EP0204162A2 - Method of fat liquoring leather and its use in direct spraying polyurethane for leather/polyurethane bonding - Google Patents

Abstract

Aqueous fatliquoring solutions, dispersions or emulsions are made with (a) polyethers having at least two hydroxyl groups and a molecular weight of from 200 to 20,000 and/or (b) polyester containing at least two hydroxyl groups and a molecular weight of from 200 to 20,000 and/or (c) polycarbonates containing at least two hydroxyl groups and a molecular weight of from 200 to 20,000 and/or mixtures thereof. These fatliquoring agents are used to treat tanned leathers until from 0.1 to 20 wt % has been taken up. The thus-treated leather is particularly useful in the production of leather-polyurethane compositions such as shoes without the use of an adhesive.

Description

The invention relates to a process for the greasing treatment of leather, in particular for preparing the direct injection of polyurethane reactive compositions while increasing the separating forces between leather and polyurethane within the composites, in particular within leather shaft / polyurethane sole composites.

• a) mindestens zwei Hydroxylgruppen enthaltenden Polyethern mit einem Molekulargewicht von 200 bis 20.000 und/oder
• b) mindestens zwei Hydroxylgruppen aufweisenden Polyestern mit einem Molekulargewicht von 200 bis 20.000 und/oder
• c) mindestens zwei Hydroxylgruppen enthaltendenden Polycarbonaten mit einem Molekulargewicht von 200 bis 20.000 bzw.
• d) Gemischen von Komponenten der Kategorien a), b) oder c)

anstelle von üblichen Trennungsmitteln oder zusammen mit üblichen Fettungsmitteln enthalten,
bis zur Aufnahme von 0,1 bis 20 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-% der Fettungsmittelprodukte, bezogen auf das Falzgewicht des Leders, behandelt.characterized in that the tanned leather with aqueous liquors of fatliquoring agents, in the form of aqueous, optionally solvent-containing solutions, emulsions or dispersions

• a) at least two hydroxyl-containing polyethers with a molecular weight of 200 to 20,000 and / or
• b) at least two hydroxyl-containing polyesters with a molecular weight of 200 to 20,000 and / or
• c) at least two hydroxyl-containing polycarbonates with a molecular weight of 200 to 20,000 or
• d) Mixtures of components of categories a), b) or c)

instead of usual release agents or together with common fatliquoring agents,
treated up to the absorption of 0.1 to 20 wt .-%, preferably 0.2 to 10 wt .-% of the fat products based on the shaved weight of the leather.

The subject of the invention is in particular the use of the leather prepared according to the described method for direct injection of polyurethane reactive compositions into leather / polyurethane composites, in particular the use of the leather pretreated according to the described method in the form of shafts with polyurethane reactive compositions in automatic spraying machines, with the formation of adhesive-free Shank leather-PU soles connected.

It has also been shown that the leather aftertreated in accordance with the process with the new fatliquoring agents gives an excellent, very deep and very uniform color.

The processing of leather for shoes with molded-e directly ^g PUR or PVC sole, ie without additional adhesive connection between sole and (shaft) leather material, has in the last few years, especially in the Sports shoe sector, increasingly important. Here, for example, you pull a shoe upper over a (metal) last on suitable machines, insert the upper into a relatively tight-fitting shape and spray the sole - without additional gluing - directly with a polyurethane reactive mixture or possibly a PVC mixture. This saves an otherwise necessary gluing process between the upper and the sole.

This process can be carried out economically if the leather used is finished with products which have good adhesion under the processing conditions with polyurethanes, as is the case, for example, with with PU-coated split leather. This direct injection creates problems, however, when the leather is to be processed naturally, because the products necessary for the usual greasing of the leather usually only appear superficially and thus act as a release agent between leather and PUR material. A high level of adhesion, such as is required for sports shoes in particular, cannot be achieved because the polyurethane cannot bond sufficiently to the grease material diffused to the surface of the leather and therefore not to the leather itself under the heat generated during the injection process .

One way to circumvent this effect is to treat the leather with polycation-active substances after greasing in order to fix the greasing agent to the leather. However, this method does not lead to the desired success because the polycation-active substances also appear - along with the Greasing agents - knock down the surface like a pigment and reduce the adhesion of the PUR sole applied later.

Further possibilities for improving the adhesion between leather and PUR material were sought by using greasing agents which both have an affinity for leather and can also react with the isocyanate groups of the PUR material. Fatty acid derivatives, as described for example in SU-PS 840 220, have these abilities theoretically, but because of their C ₁₀ to C ₁₆ fatty acid residues they also act as a release agent.

The Mannich bases based on nonylphenol, which can be used in principle in the same way, or their alkoxylation products (according to US Pat. No. 3,720,606) have a catalytic effect on other isocyanate reactions, e.g. on the NCO-OH reactions or the NCO trimerization and also do not improve the adhesion. Polyglycol etheramines behave similarly in accordance with DE-OS 2 539 671).

So far, the only successful methods of producing any upper leather for direct injection of sole have been to either roughen the leather mechanically by sanding before the injection process, or to provide the leather with an adhesion promoter before the injection of the PUR sole or PVC sole Adhesion between leather and PUR material increased. Both processes represent additional and, in addition, complex work processes.

For example, when mechanically roughening the leather, it is very difficult to limit the sanding process exactly to the subsequent contact surface with the PUR sole. If sanding is carried out across the border, unsightly, rough spots appear on the upper leather. On the other hand, if you stay below this limit, the adhesion between the sole and the shaft is greatly reduced at the non-roughened areas.

The same problem, namely the extremely exact adherence to specified dimensions, is given in the second possibility for the aftertreatment of the upper leather before the injection process, namely the application of a suitable primer or adhesion promoter, if unsightly stripes on the upper material on the one hand or reduced adhesion of the sole on the other hand are avoided should be. Such primers are e.g. aromatic oligourethanes, which generally have a strong tendency to yellowing.

Unfortunately, all attempts to produce the upper leather itself have so far been unsuccessful in such a way that a PUR sole material adheres reliably to this leather without the labor-intensive steps of roughening or pretreating with a primer mentioned above.

Surprisingly it has now been found that ut ^g obtained adhering to polyurethanes, suitable for the direct injection of polyurethane reactive compositions leather, when the leather, optionally after conventional retanning, together with or instead of the normal Lederfettunasmittel with at least 2, preferably aliphatic or cycloaliphatic bound Polyesters containing hydroxyl groups and polyethers whose molecular weights are between 200 and 20,000, preferably 400 to 10,000, and which are transferable into the aqueous phase as such or, if appropriate, using emulsifiers and / or water-miscible solubilizers. It has also been found that leather treated in this way surprisingly has an excellent depth of color and levelness when dyed with conventional leather dyes. Color depth and levelness is much cheaper than when treating leather with common greasing agents.

• a) mindestens 2 Hydroxylgruppen enthaltende Hydroxy- Polyether, welche mehr als 3 Oxyalkylengruppen enthalten, mit einem Molekulargewicht von 200 bis 20.000, vorzugsweise 400 bis 10.000, insbesondere 800 bis 3000, und/oder
• b) mindestens 2 Hydroxylgruppen enthaltende HydroxyPolyester mit einem Molekulargewicht von 200 bis 20.000, vorzugsweise 400 bis 10.000, insbesondere 800 bis 3000, und/oder
• c) mindestens 2 Hydroxylgruppen enthaltende Hydroxypolycarbonate mit einem Molekulargewicht von 200 bis 20.000, vorzugsweise 400 bis 10.000, insbesondere 800 bis 3000, bzw.
• d) Gemische aus Komponenten der Kategorien a), b) oder c) anstelle von üblichen Fettungsmitteln oder zusammen mit üblichen Fettungsmitteln enthalten,

bis zur Aufnahme von 0,1 bis 20 Gew.-%, vorzugsweise 0,2 bis 10 Gew.-%, bezogen auf Fettungsmittelprodukte, behandelt.The invention thus relates to a process for the greasing treatment of leather, in particular to prepare the direct injection of polyurethane reactive compositions while increasing the separating forces of the leather / polyurethane composites, very particularly leather shaft / PU sole composites, characterized in that the tanned leather with aqueous liquors of fatliquoring agents in the form of an aqueous solution which may contain solvents,

• a) at least 2 hydroxyl-containing hydroxy polyethers which contain more than 3 oxyalkylene groups, with a molecular weight of 200 to 20,000, preferably 400 to 10,000, in particular 800 to 3000, and / or
• b) at least 2 hydroxyl-containing hydroxy polyesters with a molecular weight of 200 to 20,000, preferably 400 to 10,000, in particular 800 to 3000, and / or
• c) hydroxypolycarbonates containing at least 2 hydroxyl groups and having a molecular weight of 200 to 20,000, preferably 400 to 10,000, in particular 800 to 3000, or
• d) contain mixtures of components of categories a), b) or c) instead of conventional lubricants or together with conventional lubricants,

treated up to the absorption of 0.1 to 20 wt .-%, preferably 0.2 to 10 wt .-%, based on fat products.

The novel fat-reducing agents a) to d) according to the invention should be present in the mixture of fat-reducing agents in an amount of 20 to 100%, preferably 40 to 80% by weight.

Another subject of the invention is particularly Applicable methods dun ^g of the prepared by the method described for leather Direktanspritzen of polyurethane reactive compositions to leather / Polyurethane composites.

In particular, the subject matter of the invention is the use of the leather pretreated according to the method in the form of shafts for direct injection with PUR reactive compositions in automatic sprayers with the formation of adhesive-free shaft leather / PU sole compounds.

The compounds to be used according to the invention, if they are not water-soluble by themselves, can also be used as dispersants by using a suitable emulsifier sion or emulsion or by using a water-miscible solvent as a solubilizer in the aqueous phase.

Oxiranes such as ethylene oxide, 1,2-propylene oxide, 2,3-butylene oxide, 1,2-butylene oxide, epichlorohydrin or styrene oxide, oxetanes such as 1,3-propylene oxide and oxolanes such as tetrahydrofuran are suitable for the production of the hydroxypolyethers. These are generally reacted with di- or polyvalent, hydroxyl- and / or amino-functional starting components to give the polyethers a) by processes which are well known per se. The polyethers should contain more than 3 oxyalkylene groups.

• Hydroxylfunktionelle Starter wie Wasser, Diole, z.B. Ethylenglykol, 1,2-Propandiol, 1,3-Propandiol, Butandiol-1,4, Hexandiol-1,6, 1,4-, 3,6-Dianhydrosorbit, 4,4'-Dihydroxydiphenylpropan, Triole wie Glycerin, Trimethylolpropan, höhere Polyole wie Pentaerythrit, Sorbit, Mannit, Formit, Formose oder Sucrose, ferner aminofunktionelle Starter wie Methylamin, Ethylendiamin oder Stearylamin, sowie andere Starter, z.B. Hydrazin, Oxethyl-methylamin, die zumindest bifunktionelle Polyether ergeben. Bevorzugt werden Pol^y- merisationsprodukte von Ethylenoxid und Propylenoxid auf Basis von Startkomponenten mit zwei bzw. drei Hydroxylgruppen. Ganz besonders soll dabei das Verhältnis von Ethylenoxid zu Propylenoxid bevorzugt 100:1 bis 30:70, vorzugsweise 80:20 bis 40:60 betragen. Es war dabei überraschen, daß Polyether auf Basis von hydroxyfunktionellen Startern Fettungsmittel ergeben, die eine wesentlich verbesserte Färbung und Farbegalität bei hoher Abriebechtheit der Färbungen ergeben.

The following can be used as hydroxyl-functional (preferred) or amino-functional (less preferred) starting components:

• Hydroxyl-functional starters such as water, diols, for example ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-, 3,6-dianhydrosorbitol, 4,4'- Dihydroxydiphenylpropane, triols such as glycerol, trimethylolpropane, higher polyols such as pentaerythritol, sorbitol, mannitol, formite, formose or sucrose, furthermore amino-functional starters such as methylamine, ethylenediamine or stearylamine, and other starters, for example hydrazine, oxethyl-methylamine, which give at least bifunctional polyethers. Pol ^y are preferably merisationsprodukte of ethylene oxide and propylene based on starter components containing two or three hydroxyl groups. The ratio of ethylene oxide to propylene oxide should particularly preferably be 100: 1 to 30:70, preferably 80:20 to 40:60. It was surprising that polyethers based on hydroxy functional Starters result in greasing agents which result in significantly improved coloring and color levelness with high abrasion resistance of the dyeings.

Aminofunctional started hydroxypolyethers result as ^g E gene often with acid dyes complexes, which are reflected on the leather surface (in the form of dye salts) and result in low wear-resistant dyeings. In addition, the acidification of the dyed leather is difficult (poor bath consumption) and the fixing of the dyes on the leather surface is sometimes difficult. In the case of polyether polyols which have started on longer-chain amines (with, for example,> 10 C atoms), a lot of foam occurs during the coloring (due to the side effect), which ultimately results in uneven coloring.

The different oxiranes possibility ^g e-jointly be polymerized as a mixture or in succession in one or more blocks on the starting component or the already preformed polyol either.

The hydroxypolyesters to be used according to the invention can be prepared in a manner known per se and are, for example, reaction products of polybasic, preferably dibasic carboxylic acids or their mixtures. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower, monohydric alcohols or mixtures thereof can also be used to produce the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic, araliphatic and / or heterocyclic and ^g e- optionally substituted, for example by halogen atoms such as chlorine or bromine and / or unsaturated.

As examples of such carboxylic acids and their derivatives are mentioned: Bernsteinsäsure, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, Indomethylentetrahydrophthalsäureanhydrid, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized un ^{g e-g} Saetti te fatty acid, optionally mixed with monomeric unsaturated fatty acids such as oleic acid, dimethyl terephthalate and terephthalic acid-bis-glykolester.

As polyhydric alcohols, optionally in a mixture with one another, for example Ethylene glycol, propanediol 1,2 and 1,3, butanediol 1,4 and 2,3, hexanediol 1,6, octanediol 1,8, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl 1,3-propanediol, N, N-bis (2-hydroxypropyl) -N-methylamine, glycerin, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, trimethylolethane, pentaerythritol, quinite, mannitol, Sorbitol, formitol, methylglycoside, dianhydrohexite, furthermore in particular di-, tri-, tetra-ethylene glycols and higher polyethylene glycols, furthermore di-, tri- and higher polypropylene glycols as well as di-butylene glycol and higher polybutylene glycols.

The low molecular weight polyols can also be set in any mixtures by esterification. The polyesters to be used can also have a proportion of carboxyl groups as end groups.

Lactone polyesters, e.g. Caprolactone or hydroxycarboxylic acids, e.g. ε-hydroxycaproic acid, these compounds being used either alone or as a mixture with polyhydroxyl compounds to prepare the polyesters. Preferred polyesters are hydrophilic polyesters or else hydrophilic polycarbonates which have been produced using di-, tri-, tetra- or polyethylene glycols.

The also applicable polycarbonates can be prepared in a manner known per se and are for example reaction products of polyhydric, preferably two and ^g e-optionally three or tetrahydric alcohols, with certain carbonic acid derivatives such as phosgene, phenyl chloroformate, ethyl chloroformate, but in particular, diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene or dimethyl pyrocarbonate.

Mixed esters of polylactones and esters or polycarbonates or mixtures of polyesters, polylactones and / or polycarbonates can also be used. Unless they are inherently soluble, emulsifiable or dispersible in water, the polyethers, polyesters or polycarbonates according to the invention can be transferred into the aqueous phase by adding conventional emulsifiers. The emulsifiability of polyesters, polylactones, polycarbonates or polyethers is also simplified by incorporating small amounts of ionizable groups (cationic or anionic type or of tertiary amines which can form salts).

Possible external emulsifiers are: long-chain alkyl sulfates or alkyl sulfonates, ethoxylation products of alkylphenols, e.g. para-nonylphenol or of aromatically substituted phenols such as phenylphenol or of alkylation or benzylation products of phenylphenol; long chain alkyl carboxylic acids or quaternized long chain alkyl ammonium salts.

The products according to the invention are used together with or instead of the normal leather greasing agents. The amount of normal leather greasing agents known per se is generally restricted to amounts of less than 80% by weight.

As is well known, leather greasing is used to impart the final softness to the leather before and especially after dyeing. Frequently, the fatliquors so superficially that later operations such as dressing or, in particular, the direct injection of polyurethane soles are severely hampered by the fatliquors which act as release agents in this case. The fiction, ^g e-Maessen products do not have these disadvantages. Their use thus represents a significant improvement in the further processing of the leather treated with them. In addition, the leather treated according to the invention can be dyed excellently with deep shades with high levelness. After the oiling treatment, the leathers are subjected to the customary aftertreatment, for example dried, placed and, if necessary, finished by known methods.

So preparing for the according to the invention greased leather are now the polyurethane reactive compositions injected ^e-g directly. It has also been shown that - depending on the plasticizers used - these leathers are also well suited for the injection of PVC or can be processed using classic methods, for example after dressing.

In itself, it is irrelevant whether a polyurethane reactive mixture based on polyether or polyester is injected onto the leather treated according to the invention. However, it has been shown that the highest adhesion values are achieved when the fatliquoring agent according to the invention and the reactive polyurethane mixture consist of the same product class (e.g. a combination of polyether greasing agents with reactive polyether polyurethane mixtures, but preferably polyester lubricating agents with reactive polyester-polyurethane mixtures, the polyesters being the polylactones or the Include polycarbonates).

Particularly high adhesions are obtained when using hydroxyl-polycarbonate greasing agents, in particular hydroxy-polyalkylene oxide polycarbonates as greasing agents. With these polycarbonates, the difference in adhesive strength that is achieved with the injection-molded polyurethane reactive compositions is almost independent of the reaction composition used. The fat-reducing agents a) to d) according to the invention are generally used in the field of leather production which is characterized by "wet finishing", i.e. in the area of retanning / greasing. Exemplary applications can be found in the description in the examples.

The results which can be achieved by the process according to the invention or the use according to the invention depend on the type of leather and on the type of tanning, as well as the type of fatliquor and the polyurethane reactive injection mixture.

Chrome-tanned leathers are e.g. washed, then neutralized (to pH 4.5 to 6.0) treated with 2 to 20% by weight of vegetable, mineral or organic synthetic retanning agents and, if appropriate, colored. Then 0.1 to 20 wt. The leather is processed in machines that are common in the shoe industry.

As described above, the uppers are made from the leather, a base (mostly made of textile) is sewn in, the uppers are pulled over a (metal) last and then the polyurethane materials (soles) are molded on in suitable machines.

The polyurethane reactive mixtures contain the usual starting components, for example higher molecular weight compounds with at least 2, preferably 2 to 4, end groups reactive towards NCO, such as OH, NH ₂ , NHR, COOH or -CONHNH _{2 end} groups, with a molecular weight of about 400 to 10,000, the usual aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates, as are known in the art, and optionally low molecular weight chain extenders with the above End groups and molecular weights of 18, 32 to 399, for example water, di-polyols or di- / polyamines or other known compounds. The polyhydroxyl compounds can also be more complex natural substances such as castor oil or modified linseed oil. The reactive mixtures can furthermore have the usual PU catalysts and other customary auxiliaries and additives, for example pigments, fillers, fibers, glass tube balls, blowing agents, stabilizers, dyes and the like. Instead of the polyisocyanates, NCO prepolymers or semiprepolymers can also be used. The NCO-ratios can be varied in a conventional width, such as from 60 to measure indicators 125, preferably ratios from 90 to 115. The injection process can by automatic metering and mixing of the reaction components, preferably rhythmically, successes ^g s. The density of the pole from the ^y urethanreaktivmassen forming Polvurethanelastomeren 800 may kq / m ³ (zelliae elastomers) to the homogeneous density of the polyurethane elastomer composition, respectively.

• a) Polvetherurethan-Reaktivmischung (PÄ) 100 Teile eines verzweigten Polyethylen-polypropylenglykolethers der OH-Zahl 120, mit 0,5 bis 3 % Katalysator werden mit 42 Teilen eines handelsüblichen, flüssigen, auf 4,4'-Diisocyanato-diphenylmethan-Basis beruhenden Isocyanat (ca. 23 % NCO) vermischt und bei einer Formtemperatur von 50 bis 55°C in die Sohlenform eingetragen. Nach ca. 3 bis 5 Minuten kann man entformen. Die Sohle haftet an allen Stellen, insbesondere in der Spitze und in der Gehzohne, gut.
• b) Polyesterurethan-Reaktivmischung (PES) 55 Teile eines teilverzweigten Diethylenglykolpolyadipats der OH-Zahl 60 werden mit 40 Teilen des aromatischen Isocyanates versetzt und wie oben in die Form eingetragen.

Suitable polyurethane reactive compositions for injectable soles consist, for example, of the following mixtures:

• a) Polyether urethane reactive mixture (PA) 100 parts of a branched polyethylene-polypropylene glycol ether with OH number 120, with 0.5 to 3% catalyst are based on 42 parts of a commercially available, liquid, 4,4'-diisocyanato-diphenylmethane-based Isocyanate (approx. 23% NCO) mixed and introduced into the sole mold at a mold temperature of 50 to 55 ° C. After about 3 to 5 minutes you can demold. The sole sticks well in all places, especially in the toe and the walking teeth.
• b) Polyester urethane reactive mixture (PES) 55 parts of a partially branched diethylene glycol polyadipate having an OH number of 60 are mixed with 40 parts of the aromatic isocyanate and introduced into the mold as above.

1. Invention fat to be used based on hydroxy polyether polyester or polycarbonate Example 1.1

6 k ^{g of} a commercial, linear polyether (molecular weight 2000) terminal on the basis of a polyoxypropylene / oxyethylene diol with 15 wt .-% of oxyethylene groups are dissolved in 4 k ^{g of} warm water.

Example 1.2

Oxyethylenendgruppen of 3.6 kg containing polyether of Example 1.1 and 0.4 k ^{g of} a commercial, linear Polyoxypropylenetherdiols molecular weight of 2000 are mixed together.

Example 1.3

500 g of a hydroxy polycarbonate based on hexanediol polycarbonate with a molecular weight of 1800 are dispersed in 600 g water using 10 g of an emulsifier based on 3-benzyl-4-hydroxy-biphenyl polyglycol ether. An emulsion is formed.

Example 1.4

500 ^{g of} a bifunctional polydiethylene glycol adipate, molecular weight 2000, are in 100 g of diacetone alcohol dissolved and converted into an emulsion with 10 g of an emulsifier based on stearamine + 8 moles of ethylene oxide and 500 ^{g of} water.

Example 1.5

500 g of a difunctional mixed ester of adipic acid, hexanediol / neopentyl glycol (in a ratio of 5: 7), molecular weight 1700, were transferred into the aqueous phase with 10 g of an emulsifier on stearylamine + 8 moles of ethylene oxide and 500 g of water.

Example 1.6

500 g of a linear polyether based on oxyethylene / oxypropylene mixed ether with a molecular weight of 4000 and 18% by weight of terminal oxyethylene groups are dispersed in 500 g of water using 10 g of the above-described emulsifier and 100 ^{g of} ethyl glycol.

Example 1.7

200 g of a polyester of adipic acid, hexanediol and neopentyl glycol of Example 1.5 are with the aid of 200 g of a polyether as described in Example 1.1 (e ^g molecular-weight 4000) was dispersed in 592 g of water.

Example 1.8

200 g of the polyester as in Example 1.5 and 200 g of the polyether as in Example 1.1 are emulsified with 8 g of 3-benzyl-4-hydroxy-diphenyl-polyglycol ether as an emulsifier in water to form an emulsion containing 25% solids.

Example 1.9

200 g of a Poylesters as in example 1.5 with 200 g of a trimethylolpropane-started Polyoxypropylenethers and 8 g mentioned in Example 1.8 emulsifier to a 22% i ^g s in water emulsion emulsified.

Example 1.10

A bifunctional triethylene glycol polycarbonate with a molecular weight of 2000 is stirred with a 50% emulsion with the addition of 2% emulator, as in Example 1.8.

2. Examples of use 2.1 Chrome upper leather with polymer retanning

A chrome-tanned leather is mixed with 200% water (45 ° C) and 0.2% 10% acetic acid and 2.5% of a highly lightfast exchange tanning agent (Tanigan-3LN®,

Bayer AG, Leverkusen) added and let run for 30 minutes. The liquor is drained off, washed and again 200% water (45 ° C.) and 1.5% of a neutralizing syntan (Tanigan PC®, Bayer AG, Leverkusen) and 0.5% sodium bicarbonate are added. A pH of 4.6 is established. After 45 minutes, the water is removed. Without a liquor, 3% of a 40%, partially neutralized polymethacrylic acid (1: 4 diluted with water) (Baytigan AR®, Bayer AG, Leverkusen) and 2% of a retanning agent diluted 1: 4 with water based on a 40% polyester carboxylic acid are now used (Levotan®-C, Bayer AG, Leverkusen) adds, after 30 minutes (pH = 4.7) 0.5% of a 1: 4 diluted with water, 60% cationic fatliquor based on synthetic fat substances (product Eucoriol®- KSP, Stockhausen, Krefeld) and after a further 20 minutes 2% of a lightfast dispersant based on sulfonic acid (Baykanol®-HLX, Bayer AG, Leverkusen). After 10 minutes, 9% of a light-fast substitute (Taniaan®-LD) is added, left to run for 45 minutes, deflottled and finally washed twice with 100% water at 50 ° C.

Comparable halves were treated on the one hand with a lubricant mixture known to be well effective according to the state of the art (Coripol-DX-902, Stockhausen, sperm oil replacement product Chromopol-UFB / W + chloroparaffin Coripol-ICA, Stockhausen, Krefeld - 8% refatting fat) , or (according to the invention) with 4% of the fat mixture from Example 1.1.

Both samples were injected with a commercially available polyether (PÄ> -PU reactive sole mixture or a polyester urethane reactive mixture (PES). The greased leather was bonded to the PU reactive mixture on one of the machines already described in the form of leather + Sole.

The results were:

Das Leder wurde ohne Aufrauhen direkt angespritzt. Die Trennkraft der PU-Sohlenmischung am Leder (in N/cm) wurde auf einer Reißmaschine analog DIN 53 328 ermittelt.

The leather was molded directly without roughening. The separating force of the PU sole mixture on the leather (in N / cm) was determined on a tearing machine in accordance with DIN 53 328.

Bold 2 (according to the invention)

on comparison leather with 12.5% of the product from Example 1.3.

Bold 3 (according to the invention)

on comparison leather with 12% of the product from example 1.4.

The leather can be dyed with leather dyes. A very full or full coloration of the leather is achieved with the leathers greased according to the invention (greasing 2 or 3), with good to very good levelness of the coloring. On the other hand, the color depth that can be achieved on the comparison leather with bold 1 is only slight (light) with only a moderate level.

Die Trennkräfte zwischen angespritzter Sohle und ^ge-fettetem Leder zeigen erfindungsgemäß deutlich höhere Werte, insbesondere wenn man sowohl zur Lederfettung wie auch zur Reaktiv-PU-Masse Produkte aus jeweils Ether bzw. jeweils Esterbasis verwendet.

The leather with grease 1, 2 and 3 was sprayed with reactive PU mixtures on a conventional automatic spray gun. The results of the gating tests were:

According to the invention, the separating forces between the molded-on sole and ^g e-greased leather show significantly higher values, in particular if products made from ether or ester base are used both for leather greasing and for the reactive PU composition.

Bold 2

10% product according to example 1.4.

Bold 3

10% product according to example 1.6.

Bold 4

10% product according to example 1.5.

Example 2.3

Examples 2.1 and 2.2 were repeated and the fat products according to the invention varied as follows: (as emulsions, used with the addition of an emulsifier). The results are summarized in the table.

Claims (10)

1. A process for fatliquoring treatment of leather, characterized in that the tanned leather with aqueous liquors of fatliquoring agents in the form of an aqueous solution, emulsion or dispersion, optionally containing solvents a) at least 2 hydroxyl-containing hydroxy polyethers with a molecular weight of 200 to 20,000 and / or b) hydroxypolyesters containing at least 2 hydroxyl groups with a molecular weight of 200 to 20,000 and / or c) hydroxypolycarbonates containing at least 2 hydroxyl groups and having a molecular weight of 200 to 20,000 or d) mixtures of components of categories a), b) or c)
contained instead of conventional fatliquoring agents or together with conventional fatliquoring agents, up to the absorption of 0.1 to 20% by weight of the fat-reducing agent products, based on the fold weight of the leather. 2. The method according to claim 1, characterized in that one carries out the greasing treatment with aqueous solutions, dispersions or emulsions of hydroxy polyethers, hydroxypolyesters and / or hydroxypolycarbonates with molecular weights of 400 to 10,000. 3. The method according to claims 1 and 2, characterized in that the fatliquoring treatment with aqueous solutions, dispersions or emulsions of hydroxy polyethers and / or hydroxypolyesters and / or polycarbonates with molecular weights of 800 to 3000 is carried out until the absorption of the fatliquor 0, 2 to 10 wt .-%, based on the fold weight of the leather. 4. The method according to claims 1 to 3, characterized ekenn- ^g is characterized in that are made with Hydroxypolyethern which are selected on the basis of hydroxy-functional starter components from the series comprising water, di- or polyols and with oxiranes, oxolanes andlor oxethanes, the Fettungsbehandlung carries out. 5. Process according to Claims 1 to 4, characterized in that hydrophilic hydroxypolyethers with at least 30% oxyethylene groups are used in addition to oxypropylene groups. 6. Process according to Claims 1 to 4, characterized in that hydrophilic hydroxypolyesters or hydroxypolycarbonates are used, in which di-, tri-, tetra- or polyethylene glycols serve as the structural component. 7. Use of the leather prepared by the method according to claims 1 to 6 for the direct injection of polyurethane reactive compositions to leather-polyurethane composites with increased separation resistance. 8. Use according to claim 7, characterized in that the leather pretreated according to claims 1 to 6 is used in conventional automatic spraying machines in the form of leather shafts with polyurethane reactive compositions with the formation of adhesive-free upper leather / PU sole compounds. 9. Use according to claims 7 and 8, characterized in that greasing agents based on hydroxypolyesters and / or hydroxypolycarbonates are used for treating the leather and the polyurethane reactive compositions based on polyester or polycarbonate are used for injection molding. 10. Use according to claims 7 and 8, characterized distinguished ^g ekenn-, that fatliquors used on the basis of Hydroxypolyethern for the treatment of the leathers and polyurethane reactive compositions based on polyethers used for the molding.