diluted 1:8) was added and then stirred for 15 minutes. Thereafter, a 3.0% polyacrylate-based filled polymer hydrazine formulation (eg, product LEUKOTAN 1084 from Dow Chemical Company) (diluted 1:3) was added and then stirred for an additional 45 minutes. It was then acidified to pH 3.8 twice with 1.3% formic acid (1:10 dilution). After 45 minutes, the bath was dropped and the raw hide was washed.

For dyeing, a fresh bath was used: 50% water (20 ° C) and 3.0% milk fatliquor (eg BAYKANOL Licker SL from LANXESS) (diluted 1:8), then drum treatment 60 minutes. After a few minutes of pre-execution time using a 2% naphthalenesulfonic acid condensate (eg TANIGA PR from LANXESS), add 3.0% anionic dye (eg BAYGENAL Black TDE from LANXESS, (CI Black) (Acid Black) 210)), followed by stirring for 60 minutes. Then 100% water (60 ° C) was added and the temperature was raised to 50 °C. It was then fixed with 3% formic acid (diluted 1:10). After 30 minutes, a pH of 3.2 has been reached. In order to dye the top, 1% anionic dye (for example BAYGENAL Black TDE from LANXESS, (C.I. Acid Black 210)) was added and the drum was stirred for 20 minutes. This was followed by final fixation with 1.0% formic acid for 30 minutes, allowing the bath to drip and wash with 200% water. The leather is unloaded and finally processed by flattening, suspension drying and softening as is common in the industry.

A soft, plump, evenly dyed dark black leather with good dye penetration and high color brightness is obtained. The fastness characteristics are particularly good (light fastness rating 3, sweat fastness rating 4-5). The migration fastness (PVC) is grade 5.

Example C2: Production of retanning leather with wet white from Example B1A

The shaved white (thickness 1.3/1.4 mm) from Example B 1A was used with 300% water (40 ° C) and 0.2% fatty alcohol ethoxylate (eg CIS MOLLAN AN from LANXESS) The bath composed of 90) (diluted 1:5) was washed in a tanning drum for 10 minutes. The bath had a pH of 4.3 and dripped. Then add 50% water (30 ° C), 3.0% neutralized bismuth preparation (such as TANIGAN PAK from LANXESS), 1.5% sodium formate and 3% milk fatliquor (such as BAYKANOL Licker SIS from LANXESS) ) (diluted 1:8). The drum was stirred for 30 minutes and the bath had a pH of 5.5. Then add a 3.0% softening polymer oxime formulation based on modified polyamidocarboxylic acid (eg LEVOTAN LB from LANXESS) (diluted 1:3 with water) and add 5.0% aromatic sulphur after 10 minutes Polycondensate of acid and phenolic compounds (eg TANIGA BN from LANXESS) and 8.0% Additives (eg Granofin TA from Clariant). After 30 minutes (pH 4.8), 5.0% of a polycondensate based on aromatic sulfonic acid and phenolic compounds (eg TANIGA BN from LANXESS) and 8.0% based on 4,4'- containing plant extracts were added. A synthetic tanning agent of dihydroxydiphenyl hydrazine (for example, TANIGA F from LANXESS) and a 4.0% formaldehyde-free resin bismuth preparation (for example, RETINGAN ZF from LANXESS), followed by stirring for 150 minutes. At this time, the pH was 4.9.

Then 50% warm water (50 ° C) was added and the drum was heated to 50 °C. After 10 minutes, a milky fatliquor consisting of 8.0% Atlasol 170 (product from Atlas), 3.0% BAYKANOL Licker TSI (product from LANXESS), 3.0% Atlasol WRM (product from Atlas) was added. The mixture was then stirred for 15 minutes. Thereafter, a 3.0% polyacrylate-based filled polymer hydrazine formulation (eg, LEUKOTAN 970 from Dow Chemical Company) (diluted 1:3) was added and then stirred for an additional 60 minutes. It was then acidified to pH 3.8 with 2.0% formic acid (diluted 1:10). After 30 minutes, the bath was dropped and the raw hide was washed.

For dyeing, a fresh bath was used: 50% water (20 ° C) and 3.0% milk fatliquor (eg BAYKANOL Licker SL from LANXESS) (diluted 1:8), then drum treatment 60 minutes. After a pre-execution time of 15 minutes using a 2% naphthalenesulfonic acid condensate (eg TANIGA PR from LANXESS), add 3.0% anionic dye (eg BAYGENAL Yellow 4GL from LANXESS, (CI yellow) (Acid Yellow) 79)), followed by stirring for 60 minutes. Then 100% water (60 ° C) was added and the temperature was raised to 50 °C. It was then fixed with 3% formic acid (diluted 1:10). After 30 minutes, a pH of 3.2 has been reached. For top dyeing, 1% anionic dye (for example BAYGENAL Yellow 4GL from LANXESS, (C.I. Acid Yellow 79)) was added and the drum was stirred for 20 minutes. This was followed by final fixation with 1.0% formic acid for 30 minutes, allowing the bath to drip and wash with 200% water. The leather is unloaded and finally processed by flattening, suspension drying and softening as is common in the industry.

This produces a white, plump, uniformly dyed bright yellow leather with good dye penetration and high color brightness. The fastness characteristics are particularly good (light fastness level 6, sweat fastness level 5). The migration fastness (PVC) is grade 5.

Example C3: Production of retanning leather with wet white from Example B3A

Example C2 was repeated except that the wet white from Example B3A was used and the anionic dye used was BAYGENAL Red GX (Sour Red 374). This produces a soft, plump, evenly dyed red leather with good dye penetration and high color brightness.

Example C4: Production of retanning leather with wet white from Example B4A

Example C2 was repeated except that the wet white from Example B4A was used and the anionic dye used was BAYGENAL Brown CGG New (Sour Brown 83). This produces a soft, plump, uniformly dyed brown leather with good dye penetration and high color brightness.

Example C5: Production of retanning leather with wet white from Example B5A

Example C2 was repeated except that the wet white from Example B5A was used and the anionic dye used was BAYGENAL Brown CGG New (Sour Brown 83). This produces a soft, plump, uniformly dyed brown leather with good dye penetration and high color brightness.

Example C6: Comparative Example / Production of retanning 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 the anionic dye used was BAYGENAL Yellow 4GL (C.I. Acid Yellow 79). This produces a soft, less plump, dull yellow leather with lesser dye penetration. The leather undergoes a dirty yellow color shift during storage. Therefore, this leather has a critical disadvantage compared to the embodiment C2 of the present invention.

Claims (10)

A method for dyeing a collagen fiber substrate treated with at least one amine mesylate compound, characterized in that the collagen fiber substrate thus treated is subsequently dyed with at least one anionic dye, the amine The mercapto sulfonate compound is a reaction product of at least one organic polyisocyanate with at least one bisulfite and/or disulphite, characterized in that the organic polyisocyanate has less than 400 g/mol The molecular weight and a plurality of NCO groups attached to the aliphatic or alicyclic group. A dyeing method according to the first aspect of the invention, characterized in that the at least one anionic dye is acid black 2, acid black 52, acid black 71, acid black 84, acid black 107, acid black 173, acid black 194, acid Black 210, acid black 220, acid black 234, acid blue 25, acid blue 90, acid blue 113, acid blue 158, acid blue 193, acid blue 284, acid blue 349, acid brown 75, sour brown 83, sour brown 161 , Acid Brown 194, Acid Brown 282, Acid Brown 298, Acid Brown 311, Acid Brown 314, Acid Brown 322, Acid Brown 324, Acid Brown 349, Acid Brown 355, Acid Brown 365, Acid Brown 413, Acid Brown 414, Acid Brown 425, sour brown 431, sour brown 432, sour brown 434, sour brown 452, sour brown 75, sour brown 97, acid brown mixed, acid green 26, acid green 68, acid green 104, acid green 111, lime 33 , Lime 61, Lime 74, Lime 142, Lime 56, Acid Red 119, Acid Red 131, Acid Red 374, Acid Red 414, Acid Red 425, Acid Red 434, Acid Red 97, Acid Violet 48, Acid Yellow 42, yellow yellow 49, yellow acid 79, Acid Yellow 99, Acid Yellow 194, Acid Yellow 232, Direct Black 168 and/or Direct Blue 59. The dyeing method according to the first aspect of the invention, characterized in that the anionic dye used is at least acid black 2, acid black 52, acid black 71, acid black 84, acid black 107, acid black 173, acid black. 194, acid black 210, acid black 220, acid black 234, acid blue 25, acid blue 90, acid blue 113, acid blue 158, acid blue 193, acid blue 284, acid blue 349, sour brown 75, sour brown 83, Acid Brown 161, Acid Brown 194, Acid Brown 282, Acid Brown 298, Acid Brown 311, Acid Brown 314, Acid Brown 322, Acid Brown 324, Acid Brown 349, Acid Brown 355, Acid Brown 365, Acid Brown 413, Acid Brown 414, sour brown 425, sour brown 431, sour brown 432, sour brown 434, sour brown 452, sour brown 75, sour brown 97, acid brown mixed, acid green 26, acid green 68, acid green 104, acid green 111, Lime 33, Lime 61, Lime 74, Lime 142, Lime 56, Acid Red 119, Acid Red 131, Acid Red 374, Acid Red 414, Acid Red 425, Acid Red 434, Acid Red 97, Acid Purple 48, acid yellow 42, acid yellow 49, acid yellow 79, acid yellow 99, acid yellow 194, acid yellow 232, direct black 168, direct blue 59 or a mixture thereof. A dyeing method according to the first aspect of the invention, characterized in that the amine mercaptosulfonate compound is a reaction product of an organic polyisocyanate with a hydrogensulfite and/or a metabisulfite, wherein the organic polyisocyanate A polyisocyanate having an NCO functionality of from 1.8 to 2.5. A dyeing method according to the first aspect of the invention, characterized in that the organic polyisocyanate is 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 1,5 -diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane (TMHI), 1 , 3- and 1,4-diisocyanatohexane, 1,3- and 1,4-diisocyanatocyclohexane (CHDI) and also any desired mixtures of such isomers , 1-isocyanato-2-isocyanatomethylcyclopentane, 1,2-, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane and also Any desired mixture of isomers, 1,2-, 1,3- and 1,4-bis(isocyanatoethyl)cyclohexane and also any desired of such isomers Mixture, 1,2-, 1,3- and 1,4-bis(isocyanato-n-propyl)cyclohexane and also any desired mixture of such isomers, 1-isocyanato Propyl-4-isocyanatomethylcyclohexane and isomer, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) , 1-isocyanato-1-methyl-4-isocyanatomethylcyclohexane (IMCI), 2,4'- and 4,4'-diisocyanatosyl Hexyl methane (H ₁₂ MDI) and isomers thereof, dimer diisocyanate group (the DDI), bis (isocyanatomethyl) - bicyclo [2.2.1] heptane (NBDI), bis (iso Cyanate methyl)tricyclo[5.2.1.0 ^2,6 ]decane (TCDDI) and isomers, and any desired mixtures of such diisocyanates and benzoyl diisocyanate having the formula The method of claim 1, wherein the amine mercaptosulfonate compound is associated with at least one nonionic, alkoxylated polyol comprising an ester group and having an HLB value of at least 13. (c1) and/or an alkyl glycoside (c2) and/or a nonionic, alkoxylated, ester-free alcohol (c3) used in combination. The method of claim 1, wherein the amine mercaptosulfonate compound is used in the absence of an emulsifier. The method of claim 8, wherein the collagen fiber substrate used is leather or fur. Anionic dyes for the dyeing of collagen fibrous substrates, in particular leather and fur, in the presence of an amine mesylate compound and optionally an organic hydrazine formulation, but without the presence of minerals or other organic The treatment is carried out in the case of a reactive hydrazine preparation. A collagen fibrous substrate, especially leather or fur, which is tanning with at least one amine mercaptosulfonate compound and dyed with at least one anionic dye.