EP2557181A1 - Method for hydrophobic finishing of substrates containing collagen fibre - Google Patents

Abstract

Hydrophobizing a collagen fiber containing substrate comprises treating the substrates with at least one carbamoyl sulfonate group containing compound and hydrophobizing the treated substrates in the presence of at least one polysiloxane. An independent claim is included for the collagen fiber containing substrate, preferably leather or furskin tanned with the carbamoyl sulfonate group containing compound and hydrophobized with polysiloxane.

Description

The invention relates to a process for the hydrophobing of collagen fiber-containing substrates which have been tanned with at least one carbamoylsulfonate-containing compound.

Due to the very high water absorption of the metal-free tanned leather produced by conventional methods, a hydrophobization of such leather is usually not or only very insufficiently possible. By means of a so-called closed hydrophobing with molten paraffins or waxes in a warm air drum, a certain water-repellent effect can be achieved; However, in addition to the disadvantages of handling such as smeared Walkfässem this leads to an insufficient water vapor permeability. Also in the so-called open hydrophobing using silicones lighter leather and a better water vapor permeability of the leather are achieved, but the hydrophobic effects are also insufficient here.

Already in the WO98 / 04748 An attempt was made to solve the problem for wet whites tanned with aldehydes or reactive carbonyl compounds. But even there are still insufficient results.

The object of the present invention was therefore to find a way in which chromium-free tanned collagen fiber-containing substrates, in particular leather or fur skins, can be rendered hydrophobic with satisfactory results which no longer have the abovementioned disadvantages.

Surprisingly, a process has now been found for the hydrophobing of collagen fiber-containing substrates treated with at least one carbamoylsulfonate-containing compound, which comprises hydrophobing in the presence of at least one polysiloxane after treatment of the collagen fiber-containing substrate with at least one carbamoylsulfonate-containing compound.

• Die Umsetzung von Isocyanat mit Polyetheralkohol muss unter Ausschluss von Wasser und bevorzugt ohne viskositätserniedrigende Lösungsmittel durchgeführt werden und erfordert daher technisch hochwertige und teure Hardware sowie einen zusätzlichen Syntheseschritt.
• Durch die Reaktion des Polyetheralkohols mit dem Isocyanat wird ein Teil der Isocyanat-Funktionen verbraucht und somit die Gerbwirkung des Produktes reduziert.

In EP-A 0 690 135 and EP-A 0 814 168 Carbamoylsulfonatgruppen-containing compounds are already described as tanning agents, which are substantially inert to the reaction with water. An aqueous dispersion having a stability sufficient for use in the tanning process is obtained. However, this process has two serious disadvantages:

• The reaction of isocyanate with polyether alcohol must be carried out with the exclusion of water and preferably without viscosity-lowering solvents and therefore requires technically high-quality and expensive hardware and an additional synthesis step.
• The reaction of the polyether alcohol with the isocyanate consumes part of the isocyanate functions and thus reduces the tanning effect of the product.

Also from EP-A-1647563 are known aqueous compositions containing at least one carbamoylsulfonate group-containing compound and at least one alcohol alkoxylate.

Under collagen fiber-containing substrates, for the treatment, in particular tanning, with a Carbamoylsulfonatgruppenhaltigen connection in the context of the invention, in particular the usual derived from animals raw material, especially hides and skins, for example, Grossviehhäute and skins of cattle, calf, buffalo, hides and skins of Pig, sheep, goat, reindeer, deer, kangaroo, hides and skins of other small animals such as sable, fox, rabbit, hides of reptiles (eg snakes), fish or birds, as well as split skins (eg crevices, meat split, cleft with hair) and pre-tanned semifinished products (eg wet white) understood.

In this case, the collagen fiber-containing substrates may be associated with keratinic constituents or be free from keratinic constituents. By keratinic constituents animal hairs are to be understood in particular.

Collagen fiber-containing substrates with associated keratinic constituents are, in particular, skins and hides in which the keratinic constituents, in particular the animal hairs, are not removed during the work in the water workshop, during the tanning and the subsequent steps in the reproduction and finishing to the ready-to-use material and are not damaged but remain firmly connected to the surface support of the collagen fiber-containing substrate, the so-called dermis. The tanned hides and skins made from this raw material, in which the hair is intact and firmly attached to the dermis, are summarized below under the term fur skins. These also have disadvantages in the hydrophobic treatment.

Collagen fiber-containing substrates without keratinic constituents are in particular skins and skins in which the keratinic constituents, in particular animal hairs, were removed in the liming mill in the water workshop and which were used as un-split blossoms or after splitting as crevices, meat crevices or middle crevices and then during tanning and in the subsequent steps in the retanning and, if necessary, dressing are processed to ready-to-use material. The tanned hides and skins made of this raw material, in which the hair was removed in the water workshop in the so-called limber, are summarized below under the term leather. These also have disadvantages in the hydrophobic treatment.

In the EP-A-1 647 563 Carbamoylsulfonatgruppenhaltige compounds are also described for the tanning of sheep skins. However, the method used there is still in need of improvement in terms of process duration and softness and hydrophobicity of the resulting skins. Carbamoylsulfonate-containing compounds (component a) are understood as meaning those having the following structural unit:

-NH-CO-SO ₃ ^- K ⁺

where K ^{+ is} a cation equivalent.

Suitable carbamoylsulfonate-containing compounds of component a) are preferably reaction products of at least one organic polyisocyanate and at least one bisulfite and / or disulfite.

Suitable organic polyisocyanates are, in particular, aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates, as used, for example, by W. Siefken in Liebig's Annalen der Chemie 562, pages 75 to 136 to be discribed.

Preference is given to organic polyisocyanates having an NCO functionality of from 1.8 to 4.2 with a molecular weight of preferably below 800 g / mol, in particular organic polyisocyanates having an NCO functionality of from 1.8 to 2.5 and a molecular weight of less than 400 g / mol.

Preferred polyisocyanates are compounds of the formula Q (NCO) _n having an average molecular weight below 800, wherein n is a number of at least 1.8, preferably from 1.8 to 4.2, Q is an aliphatic C ₄ -C ₁₂ hydrocarbon radical, a cycloaliphatic C ₆ -C ₁₅ -hydrocarbon radical or a heterocyclic C ₂ -C ₁₂ radical having 1 to 3 heteroatoms from the series oxygen, sulfur, nitrogen, for example (i) diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6 Hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 2-isocyanatomethyl-1,8-octamethylene diisocyanate, 1,3-diisocyanato-cyclobutane, 1-isocyanato-2-isocyanatomethyl-cyclopentane, 1,3- and 1,4-diisocyanato-cyclohexane, and any mixtures of these isomers, 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) -cyclohexane and any desired mixtures of these isomers, 1,2-, 1,3- and 1,4-bis (isocyanatoethyl) - cyclohexane and any mixtures of these isomers, 1,2-, 1,3- and 1,4-bis (isocyanato-n-propyl) cyclo hexane and any mixtures of these isomers, 1-isocyanatopropyl-4-isocyanatomethyl-cyclohexane and isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluylene diisocyanate and Any mixtures of these isomers, 2,4'- and 4,4'-diisocyanato-dicyclohexyl-methane and isomers, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and any mixtures these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthalene-1,5-diisocyanate, uretdione-containing polyisocyanates such as bis (6-isocyanatohexyl) uretdione or containing the uretdione structure Dimers of 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane and any mixtures of the aforementioned polyisocyanates; (ii) tri- and higher functional polyisocyanates such as the triisocyanatotriphenylmethane series isomers (such as triphenylmethane-4,4 ', 4 "-triisocyanate) and mixtures thereof; (iii) compounds prepared by allophanatization, trimerization or biuretization from the polyisocyanates (i) and / or (ii); Examples of polyisocyanates prepared by trimerization are the trimer of isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane obtainable by isocyanurate formation and by trimerization of hexamethylene diisocyanate, optionally mixed with Examples of polyisocyanates prepared by biuretization are tris (isocyanatohexyl) biuret and mixtures thereof with its higher homologs, as described, for example, in US Pat DE-OS 23 08 015 are accessible. Particularly preferred are diisocyanates.

Particularly preferred polyisocyanates are those having a molecular weight of less than 400 g / mol with NCO groups attached to aliphatics or cycloaliphatic compounds, for example 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 1,5-diisocyanato-2, 2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane (TMHI), 1,3- and 1,4-diisocyanatohexane, 1,3- and 1,4-diisocyanato cyclohexane (CHDI) and any mixtures of these isomers, 1-isocyanato-2-isocyanatomethyl-cyclopentane, 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) -cyclohexane and any desired mixtures of isomers, 1,2 -, 1,3- and 1,4-bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1,2-, 1,3- and 1,4-bis (isocyanato-n-propyl) -cyclohexane and any mixtures these isomers, 1-isocyanatopropyl-4-isocyanatomethyl-cyclohexane and isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI), 1-isocyanato-1-methyl-4-isocyanatomethyl-cyclohexane ( IMCI), 2,4'- and 4,4'-diisocyanatodicyclohexylmethane (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 mixtures of such diisocyanates. Also araliphatic polyisocyanates such as the xylylene diisocyanates of the formulas

can be used.

Preference is given to using the above diisocyanates. 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 polyisocyanates having an average NCO functionality of 2.2 to 4.2.

The higher-functional polyisocyanates are preferably composed of trimeric 1,6-diisocyanatohexane, trimeric 1,2-, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, trimeric 1,2-, 1,3- or 1,4-bis (isocyanatoethyl) cyclohexane, trimeric 1,2-, 1,3- or 1,4-bis (isocyanato-n-propyl) -cyclohexane, trimeric 1-isocyanatopropyl-4-isocyanatomethyl-cyclohexane and isomers or trimeric 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and optionally dimeric 1,6-diisocyanatohexane, dimeric 1,2-, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, dimeric 1,2-, 1,3- or 1,4-bis (isocyanatoethyl) cyclohexane, dimeric 1,2-, 1,3- or 1,4-bis (isocyanato-n-propyl) -cyclohexane, dimeric 1 -Isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, or dimeric 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and the corresponding higher homologs existing isocyanurate groups and optionally uretdione polyisocyanate having an NCO-G content of from 19 to 24% by weight, as determined by catalytic trimerization known per se and with isocyanurate formation of 1,6-diisocyanatohexane, 1,2-, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,3- or 1,4-bis (isocyanatoethyl) cyclohexane, 1,2-, 1,3- or 1,4-bis (isocyanato-n-propyl) -cyclohexane, 1-isocyanatopropyl- 4-isocyanatomethylcyclohexane and isomers, or from 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, and which preferably have an (average) NCO functionality of from 3.2 to 4.2.

Further suitable polyisocyanates are polyisocyanates prepared by modifying aliphatic or cycloaliphatic diisocyanates with uretdione and / or isocyanurate, urethane and / or allophanate, biuret or oxadiazine structure, as described, for example, in US Pat DE-A 1 670 666 . DE-A 3 700 209 and DE-A 3 900 053 and in the EP-A 336,205 and EP-A 339 396 are described by way of example. Suitable polyisocyanates are, for example, the polyisocyanates containing ester groups, such as, for example, the tetrakis or triisocyanates obtainable by reaction of pentaerythritol or trimethylolpropane silyl ethers with isocyanatocaproic acid chloride (cf. DE-A 3 743 782 ). In addition, it is also possible to use triisocyanates such as tris-isocyanatodicyclohexylmethane.

The use of monofunctional and of more than difunctional isocyanates in both cases is preferably limited to amounts of not more than 10 mol%, based on all polyisocyanates.

However, very particular preference is given to the abovementioned aliphatic, cycloaliphatic and araliphatic diisocyanates. Particularly preferred are hexamethylene diisocyanate (HDI), diisocyanato-cyclohexane, 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane and any desired mixtures of isomers, 1,2-, 1,3- and 1, 4 bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1,2-, 1,3- and 1,4-bis (isocyanato-n-propyl) -cyclohexane and any mixtures of these isomers, 2,4'- and 4,4'-diisocyanato-dicyclohexylmethane, 1-isocyanatopropyl-4-isocyanatomethyl-cyclohexane and isomers and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI). Hexamethylene diisocyanate (HDI), 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) -cyclohexane and mixtures of these isomers are especially preferred from this latter group.

Preferred bisulfites and / or disulfites are their alkali metal or ammonium salts, in particular the sodium salts of sulfurous or disulfurous acid, ie sodium bisulfite (NaHSO ₃ ) or sodium disulfite (Na ₂ S ₂ O ₅ ).

The other alkali metal and ammonium salts of these acids, namely potassium bisulfite, potassium bisulfite, lithium bisulfite, lithium disulfite, ammonium bisulfite, ammonium bisulfite and simple tetraalkylammonium salts of these acids, such as, for example, tetramethylammonium bisulfite, tetraethylammonium bisulfite, etc., can also be used to advantage. The alkali metal salts are very particularly preferred. The salts are preferably used as aqueous solutions with solids contents of 5 to 40 wt .-%.

In a preferred embodiment of the invention, the carbamoylsulfonate-containing compounds based on aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanato) cyclohexane, 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane and any mixtures of Isomers, 1,2-, 1,3- and 1,4-bis (isocyanatoethyl) -cyclohexane and any desired mixtures of these isomers, 1,2-, 1,3- and 1,4-bis (isocyanato-n-propyl) Cyclohexane and any mixtures of these isomers, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 2,4 'and 4,4'-diisocyanato-dicyclohexylmethane or nonyl triisocyanate and mixtures thereof, but especially hexamethylene diisocyanate 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane and any mixtures of isomers, 1,2-, 1,3- and 1,4-bis (isocyanatoethyl) cyclohexane and any mixtures of these isomers, 1,2-, 1,3 - And 1,4-bis (isocyanato-n-propyl) -cyclohexane and any mixtures of these isomers and / or isopho rondiisocyanat, particularly preferably hexamethylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and 2,4'- and 4,4'-diisocyanato-dicyclohexylmethane. For this last-mentioned group, the carbamoylsulfonate-containing compounds are particularly preferably based on hexamethylene diisocyanate (HDI), 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) -cyclohexane and mixtures of these isomers.

Gerbstoffform

The carbamoylsulfonate group-containing compound used for tanning can be used in liquid form, for example as an aqueous composition or as a particulate solid.

In the case of aqueous compositions, these may be present, for example, as a solution or suspension. A solution is preferred.

Preferably, the dry residue of the aqueous composition, i. the total concentration of the ingredients of the aqueous composition, preferably 25 to 50%. In particular, a total concentration of the aqueous composition of from 30 to 40% is advantageous, with the proportion of the carbamoylsulfonate group-containing compound in the composition being particularly advantageously from 28 to 35%.

When other additives are used, it is preferred that the proportion of the carbamoylsulfonate group-containing compound decreases in the corresponding ratio according to the proportions of the further additional component, so that the total concentration of the solids in the aqueous solution is preferably not more than 50%.

Also preferably, the carbamoylsulfonate-containing compound is used as a particulate solid, which preferably has a melting point of greater than 20 ° C, preferably greater than 60 ° C, in particular greater than 100 ° C.

By "particulate" is meant in particular a material having an average particle size of 0.1 .mu.m to 1000 .mu.m, preferably 1 to 800 .mu.m, in particular 50 to 300 microns, wherein the average value based on the mass (weight average) of all particles. Other means (volume means) can be calculated by analytical methods and vice versa. The average particle size can be determined, for example, microscopically. Preferably, the solid material is present as powder or granules.

Preferably, the particulate solid material has a residual moisture of 0 to 10 wt .-%, in particular 0 to 5 wt .-%, particularly preferably 0 to 2 wt .-%, based on the material. The particulate solid material is usually based on any, preferably a spherical or spherical shape-like or derived particle structure. There are also agglomerates of particles from the mentioned forms in the range of the specified particle size in question.

The particulate solid material contains 1 to 100%, preferably 10 to 100%, most preferably 25 to 100% of compounds containing carbamoylsulfonate groups.

Very particular preference is given to compounds containing carbamoylsulfonate groups and their preparations using component d) and optionally component e), which contain no emulsifier and which have a pH of less than 4.5, based on a 35% solution in water. Particularly preferred is the use of carbamoylsulfonate-containing compounds for tanning in the form of particulate solids.

emulsifiers

The carbamoylsulfonate group-containing compound used for tanning may contain one or more emulsifiers of component c) or contain no emulsifier. Preferred carbamoylsulfonate-containing compounds contain no emulsifier. Suitable emulsifiers are, for example, cationic, anionic, amphoteric and nonionic surfactants, which are preferably capable of reducing the interfacial tension between an organic and an aqueous phase, so that an oil-in-water emulsion can form.

Preferred cationic emulsifiers are quaternary ammonium compounds, for example cetyltrimethylammonium bromide or benzyllauryldimethylammonium chloride.

Preferred anionic emulsifiers are soaps, metal soaps, organic soaps such as mono-, di- or triethanolamine oleate, stearate, diethylethanolamine oleate, stearate or 2-amino-2-methylpropane-1-ol stearate, sulfurized compounds such as sodium dodecyl sulfate or Turkish red oil and sulfonated compounds such as sodium cetylsulfonate ,

Preferred amphoteric emulsifiers are phosphatides such as lecithins, various proteins such as gelatin or casein and the actual amphoteric surfactants.

Preferred nonionic emulsifiers are fatty alcohols such as lauryl, cetyl, stearyl or palmityl alcohol, partial fatty acid esters of polyhydric alcohols with saturated fatty acids such as glycerol monostearate, pentaerythritol monostearate, ethylene glycol monostearate or propylene glycol monostearate, partial fatty acid esters of polyhydric alcohols with unsaturated fatty acids such as glycerol monooleate, pentaerythritol monooleate, furthermore polyoxyethylene esters of fatty acids such as polyoxyethylene stearate, polymerization products of ethylene oxide and propylene oxide with fatty alcohols such as fatty alcohol polyglycol ethers or fatty acids such as fatty acid ethoxylates.

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

Component c1)

The preferred nonionic, ester group-containing, alkoxylated polyols of component c1) have an HLB value of from 13 to 19, in particular from 14 to 18, the HLB value being determined by the method Griffin, WC: Classification of surface active agents by HLB, J. Soc. Cosmet. Chem. 1, 1949 , In addition, preferred compounds of component (c1) have a water solubility at 20 ° C. of at least 10 g per liter, in particular at least 20 g per liter.

Preferred compounds of component c1) are those which are obtainable in a manner known per se from polyols by alkoxylation and partial esterification of the hydroxyl groups with a carboxylic acid. Suitable starting polyols, for example, polyhydric (cyclo) aliphatic alcohols such as glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, derived from mono- or polysaccharides polyols, preferably the molecular weight of 92 to 2000 are used as starter molecules. Particularly preferred starter alcohols are polyols having 3 to 10 hydroxyl groups, in particular glycerol and those having a sorbitan skeleton, in particular 1,4- or 1,5-sorbitan, preferably 1,4-sorbitan.

Preferred carbamoylsulfonate group-containing compounds are characterized in that the compound of component c1) used is the reaction product of a polyol with at least one alkylene oxide having 2 to 6 carbon atoms, preferably in an amount of 10 to 60 molar equivalents, based on the Polyol and subsequent reaction with at least one carboxylic acid having 6 to 30 carbon atoms. The polyol used is preferably a polyol selected from the group consisting of glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and mono- and polysaccharide-derived polyols, in particular sorbitol and polyols having a sorbitan skeleton.

The compounds of component c1) are particularly preferably partially esterified sorbitan alkoxylates whose hydroxyl groups are esterified before or preferably after the alkoxylation with carboxylic acids having a chain length of 6 to 30 carbon atoms, each hydroxyl group of the base polyol having an independent number of Have alkoxy units and per sorbitan unit on average 10 to 60 alkoxy units are present. The preferred esterified sorbitan alkoxylates have a random distribution of the alkoxy groups.

X

ein Sorbitanrest, insbesondere ein 1,4-Sorbitanrest ist und

m für die Zahl 4 stehtPreference is given to partially esterified alkoxylated sorbitan derivatives by reaction of a sorbitan of the formula

X- (OH) _m

wherein

X

a sorbitan residue, especially a 1,4-sorbitan residue, and

m stands for the number 4

With

10 to 60 equivalents, per mole of sorbitan, preferably 10 to 40, particularly preferably 10 to 30 and very particularly preferably 15 to 25 equivalents of identical or different C ₂ -C ₆ -alkylene oxides, in particular C ₂ - and / or C ₃ -alkylene oxides, preferably ethylene oxide and with

1 to 3, preferably 0.8 to 1.2 equivalents, based on the sorbitan, of an aliphatic, optionally unsaturated carboxylic acid, preferably having a chain length of 6 to 30 carbon atoms, which is unsubstituted or substituted by hydroxy groups, preferably straight-chain, in made in any order. The reaction with the alkylene oxide is preferably carried out first, followed by the reaction with the carboxylic acid.

Preferred are sorbitan polyoxyethylene monoesters, which are alkoxylated with 10-60 moles of ethylene oxide units per sorbitan unit, and preferably have a 1,4-sorbitan skeleton.

R

für einen ggf. durch Hydroxylgruppen substituierten Alkyl- oder Alkenylrest der Carbonsäure steht und

m, n, p und q

unabhängig voneinander sind, statistische Werte sind und jeweils für eine Zahl von 0 bis 60 stehen, mit der Maßgabe, dass die Summe der Anzahl der Oxyethylen-Einheiten m+n+p+q von 10 bis 60, vorzugsweise 18 bis 22, insbesondere 20 ist.

These preferably correspond to the following structural formulas in which

R

represents an optionally substituted by hydroxyl groups alkyl or alkenyl radical of the carboxylic acid and

m, n, p and q

are independent of each other, are statistical values and each represents a number from 0 to 60, with the proviso that the sum of the number of oxyethylene units m + n + p + q is from 10 to 60, preferably 18 to 22, in particular 20 is.

Also suitable are corresponding alkoxylated sorbitan diesters and mixtures thereof.

Furthermore, alkoxylated sorbitan esters are suitable in which a hydroxyl group of the sorbitan unit, in particular in the formulas given above, is esterified directly with the carboxylic acid, ie in which there is no alkylene oxide unit between the sorbitan unit and the carboxylic acid residue and the three are not acylated Hydroxyl groups are etherified with a correspondingly higher number of alkylene oxide units. Such compounds are obtainable, for example, by first esterifying the sorbitan with a carboxylic acid and subsequently alkoxylating the resulting product, consisting of a mixture of the isomeric monoesters, which may also contain mixtures of the isomeric diesters in the presence of an excess of carboxylic acid.

The alkylene oxide used for the alkoxylation of sorbitan is preferably selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. It is also possible that the sorbitan with various of the above alkylene oxides, e.g. Ethylene oxide and propylene oxide, to obtain sorbitan alkoxylates each containing blocks of several units of an alkylene oxide, e.g. Ethylene oxide, in addition to blocks of several units of another alkylene oxide, e.g. Propylene oxide. Particularly preferably, the sorbitan alkoxylates contain ethylene oxide (EO) units, preferably exclusively. In such a case, the alkylene oxide used is particularly preferably ethylene oxide.

Furthermore, it is possible in the reaction of a sorbitan with various of said alkylene oxides, e.g. To obtain ethylene oxide and propylene oxide, sorbitan alkoxylates in which the incorporation of the various alkylene oxides is carried out statistically. The amounts of alkylene oxide used are preferably 10 to 60 moles of alkylene oxide per mole of sorbitan, preferably 10 to 40 moles, more preferably 10 to 30 moles and most preferably 15 to 25 moles. Very preferred alkylene oxide is ethylene oxide.

The carboxylic acids suitable for the esterification of the starting polyol, especially the sorbitan alkoxylate, are preferably saturated or unsaturated and linear or branched and may optionally be substituted by hydroxyl groups. The following carboxylic acids may be mentioned as examples: hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, octadecenoic acid (oleic acid), undecenoic acid. Particular preference is given to decanoic acid, undecanoic acid, dodecanoic acid (lauric acid), tetradecanoic acid, hexadecanoic acid (palmitic acid) and octadecanoic acid (stearic acid)., Ricinoleic acid. Very particular preference is given to dodecanoic acid (lauric acid), hexadecanoic acid (palmitic acid) and octadecanoic acid (stearic acid) and octadecenoic acid (oleic acid).

Commercially available compounds, for example sorbitan polyoxyethylene (20) monolaurate (for example Polysorbat® 20 or Tween® 20 (Croda Oleochemicals) or Eumulgin® SML 20 (Cognis)), sorbitan, can be used as compounds of component c1), for example polyoxyethylene (20) monopalmitate (for example polysorbate 40 or Tween® 40 (Croda Oleochemicals)), sorbitan polyoxyethylene (20) monostearate (for example polysorbate 60 or Tween® 60 (Croda Oleochemicals) or Eumulgin® SMS 20 (Cognis)), sorbitan polyoxyethylene ( 20) monooleate (for example Polysorbate 80 or Tween® 80 (Croda Oleochemicals)).

Further preferred compounds of component c1) are, for example, alkoxylates of mono- and polyglycerol esters. The preparation of such alkoxylated (poly) glycerol esters is carried out either by alkoxylation of glycerol or a polyglycerol and subsequent esterification with a Fatty acid or by esterification of glycerol or polyglycerol with a fatty acid and subsequent alkoxylation. Particularly suitable for the compositions according to the invention are alkoxylates of mono- and polyglycerol esters which have an HLB value of at least 13 and preferably have a water solubility at 20 ° C. of more than 10 g per liter. Also suitable are alkoxylated glycerol esters or polyglycerol esters which have been esterified with more than one carboxylic acid. Particularly preferred are alkoxylated monoglycerol monoesters.

Suitable for alkoxylation are C ₂ to C ₆ alkylene oxides, particularly preferably ethylene oxide, preference is given to alkoxylation with 10 to 100 alkylene oxide units, in particular with 20 to 60 alkylene oxide units. The hydroxyl groups of glycerol or of polyglycerol have, independently of one another, on average, a different number of alkylene oxide units.

For example, be particularly suitable alkoxylates of mono- and polyglycerol esters. called glycerol monostearate ethoxylates with an average of 15 to 30, especially with an average of 20 EO units, glycerol monooleate ethoxylates with 20 to 40 EO units, diglycerol monostearate with 20 to 40 EO units, polyglycerol monostearate with 20 to 40 EO units Units, castor oil alkoxylates and hydrogenated castor oil alkoxylates, short (hydrogenated) castor oil alkoxylates. The latter are products which are obtainable by alkoxylation of castor oil or hydrogenated castor oil with alkylene oxides, in particular ethylene oxide and propylene oxide, preferred are those containing from 20 to 100 alkylene oxide units per (hydrogenated) castor oil unit, preferably from 20 to 60 Have ethylene oxide units per (hydrogenated) castor oil unit.

Corresponding glycerol-based compounds of components c1) are likewise available as commercial products, for example glycerol monostearate ethoxylate with an average of 20 EO units as Cutina® E 24 (Cognis), hydrogenated castor oil ethoxylate with an average of 40 EO units as Eumulgin® HRE 40 (Cognis).

Component c2)

As preferred compounds of component c2), for example, alkyl monoglycosides, alkyl diglycosides, alkyl triglycosides and higher homologs, generally referred to herein as alkyl glycosides, in particular monoglucosides, diglucosides, triglucosides, or higher homologues and mixtures thereof, whose hydroxyl groups partially with C ₆ -C ₁₈ Alkyl groups are substituted. Preference is given to mixtures of mono-, di-, triglucosides and higher homologues with C ₆ -C ₁₈ -alkyl groups, and a degree of polymerization (DP) of 1 to 5. Particular preference is given to alkylglucosides whose alkyl groups have a chain length of 6 to 18 carbon atoms , in particular 6 to 12 C atoms. Also preferred are alkylglucosides whose alkyl groups have a chain length distribution or represent mixtures of alkylglucosides with different alkyl chains.

G

für eine glycosidische Einheit steht,

R'

für den Alkylrest eines Alkohols steht, der zur Bildung des glycosidischen Acetals verwendet wird, und

w

für den mittleren Polymerisationsgrad, d. h. die Anzahl an verknüpften glycosidischen Einheiten steht und für eine Zahl von 1 bis 5 steht.

Alkyl glycosides are preferably substances consisting of a single ring of a sugar or a chain of rings of a sugar linked together with glycosidic linkages, the last ring of the glycosidic chain being acetalated with an alcohol. Alkyl glycosides have the following general formula

H- (G) WO-R '

in which

G

represents a glycosidic unit,

R '

represents the alkyl radical of an alcohol used to form the glycosidic acetal, and

w

represents the average degree of polymerization, ie the number of linked glycosidic units and is a number from 1 to 5.

Suitable are alkyl glycosides in which w is a number from 1 to 5 and R 'is the radical of a linear or branched aliphatic alcohol having 6 to 30 carbon atoms. These products are known per se and commercially available. The value w can be influenced in the synthesis by adjusting the molar ratio of alcohol to saccharide accordingly. By increasing this ratio, alkyl glycosides having a lower average value of w are obtained. Conversely, a higher degree of polymerization is achieved by a low molar ratio of alcohol to saccharide.

For example, mention the structure of an alkylglucoside wherein R 'is an alkyl radical and v has values of 1 to 4:

The compounds are usually present as isomer mixtures. In particular, the anomeric carbon atoms (glycosidic C atoms) are present as mixtures of the stereoisomers.

Depending on the molar ratio of the starting materials and depending on the process conditions, the preferred alkyl polyglucosides are mixtures of alkyl monoglucoside, alkyldiglucoside and alkyl triglucoside and optionally alkyl oligoglucoside, which may also contain (poly) glucoses and small proportions of the free alcohol R'OH.

The preparation of alkyl polyglucosides is possible, for example, by a direct synthesis starting from sugar with an excess of one or more alcohols. In an alternative method of synthesis, starch is used which is first reacted with lower alcohols (eg methanol, ethanol, butanol) in the presence of an acidic catalyst to give an alkylglucoside having a short-chain glycosidic group (eg methyl, ethyl, butyl). This intermediate is then reacted under vacuum with the long-chain alcohol R'-OH in the presence of an acid as a catalyst by transacetalization, the equilibrium being shifted by distilling off the lower alcohol. For example, the preparation of alkyl glucosides in WO90 / 001489 . US 5576425 . DE 69824366 or in a publication of M. Biermann (Henkel KGaA), K. Schmid, P. Schulz in Starch - Stärke, vol. 45 (8), p. 281-288 (1993 ).

Particularly preferred alkylglucosides are, in particular, hexylglucoside, octylglucoside, decylglucoside, undecylglucoside, and dodecylglucoside and also their homologs, and the mixture of alkylmono-, di-, tri-, and optionally polyglucoside and mixtures from this series.

Also suitable are alkyl glycosides whose sugar moiety is composed of various sugar units. However, alkyl glycosides which are composed exclusively of glucose units are particularly preferred.

The compounds of component c2) are available as commercial products: for example, a C ₈ -C ₁₀ -alkyl polyglucoside having a degree of polymerization (DP) of 1.6 is available under the trade name Glucopon® 215 CS UP (Cognis). A C ₁₂ -C ₁₆ -alkylpolyglucoside with a DP of 1.4 is available, for example, under the trade name Glucopon® 600 CS UP (Cognis).

Component c3)

As preferred nonionic, ester group-free alcohol alkoxylates of component c3) polyether alcohols are suitable, which are accessible in a conventional manner by alkoxylation of suitable starter molecules. Such are for example EP-A-1647563 known. For the preparation of the polyether alcohols, any mono- or polyhydric alcohols of molecular weight 88 to 438 can be used as starter molecules.

Particularly preferred are alkoxylates of aliphatic alcohols having a chain length of 5 to 30 carbon atoms and 1-25 alkoxy units.

It is preferred to use linear or branched, saturated or unsaturated alcohol alkoxylates which are obtained by reacting at least one alcohol ROH with n moles of at least one alkylene oxide per mole of alcohol ROH,
wherein
R is an alkyl radical having 5 to 30 carbon atoms, which has a main chain having 4 to 29 carbon atoms, which is branched in the middle of the chain with at least one C ₁ -C ₁₀ alkyl radical,
the alkylene oxide has 2 to 6 carbon atoms
and
where n is a value from 1 to 25.

For the purposes of the present invention, chain center means those carbon atoms of the main chain, ie the longest alkyl chain of the radical R, beginning with the carbon atom C # 2, the numbering starting from the carbon atom (C # 1) which is directly attached to the carbon atom Rest R adjacent oxygen atom is bound, and ending with the carbon atom ω, which is the terminal carbon atom of the main chain, wherein C # 2 and the carbon atom ω-2 are included. This means that at least one of the carbon atoms C # 2, C # 3,... To C _{ω-2 of} the main chain of the radical R is substituted by a C ₁ to C ₁₀ alkyl radical. The carbon atom C # 2 of the main chain of the radical R is preferably substituted by a C ₁ - to C ₁₀ -alkyl radical. In addition, it is also possible that one or more carbon atoms in the middle of the chain are substituted with two C _{1 to} C ₁₀ alkyl radicals, ie that one or more carbon atoms in the middle of the chain are quaternary carbon atoms.

Particularly preferred is a mixture of alcohol alkoxylates based on 1 to 3 different alcohols ROH, more preferably on 1 or 2 different alcohols ROH. In this case, the number of carbon atoms of the radical R may be different and / or the type of branching.

Preferably, the main chain of the alcohols ROH has 1 to 4 branches, provided that the chain length allows more than one branch in the middle of the chain, more preferably 1 to 3, most preferably 2 or 3. These branches are generally independently 1 to 10 carbon atoms, preferably 1 to 6, more preferably 1 to 3 Particularly preferred branches are therefore methyl, ethyl, n-propyl or iso-propyl groups.

The radical R of the alcohol ROH preferably has 5 to 30 carbon atoms. Since the group R preferably has at least one branch with at least one carbon atom, the main chain comprises 4 to 29 carbon atoms. Preferably, the radical R has from 6 to 25 carbon atoms, more preferably from 10 to 20. That is, the main chain preferably has 5 to 24 carbon atoms, more preferably 9 to 19. Most preferably, the main chain has 9 to 15 carbon atoms and the others Carbon atoms of the radical R are distributed over one or more branches.

Preferred linear alcohols ROH are, for example, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, octadecyl alcohol, octadecenyl alcohol or hexadecenyl alcohol and also their technical mixtures.

The alkylene oxide reacted with the branched alcohols ROH to the alcohol alkoxylates used is preferably selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide. It is also possible that a single alcohol ROH with various of said alkylene oxides, e.g. Ethylene oxide and propylene oxide, whereby alcohol alkoxylates each containing blocks of several units of an alkylene oxide, e.g. Ethylene oxide, in addition to blocks of several units of another alkylene oxide, e.g. Propylene oxide. The alcohol alkoxylates used according to the invention particularly preferably comprise ethylene oxide (EO) units, that is to say that the alkylene oxide used is preferably ethylene oxide.

Furthermore, in the reaction of a single alcohol, it is possible to use ROH with various of the alkylene oxides mentioned, e.g. Ethylene oxide and propylene oxide to obtain alcohol alkoxylates in which the incorporation of the various alkylene oxides is carried out statistically. The amounts of alkylene oxide used are preferably 1 to 25 moles of alkylene oxide per mole of alcohol, preferably 1 to 20 moles, more preferably 3 to 15 moles and most preferably 5 to 12 moles.

Particular preference is given to using the compound containing carbamoylsulfonate groups in a mixture with an emulsifier, in particular one of component c1), c2 and / or c3), preferably component c1) and / or c2), in particular c1).

• 5 bis 50 Gew.-%, insbesondere 10 bis 40 Gew.-% der Carbamoylsulfonatgruppen-haltigen Verbindung der Komponente a) und
• 0,05 bis 5 Gew.-%, insbesondere 0,1 bis 2 Gew.-% der Komponente c), insbesondere der Komponente c1), jeweils bezogen auf die Zusammensetzung.

Preferably, the carbamoylsulfonate group-containing compound is used as an aqueous composition containing

• 5 to 50 wt .-%, in particular 10 to 40 wt .-% of the carbamoylsulfonate groups-containing compound of component a) and
• 0.05 to 5 wt .-%, in particular 0.1 to 2 wt .-% of component c), in particular component c1), each based on the composition.

Other additives

In addition to the preferred emulsifiers, the carbamoylsulfonate-containing compound may or may not also contain other additives, for example carboxylic acids of component d) or salts thereof.

Component d)

Suitable compounds of component d) are, in particular, monocarboxylic or polycarboxylic acids, preferably hydroxypolycarboxylic acids. Examples which may be mentioned are: formic acid, acetic acid, oxalic acid, glyoxylic acid, malonic acid, lactic acid, tartaric acid, maleic acid, glutaric acid, phthalic acid, adipic acid, malic acid, succinic acid, citric acid, or polycarboxylic acids such as (co) polymers of (meth) acrylic acid, maleic acid, crotonic acid or Itaconic acid or its derivatives with optionally further monomers such as ethene, propene, styrene, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, especially those having an average molecular weight (weight average MW) of 500 to 100000 g / mol, in particular 500 to 30,000 g / mol.

Particularly preferred as component d) is at least one carboxylic acid, preferably oxalic acid, succinic acid, glutaric acid or adipic acid, in particular at least one hydroxy-polycarboxylic acid, preferably citric acid, tartaric acid or lactic acid or mixtures thereof.

Component e)

Preferred further additives of component e) may preferably be auxiliaries, such as fatliquoring agents, dedusting agents, organic tanning agents of component b), buffers and / or fillers, or may not be present.

Fatliquoring agents are preferably substances based on biological, mineral or synthetic oils which can be provided with hydrophilic groups in order to improve the usability in water, eg. B. by complete or partial sulfation, sulfitation, carboxylation or phosphating.

Suitable fillers are preferably inert inorganic salts and organic polymers in question, for. As sulfates such as sodium sulfate or calcium sulfate, talc, silica compounds, starch or lignosulfonates into consideration.

Suitable buffers are those which can be adjusted and stabilized by addition in a sufficient amount of a pH range, in particular a pH range of 1 to 5, preferably 2.0 to 3.5. Suitable buffers for this are preferably mixtures of compounds of component d) and their salts in question. Preferred salts are in particular alkali metal salts, preferably sodium or potassium salts.

Preferred dedusting agents in the case of a solid, particulate form of the carbamoylsulfonate-containing compound include, for example, alkoxylates of aromatic compounds or polyethers or certain mono- or diesters or certain mono- or diethers. Examples which may be mentioned specifically: ethoxylates, propoxylates or mixed polyethers based on EO / PO, wherein mentioned as aromatic compounds hydroquinone or phenol-styrene, polyethylene glycol having an average molecular weight of 100 to 800, polypropylene glycol having an average molecular weight of 100 to 800, EO / PO mixed polyether having an average molecular weight of 100 to 800, monoalkyl ethers or dialkyl ethers of the abovementioned polyethers, where the alkyl radical may have 1 to 4 carbon atoms, and mono- or dialkyl esters of the abovementioned polyethers with aliphatic carboxylic acids, such as, for example, acetic acid, Propionic acid, maleic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, citric acid. Dustproofing agents based on mineral oil are also suitable. Dust removing agents are preferably used in an amount of 0 to 5.0, preferably 0.05 to 2.0%, based on inventive solid material.

In a likewise preferred embodiment, the carbamoylsulfonate group-containing compound used contains less than 1% by weight of organic or inorganic tannins, preferably less than 0.1% by weight. In particular, the carbamoylsulfonate group-containing compound used is substantially free of organic or inorganic tannins, most preferably it is free of organic or inorganic tannins.

• 10 bis 90 Gew.-%, insbesondere 30 bis 70 Gew.-% der Carbamoylsulfonatgruppen-haltigen Verbindung der Komponente a),
• 10 bis 90 Gew.-%, insbesondere 30 bis 70 Gew.-% der Komponente b), und
• 0 bis 5 Gew.-%, insbesondere 0 bis 2 Gew.-% Wasser (Restfeuchte), jeweils bezogen auf das Material.

In a further preferred embodiment, the carbamoylsulfonate-containing compound used can also be used together with organic tanning agents, in particular those of component b). Preferably contains such a composition, which is present in particular as a particulate solid,

• From 10 to 90% by weight, in particular from 30 to 70% by weight, of the carbamoylsulfonate-containing compound of component a),
• 10 to 90 wt .-%, in particular 30 to 70 wt .-% of component b), and
• 0 to 5 wt .-%, in particular 0 to 2 wt .-% water (residual moisture), in each case based on the material.

It is also preferable for such a tanning agent combination to contain less than 1% by weight, preferably less than 0.1% by weight, of inorganic tannins, but essentially free of inorganic tannins, in each case based on the tanning agent composition.

Preparation of the carbamoylsulfonate group-containing composition

The carbamoylsulfonate group-containing compound used can be prepared, for example, as an aqueous composition by mixing the components a) and optionally further additives in water.

The compound of component a) can also be prepared, for example, by reacting at least one organic polyisocyanate with at least one bisulfite and / or disulfite in an organic or aqueous-organic solvent such as, for example, water / dioxane analogously to the procedure DE102006056479-A1 to be obtained.

Preference is also given to a process for preparing the carbamoylsulfonate-containing compounds, in which at least one organic polyisocyanate with at least one bisulfite and / or disulfite in the presence of water and optionally in the presence of an emulsifier of component c) and optionally in the presence of component d) and optionally mixed with further additives and then optionally dried, preferably spray-dried.

method

As a raw material for the production of hydrophobic leather and fur skins collagen fiber-containing substrates, especially animal skins and skins are used with or without hair. These are first prepared in a manner known to those skilled in the art and as usual in the water workshop. The skins and skins prepared in this way are generally converted into a tanned product by treatment with carbamoylsulfonate-containing compounds, which preferably has a shrinkage temperature of at least 65 ° C., preferably at least 68 ° C., particularly preferably at least 70 ° C. The shrinkage temperature is determined by methods known to those skilled in the art, for example by heating the tanned intermediate by immersion in a water bath whose temperature is increased at a certain heating rate until the contraction of the material is observed. The temperature reached on contraction is read on the display of the tester (Leather Shrinkage Tester). The shrinkage temperature can also be determined by means of the differential scanning calorimetry (DSC) method known to the person skilled in the art.

The entire process for producing hydrophobized leathers and furskins involves various sub-steps, comprising simplified wet-end finishing and finishing of dry leather or fur skins. The wet treatment steps include the

Water workshop, tanning and retanning. The water workshop again comprises several pretreatment steps: For the production of leather (hides and skins without hair) these are the steps soft, liming, deliming and stain, for the production of fur skins (skins and skins with hair) these are the steps dirt soft / soft, laundry and degreasing. Subsequent tanning involves the steps of actual tanning, in which the shrinkage temperature of the collagen-containing substrate is increased and the folding. The retanning generally comprises the partial steps of the actual retanning, greasing, dyeing, hydrophobing and fixing. The finished leather (crust) obtained after completion of the work in wet end are finished as usual, for example, Ausgereckt, dried and usually staked. In addition, the dry leather can optionally be provided in the usual manner in finishing with finishes or coatings to adapt the properties of the leather surface to the respective requirements for later use. The fur skins obtained after completion of the work in wet end are completed as usual, for example by drying, cleats, degreasing, combing and ironing the hair coat. If desired, the fur skins can be further treated in order to adapt the properties of the leather surface to the respective requirements for later use.

The treatment with carbamoylsulfonate group-containing compounds is generally understood as the actual tanning.

The (tanned) material treated in the process according to the invention with the carbamoylsulfonate-containing compound can therefore already be referred to as leather, the so-called wet white. With the material obtained in the tanning, you can already perform conventional mechanical treatments such as wilting or folding. For the production of a ready-to-use leather (Crust), which may optionally be finished, however, further treatment steps known per se, such as in particular retanning, are required.

Preference is given in the process according to the invention to treatment with carbamoylsulfonate-containing compounds (tanning) and before the hydrophobization further Nachgerbschritte, in particular containing the steps actual retanning with a treatment with organic tanning agents, preferably with the component b) and optionally Fettung and optionally coloring ,

The process for the tanning of collagen fiber-containing substrates, in particular hides and skins, is preferably characterized in that, after the steps of the water workshop, hides pretreated as usual are treated with a compound containing carbamoylsulfonate groups.

It is preferred that the collagen fiber-containing substrate is not pickled prior to treatment with a carbamoylsulfonate group-containing compound. Pimples are understood a treatment step of the collagen fiber-containing substrate to be tanned, in particular the hides and skins, in which the collagen fiber-containing substrate is treated with strong acids and salt, preferably with a mixture containing formic acid and / or sulfuric acid in the presence of sodium chloride, at which the pH the aqueous tanning liquor is set to 2 to 3.5.

It is therefore a particular advantage of the inventive method over known methods for the production of wet white, that a pimple is no longer required. Thus, the tanner can be spared an additional step and at the same time the burden of the wastewater can be avoided by a high input of salt.

The treatment with a carbamoylsulfonate group-containing compound and in particular also all subsequent steps of the process according to the invention are preferably carried out in the absence of mineral or other organic reactive tanning agents other than compounds containing carbamoylsulfonate groups.

Organic reactive tannins in this context are, for example, those with aldehyde functions such as glutaric dialdehyde, glyoxal, succinic dialdehyde, adipic dialdehyde or degraded dialdehyde starch.

The organic tanning agents of component b) are not organically reactive tanning agents in the context of the invention.

The invention also relates to the use of polysiloxanes for hydrophobing collagen fiber-containing substrates, in particular tanned hides and skins, i. leather and furskins treated in the absence of mineral or other organic reactive tanning agents other than carbamoylsulfonate group-containing compounds and optionally in the presence of organic tanning agents, preferably those of component b).

Preference is given to the prepared in the water workshop collagen fiber-containing substrates, especially hides and skins, the carbamoylsulfonate-containing compound at a pH in the section of the substrate from pH 5 to pH 10, preferably from pH 7 to pH 10, particularly preferably from pH 8 to pH 10, and at a pH in the liquor of pH 5 to 10, preferably pH 6 to pH 9, more preferably pH 6 to pH 8 is added and leaves it for 0.1 to 8 hours, preferably 0.2 to 2 Hours penetrate into the entire cross-section of the substrate and then adds a fixative. Suitable fixatives in the tannery known bases or mixtures thereof, for example, sodium hydroxide, alkali metal carbonates, Alkalihydrogencarbonate, magnesium oxide, dolomite, tertiary amines, etc., but especially dolomite, magnesium oxide, sodium carbonate and sodium hydroxide. The fixation is preferably carried out over a period of 2 to 24 hours, preferably 4 to 12 hours at a pH in the float of pH 7 to pH 10, preferably from pH 7.5 to pH 9.0, particularly preferably 7.8 to 8.8. The temperature in the fixing is preferably 15 to 60 ° C, more preferably 20 to 50 ° C, most preferably 25 to 45 ° C.

The correspondingly prepared collagen fiber-containing substrates, in particular the pretreated skins and skins pretreated in the water workshop, are preferably in a commercial Gerbfass in aqueous liquor at a temperature of 10 ° C to 60 ° C and a pH of 5 to 10, preferably 7 to 9, with 0.5 to 10%, preferably 1 to 4% of the carbamoylsulfonate-containing compound based on pumice weight, wherein a tanned intermediate (leather) having a shrink temperature of at least 65 ° C, preferably at least 68 ° C, especially preferably at least 70 ° C receives. The shrink temperature is determined by the methods known to those skilled in the art, for example by heating the tanned intermediate by immersion in a water bath whose temperature is raised at a certain heating rate until the contraction of the material is observed. The temperature reached on contraction is read on the display of the tester (Leather Shrinkage Tester). The shrinkage temperature can also be determined by means of the differential scanning calorimetry (DSC) method known to the person skilled in the art.

It is also possible to slow down or interrupt the tanning by acidification to pH 3 to pH 6, preferably to pH 3.5 to pH 5.5, or by addition of ammonia or a primary or secondary amino compound. This is particularly advantageous if an excessive astringency of the liquor is to be avoided and a partial inactivation of the tanning agent is desired. These additional measures are suitable for influencing the tanning process in an advantageous manner.

In the process according to the invention, it is very particularly preferred to choose a low initial pH of the liquor of from 6 to 8 for the penetration of the compound containing carbamoylsulfonate groups and to fix in a pH range of from 7.8 to 8.8 and by increasing the Temperature to regulate up to 60 ° C.

The tanned intermediates obtained from the bloom material, which are also referred to as wet white due to the light color, are suitable for mechanical further processing by z. B. Wilting, folding or splitting. In addition, these intermediates are characterized by a very white, clear and light-fast intrinsic color, which is a clear advantage, for example, compared with glutardialdehyde tanned leathers, especially for the production of white leather.

The so-tanned leather can be retanned by other methods, and with well-known steps such as dyeing, greasing, water repellency soft and airy crust leather finished with the appropriate shades.

The actual tanning essentially serves to stabilize the hides and skins, which thereby become falzbar. The preferably subsequent retanning with organic tanning agents, in particular those of component b), completes the leather production and serves to refine and adjust the properties in order to obtain useful leathers for the respective leather articles.

When retanning, it is often useful to simultaneously make a fatliquoring of the leather and to use appropriate fatliquors. Organic tanning agents are, for example, those of component b), which often have simultaneously more or less extensive filling and softening properties, in some cases by modification in the tannin formulation, such as the addition of resin tanning agents, filling polymer tanning or plasticizing polymer tanning agents, to the dominant characteristic can be made. In principle, however, all the usual non-tanning fatliquoring agents in the process according to the invention can also be used during the retanning. The working steps of the actual retanning, dyeing and greasing are advantageously carried out in the pH range from 3.5 to 6.0, it being possible to co-use hydrophobicizing agents. Preferably, the actual hydrophobization is carried out at a pH of 3.5 to 7.0, preferably 3.5 to 6. Finally, the hydrophobized leather for fixing to a pH of 2.5 to 4.0, preferably 2 , 5 to 3.5 acidified, washed and finished as usual, for example by storage on the box, stretching, vacuum drying and hanging drying and studs. If particularly high hydrophobicity values are required, aluminum salts such as basic aluminum chloride, aluminum formate, titanium or zirconium salts such as zirconium sulfate may be added during the fixing step.

The mentioned non-tanning fatliquoring agents are usually pre-emulsified in aqueous systems and usually contain emulsifiers. Furthermore, such emulsions or dispersions may sometimes contain organic solvents to promote deeper penetration and uniform distribution throughout the leather surface.

When co-use of non-tanning fatliquoring in Nachgerbschritt these can be used in amounts of up to 80 wt .-%, preferably up to 40 wt .-% solids, based on the shaved weight. The weight ratio of organic tannins of component b) to non-tanning fatliquoring agents is in particular 99: 1 to 20:80, especially 95: 5 to 35:65.

The tanning described above can also be carried out with the concomitant use of organic tannins of component b), wherein these can be used or not be co-used. The tanning agents of component b) can be used together with the carbamoylsulfonate group-containing compound or in succession.

The tanning is followed, preferably by retanning, by treatment with organic tanning agents of component b), preferably with syntans and vegetable tanning agents. During the actual retanning, the desired leather properties are set. In turn, organic tanning agents, syntans and vegetable tanning agents are preferably used. In addition, polymeric retanning agents, for example those based on (co) polymers, as well as resin tanning agents, dyes, fatliquoring agents and proportionately hydrophobicizing agents, are advantageously used here. Preferably, these agents are used during the retanning in the usual quantities for wet white.

The advantage of the tanning process according to the invention is that pimple is no longer required, leather with a wide range of properties is obtained and the folding chips resulting from the mechanical processing do not contain any harmful compounds and can be used in many ways as raw materials, i.a. also for the production of valuable products, which in turn can be used in the leather manufacturing process. This provides a significant contribution to reducing wastes in leather production and simplifying the processing of shavings.

The wetted on the basis of Carbamoylsulfonatgruppenhaltigen compounds wet whites yield white, yellowing resistant, hydrophobized leather and fur skins whose softness is adjusted by the products used in the retanning. The hydrophobized leathers are suitable, for example, for Waterproof shoe upper leather, as they show a very high level of waterproofness under dynamic load in the Bally Penetrometer or Maeser tester.

• Als Rohware werden vorzugsweise entwässerte, insbesondere gesalzene und/oder luftgetrocknete Schaffelle eingesetzt. Die Behandlung der Rohware wird üblicherweise in einer Haspel durchgeführt, die Einsatzmengen der verwendeten Mittel werden beispielsweise in Gramm pro Liter Flotte oder in Gewichtsprozent, bezogen auf das Nassgewicht der Häute und Felle, angegeben.

For collagen fiber-containing substrates with associated keratinic constituents, in particular hides and skins with hair, the production processes to finished furskins, in which the keratinic constituents, in particular hair, are to be preserved, can be very different. By way of example, the basic production process for the production of sheepskins will be described in simplified form below:

• The raw material used is preferably dehydrated, in particular salted and / or air-dried, sheepskin. The treatment of the raw material is usually carried out in a reel, the amounts of the funds used are given, for example, in grams per liter of liquor or in percent by weight, based on the wet weight of the hides and skins.

• Wasserwerkstatt:
  • Schritt 1) Schmutzweiche / Weiche in Wasser in Gegenwart von Weichhilfsmitteln oder Waschmitteln (Tensiden),
  • Schritt 2) Entfleischung, gegebenenfalls Spalten der Rohhäute
  • Schritt 3) Wäsche mit Wasser in Gegenwart von Waschmitteln (Tensiden) und Aufhellern,
  • Schritt 4) gegebenenfalls Pickel zum Hautaufschluss mit Wasser, Kochsalz und Ameisensäure, meist in Gegenwart eines Bleichmittels, Waschmittels und mit Zusatz eines elektrolytbeständigen Fettungsmittels,
• Gerbung:
  • Schritt 5) Gerbung mit Carbamoylsulfonatgruppen-haltigen Verbindungen
• Nachgerbung:
  • Schritt 6a) eigentliche Nachgerbung mit organischen Gerbstoffen, Fettung, ggf. Färbung Schritt 6b) Hydrophobierung mit Polysiloxanen
  • Schritt 7) Trocknung und Fertigstellung der Felle: Abtropfen lassen, Hängetrocknung, Konditionieren (z.B. Feuchtläutern mit feuchten Sägespänen), Stollen und Schleifen der Lederseite, Kämmen des Haarkleids, dann Trockenläutern (Entfetten z.B. mit Sägespänen oder ggf. Verwendung von speziellen geschlossenen Apparaturen und Behandlung mit organischen Lösemitteln wie bei einer chemischen Reinigung), Kämmen und Bügeln des Haarkleids.

The method is preferably divided into the following steps, wherein the invention is not limited to this described embodiment, but includes any procedure for the treatment of fur skins with carbamoylsulfonate-containing compounds:

• Water Workshop:
  • Step 1) Dirt switch / switch in water in the presence of softeners or detergents (surfactants),
  • Step 2) Deflocculation, optionally splitting the raw hides
  • Step 3) washing with water in the presence of detergents (surfactants) and brighteners,
  • Step 4) optionally pimples for skin disruption with water, common salt and formic acid, usually in the presence of a bleaching agent, detergent and with the addition of an electrolyte-resistant fatliquoring agent,
• Tanning:
  • Step 5) Tanning with carbamoylsulfonate group-containing compounds
• retanning:
  • Step 6a) actual retanning with organic tanning agents, fatliquoring, optionally coloring step 6b) hydrophobing with polysiloxanes
  • Step 7) Drying and finishing of the skins: draining, hanging drying, conditioning (eg wet with wet sawdust), cleats and sanding the leather side, combing the hair coat, then dry-cleaning (eg degreasing with sawdust or possibly use of special closed equipment and treatment with organic solvents such as a chemical cleaning), combing and ironing the hair coat.

Any commercial raw material is suitable and the hides and skins are usually treated in a reel. Most preferably, the hides and skins are first pretreated by a soak, switch, defibering and wash and then thoroughly washed.

The inventive method can also be carried out without pimples. When working with pimples, the washed hides and skins are treated in an aqueous sodium chloride solution (eg 5 ° Be) with the addition of carboxylic acids at pH 2 to 4 for several hours. Then it will be washed and then de-pipetted and degreased by means of sodium formate, sodium bicarbonate and surface-active compounds (surfactants), wherein the pH is gradually raised to pH 5 to 10. The pickled material is then used for tanning.

When working without pimples, the washed hides and skins are used directly for tanning. It is preferred that the hides and skins are not pickled prior to treatment with a carbamoylsulfonate group-containing compound.

The progress of the tanning is advantageously followed by measuring the shrinkage temperature of the substrate. If at least a shrinkage temperature of 65 ° C, preferably of at least 68 ° C, more preferably of at least 70 ° C is reached, the pH is lowered, drained the fleet and washed the fur skins.

The (tanned) material treated in the process according to the invention with the carbamoylsulfonate-containing compound can therefore already be referred to as wet white.

6a-1

organischen Gerbstoffen, insbesondere mit solchen der Komponente b) wie Syntanen, polymeren Nachgerbstoffen, weichmachenden Polymergerbstoffen,

6a-2

Fettungsmitteln und

6a-3

gegebenenfalls Farbstoffen

6b)

und Hydrophobierungsmitteln

behandelt.The tanned fur skins can then be retanned (step 6)
With

6a-1

organic tanning agents, in particular with those of component b), such as syntans, polymeric retanning agents, plasticizing polymer tanning agents,

6a-2

Fatliquors and

6a-3

optionally dyes

6b)

and water repellents

treated.

Reservation agents may be added prior to staining if the hair is not to be dyed as well. The dye is advantageously fixed by the addition of cationic auxiliaries after dyeing.

For certain skins, preferably for sheepskins for medical purposes or for direct skin contact, it may be advantageous to dispense with coloring.

At the end of the retanning step (step 6), the liquor is preferably adjusted to a pH of from 2.5 to 4.5, preferably from 3 to 4, by addition of formic acid, and the fur is washed.

The retanned fur skins are then usually taken from the reel (step 7). It is drained and dried by hanging. Then the fur skins are struck, and if necessary. degreased moist in the lautering barrel and dried. The meat side is ground if necessary. Finally, the hair is combed and ironed. It is also possible to treat the fur skins with tools against staining or against static charge, etc., for example, by a spray application of appropriate means.

The individual process steps are described in detail below.

For tanning the pretreated in the water workshop hides and skins with hair preferably in a coiler in an aqueous liquor with a fleet length of 300 to 1000%, based on wet weight, at a temperature of 10 ° C to 50 ° C with 0.5 to 10 %, preferably 1 to 5% of at least one compound containing carbamoylsulfonate groups, based on the wet weight of the hides and skins. This gives preferably a tanned intermediate (fur, wet white) with a shrink temperature of at least 65 ° C, preferably at least 68 ° C, particularly preferably at least 70 ° C.

The skins and hides pretreated in the water workshop are preferably conditioned in the reel to a pH in the substrate cross section of pH 5 to pH 10, preferably pH 7 to pH 10, particularly preferably pH 8 to pH 10. Then, the carbamoylsulfonate group-containing compound at an initial pH in the substrate cross section of pH 5 to pH 10, preferably pH 7 to pH 10, more preferably pH 8 to pH 10 and an initial pH in the liquor of pH 5 to 10 , preferably pH 6 to pH 9, more preferably pH 6 to pH 8 added and allowed to penetrate for 0.1 to 8 hours, preferably 0.2 to 2 hours in the entire cross-section of the substrate and then adds a fixing agent. Suitable fixatives in the tannery known bases or mixtures thereof, for example, sodium hydroxide, alkali metal carbonates, Alkalihydrogencarbonate, magnesium oxide, dolomite, tertiary amines, etc., but especially dolomite, magnesium oxide, sodium carbonate and sodium hydroxide. The fixation is preferably carried out over a period of 2 to 24 hours, preferably 4 to 12 hours at a pH in the liquor of pH 7 to pH 10, preferably from pH 7.5 to pH 9.0, particularly preferably 7, 8 to 8.8. The temperature in the fixing is preferably 15 to 60 ° C, more preferably 20 to 50 ° C, most preferably 25 to 45 ° C.

In the tanning reaction of the collagen fiber-containing substrates bisulfite is released, causing the pH of the fleet falls. It is particularly advantageous to maintain the pH in the above-mentioned range during tanning by addition of the fixing agent. In general, addition of the fixative in 2 to 3 portions after complete penetration is sufficient to adjust the preferred pH range. By treatment with the fixative, the covalent bond of the Carbamoylsulfonatgruppen-containing compounds to collagen fiber-containing substrate completed.

Preferred organic tanning agents of component b) are syntans, resin tanning agents, polymeric retanning agents and vegetable tanning agents.

1. A) sulfonierten Aromaten,
2. B) Aldehyden und/oder Ketonen und gegebenenfalls
3. C) einer oder mehreren Verbindungen, ausgewählt aus der Gruppe der nicht sulfonierten Aromaten, Harnstoff und Harnstoffderivaten.

The syntans are, for example, at least one condensation product based on

1. A) sulfonated aromatics,
2. B) aldehydes and / or ketones and optionally
3. C) one or more compounds selected from the group of unsulfonated aromatics, urea and urea derivatives.

On a "basis of" means that the condensation product was optionally prepared from other reactants besides A, B and optionally C. However, the condensation products in the context of this application are preferably prepared only from A, B and, if appropriate, C.

For the purposes of this application, sulfonated aromatics are also understood to mean sulfomethylated aromatics. Preferred sulfonated aromatics are: naphthalenesulfonic acids, phenolsulfonic acid, sulfonated ditolyl ethers, 4,4'-dihydroxydiphenylsulfone, sulfonated diphenylmethane, sulfonated diphenyl, sulfonated terphenyl or benzenesulfonic acids, toluenesulfonic acids.

Suitable aldehydes and / or ketones are in particular aliphatic, cycloaliphatic and aromatic in question. Preference is given to aliphatic aldehydes, particular preference being given to formaldehyde and other aliphatic aldehydes having 3 to 5 C atoms.

Suitable non-sulfonated aromatics are, for example, phenol, cresol or dihydroxydiphenylsulfone, dihydroxydiphenylmethane, ditolyl ether, dihydroxyditolyl ether, dihydroxyditolylsulfone, hydroxybenzoic acid.

As urea derivatives, for example dimethylolurea, melamine or guanidine can be mentioned.

Phenol and phenol derivatives such as phenolsulfonic acid, are often linked by the simultaneous action of formaldehyde and urea or by dimethylolurea ( DE-A 1 113 457 ). Sulfonation products of aromatic compounds are (according to Ullmann's Encyclopedia of Industrial Chemistry Volume 16 (4th edition) Weinheim 1979, p. 138) in general . without separating the unreacted starting compounds, alone or together with other starting compounds condensed with formaldehyde. A solubilizing group can also be introduced in phenols by sulfomethylating with the simultaneous action of alkali hydrogen sulfite and formaldehyde together with the condensation. This sulfomethylation is eg in DE-A 848 823 described.

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

Particularly preferred condensation products are those which are obtained by condensation of sulfonated and optionally non-sulfonated aromatics with aliphatic aldehydes, preferably formaldehyde, sulfonated aromatics in particular meaning no sulfomethylated aromatics.

Such condensation products are preferably obtained by condensation of sulfonated naphthalene and sulfonated phenol or 4,4'-dihydroxydiphenylsulfone with formaldehyde or by condensation of naphthalenesulfonic acid and formaldehyde or by condensation of sulfonated ditolyl ether, sulfonated phenol with formaldehyde or by condensation of sulfonated phenol, urea, phenol Formaldehyde or by condensation of sulfonated phenol, urea, phenol, sulfonated ditolyl ether with formaldehyde.

The condensation product preferably obtained in the condensation preferably has an average degree of condensation of 1 to 150, preferably from 1 to 20, in particular from 1 to 12.

Preference is given here to products based on the condensation of naphthalenesulfonic acids, ditolyl ether sulfonic acids, phenolsulfonic acids, dihydroxydiphenylsulfone and phenol and combinations of these raw materials with formaldehyde, glyoxal or glutaric dialdehyde and optionally urea or urea derivatives.

Also suitable organic tanning agents are polycondensates based on dihydroxydiphenylsulfone / naphthalenesulfonic acid and formaldehyde, dihydroxydiphenylsulfone / ditolyl ether sulfonic acid and formaldehyde, dihydroxydiphenylsulfone / phenolsulfonic acid / ditolyl ether sulfonic acid / urea and formaldehyde (commercial tanning agents such as TANIGAN® BN, TANIGAN® PR, TANIGAN® 3LN, TANIGAN ® HO, TANIGAN® UW from Lanxess or mixtures thereof).

The organic tanning agents used, in particular the syntans, may contain other additives such as buffers or lignosulfonates.

Resin tanning agents are also suitable as organic tanning agents and are preferably polycondensates based on melamine, dicyandiamide, urea, lignin sulfonate or mixtures thereof with formaldehyde or glutardialdehyde.

The preferred polymeric retanning agents are high molecular weight water-soluble or water-dispersible products, e.g. B. from the (co) polymerization reaction of unsaturated acids and their derivatives with z. B. filling or greasing effect on leather. Preference is given to (co) polymerization of acrylic and methacrylic acid and their esters.

1. A. Polysuccinimid mit einem als Zahlenmittel bestimmten Molekulargewicht von 500 bis 10 000, vorzugsweise 500 bis 6 000, insbesondere 1 000 bis 4 000, mit
2. B. 5 bis 90, vorzugsweise 20 bis 80 Mol-%, bezogen auf Succinimideinheiten des Polysuccinimids A, primärem und/oder sekundärem Amin, dessen Stickstoffsubstituenten 1 bis 60, vorzugsweise 1 bis 36 Kohlenstoffatome enthalten, durch Fluoratome, Hydroxyl-, Aminogruppen und/oder Siliciumorganische Reste substituiert und/oder durch Sauerstoffatome, Ester-, Amid-, Harnstoff-, Urethangruppen unterbrochen sein können, wobei mindestens 2,5, vorzugsweise mindestens 15, insbesondere mindestens 30 Mol-% der Stickstoffsubstituenten des Amins mindestens 12 Kohlenstoffatome enthalten, gegebenenfalls
3. C. (i) Derivaten von C₁-C₁₈-Monocarbonsäuren und/oder C₂-C₁₀-Dicarbonsäuren und/oder (ii) Monoisocyanaten, Diisocyanaten oder Epichlorhydrin (zur Umsetzung von Amino-und/oder Hydroxylgruppen an den Stickstoffsubstituenten des Umsetzungsprodukts aus A und B), und (obligatorisch)
4. D. 95 bis 10, vorzugsweise 80 bis 20 Mol-% ringöffnende Base in Gegenwart von Wasser.

Other polymeric retanning agents are those in WO 97/06279 Polyasparaginsäureamide described, having a number average molecular weight of 700 to 30,000, preferably 1 300 to 16 000, obtainable by reaction of

1. A. Polysuccinimide having a number average molecular weight of 500 to 10,000, preferably 500 to 6,000, in particular 1,000 to 4,000, with
2. B. 5 to 90, preferably 20 to 80 mol%, based on Succinimideinheiten of polysuccinimide A, primary and / or secondary amine whose nitrogen substituents contain 1 to 60, preferably 1 to 36 carbon atoms, by fluorine atoms, hydroxyl, amino groups and / or organosilicon radicals may be substituted and / or interrupted by oxygen atoms, ester, amide, urea, urethane groups, wherein at least 2.5, preferably at least 15, especially at least 30 mol% of the nitrogen substituents of the amine contain at least 12 carbon atoms, optionally
3. C. (i) Derivatives of C ₁ -C ₁₈ monocarboxylic acids and / or C ₂ -C ₁₀ dicarboxylic acids and / or (ii) monoisocyanates, diisocyanates or epichlorohydrin (for reacting amino and / or hydroxyl groups on the nitrogen substituents of the reaction product from A and B), and (obligatory)
4. D. 95 to 10, preferably 80 to 20 mol% ring-opening base in the presence of water.

The preferred polyaspartic acid amides of WO 97/06279 should be hereby incorporated as incorporated.

1. a) Struktureinheiten der allgemeinen Formel I
   
   enthalten, wobei

   W

   für einen dreiwertigen Rest aus der Gruppe

   
   
   
   
   steht, in der
   * die Orientierung für den Einbau des Restes W in die Formel I angibt, und

   Z

   für die Reste -OH, -O ^- M ⁺ oder -N-R¹R² steht, wobei R¹ und R² unabhängig voneinander für Wasserstoff, gegebenenfalls substituierte Alkylreste, Alkenylreste, Aralkyl-Reste oder Cycloalkyl-Reste stehen, die durch O-Atome, N-Atome, Si-Atome oder Amid-, Carbonat-, Urethan-, Harnstoff-, Allophanat-, Biuret-, Isocyanurat-Gruppen oder Mischungen daraus unterbrochen sein können und

   M⁺

   für H⁺ oder ein Alkaliion, ein NH₄-Ion oder einen primären, sekundären, tertiären oder quartären aliphatischen Ammoniumrest, der vorzugsweise eine C₁-C₂₂-Alkyl- oder -Hydroxyalkylgruppe trägt, steht,

2. b) wenigstens 10 Mol%, bezogen auf die Einheiten der Formel I, Struktureinheiten der allgemeinen Formel Ia
   
   enthält, wobei

   R³

   für einen Kohlenwasserstoffrest mit C₁-C₆₀-Atomen, vorzugsweise einen gesättigten C₁-C₆₀-Alkylrest, insbesondere C₈-C₃₀-Alkylrest steht und

   R⁴

   für Wasserstoff steht oder die gleiche Bedeutung hat wie R³, und

3. c) Polyether-Einheiten mit einem mittleren Molekulargewicht von 200-6000 g/mol enthalten.

Further polymeric retanning agents are, for example, (co) polymers, which

1. a) structural units of the general formula I
   
   contain, where

   W

   for a trivalent residue from the group

   
   
   
   
   stands in the
   * indicates the orientation for the incorporation of the radical W into the formula I, and

   Z

   represents the radicals -OH, -O ^- M ⁺ or -NR ¹ R ² , wherein R ¹ and R ^{2 are} independently hydrogen, optionally substituted alkyl radicals, alkenyl radicals, aralkyl radicals or cycloalkyl radicals represented by O atoms , N atoms, Si atoms or amide, carbonate, urethane, urea, allophanate, biuret, isocyanurate groups or mixtures thereof may be interrupted and

   M ⁺

   represents H ⁺ or an alkali ion, an NH ₄ ion or a primary, secondary, tertiary or quaternary aliphatic ammonium radical which preferably bears a C ₁ -C ₂₂ -alkyl or -hydroxyalkyl group,

2. b) at least 10 mol%, based on the units of the formula I, structural units of the general formula Ia
   
   contains, where

   R ³

   is a hydrocarbon radical having C ₁ -C ₆₀ atoms, preferably a saturated C ₁ -C ₆₀ -alkyl radical, in particular C ₈ -C ₃₀ -alkyl radical, and

   R ⁴

   is hydrogen or has the same meaning as R ³ , and

3. c) contain polyether units having an average molecular weight of 200-6000 g / mol.

Vegetable tannins are derived, for example, from vegetable sources tannins from the classes of condensed tannins or hydrolyzable tannins z. As chestnut extract, Mimosa, Tara or Quebracho. Vegetable tanning agents also include those derived from vegetable sources such as algae, fruits, e.g. Rhubarb, olives, plant parts such as leaves, tree bark, roots, wood may optionally be obtained after a chemical or enzymatic modification and / or by extractive methods.

The organic tanning agents of component b) are usually in the form of aqueous solutions or aqueous dispersions in amounts of 3 to 100 wt .-%, preferably 10 to 50 wt .-% solids, based on the shaved weight of the leather or based on the wet weight the fur skins, in the Nachgerbschritt and in amounts of 0 to 50 wt .-%, preferably 0 to 30 wt .-% solids, based on the bladder weight of hides and skins (without hair) or based on the wet weight of hides and skins ( with hair), used in tanning.

The hydrophobing can be done in one or more steps. It is particularly advantageous to add a subset of the hydrophobizing agent before or during the addition of organic tanning agents, the actual retanning. The majority of the hydrophobizing agent is preferably used after the actual retanning, optionally together with other fatliquoring agents and / or plasticizing polymers. Finally, the hydrophobizing agents are preferably fixed in the customary manner by acidification to, for example, pH 2.5 to 4, preferably with formic acid. Optionally, salts such as aluminum sulfate, aluminum formate, zirconium sulfate, titanyl sulfate may also be used as auxiliary for fixing.

For the process according to the invention, polysiloxanes are suitable as water repellents.

Polysiloxanes are here to be understood as meaning relatively high molecular weight (polymeric) oxygen compounds of silicon, which have as repeat units Si-O-Si groupings; the Si atoms contribute to the saturation of the remaining valences hydrogens, heteroatoms such as N, Cl or F or in particular organic radicals, especially methyl groups (polyorganosiloxanes). Often called such polysiloxanes as silicones, silicone oils or silicone polymers. A typical example of such a polysiloxane is poly (dimethylsiloxane) of the general formula

(CH ₃ ) ₃ Si-O- [Si (CH ₃ ) ₂ -O] _x -Si (CH ₃ ) ₃

Furthermore, however, phenylmethylpolysiloxanes are also of interest.

Most are production-related mixtures of different types of structures of polysiloxanes before: chain polymer siloxanes (usually the main components of the mixtures), branched siloxanes, cyclic siloxanes and crosslinked siloxanes. Typical molecular weights for polysiloxanes are 500 to 150,000.

The polysiloxanes may be free of functional groups or carry functional groups. In a preferred embodiment, the designated polysiloxanes carry as functional groups amino groups, hydroxyl groups, mercapto groups, carboxyl groups, phosphonate groups, sulfo groups and / or sulfosuccinic acid monoester groups. Such functional groups improve the emulsifiability of the polysiloxanes in aqueous liquors and improve the binding of the polysiloxanes to the leather fibers.

The functional groups mentioned, in particular the amino, hydroxyl, mercapto, carboxyl and sulfo groups, are preferably not attached directly to the polymer main chain but via spacer groups, for example C ₂ -C ₄₀ -alkylene groups. The polysiloxanes generally contain on average from 1 to 10 per molecule of these functional groups. Join sulfo or Carboxyl groups, these are usually in partially or completely neutralized form, ie usually as alkali metal, for example sodium or potassium, or ammonium or amine salts, before. Typical carboxyl group-containing polysiloxanes are generally used as leather water repellents, for example in US Pat EP-B 324 345 described.

Furthermore, however, the polysiloxanes can also be substituted by hydroxyl groups, alkoxy groups, chlorine atoms and / or fluorine atoms on the Si atoms or on the C atoms of the organic radicals.

In a particularly preferred embodiment, comb-type carboxyl-functionalized polysiloxanes are used as hydrophobizing agents in which the carboxyl groups are interrupted via spacer groups in the form of linear or branched C ₂ -C ₄₀ -alkylene groups which are interrupted by up to 8 non-adjacent oxygen atoms or amino groups, carbonyl groups or carboxamide groups and additionally may carry up to 5 carboxyl groups or carboxamide groups attached to the polymer backbone, the spacer groups being linked to the polymer backbone via a direct bond or via an oxygen atom or an amino group, carbonyl group, carboxylic acid amide group or carboxylic acid ester group. Such comb-like carboxyl-functionalized polysiloxanes are in the WO-A 95/22627 described.

A

für einen carboxylgruppen-haltigen Rest der Formel

steht, in der
R1, R2 und R3 unabhängig voneinander für Wasserstoff oder für einen einwertigen C₂-C₆₀-Kohlenwasserstoffrest stehen, der gegebenenfalls eine oder mehrere nicht benachbarte Ether-, Imino-, Amid-, Harnstoff-, Urethan-, Ester- oder Carboxylgruppen enthält und der gegebenenfalls mit einer oder 2 Carboxylgruppen -COOM und/oder 1 oder 2 Hydroxylgruppen substituiert ist, und
wobei der Rest A mindestens mit einer Gruppe COOM substituiert ist,
wobei

M

für Wasserstoff oder Na+, K+, Li+, (NH₄)+,

steht,
wobei R4, R5 und R6 unabhängig voneinander für C1-C18-Alkyl, insbesondere C1-C4-Alkyl oder
substituiertes C1-C18-Alkyl, insbesondere Hydroxyalkyl, oder Aralkyl, insbesondere Benzyl, stehen,
und wobei R1 bis R3 unabhängig voneinander über eine Einfachbindung, eine Gruppe -COO-, -CO-oder -CONH- mit dem Stickstoffatom verknüpft sind, und
wobei R1 und R2 nicht gleichzeitig für H stehen und auch nicht gleichzeitig über eine Carbonylgruppe mit dem Stickstoffatom verknüpft sind,
D und E unabhängig voneinander für einen zweiwertigen C₂-C₂₀-Kohlenwasserstoffrest stehen, der durch Hydroxyl substituiert oder durch nicht benachbarte O-Atome unterbrochen sein kann,

q

für 0 bis 3 steht,

R

für einen C₁ bis C₁₂-Alkylrest oder einen Phenylrest steht,

a

für 0 oder 1 steht,

k

für 0 bis 50 steht

c

für 1 oder 2 steht, und

n

für 10 bis 1000 steht,

mit der Maßgabe, dass mindestens eine Endgruppe der Formel (3a) vorhanden ist für den Fall, dass die Polysiloxankette nur Struktureinheiten der Formel (2) enthält.Further particularly preferred carboxyl-containing polysiloxanes are, for example, from EP-A-1108765 known, which are characterized
in that the polysiloxane chain contains at least one structural unit of the formula (1)

[AR _a SiO _{(3-a) / 2} ] _k (1)

and / or at least one structural unit of the formula (2)

[RcSiO (4-c) / 2] n (2)

and optionally at least one end group selected from the formulas

R3SiO1 / 2 (3)

and

AR2SiO1 / 2 (3a)

contains, where

A

for a carboxyl group-containing radical of the formula

stands in the
R 1, R _{2 and} R 3 are independently hydrogen or a monovalent C ₂ -C ₆₀ hydrocarbyl radical optionally containing one or more non-adjacent ether, imino, amide, urea, urethane, ester or carboxyl groups, and optionally substituted with one or 2 carboxyl groups -COOM and / or 1 or 2 hydroxyl groups, and
wherein the radical A is at least substituted by a group COOM,
in which

M

for hydrogen or Na +, K +, Li +, (NH ₄ ) +,

stands,
wherein R4, R5 and R6 independently of one another are C1-C18-alkyl, in particular C1-C4-alkyl or
substituted C 1 -C 18 -alkyl, in particular hydroxyalkyl, or aralkyl, in particular benzyl,
and wherein R1 to R3 independently of one another via a single bond, a group -COO-, -CO- or -CONH- are linked to the nitrogen atom, and
where R 1 and R 2 are not simultaneously H and are not simultaneously linked via a carbonyl group to the nitrogen atom,
D and E independently of one another represent a divalent C ₂ -C ₂₀ -hydrocarbon radical which may be substituted by hydroxyl or interrupted by nonadjacent O atoms,

q

stands for 0 to 3,

R

is a C ₁ to C ₁₂ -alkyl radical or a phenyl radical,

a

stands for 0 or 1,

k

stands for 0 to 50

c

stands for 1 or 2, and

n

stands for 10 to 1000,

with the proviso that at least one end group of the formula (3a) is present in the event that the polysiloxane chain contains only structural units of the formula (2).

1. a) das beschriebene carboxylgruppenhaltige Polysiloxan und als Komponente
2. b) wenigstens eine Komponente aus der Gruppe B1 bis B4,

wobei

B1

ein anionisches Copolymerisat ist,

B2

Polyasparaginsäure oder ein Derivat davon ist,

B3

ein Paraffin ist und

B4

ein Isocyanat-Additionsprodukt

ist.Preference is also given in the EP-A-1108765 described hydrophobizing agent systems containing as a component

1. a) the described carboxyl-containing polysiloxane and as a component
2. b) at least one component from the group B1 to B4,

in which

B1

is an anionic copolymer,

B2

Polyaspartic acid or a derivative thereof,

B3

a paraffin is and

B4

an isocyanate addition product

is.

B₁

für ein anionisches Copolymerisat, hergestellt durch radikalisch initiierte Copolymerisation von (jeweils bezogen auf Monomergemisch)
α ) 10-90 Mol-% des Esters einer monoethylenisch ungesättigten C₃-C₅-Carbonsäure auf Basis eines Alkohols mit 4 bis 40 C-Atomen
β ) 90-10 Mol-% einer monoethylenisch ungesättigten Carbonsäure
γ ) 0-20 Mol-% eines monoethylenisch ungesättigten C₄-C₆-Dicarbonsäureanhydrids
δ ) 0-30 Mol-% eines C₂-C₈-Olefins (Isobuten, Diisobutylen) und
ε ) 0-10 Mol-% eines weiteren Comonomers aus der Gruppe Styrol, alpha-Methylstyrol, Vinylester von C₁-C₈-Carbonsäuren

und gegebenenfalls anschließende partielle Umsetzung der Anhydridgruppen mit einem primären oder sekundären C₁-C₄₀-Alkohol und/oder einem primären oder sekundären Amin mit einem oder zwei C₁-C₁₈-Alkyl- oder Alkenylresten, mit der Maßgabe, daß mindestens 20 Mol-% der den Anhydridgruppen entsprechenden Carboxylgruppen nicht mit Alkohol und/oder Amin umgesetzt werden, sondern mit einer Base neutralisiert werden, wobei wenigstens 50 Mol-% der Carboxylgruppen neutralisiert werden. Bevorzugt liegt die Komponente B₁ als wäßrige Dispersion vor.In a preferred variant of the hydrophobizing agent system

B ₁

for an anionic copolymer prepared by free-radically initiated copolymerization of (in each case based on monomer mixture)
α) 10-90 mol% of the ester of a monoethylenically unsaturated C ₃ -C ₅ -carboxylic acid based on an alcohol having 4 to 40 carbon atoms
β) 90-10 mol% of a monoethylenically unsaturated carboxylic acid
γ) 0-20 mol% of a monoethylenically unsaturated C ₄ -C ₆ dicarboxylic acid anhydride
δ) 0-30 mol% of a C ₂ -C ₈ olefin (isobutene, diisobutylene) and
ε) 0-10 mol% of a further comonomer from the group consisting of styrene, alpha-methylstyrene, vinyl esters of C ₁ -C ₈ -carboxylic acids

and optionally subsequent partial reaction of the anhydride groups with a primary or secondary C ₁ -C ₄₀ -alcohol and / or a primary or secondary amine having one or two C ₁ -C ₁₈ -alkyl or alkenyl radicals, with the proviso that at least 20 mol % of the carboxyl groups corresponding to the anhydride groups are not reacted with alcohol and / or amine, but are neutralized with a base, wherein at least 50 mole% of the carboxyl groups are neutralized. Preferably, the component B _{1 is present} as an aqueous dispersion.

Particularly preferred are copolymers prepared by copolymerizing a monomer mixture of 20-90% by weight of a hydrophobic monomer, especially stearyl methacrylate, hexadecyl methacrylate, eicosanyl methacrylate, dodecyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, and 80-10% by weight of a hydrophilic monomer , in particular methacrylic acid, acrylic acid, maleic anhydride, and 0-30% by weight of another comonomer from the group of styrene, alpha-methylstyrene, diisobutylene.

In a particularly preferred embodiment, polyacrylate dispersions prepared by radical polymerization in the presence of a chain regulator and whose carboxyl groups have been neutralized with a base, wherein the monomer mixture used from 60 to 85 wt .-% of stearyl methacrylate or C _17.4- methacrylate and 15-40% by weight of acrylic acid. Dispersions which are prepared by dispersion in the presence of component B ₃ described below are also preferred. As component B ₃ , especially white oil or a liquid C ₁₄ -C ₁₇ paraffin oil or a wax melting at 30-40 ° C. is particularly preferred in this embodiment. The proportion of component B ₃ , based on the active ingredient of B ₁ + B ₃ , is preferably between 30 and 80 wt .-%, the proportion of solid resin B ₁ between 20 and 70 wt .-%.

Particularly preferred polyacrylate dispersions have an average molecular weight of 2,000 to 50,000 g / mol, preferably 2,000 to 20,000 g / mol. Such dispersions may, for example, be EP 579,267 . EP 498 634 . U.S. Patent 5,348,807 getting produced. The dispersions of component B ₁ preferably have a solids content of from 10 to 60% by weight, preferably from 20 to 50% by weight. Suitable polyacrylate dispersions are known per se. Examples of particularly suitable polyacrylate dispersions are the products available from LANXESS the Lubritan ^® / Leukotan ^® series (Dow Chemical), especially Lubritan ^® WP, Leukotan ^® NS3, Lubritan ^® XB, Lubritan ^® AS, Lubritan ^® SP.

B2-A)

Polysuccinimid mit einem als Zahlenmittel bestimmten Molekulargewicht von 500 bis 10 000, vorzugsweise 500 bis 6 000, insbesondere 1 000 bis 4 000, erhältlich durch Umsetzung von Maleinsäureanhydrid und NH₃-Lösung und anschließende Kondensation, mit

B2-B)

5 bis 90, vorzugsweise 20 bis 80 Mol-%, bezogen auf Succinimideinheiten des Polysuccinimids, primärem und/oder sekundärem Amin, dessen Stickstoffsubstituenten 1 bis 60, vorzugsweise 1 bis 36 Kohlenstoffatome enthalten, die durch Hydroxyreste substituiert und/oder durch Sauerstoffatome unterbrochen sein können, wobei mindestens 2,5 Mol-%, vorzugsweise mindestens 15 Mol-%, insbesondere mindestens 30 Mol-% der Stickstoffsubstituenten des Amins mindestens 12 Kohlenstoffatome enthalten, und

B2-C)

mit 95 bis 10 Mol-%, vorzugsweise 80 bis 20 Mol-% ringöffnender Base in Gegenwart von Wasser.

A preferred component B ₂ is a polyaspartic acid derivative having a number average molecular weight of from 700 to 30,000, preferably from 1,300 to 16,000, obtainable by reacting

B2-A)

Polysuccinimide having a number average molecular weight of 500 to 10,000, preferably 500 to 6,000, in particular 1,000 to 4,000, obtainable by reaction of maleic anhydride and NH ₃ solution and subsequent condensation, with

B2-B)

5 to 90, preferably 20 to 80 mol%, based on Succinimideinheiten of polysuccinimide, primary and / or secondary amine whose nitrogen substituents contain 1 to 60, preferably 1 to 36 carbon atoms which may be substituted by hydroxy and / or interrupted by oxygen atoms wherein at least 2.5 mol%, preferably at least 15 mol%, in particular at least 30 mol% of the nitrogen substituents of the amine contain at least 12 carbon atoms, and

B2-C)

with 95 to 10 mol%, preferably 80 to 20 mol% ring-opening base in the presence of water.

Suitable components B2 are known per se and in the DE 195 28 782 respectively. EP 842 300 described.

A preferred component B ₃ is a paraffinic hydrocarbon which may optionally be substituted by hydroxyl and / or carboxyl groups (white oil 285, paraffin oil, paraffin wax, montan wax, carnauba wax, oxidized polyethylene, long-chain fatty alcohols such as Guerbet alcohols, fatty acids, fatty acid esters, phospholipids). , wherein the paraffinic hydrocarbon preferably together with the component B ₁ and / or B ₂ gives a stable dispersion.

Preferably, the components B _{3 are present} as aqueous dispersions. The solids content of such dispersions is 5 to 60 wt .-%, preferably 10 to 35 wt .-%. It is furthermore particularly preferred to use component B ₃ together with component B ₁ and B ₂ . For this purpose, component B ₃ is preferably added to component B ₁ and / or B ₂ and converted into a stable dispersion by using high shear forces with the aid of customary dispersing machines, dissolvers, homogenizers or ultrasound machines.

B₄-a)

einem organischen Polyisocyanat

B₄-b)

pro Äquivalent in B₄-a) enthaltenem NCO oder latentem NCO 0,0 bis 0,9 Äquivalente C₆-C₂₄, vorzugsweise C₁₂-C₁₈-Alkohol,

B₄-c)

pro Äquivalent in B₄-a) enthaltenem NCO oder latentem NCO 0,1 bis 1,0 Mol Cyanamid und

B₄-d)

Ammoniak oder flüchtigem Amin als Neutralisationsmittel für die Cyanamidgruppen, wobei die Umsetzungsprodukte frei von Polyester- oder Polyethergruppen und frei von Halogenatomen sind.

A preferred component B ₄ is a reaction product

B ₄ -a)

an organic polyisocyanate

B ₄ -b)

per equivalent of NCO or latent NCO contained in B ₄ -a) from 0.0 to 0.9 equivalents of C ₆ -C ₂₄ -alcohol, preferably C ₁₂ -C ₁₈ -alcohol,

B ₄ -c)

per equivalent of NCO or latent NCO contained in B ₄ -a) 0.1 to 1.0 mol of cyanamide and

B ₄ -d)

Ammonia or volatile amine as a neutralizing agent for the cyanamide groups, wherein the reaction products are free of polyester or polyether groups and free of halogen atoms.

It is particularly preferred to use the component B ₄ as a self-inhibiting emulsifier in admixture with component a) and / or in a mixture with the components B ₁ to B ₃ or mixtures thereof.

It is very particularly preferred to use component B ₄ in combination with component a). Preferably, these mixtures have the following composition: 1 to 20% by weight Component B ₄ (based on solids content) 0.01 to 40% by weight Component a) (based on active ingredient / solids content) 40 to 99.89% by weight Water (sum = 100%).

It can also be used, for example, in EP-A-757 108 . EP-A-891430 . DE-A-4214150 . EP-A-579267 and EP-A-372 746 described means are used.

The polysiloxanes described as hydrophobizing agents are usually employed as aqueous emulsions or dispersions, in particular as microemulsions or macroemulsions, preferably microemulsions.

The hydrophobicizing process according to the invention requires no organic solvents and can be carried out particularly well in many cases if the aqueous emulsion of the polysiloxanes additionally paraffins, which may be solid and / or liquid, for example those having a melting point of up to 100 ° C, paraffin oils or white oils, Mineral oils, natural fats or natural, for example fish oil or bone oil, or synthetic or natural waxes, for example polyethylene waxes, polyisobutylene waxes, beeswax or carnauba wax, normally in an amount of up to 90% by weight, in particular up to 50% by weight all up to 30 wt .-%, contains.

In general, it is also advisable to use emulsifiers. Suitable emulsifiers are, in principle, all surface-active compounds in aqueous systems of nonionic, anionic, cationic or amphoteric character, which sufficiently emulsify the polysiloxanes and paraffins, paraffin oils, fats, oils and waxes used and does not impair the hydrophobization, but in particular N- (C ₉ -C ₂₀ acyl) amino acids having 2 to 6 carbon atoms in the amino acid parent such as N-oleoylsarcosine, N-stearoylsarcosine, N-lauroylsarcosine or N-isononanoylsarcosine; the latter are mostly in the form of their alkali metal, ammonium or trialkanolamine salts. The polysiloxane emulsion usually contains 3 to 30 wt .-%, in particular 5 to 25 wt .-%, especially 7 to 18 wt .-% emulsifiers, wherein mixtures of said emulsifiers can be used. Such combinations of polysiloxanes and Emulsifiers are generally used as leather water repellents in the EP-B 213 480 described. The emulsifiers mentioned under component c) are also suitable.

The described polysiloxane emulsions usually contain 3 to 90 wt .-%, in particular 5 to 60 wt .-%, especially 7 to 40 wt .-% polysiloxanes. The emulsions are normally used in amounts of from 0.1 to 20% by weight, in particular from 0.5 to 15% by weight, based on the shaved weight of the leather or the wet weight of the furs. It may be advisable to dilute the emulsions (concentrates) described in the ratio of 1: 2 to 1: 5 with water and add the working stock in the leather hydrophobing.

In a further, particularly preferred embodiment, polysiloxanes are used which are based on microemulsions of polysiloxane active substances known per se. Suitable microemulsions are known from WO2011 / 042409 known. Particularly preferred polysiloxanes contain trimethylsiloxy units as end groups and in a chain randomly arranged methyl (N-2-aminoethyl-3-aminopropyl) siloxy units and dimethylsiloxy units, wherein polysiloxane active substances with a content of 0.3 to 1.0 mmol N / g are preferred. The preparation of microemulsions is known per se to those skilled in the art and is carried out using emulsifiers and co-surfactants. Particular preference is given to microemulsions based on emulsifiers which belong to the group of alkyl polyglycosides and based on cationic and amphoteric or zwitterionic cosurfactants or surfactants. They are characterized in that they have an improved storage stability compared to macroemulsions because they represent thermodynamically stable mixtures. Suitable microemulsions have a dry residue of 30 to 50 weight percent, the concentration of polysiloxane is 15 to 35 weight percent, based on microemulsion. Very particularly preferred polysiloxane-containing microemulsions are, for example, from WO 2011/042409 known, comprising a) 100 parts by weight of one or more polyorganosiloxanes having one or more polar Si-C-bonded hydrocarbon radicals, b) from> 50 to 150 parts by weight of one or more alkyl polyglucosides, c) 0.1 to 150 parts by weight of one or more Co Surfactants selected from the group of amphoteric or zwitterionic surfactants, amine oxide surfactants and cationic surfactants, and d) water.

1. 1) 100 Gewichtsteile eines oder mehrerer Polysiloxane, die eine oder mehrere Amino-, Hydroxy- oder Carboxygruppen enthalten, die über eine Si-C-gebundenen Kohlenwasserstoffrest an die Polysiloxankette gebunden sind, vorzugsweise in Form von N-(2-Aminoethyl)-3-aminopropyl-methylsiloxy-Gruppen
2. 2) >50 bis 150 Gewichtsteile eines oder mehrerer Alkylpolyglucoside
3. 3) 0,1 bis 150 Gewichtsteile eines oder mehrerer kationischer oder amphoterer Coemulgatoren und
4. 4) Wasser,

wobei die Polysiloxane vorzugsweise 0,3 bis 1,0 mmol N /g, vorzugsweise 0,3 bis 0,6 mmol N /g an Aminogruppen enthalten, das Verhältnis von Komponente 2) zu 1) weniger als 1 beträgt und die Emulsionen eine mittlere Teilchengröße d50 von weniger als 100 nm (Laserlichtstreuung) aufweisen.In a particularly preferred embodiment, aqueous silicone emulsions are used as hydrophobizing agents in the process according to the invention, comprising

1. 1) 100 parts by weight of one or more polysiloxanes containing one or more amino, hydroxy or carboxy groups which are bonded to the polysiloxane chain via a Si-C-bonded hydrocarbon radical, preferably in the form of N- (2-aminoethyl) -3 aminopropyl methylsiloxy groups
2. 2)> 50 to 150 parts by weight of one or more alkyl polyglucosides
3. 3) 0.1 to 150 parts by weight of one or more cationic or amphoteric coemulsifiers and
4. 4) water,

wherein the polysiloxanes preferably contain 0.3 to 1.0 mmol N / g, preferably 0.3 to 0.6 mmol N / g of amino groups, the ratio of component 2) to 1) is less than 1, and the emulsions have a mean Particle size d50 of less than 100 nm (laser light scattering) have.

The hydrophobization according to the invention can be carried out in one or more stages. As dyes which can be used simultaneously, for example, the commonly used acidic, substantive or basic aniline dyes come into consideration.

It is also advantageous to co-use polycarbamoylsulfonate-containing compounds during or after treatment with certain polysiloxanes for hydrophobization. This procedure is particularly advantageous when using polysiloxanes which contain amino groups. By the use of the fixation of the polysiloxanes can be influenced in an advantageous manner and it can be obtained even more hydrophobized leather.

The actual hydrophobing according to the invention is generally carried out by walking in a suitable apparatus in a conventional manner, i. at liquor lengths of 50 to 2000%, preferably 100 to 400%, based on the shaved weight of the leather or the wet weight of the fur skins, and at temperatures of 20 to 60 ° C, preferably 35 to 50 ° C, wherein at the beginning the pH values usually between 4.5 and 45 8.0, preferably 4.8 to 5.5, lie. In general, the hydrophobing is completed in a time of 20 to 240, preferably 30 to 120 minutes.

At the end of the hydrophobing, an optionally used emulsifier is usually fixed with acid, preferably formic acid, by adjusting a pH from 3.0 to 5.0, preferably from 3.8 to 4.0.

The effect of the hydrophobization can be enhanced by an aftertreatment with a ternary, trivalent or tetravalent metal salt, in particular with a basic aluminum chloride, with aluminum sulfate, aluminum formate, titanium sulfate, zirconium sulfate, calcium chloride or magnesium sulfate. Of the salts mentioned, expediently, based on the shaved weight of the leather or the wet weight of the fur skins, 0.5 to 5 wt .-%, preferably 1 to 2 wt .-%, is used. Of the indicated salts, basic aluminum chloride, aluminum triformate, titanium and zirconium sulfate are preferred. Many of the polysiloxanes described above as hydrophobizing agents require no metal salt fixation in order to achieve a good hydrophobicizing effect.

The invention also relates to collagen fiber-containing substrates, in particular leather and fur skins, which have been tanned with at least one carbamoylsulfonate-containing compound and have been rendered hydrophobic with at least one polysiloxane. In each case, the preferred forms described above also apply here.

Examples A) Production examples Example A1: Preparation of polycarbamoylsulfonate and Syntan

To a solution of 95.5 g of sorbitan polyethylene glycol (20) monododecanoate (eg Eumulgin SML 20 (Cognis) or Tween 20 (Croda)) alkoxylated with a total of 20 ethylene oxide units per sorbitan unit (HLB 16.7 ), in 3199.5 g of water and 4524.8 g of sodium bisulfite solution (NaHSO ₃ , 38-40% in water) at 25 ° C and a pH of 4.36 with stirring 1358.3 g of hexamethylene diisocyanate within 40 minutes metered in, wherein the temperature of the reaction mixture is adjusted within 50 ° C. The pH is 5.62. Then 70.3 g of citric acid (anhydrous) dissolved in 70.3 g of water are added.

The mixture is stirred for 1 hour at 50 ° C, the reaction mixture is clear. Then it is cooled to 25 ° C within 2 hours. It is stirred for 1 hour at room temperature (20-23 ° C). The pH of the solution is 4.67. Then 211.3 g of citric acid (anhydrous) dissolved in 211.3 g of water are added and stirred for 15 minutes. The concentration is adjusted by adding 258.7 g of water. A clear 35.0% solution with a pH of 3.11 is obtained.

5000 g of a 35% solution of the above-described carbamoylsulfonate-containing compound and 5000 g of the 50% aqueous solution of a methylene-bridged aromatic polycondensate based on sulfonated ditolyl ether and 4,4'-dihydroxydiphenyl sulfone are fed by means of a pump into a spray dryer with disc atomizer with the inlet temperature set to 165 ° C. The starting temperature was between 70 and 80 ° C. Caking in the dryer was not observed. An almost white finely divided powder with a bulk density of 562 g per 1000 ml was obtained, which had a dry residue of 99.27% (Mettler IR dryer HR 73P, 120 ° C., standard drying to constant weight). The obtained dust-free powder had a particle size of 5.0 μm to 300 μm. It dissolves very quickly in water without clumping. A solution of 5 g of powder in 50 ml of water had a pH of 3.40.

Example A 2a: Polycarbamoylsulfonate without syntan

To a solution of 391.4 g of water and 527.6 g of sodium bisulfite solution (NaHSO ₃ , 38-40% in water) are added 166.3 g of hexamethylene diisocyanate at 23 ° C in one portion, wherein the mixture by means of a dispersing machine with rotor Stator principle (Ultraturrax aggregate from IKA) is dispersed at 15,000 revolutions per minute. The temperature of the reaction mixture is raised to 60 ° C. within 60 minutes after addition of the isocyanate. The pH is 3.02 initially and increases to 5.84 during the reaction. After a reaction time of 180 minutes, a turbid solution has formed. The speed is reduced to 12,000 revolutions per minute and cooled to 34 ° C within 2 hours. The batch is filtered. The clear solution has a pH of 4.34. There are added 28.3 g of citric acid monohydrate dissolved in 23.4 g of water. A solution having a solids content of 35.25% by weight and a pH of 2.12 is obtained.

To this solution is added 3000 ml of acetone. It is stirred for 2 hours. The precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 90.3%, residual moisture 0.5 wt .-%). A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.20.

Example A 2b: Polycarbamoylsulfonate without Syntan

To a solution of 431.8 g of water and 554.1 g of sodium bisulfite solution (NaHSO ₃ , 38-40% in water) are added 191.8 g of bis (isocyanatomethyl) cyclohexane (mixture of isomers, ie 1.4- and 1.3- Isomer) at 20 ° C. in one portion, the mixture being dispersed by means of a dispersing machine with a rotor-stator principle (Ultraturrax aggregate from IKA) at 15,000 revolutions per minute. After 2 hours, the setting of the dispersing unit is increased to 18,000 revolutions per minute. After another 30 minutes, the speed is increased to 20,000 revolutions per minute. The temperature of the reaction mixture is 3 hours after addition of the isocyanate 60 ° C. After a reaction time of 3.5 hours, the organic phase has disappeared. It is then cooled in 1.5 hours to 40 ° C, while further dispersed at 15000 revolutions per minute. After a total reaction time of 5 hours, the mixture is filtered and mixed with a solution of 28.3 g of citric acid monohydrate in 23.4 g of water, resulting in a pH of 2.58. A 35.0% solution with a pH of 2.58 is obtained.

At room temperature, 3000 ml of acetone are added to this solution. It is stirred for 2 hours. The precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 80.5%, residual moisture content 0.9 wt .-%). A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.60.

Example A 2c: polycarbamoylsulfonate without syntan

A solution of 326.5 g of water, 461.7 g of sodium bisulfite solution (NaHSO ₃ , 38-40% in water) and 9.8 g of an adduct of 2 moles of citric acid and 1 mole of hexamethylene diisocyanate (obtained by drying the aqueous solution, Dispersion at 12000 revolutions per minute). To this template are added at 20 ° C 138.6 g of hexamethylene diisocyanate in one portion. The temperature of the reaction mixture is increased to 50 ° C. with dispersion within 60 minutes. After reaching 50 ° C., 7.8 g of citric acid monohydrate dissolved in 6.5 g of water are added, resulting in a pH of 3.05. The mixture is kept for 1 hour at 50 ° C and then cooled to 25 ° C within 2 hours. The pH of the clear solution is 2.92 at room temperature. There are 23.6 g of citric acid monohydrate dissolved in 19.5 g of water. After adjusting the solids content with 26.4 g of water to obtain a clear 35.0% solution with a pH of 2.30.

At room temperature, 3000 ml of acetone are added to this solution. It is stirred for 2 hours. The precipitated white solid is filtered off, washed with acetone and dried in vacuo at 20 ° C to constant weight (yield 93.5%, residual moisture 0.7 wt .-%). A solution of 1.75 g of powder in 5 ml of water is clear and has a pH of 2.4.

Example A3: Preparation of a water repellent emulsion Preparation of isocyanate addition product

587 g of cyanamide (10% in water) are presented at 20 ° C. With cooling, 147.2 g of triethylamine are added in 30 minutes at 20-25 ° C. Immediately afterwards, 800 g of acetone are added. Thereafter, 265.8 g of a obtained by trimerization of hexamethylene diisocyanate and having biuret polyisocyanate, characterized by an average NCO functionality of about 3.5 (NCO content = 23 wt .-%) and a viscosity of 2500 within 60 minutes mPas at 20 ° C (eg DESMODUR ^® N 3200, product Bayer MaterialScience AG) dissolved in 200 g of acetone at 20-30 ° C added dropwise. Then it is stirred for 30 minutes. The solvent is distilled off at 40 ° C and 150-600 mbar from the reaction mixture. This gives a clear, aqueous solution with about 47 wt .-% solids (pH 7.7, viscosity 60 mPas).

Preparation of the silicone emulsion

524 g of a polydimethylsiloxane with trimethylsilyl end groups (viscosity 1000 mm ² / s, 25 ° C) are presented. Then, 23.5 g of 2-aminoethyl-3-aminopropyl-methyl-dimethoxysilane and then 0.32 g of sodium hydroxide solution (50%) was added. The batch is heated to 140 ° C over 2 hours. It is stirred for 6 hours at 140 ° C, with a slight N ₂ stream is transferred.

Then it is stirred for 1 hour under vacuum and 8 g of distillate removed. A polydimethylsiloxane functionalized with 2-aminoethyl-3-aminopropyl side chains (base N content = 0.52% by weight, 0.37 mmol N / g viscosity at 20 ° C./100 s ^-1 = 110 mPas) is obtained ). The intermediate thus prepared is added at 55 ° C with 12.5 g of caprolactone and 100 g of ethyl acetate. Then 0.16 g of zinc octoate and 10 g of ethyl acetate are added. The mixture is stirred for 10 hours at about 75 ° C. Then the ethyl acetate is distilled off (about 110 g). After cooling to 30-40 ° C, 115 g of acetone and 21.1 g of succinic anhydride in 20 g of acetone are added and stirred at 65 ° C for 2 hours (anhydride no longer detectable). Thereafter, 23.6 g of triethylamine in 270 g of isopropanol are added with stirring. At 55 ° C 950 g of water are added within 3 hours with rapid stirring. After adding 0.3 g of a suitable defoamer in 50 g of water, 16 g of the above-described isocyanate addition product are added. The resulting dispersion is freed from the solvent at 50 ° C. and 140-250 hPa (500 g of distillate) and adjusted to pH 8-9 with ethanolamine. A white finely divided emulsion having a solids content of 37% by weight, a pH of 8.5 (undiluted) and an average particle size of 250 nm (LS) is obtained. The viscosity is 23 mPas (at 100 sec ^-1 , 20 ° C). The product is miscible with water in any ratio and shows good electrolyte stability.

Example A4 Preparation of a Hydrophobizing Microemulsion (according to Example 1, WO 2011/042409)

Microemulsion of aminopolysiloxane 1, alkyl polyglycoside and cationic cosurfactant with a ratio of alkylpolyglucoside / polysiloxane = 0.83

20 g of a 62% solution of an alkylpolyglycoside (Glucopon 215 UP, product of Cognis GmbH), 15 g of an aminopolysiloxane 1 with polar side chains consisting of dimethylsiloxy units, methyl (N- [2-aminoethyl] -3-aminopropyl) siloxy units and trimethylsiloxy end groups and having a viscosity of 1015 mPas * s at 25 ° C and an amino group content of 0.45 mmol / g, 4 g of a 75% solution of dicocoalkyldimethylammonium chloride (Arquad 2C-75, product of Akzo Nobel ) and 56.8 g of deionized water were mixed at room temperature. The mixture was acidified to pH 5 with 1.2 g of acetic acid and heated to 70 ° C for 30 minutes. A clear microemulsion was obtained. Neutralization with 2.0 g of a 60% solution of triethanolamine gave a final pH of 8. Then 1.0 g of a 30% solution of parabens in 2-phenoxyethanol was added as a material protection agent. It was an optically clear emulsion having an average particle size of 65 nm (LS), a silicone content of 20 wt .-% and a total solids content of 34.2 wt .-%, a viscosity of 4.3 mPa * s at 23 ° C. receive. After 5 weeks storage at 40 ° C, the emulsion was unchanged. Dilution with a 10% NaCl solution in the ratio 5: 2 showed no change. The emulsion was also stable against dilution with a 10% soda solution.

Example A5: Preparation of a Hydrophobizing Microemulsion (according to Example 2, WO 2011/042409)

Microemulsion of aminopolysiloxane 2, alkylpolyglycoside and zwitterionic cosurfactant with a ratio of alkylpolyglucoside / polysiloxane = 0.75

30 g of a 50% solution of an alkylpolyglycoside ( Plantacare 2000 UP, product of Cognis Care Chemicals ), 20 g of an aminopolysiloxane 2 having polar side chains consisting of dimethylsiloxy units, methyl (N- [2-aminoethyl] -3-aminopropyl) -siloxy units and trimethylsiloxy end groups and having a viscosity of 1960 mPas * s at 25 ° C and an amino group content of 0.77 mmol / g, 4 g of a 33% solution of cocoamidopropylbetaine (Amonyl 380 BA, product of SEPPIC) and 42 g of deionized water were mixed at room temperature. The mixture was acidified to pH 5 with 1.3 g of acetic acid. A clear microemulsion was obtained. Neutralization with 2.0 g of a 60% triethanolamine solution gave a final pH of 8. Finally, 1.0 g of a 30% solution of parabens in 2-phenoxyethanol was added as a material protection agent. The product obtained was an optically clear emulsion having an average particle size of 66 nm (LS), a silicone content of 20% by weight, a total solids content of 38.9%. After 5 weeks at 40 ° C, the emulsion was unchanged. The dilution of the emulsion with 10% NaCl solution in the ratio 5: 2 showed no change. The emulsion was also stable when diluted with a 10% soda solution.

Example A6: Preparation of a Hydrophobizing Microemulsion (according to Example 3, WO 2011/042409)

Microemulsion of aminopolysiloxane 2, alkylpolyglycoside and a cationic cosurfactant with a ratio of alkylpolyglucoside / polysiloxane = 0.83

20 g of a 62% solution of an alkylpolyglycoside (Glucopon 215 UP), 15 g of an aminopolysiloxane 2 with polar side chains consisting of dimethylsiloxy units, methyl (N- [2-aminoethyl] -3-aminopropyl) -siloxy units and trimethylsiloxy And having a viscosity of 1960 mPas * s at 25 ° C and an amino group content of 0.77 mmol / g and 5 g of a 75% solution of dicocoalkyldimethylammonium chloride (Arquad 2C-75) and 58.8 g of deionized water were at Room temperature mixed. A slightly opaque emulsion was obtained. The emulsion was acidified to pH 5 with 1.2 g of acetic acid and heated at 60 ° C. for 1 hour to give a microemulsion. The resulting product was an optically clear emulsion having an average particle size of 87 nm (LS), a silicone content of 15% by weight, a total solids content of 33.85% and a viscosity of 8.15 mPa * s at 23 ° C. After 5 weeks at 40 ° C, the emulsion was unchanged. Dilution of the emulsion with a 10% NaCl solution in the ratio 5: 2 showed no change. The emulsion was also stable to pH 8 on neutralization with triethanolamine or a soda solution. In each of these cases, the neutralized emulsion remained clear and stable at 40 ° C for a period of more than 6 weeks.

B) Process Examples (Wet White Preparation)

The amounts of each of the products used (for example commercial products as supplied) are based on the weight of the raw materials or intermediates used.

Example B 1A: Preparation of Wet White for Upper Shoe Leather

Salted cowhides are washed commercially, limed, depilated, fleshed, and split. The pumice material (2.6 mm) is washed with 200% liquor and drained the liquor. For pre-decalcification, the pots are casked in 100% liquor and 0.2% sodium bisulfite, 0.1% of an ammonium-free decalcifying agent (eg Cismollan DLP, product of LANXESS) and 0.2% of a mixture of dicarboxylic acid derivatives (eg Cismollan DL, product of LANXESS) for 30 minutes at 30 ° C. The fleet is drained. Then for further deliming 30% water, 0.2% sodium bisulfite and 0.1% of an ammonium-free decalcifying agent (eg Cismollan DLP, product of LANXESS) and 0.2% of a mixture of dicarboxylic acid derivatives (eg Cismollan DL, product of LANXESS ) and the barrel is stirred for 1 hour at 30 ° C. At pH 7.7, 1% of a beeignem (e.g., Levazyme AF, product of LANXESS) and 0.1% of a fatty alcohol ethoxylate-based degreaser (e.g., Cismollan AN 90) are added and agitated for an additional 45 minutes. The liquor is then drained and the pats washed twice.

(The following quantities of the products are based on the weight of the pollen).

The prepared pelt is conditioned for 30 minutes with 50% water, 0.2% sodium bicarbonate and 1% sodium acetate to pH 9.0 and treated with 1.7% of the product from Example A1 (powder). After a penetration time of 20 minutes, a further 3.4% of the product from Example A1 (powder) are added. During the following 1.5 hours at 40 ° C, the pH is adjusted to 8.1 by adding a total of 0.5% sodium carbonate (diluted 1:10 with water). Then the drum is moved for a further 2 hours at 40 ° C and the shrinkage temperature is measured (pH 7.65, Ts 68 ° C). The cask is moved for 2 hours in automatic mode (10 minutes / hour) and the pH is measured. Then, 0.2% of a preservative (eg Preventol U-Tec G, product on LANXESS) is added and the pH is reduced to 4.3 with 0.3% formic acid (85%, 1: 1 of 0). You move the barrel for 1.5 hours. Then the fleet is drained. The wet white leather are washed and stored on the box. The shrink temperature is measured again (70 ° C). The leathers can wither without problems and fold to a thickness of 1.2 mm.

Comparative Example B 2A: Preparation of Wet White for Upper Leather with Glutaraldehyde (GTA)

Salted cowhides are washed commercially, limed, depilated, fleshed, and split. The pumice material (2.6 mm) is washed with 200% liquor and drained the liquor. The pods are now delimed in the barrel in 100% liquor and 0.3% sodium bisulfite, 2.5% ammonium chloride, 0.2% formic acid 85% for 30 minutes. Then 0.5% of a Beizenzym (1000 trypsin units) is added and the barrel is agitated for 1 hour. The pH is 8.5. The fleet is drained and the pelts washed for 10 minutes and drained the fleet again.

(The following quantities of the products are based on the weight of the pollen).

The pots are now filled with 30% water, 6% sodium chloride, 0.3% of a preservative (eg Preventol WB Plus L, product of LANXESS) 0.5% formic acid 85%, 0.90% sulfuric acid 96% for 70 minutes at 30 ° C moves. Then 1.00% of a fatliquor (e.g., Eureka 975 ES-I) is added and agitated for 3 hours. The liquor pH is 2.9. Subsequently, 3.0% of an aqueous glutaraldehyde solution (GTA, about 24%, pH 1.5-2.5) are added and pre-tanned for 2 hours. The drum is moved for another 2 hours in automatic mode (10 minutes / hour) and the pH is measured (pH 2.9).

For neutralization, 1.00% sodium formate is added and after 15 minutes runtime, another 1.00% sodium formate is added, resulting in a pH of 3.6. After a running time of 30 minutes, 1.00% of a neutralizing tanning agent based on aromatic sulfonic acids (e.g., TANIGAN PAK, product of LANXESS) is added. The barrel is agitated for 20 minutes, the pH is 3.75. Then 0.2% sodium bicarbonate is added and agitated for 30 minutes (pH 4.0). Now 3.0% of a 4,4'-dihydroxydiphenylsulfone based tanning agent (e.g., Tanigan HO, product of LANXESS) is added and the barrel is agitated for 1 hour.

Thereafter, the liquor is drained, washed with 200% water and drained again. The Wet White is stored on the box. The shrink temperature is measured again (70 ° C). The leathers can wither without problems and fold to a thickness of 1.2 mm.

Example B 3A: Preparation of wet white for shoe upper leather with tannins from Example A2a

Wet white was prepared analogously to Example B 1A using 2.1%, based on pum weight, of the tanning agent from Example A2a.

Example B 4A: Preparation of wet white for shoe upper leather with tannins from example A2b

Wet white was prepared analogously to Example B 1A using 2.1%, based on pum weight, of the tanning agent from Example A2b.

Example B 5A: Preparation of wet white for shoe upper leather with tannins from example A2c

Wet white was prepared analogously to Example B 1A using 2.1%, based on pum weight, of the tanning agent from Example A2c.

C) Process examples (hydrophobization)

The amounts used of the products in the examples under C) refer to the shaved weight.

Example C1): Preparation of a hydrophobized shoe upper with silicone from example A3 without chromium, capping with 2% A1 + 2% Zr

Folded wet white (thickness 1.3 / 1.4 mm) according to Example B 1A is applied in a tanning drum with a liquor of 120% water (40 ° C.) and 0.5% of a carboxylic acid mixture (eg BLANCOROL CGA, product of LANXESS) Washed for 40 minutes. The fleet has a pH of 4.3 and is drained. Then 80% water (30 ° C), 3.0% of a plasticizing polymer tanning agent based on a modified polyamide carboxylic acid (eg LEVOTAN LB, product of LANXESS) (diluted 1: 3 with water) and after 5 minutes 5.0% of a polycondensate based on aromatic sulfonic acid and phenolic compounds (eg TANIGAN VR, product of LANXESS). After 15 minutes, 3.0% of a polyacrylate-based filler polymer tanning material (eg, Leukotan 8090, product of Dow Chemical) is added. Then, a mixture of 4.0% of a long chain hydrocarbon polyacrylate dispersion (eg, Lubritan XB, product of Dow Chemical) and 1.0% jaw oil (30 ° CT) (diluted 1: 3 with water) is added and agitated for 10 minutes , This first hydrophobing step is completed by subsequent addition of 4.0% of the hydrophobing agent according to Example A3 and a running time of 30 minutes. Now, with a mixture of 8.0% of a polycondensate based on 4,4'-dihydroxydiphenylsulfone, aromatic sulfonic acids and vegetable tanning agents (eg TANIGAN F, product of LANXESS), 2.0% dye (eg BAYGENAL Yellow Brown 3G, product of LANXESS), 3.0% Chestnut (regular) and 8.0% of a polycondensate based on aromatic sulfonic acids and phenolic compounds (eg TANIGAN VR, product of LANXESS) and stained for 120 minutes. Subsequently, 5.0% of a polyacrylate-based filler polymer tanning material (eg, Leukotan 1093, product of Dow Chemical) is added and agitated for 60 minutes. After adding 100% water and 1.0% formic acid (diluted 1:10 with water) is stirred for 15 minutes. The liquor has a pH of 4.4 and is further reduced to pH with 1.2% formic acid (diluted 1:10 with water) Acidified 3.9. After stirring for 30 minutes in a barrel, the liquor is drained and the leather washed. Then, in a second hydrophobing step, 150% water, 4.0% of a polyacrylate dispersion with long-chain hydrocarbons (eg Lubritan XB, product of Dow Chemical), 4.0% of the hydrophobizing agent according to Example A3, 2.0% of a fatliquoring agent (eg Atlasol WRM, product of Atlas) and 1.0% claw oil (30 ° CT) (diluted 1: 5 with water) was added and the barrel was agitated for 60 minutes. Then 0.6% formic acid is added. The liquor has a pH of 3.6 after 60 minutes and is drained off. Then it is fixed with 100% water, 2.0% of an aluminum salt (eg Lutan BN, product of BASF) and 2.0% of a zirconium salt (eg Blancorol ZB33, product of LANXESS) for 90 minutes (pH 2.65) and after addition of 0.3% sodium bicarbonate for 15 minutes. The liquor pH is 2.9 at the end. After draining the liquor and washing the leather is stored on the box and as usual by stretching, vacuum drying (3 minutes at 45 ° C) and hanging drying and studs completed.

A hydrophobized leather with very good values is obtained in the Bally penetrometer test: Penetration takes place only after more than 8 hours (compression 10%). With the help of the Maeser tester, a first water passage in the water bath was observed after about 35000 buckling.

Example C2): Preparation of a hydrophobized shoe upper with silicone from example A3, metal-free, capping with Retingan R4-B

Folded wet white split leather (thickness 1.6 mm) according to example B1A is washed in a tannery with a liquor of 120% water (40 ° C.), and 0.5% of a carboxylic acid mixture (eg BLANCOROL CGA, product of LANXESS) for 60 minutes , The fleet has a pH of 4.4 and is drained. Then 80% water (30 ° C), 3.0% of a softening polymer tanning agent based on a modified polyamide carboxylic acid (eg LEVOTAN LB, product of LANXESS) (diluted 1: 3 with water) and 5.0% of a polycondensate based on aromatic Sulfonic acids and phenolic compounds (eg TANIGAN VR, product of LANXESS). After 15 minutes, add 3.0% of a polyacrylate-based filler polymer tanner (eg, Leukotan 1093, product of Dow Chemical) (diluted 1: 3 with water). After a lead time of 10 minutes, a mixture of 4.0% of a polyacrylate dispersion with long chain hydrocarbons (eg, Lubritan XB, product of Dow Chemical), and 1.0% jaw oil (30 ° CT) and 4.0% of the hydrophobizing agent added according to Example A3. After a running time of 30 minutes, with a mixture of 8.0% of a polycondensate based on 4,4'-dihydroxydiphenylsulfone, aromatic sulfonic acids and vegetable tanning agents (eg TANIGAN F, product of LANXESS), 2.0% dye (eg BAYGENAL Yellow-brown 3G, product of LANXESS), 3.0% chestnut (regular) and 8.0% of a polycondensate based on aromatic sulfonic acids and phenolic compounds (eg TANIGAN VR, product of LANXESS) and stained for 60 minutes. Then the keg is moved overnight. The next morning, the fleet has a pH of 4.8. Subsequently, 5.0% of a filling

Polyacrylate-based polymer tanning material (e.g., Leukotan 1093, product of Dow Chemical) (diluted 1: 3 with water) was added and agitated for 30 minutes. After adding 100% water (45 ° C) and 1.0% formic acid (diluted 1:10 with water) is stirred for 20 minutes. Then it is further acidified to pH 3.95 with 1.2% formic acid (diluted 1:10 with water). After stirring for 30 minutes in a barrel, the liquor is drained and the leather washed. Then, in a second hydrophobing step, 150% water, 4.0% of a polyacrylate dispersion with long-chain hydrocarbons (eg Lubritan XB, product of Dow Chemical), 4.0% of the hydrophobizing agent according to Example A3, 2.0% of a fatliquoring agent (eg Atlasol WRM, product of Atlas) and 1.0% claw oil (30 ° CT) (diluted 1: 5 with water) was added and the barrel was agitated for 60 minutes. Then 0.6% formic acid is added. The liquor has a pH of 3.6 after 60 minutes and is drained off.

Then, with 100% water (40 ° C), 6.0% of a resin tanning agent (e.g., RETINGAN R4-B, product of LANXESS) is agitated for 120 minutes. There are obtained hydrophobized leather with a pleasantly soft feel.

Example C3): Preparation of a hydrophobized shoe upper with silicone from example A3, metal-free, capping with MgSO4

In this experiment C3) the procedure is analogous to Example C2). However, unlike Example C2), 4.0% magnesium sulfate is added in place of RETINGAN R4-B and agitated for 120 minutes. After draining the fleet and washing, the leather (50 ° C Pasting) dried and staked. There are obtained hydrophobized leather with a pleasantly soft feel.

Example C4): Preparation of a hydrophobized shoe upper with silicone from example A3, chromium-free, capping with 2% Al + 2% Zr

Folded wet white split leather (thickness 1.8 mm) according to example B1A is washed in a tannery with a liquor of 120% water (40 ° C.), and 0.5% of a carboxylic acid mixture (eg BLANCOROL CGA, product of LANXESS) for 60 minutes , The fleet is drained. Then 80% water (30 ° C), 3.0% of a plasticizing polymer tanning agent based on a modified polyamide carboxylic acid (eg LEVOTAN LB, product of LANXESS) (diluted 1: 3 with water) and after 5 minutes 5.0% of a polycondensate based on aromatic sulfonic acids and phenolic compounds (eg TANIGAN VR, product of LANXESS). After 15 minutes, 3.0% of a polyacrylate-based filler polymer tanner (eg, Leukotan 8090, product of Dow Chemical) (diluted 1: 3 with water) is added. After a lead time of 10 minutes, a mixture of 4.0% of a polyacrylate dispersion with long chain hydrocarbons (eg Lubritan XB, product of Dow Chemical) and 1.0% jaw oil (30 ° CT) (diluted 1: 3 with water) and 4.0% of the hydrophobing agent according to Example A3. This first hydrophobing step is completed after a running time of 30 minutes. Now with a mixture of 8.0% of a polycondensate based on 4,4'-dihydroxydiphenylsulfone, aromatic sulfonic acids and vegetable tanning agents (eg TANIGAN F, product of LANXESS), 2.0% dye (eg BAYGENAL Yellow Brown 3G, product of LANXESS), 3.0% chestnut (regular) and Dyed 8.0% of a polycondensate based on aromatic sulfonic acids and phenolic compounds (eg TANIGAN VR, product of LANXESS) and stirred for 60 minutes. Then it is moved on overnight. The next morning, the fleet has a pH of 4.8. Subsequently, 5.0% of a polyacrylate-based filler polymer tanning material (eg, Leukotan 1093, product of Dow Chemical) (diluted 1: 3 with water) is added. After 45 minutes, add 100% water and 1.0% formic acid (diluted 1:10 with water) and stir for 15 minutes. Then another 1.2% formic acid (diluted 1:10 with water) is added and the liquor is acidified to pH 3.9. After 40 minutes of moving in the barrel, the liquor is drained and washed the leather. Then, in a second hydrophobing step, 150% water, 4.0% of a polyacrylate dispersion with long-chain hydrocarbons (eg Lubritan XB, product of Dow Chemical), 4.0% of the hydrophobizing agent according to Example A3, 2.0% of a fatliquoring agent (eg Atlasol WRM, product of Atlas) and 1.0% claw oil (30 ° CT) (diluted 1: 5 with water) was added and the barrel was agitated for 60 minutes. Then 0.8% formic acid is added. The liquor has a pH of 3.6 after 20 minutes and is drained off. Then with 100% water, 0.3% formic acid, 2.0% of an aluminum salt (eg Novaltan AL) and 2.0% of a zirconium salt (eg Blancorol ZB33, product of LANXESS) fixed for 120 minutes (pH 2.79) and after adding 0.3% sodium bicarbonate for 15 minutes. After draining the liquor and washing the leather is completed as usual by storage on the box, stretching, vacuum drying, hanging drying and studs.

The so-hydrophobized leathers in the Bally penetrometer test (10% compression) show water penetration only after more than 8 hours. The water absorption was 7.4% after 2 hours, after 6 hours 10.2% and after 8 hours 10.8%.

With the help of the Maeser tester, a very good water resistance of the leather was observed when buckling in a water bath: It can be achieved more than 50000 buckling.

Example C5): Preparation of a hydrophobized shoe upper with silicone from example A4, chromium-free, capping with 2% Al + 2% Zr

The procedure was analogous to Example C4), but in each case instead of the hydrophobizing agent from Example A3, the hydrophobizing agent from Example A4 was used.

In this case too, excellent water resistance and Maeser values of about 45,000 flexes were achieved.

Example C6): Preparation of a hydrophobized shoe upper with silicone from Example A5 without chromium, capping with 2% Al + 2% Zr

The procedure was analogous to Example C4), but in each case instead of the hydrophobizing agent from Example A3, the hydrophobizing agent from Example A5 was used.

Also in this case, excellent water resistance and Maeser values of about 35000 flexes were achieved.

Example C7): Preparation of a hydrophobized shoe upper with silicone from Example A6 without chromium, capping with 2% Al + 2% Zr

The procedure was analogous to Example C4), but in each case instead of the hydrophobizing agent from Example A3, the hydrophobizing agent from Example A6 was used.

In this case too, excellent water resistance and Maeser values of about 34000 flexes were achieved.

Comparative Example C8): An attempt to produce a hydrophobized shoe upper made of GTA wet-white B2A with silicone from Example A3 GTA pre-titering, capping with 2% Al + 2% Zr

Folded wet white (thickness 1.8 mm) based on glutaraldehyde tanning according to example B2A is applied in a tanning drum with a liquor of 120% water (40 ° C.) and 0.5% of a carboxylic acid mixture (eg BLANCOROL CGA, product of LANXESS ) Washed for 60 minutes. The fleet is drained. Then 80% water (30 ° C), 3.0% of a plasticizing polymer tanning agent based on a modified polyamide carboxylic acid (eg LEVOTAN LB, product of LANXESS) (diluted 1: 3 with water) and after 5 minutes 5.0% of a polycondensate based on aromatic sulfonic acids and phenolic compounds (eg TANIGAN VR, product of LANXESS). After 15 minutes, 3.0% of a polyacrylate-based filler polymer tanner (eg, Leukotan 8090, product of Dow Chemical) (diluted 1: 3 with water) is added. After a lead time of 10 minutes, a mixture of 4.0% of a polyacrylate dispersion with long chain hydrocarbons (eg Lubritan XB, product of Dow Chemical) and 1.0% jaw oil (30 ° CT) (diluted 1: 3 with water) and 4.0% of the hydrophobing agent according to Example A3. This first hydrophobing step is completed after a running time of 30 minutes. Now with a mixture of 8.0% of a polycondensate based on 4,4'-dihydroxydiphenylsulfone, aromatic sulfonic acids and vegetable tanning agents (eg TANIGAN F, product of LANXESS), 2.0% dye (eg BAYGENAL Yellow Brown 3G, product from LANXESS), 3.0% chestnut (regular) and 8.0% of a polycondensate based on aromatic sulfonic acids and phenolic compounds (eg TANIGAN VR, product of LANXESS) and stained for 60 minutes. Then it is moved on overnight. The next morning, the fleet has a pH of 4.8. Subsequently, 5.0% of a polyacrylate-based filler polymer tanning material (eg, Leukotan 1093, product of Dow Chemical) (diluted 1: 3 with water) is added. After 30 minutes, 100% water and 1.0% formic acid (diluted 1:10 with water) are added and agitated for 30 minutes. Then another 1.2% formic acid (diluted 1:10 with water) is added and the liquor is acidified to pH 3.9. After 20 minutes of moving in the barrel, the liquor is drained and the leather washed. Then, in a second hydrophobing step, 150% water, 4.0% of a polyacrylate dispersion with long-chain hydrocarbons (eg Lubritan XB, product of Dow Chemical), 4.0% of the hydrophobizing agent according to Example A3, 2.0% of a fatliquoring agent (eg Atlasol WRM, product of Atlas) and 1.0% claw oil (30 ° CT) (diluted 1: 5 with water) was added and the barrel was agitated for 60 minutes. Then 0.8% formic acid is added. The liquor has a pH of 3.6 after 20 minutes and is drained off. Then with 100% water (40 ° C), 2.0% of an aluminum salt (eg Novaltan AL) and 2.0% of a zirconium salt (eg Blancorol ZB33, product of LANXESS) fixed for 120 minutes (pH 2.90) and after Addition of 03% sodium bicarbonate for 15 minutes. After draining the liquor and washing, the leather is completed as usual by storage on the box, stretching, vacuum drying, hanging drying and studs.

The so-hydrophobized leathers show water penetration after 6 hours in the Bally penetrometer test (10% compression). The water absorption was 9.3% after 2 hours, after 3 hours 10.7% and after 6 hours 13.6%.

With the help of the Maeser tester a moderate waterproofness of the leather was observed when buckling in a water bath: It can be achieved about 2000 buckling.

Example C9): Preparation of a hydrophobized shoe upper with wet white B3A and with silicone from Example A3 chrome-free, capping with 2% Al + 2% Zr

The procedure was analogous to Example C4), but as a raw material not wet white B1A, but B3A, and each hydrophobizing agent from Example A3 was used. In this case too, excellent water resistance and Maeser values of about 31,000 flexes were achieved.

Example C10): Preparation of a hydrophobized shoe upper with wet white B4A and with silicone from example A3 chrome-free, capping with 2% Al + 2% Zr

The procedure was analogous to Example C4), but as a raw material not wet white B1A, but B4A, and in each case hydrophobing agent from Example A3 was used. In this case too, excellent water resistance and Maeser values of about 38,000 flexes were achieved.

Example C11): Preparation of a hydrophobized shoe upper with wet white B5A and with silicone from Example A3 chrome-free, capping with 2% Al + 2% Zr

The procedure was analogous to Example C4), but as a raw material not wet white B1A, but B5A, and each hydrophobizing agent from Example A3 was used. In this case too, excellent water resistance and Maeser values of approximately 40,000 flexes were achieved.

D) Examples of use Furskins

The amounts of each of the products used (for example commercial products as supplied) are based on the weight of the raw materials or intermediates used.

Example D 1: medical sheepskin, chromium-free

In a commercial reel, air-dried sheepskin is rewetted with 20 liters of water per coat and 2.0 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (e.g., Cismollan AN 90, product of LANXESS) at 25 ° C overnight and then fleshed. The thus prepared skins (3000 g wet weight) are degreased at 35 ° C twice in an aqueous liquor with 2.0 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) for every 60 minutes and After draining the fleet thoroughly rinse with warm water.

To prepare the tanning 30 minutes is treated in fresh liquor (10 L of water) and without pimples at 25 ° C with 1.0 g / l sodium bicarbonate and 0.3 g / l sodium acetate (pH on average 7.0). Then 0.9 g / l of sodium carbonate (diluted 1:10) are added in 2 portions and the skins are conditioned for 1 hour (pH 8.0 on average).

Then, 12.7 g / l of the powder product of Example A1 are added in 2 equal portions at intervals of 30 minutes. After 90 minutes, the addition of magnesium oxide in three doses of the pH gradually increased to 8.5 and then raised the temperature to 40 ° C. No foaming of the fleet is observed.

After 12 hours run time, 3.5 g / l of sulfated synthetic fatliquor and 1.0 g / l of lecithin-based dispersing aid are added to the same bath. After 1 hour, 4.0 g / l of a hydrophobizing agent according to Example A3 are added. After 1 hour, the pH is reduced to 4.0 with formic acid. After draining the fleet, rinse thoroughly with cold water and finish the skins in the usual commercial way. They have a shrinking temperature of 76 ° C.

The sheepskins are white and dry with a pleasantly soft feel. The sheepskins are hydrophobic and have a greatly reduced static water absorption of less than 30%.

Example D 2: medical sheepskin, chromium free

Example D 1 was repeated except that instead of the product from Example A1 for tanning, 6.2 g / l of the powder product from Example A2a were used.

After 90 minutes, instead of the magnesium oxide used in Example D1, the pH is increased to 8.1 by addition of 0.75 g / l sodium carbonate (diluted 1:10) in three doses and the procedure is continued as in Example D1. The hydrophobizing agent used again is the product from Example A3.

The sheepskins have a shrinking temperature of 77 ° C, are white and have a pleasantly soft feel. The static water absorption is less than 30%.

Example D 3: medical sheepskin, chromium free

Example D 1 was repeated except that instead of the product from Example A1 for tanning, 6.2 g / l of the powder product from Example A2b were used.

After 90 minutes, instead of the magnesium oxide used in Example D1, the pH is increased to 8.1 by addition of 0.75 g / l sodium carbonate (diluted 1:10) in three doses and the procedure is continued as in Example D1.

As a hydrophobing agent, the product of Example A4 is now used in the same dosage.

The sheepskins have a shrinking temperature of 75 ° C, are white and have a pleasantly soft feel. The static water absorption is less than 25%.

Example D 4: medical sheepskin, chromium free

Example D 1 was repeated except that instead of the product from Example A1 for tanning, 6.2 g / l of the powder product from Example A2c were used.

After 90 minutes, instead of the magnesium oxide used in Example D1, the pH is increased to 8.1 by addition of 0.75 g / l sodium carbonate (diluted 1:10) in three doses and the procedure is continued as in Example D1.

As a hydrophobing agent, the product of Example A5 is now used in the same dosage.

The sheepskins have a shrinking temperature of 76 ° C, are white and have a pleasantly soft feel. The static water absorption is less than 30%.

Example D 5: medical sheepskin, chromium free

Example D1 was repeated and 10 g / l of the product of Example A1 were used for tanning.

After 90 minutes, instead of the magnesium oxide used in Example D1, the pH is increased to 8.1 by addition of 0.75 g / l sodium carbonate (diluted 1:10) in three doses and the procedure is continued as in Example D1.

As a hydrophobing agent, the product of Example A6 is now used in the same dosage.

The sheepskins have a shrinking temperature of 74 ° C, are white and have a pleasantly soft feel. The static water absorption is less than 30%.

Example D 6: Sheepskin for decorative purposes, chrome-free (with pimple)

In a standard reel (5 revolutions / minute), air-dried sheepskin are mixed with 20 l of water per coat and 0.2 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) at 25 ° C Softened up the night and then defiled.

The prepared skins (3000 g wet weight, defiled) are diluted at 20 ° C. in an aqueous liquor with 0.2 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) (1: 5) ) Washed for 30 minutes.

For pickling, 20 l of water (20 ° C) are introduced and 50 g / l sodium chloride (5 ° Bé) was added. After 5 minutes, 4 g / l of a mixture of dicarboxylic acid derivatives (eg Cismollan DL, product of LANXESS) was added and pickled overnight (pH 3.9). Then 2 g / l of formic acid (1:10) are added and agitated for 2 hours (pH 3.2). The fleet is drained and thoroughly washed. Then with fresh liquor (10 L water) with 1 g / l sodium formate, 1 g / l sodium bicarbonate and 1 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) for 30 minutes at 20 ° C de-oiled / degreased and drained the fleet. In fresh liquor (10 L water) with 1 g / l sodium formate, 1g / l sodium bicarbonate and 3 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) for 30 minutes at 20 ° C. deflated / degreased a second time and drained the liquor (pH 4.8).

To prepare the tanning is in fresh liquor (10 L water) with 3 g / l sodium bicarbonate and 1 g / l sodium acetate for 30 minutes deacidified (pH on average 6.9). Then add 0.9 g / l of sodium carbonate (diluted 1:10) in 2 portions and condition the skins for 1 hour (pH on average 7.9).

Then for tanning with 5.0 g / l of the powder product of Example A1 is added. After 30 minutes, another 5.0 g / l of the powder product from Example A1 are added. After a running time of 90 minutes, the pH is increased to 7.8 in two doses by addition of 1.5 g / l sodium carbonate (diluted 1:10) and tanned for 60 minutes (TS 68 ° C). After 4 hours running time in the same bath with 2 portions per 1.5 g / l formic acid (1:10) is acidified to pH 5.8 and drained the liquor and washed. Foaming is not observed during tanning.

For retanning, 10 L of water are charged and 15 g / L of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone (e.g., Tanigan BN, product of LANXESS) and 15 g / L of tare are added. After 1 hour, a further 15 g / l of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone (eg Tanigan BN, product of LANXESS), 20 g / l of a synthetic fatliquoring agent (eg Baykanol Licker TSI, product of LANXESS) (diluted 1: 4) added and drummed for 1 hour. Then, 10 g / l of the hydrophobizing agent from Example A3 (diluted 1: 4) are added and drummed for 2 hours. Then the pH is reduced to 3.4 with formic acid (1:10). After draining the fleet is thoroughly washed with cold water and the fur skins finished commercially.

The sheepskins show a shrinkage temperature of 75 ° C and are white. They are water-repellent and have a static water absorption of less than 40%.

Example D 7: Sheepskin for decorative purposes, chrome-free (without pimples)

Analogously to Example D 6, the prepared skins (3000 g wet weight, defiled) at 20 ° C in an aqueous liquor with 2.0 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90, product of LANXESS) (diluted 1: 5) twice for 60 minutes and degreased. The fleet is drained and it is thoroughly washed.

To prepare the tanning, 0.9 g / l of sodium carbonate (diluted 1:10) are added in fresh portions (10 l of water) in 2 portions and the hides are conditioned for 1 hour (pH on average 8.0).

Then for tanning with 5.0 g / l of the powder product of Example A1 is added. After 30 minutes, another 5.0 g / l of the powder product from Example A1 are added. After a running time of 90 minutes, the pH is increased to 8.0 and tanned for 60 minutes by addition of 1.5 g / l sodium carbonate (diluted 1:10) in two doses (TS 70 ° C.). After 6 hours running time in the same bath with 2 portions per 1.5 g / l formic acid (1:10) is acidified to pH 5.8 and drained the liquor and washed. Foaming is not observed during tanning.

For retanning, 10 L of water are charged and 15 g / L of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone (e.g., Tanigan BN, product of LANXESS) and 15 g / L of tare are added. After 1 hour, a further 15 g / l of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone (eg Tanigan BN, product of LANXESS), 20 g / l of a synthetic fatliquoring agent (eg Baykanol Licker TSI, product of LANXESS) (diluted 1: 4) added and drummed for 1 hour. Then, 10 g / l of the hydrophobizing agent from example A4 (diluted 1: 4) are added and the mixture is tumbled for 2 hours. Then the pH is reduced to 3.4 with formic acid (1:10). After draining the fleet is thoroughly washed with cold water and the fur skins finished commercially.

The sheepskins show a shrinkage temperature of 74 ° C. They are water-repellent and have a static water absorption of less than 40%.

Example D 8: Sheepskin for decorative purposes, chrome-free (without pimples)

Analogously to Example D 6, the prepared skins (8500 g wet weight, uncleaved skins) at 20 ° C in aqueous liquor (5 ° Bé) with 2.0 g / l of a nonionic emulsifier based on a fatty alcohol ethoxylate (eg Cismollan AN 90 , Product of LANXESS) (diluted 1: 5) twice for 60 minutes and degreased. The fleet is drained and it is thoroughly washed.

To prepare the tanning, the skins are conditioned in fresh liquor (20 L water) with 2.0 g / l sodium carbonate (1:10 diluted) overnight (pH on average 7.5) and the liquor is drained off.

The tanning in fresh liquor (20 L water) is then first pretreated for 30 minutes with 0.1 g / l sodium acetate and 0.1 g / l sodium carbonate (diluted 1:10). Then, 15.0 g / L of the powder product of Example A1 is added. After 4 hours, add 0.75 g / l sodium carbonate (1:10 diluted) in three doses of pH increased to 8.1 and 150 minutes tanned (TS 70 ° C). The next morning (pH of the flask 7.3) 0.25 g / l of a preservative (eg Preventol U-TEC G, product of LANXESS) is added. After 15 minutes, 3 portions of 1.0 g / l formic acid (1:10) are adjusted to pH 6.5 at intervals of 15 minutes. After 90 minutes, the liquor is drained and washed. Foaming is not observed during tanning.

For retanning, 20 L of water are introduced and the pH is adjusted to pH 4.5 with 1 g / liter of formic acid. Then, 7.5 g / L of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone (e.g., Tanigan BN, product of LANXESS) is added. After 30 minutes, 7.5 g / l of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone (eg Tanigan BN, product of LANXESS), and after 30 minutes a third portion of 15 g / l of a condensation product based on naphthalenesulfonic acid and dihydroxydiphenylsulfone (eg Tanigan BN, product of LANXESS) was added and drummed for 2 hours. Heat to 40 ° C and add 20 g / L of a synthetic fatliquor (e.g., Baykanol Licker TSI, product of LANXESS) (diluted 1: 4) and tumble for 2 hours. Then, 10 g / l of the hydrophobizing agent from example A5 (diluted 1: 4) are added and the mixture is tumbled for 2 hours. Then the pH is reduced to 3.7 with formic acid (1:10). After draining the fleet is thoroughly washed with cold water and the fur skins finished commercially.

The sheepskins show a shrinkage temperature of 72 ° C. They are water-repellent and have a static water absorption of less than 40%.

Example D 9: Sheepskin for decorative purposes, chrome-free (without pimples, with coloring)

It is tanned and retanned analogously to Example D 8.

For dyeing in fresh liquor (10 l of water) at 35 ° C with 10 g / l of a naphthalenesulfonic acid polycondensate (eg Tanigan PR, product of LANXESS) and 0.5 g / l of an anionic dye (eg BAYGENAL Dark Brown LN 2G ) Treated for 90 minutes. The cut results in a complete staining of the leather.

Then a pH of 3.4 is set with 2 g / l of formic acid (1:10) and after 30 minutes the liquor is drained off. Then in fresh liquor (10 l of water) with 1 g / l of a cationic dyeing aftertreatment agent is fixed for 30 minutes. The fleet is then drained, it is thoroughly washed and finished the fur skins commercially.

The sheepskins show a uniform dark brown color and a shrinking temperature of 73 ° C.

Compared with commercially sheepskin tanned with glutaraldehyde sheepskins inventive undyed sheepskin on a white color of the leather as well as the wool and show a very high Lightfastness. In the aldehyde test according to DIN 53315A, significantly reduced measured values are obtained compared to the prior art. They are below the detection limit of the method of 20 ppm.

Claims (9)

Process for the hydrophobization of collagen fiber-containing substrates treated with at least one carbamoylsulfonate-containing compound, characterized in that , after treatment of the collagen fiber-containing substrate with at least one carbamoylsulfonate-containing compound, hydrophobization is carried out in the presence of at least one polysiloxane. Process for the hydrophobization of collagen fiber-containing substrates according to claim 1, characterized in that one uses for hydrophobing polysiloxanes, which carry as functional groups amino groups, hydroxyl groups, mercapto groups, carboxyl groups, phosphonate groups, sulfo groups and / or sulfosuccinic monoester groups. Process for the hydrophobization of collagen fiber-containing substrates according to claim 1, characterized in that the collagen fiber-containing substrates are associated with keratinic constituents or are free of keratinic constituents. A process for the hydrophobing of collagen fiber-containing substrates according to claim 1, characterized in that comb-like carboxyl-functionalized polysiloxanes are used as hydrophobing agents in which the carboxyl groups via spacer groups in the form of linear or branched C ₂ - to C ₄₀ -alkylene groups which are not adjacent by up to 8 Oxygen atoms or amino groups, carbonyl groups or carboxamide groups may be interrupted and may additionally carry up to 5 carboxyl groups or Carbonsäureamidgruppen are bound to the polymer main chain, wherein the spacer groups via a direct bond or via an oxygen atom or an amino group, carbonyl group, carboxylic acid amide group or carboxylic acid ester group connected to the polymer main chain are. A method of hydrophobing according to claim 1, characterized in that the carbamoylsulfonate-containing compound is a reaction product of organic polyisocyanates and bisulfite and / or disulfite, wherein the organic polyisocyanate is a polyisocyanate having an NCO functionality of 1.8 to 4.2 and preferably has a molecular weight of <800 g / mol, in particular a polyisocyanate having an NCO functionality of 1.8 to 2.5 and a molecular weight <400 g / mol. A method of hydrophobing according to claim 1, characterized in that the carbamoylsulfonate-containing compound is a reaction product of organic Polyisocyanates and bisulfite and / or disulfite, wherein the organic polyisocyanate has a molecular weight of less than 400 g / mol and NCO groups bonded to aliphatic or cycloaliphatic, in particular 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 1 , 5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane (TMHI), 1,3- and 1,4-diisocyanatohexane, 1,3 - And 1,4-diisocyanato-cyclohexane (CHDI) and any mixtures of these isomers, 1-isocyanato-2-isocyanatomethyl-cyclopentane, 1,2-, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane and any Mixtures of isomers, 1,2-, 1,3- and 1,4-bis (isocyanatoethyl) -cyclohexane and any desired mixtures of these isomers, 1,2-, 1,3- and 1,4-bis (isocyanato-n- propyl) -cyclohexane and any desired mixtures of these isomers, 1-isocyanatopropyl-4-isocyanatomethylcyclohexane and isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 1-isocyanato-1-methyl-4 -isocyanatomethylcyclohexane (IMCI), 2,4 '- and 4,4'-diisocyanato-dicyclohexyl-methane (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 mixtures of such diisocyanates and xylylene diisocyanates of the formulas

A process according to claim 1, characterized in that the carbamoylsulfonate group-containing compound is used in combination with at least one nonionic, ester group-containing, alkoxylated polyol having an HLB value of at least 13 (c1) and / or an alkyl glycoside (c2) and / or a nonionic ester group-free alkoxylated alcohol (c3) is used. Use of polysiloxanes for hydrophobicizing collagen fiber-containing substrates, in particular leathers and furskins, which have been treated in the absence of mineral or other organic reactive tanning agents other than carbamoylsulfonate group-containing compounds and optionally in the presence of organic tanning agents, preferably those of component b). Collagen fiber-containing substrates, in particular leather or fur skins, which have been tanned with at least one carbamoylsulfonate group-containing compound and have been rendered hydrophobic with at least one polysiloxane.