EP0204162B1 - Method of fat liquoring leather and its use in direct spraying polyurethane for leather/polyurethane bonding - Google Patents

Method of fat liquoring leather and its use in direct spraying polyurethane for leather/polyurethane bonding Download PDF

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Publication number
EP0204162B1
EP0204162B1 EP86106114A EP86106114A EP0204162B1 EP 0204162 B1 EP0204162 B1 EP 0204162B1 EP 86106114 A EP86106114 A EP 86106114A EP 86106114 A EP86106114 A EP 86106114A EP 0204162 B1 EP0204162 B1 EP 0204162B1
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Prior art keywords
leather
fat
liquoring
molecular weight
contain
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EP86106114A
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German (de)
French (fr)
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EP0204162A3 (en
EP0204162A2 (en
Inventor
Harro Dr. Träubel
Helmut Dr. Woynar
Hans-Werner Müller
Hans Jürgen Focks
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Bayer AG
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Bayer AG
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Priority to AT86106114T priority Critical patent/ATE51031T1/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • FR-A-1 573 918 describes a process for treating leather with aqueous emulsions of certain polyoxyalkylene glycols, e.g. Polyoxyethylene glycol, polyoxypropylene glycol, known.
  • 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 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 separating agent between leather and PUR material.
  • a high level of adhesion, as required in particular for sports shoes, cannot be achieved because the polyurethane cannot bond sufficiently to the greasing material that has diffused to the surface of the leather and therefore not to the leather itself under the heat generated during the injection process .
  • the Mannich bases based on nonylphenol, or their alkoxylation products (according to US Pat. No. 3,720,606), which can in principle be used in the same way, have a catalytic effect on other isocyanate reactions, for example on the NCO-OH reactions or the NCO trimerization, and improve the adhesion not either.
  • Polyglycol etheramines behave similarly in accordance with DE-OS 2 539 671).
  • leather which adheres well to polyurethanes and is suitable for the direct injection of PUR reactive compositions is obtained if the leather, optionally after customary retanning, together with or instead of the normal leather greasing agent with at least 2, preferably aliphatic or cycloaliphatic, bonded hydroxyl groups containing polyesters and polyethers, the molecular weights of which 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.
  • the compounds to be used according to the invention if they are not inherently water-soluble, can also be transferred into the aqueous phase by using a suitable emulsifier as a dispersion or emulsion or by using a water-miscible solvent as solubilizer.
  • 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 preparation 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.
  • Hydroxyl functional initiators such as water, diols, e.g. 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 result in at least bifunctional polyethers.
  • diols e.g. Ethylene glycol, 1,2-propanediol, 1,3-propaned
  • Polymerization products of ethylene oxide and propylene oxide based on starting components with two or three hydroxyl groups are preferred.
  • 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 produce fatliquoring agents which result in significantly improved coloring and color levelness with high dyeing fastness to rubbing.
  • amino-functional hydroxypolyethers often give rise to complexes with acid dyes, which are deposited on the leather surface (in the form of color salts) and give low-abrasion-resistant dyeings.
  • acidification of the dyed leather is difficult (poor bath consumption) and the fixing of the dyes on the leather surface is sometimes difficult.
  • polyether polyols that have started on longer-chain amines (e.g. with & 10 C atoms)
  • a lot of foam occurs during the coloring (due to the side effect), which ultimately results in uneven coloring.
  • the suitable hydroxypolyesters to be used according to the invention can be prepared in a manner known per se and are e.g. Reaction products of polyvalent, preferably dibasic carboxylic acids or their mixtures.
  • 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 can be aliphatic, cycloaliphatic, aromatic, araliphatic and / or heterocyclic in nature and optionally substituted, e.g. by halogen atoms such as chlorine or bromine and / or unsaturated.
  • carboxylic acids and their derivatives are: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, indomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized unsaturated fatty acid, such as a mixture of fatty acids, unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids and unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as
  • polyhydric alcohols optionally in a mixture with one another, for example Ethylene glycol, 1,2-and 1,3-propanediol, 1,4-butanediol and 2,3-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3 -propanediol, N, N-bis- (2-hydroxypropyl) -N-methylamine, glycerin, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4, trimethylolethane, pentaerythritol, quinite, mannitol, sorbitol, formitol , Methylglycoside, dianhydrohexite, ° furthermore in particular di-, tri-, tetra-ethylene glycols and higher polyethylene glycols, furthermore di-
  • 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. e-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 polycarbonates which can also be used can be prepared in a manner known per se and are e.g. Reaction products of polyhydric, preferably two and optionally three or tetravalent alcohols, with certain carbonic acid derivatives such as phosgene, phenyl chloroformate, ethyl chloroformate, but especially diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate or dimethyl pyrocarbonate.
  • polyhydric preferably two and optionally three or tetravalent alcohols
  • certain carbonic acid derivatives such as phosgene, phenyl chloroformate, ethyl chloroformate, but especially diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate or dimethyl pyrocarbonate.
  • 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 which can be used 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.
  • leather greasing is used to impart the final softness to the leather before and especially after dyeing.
  • 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 products to be used according to the invention do not show these disadvantages. Their use thus represents a significant improvement in the further processing of the leather treated with them.
  • the leather treated according to the invention can be dyed excellently with deep shades with high levelness.
  • the leathers are subjected to the usual post-treatment, e.g. dried, pounded and optionally prepared by known methods.
  • the polyurethane reactive compositions are now sprayed directly onto the leather which has been greased in accordance with the invention and has been prepared in this way. It has also been shown that - depending on the plasticizers used - these leathers are also well suited for the injection of PVC or using classic methods, e.g. after preparation, can be processed.
  • hydroxyl-polycarbonate greasing agents in particular hydroxy-polyalkylene oxide polycarbonates as greasing agents.
  • the fatliquoring agents a) to d) according to the invention are generally used in the field of leather production which is carried out with "wet finishing". is marked, ie in the area of retanning / greasing. Exemplary applications can be found in the description in the examples.
  • results that 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% by weight of the products according to the invention and, if appropriate, additional commercially available fatliquoring agents are used and finished as usual.
  • the leather is processed in machines that are common in the shoe industry.
  • 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 up to 10,000, the usual aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates as known in the prior art, and optionally low molecular weight chain extenders with the end groups mentioned and molecular weights from 18, 32 to 399, for example water, di-polyols or di- / 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.
  • NCO prepolymers or semi-prepolymers can also be used.
  • the NCO key figures can be varied in a customary range, for example from key figures 60 to key figure 125, preferably key figures 90 to 115.
  • the spraying process can be carried out by automatic metering and mixing of the reaction components, preferably in cycles.
  • the density of the polyurethane elastomers formed from the polyurethane reactive compositions can be 800 kg / m (cellular elastomers) up to the homogeneous density of the polyurethane elastomer composition.
  • 500 g of a hydroxy polycarbonate based on hexanediol polycarbonate of molecular weight 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.
  • 500 g of a bifunctional polydiethylene glycol adipate, molecular weight 2000, are dissolved in 100 g of diacetone alcohol and converted into an emulsion with 10 g of an emulsifier based on stearylamine + 8 moles of ethylene oxide and 500 g of water.
  • 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.
  • 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.
  • 200 g of a polyester as in Example 1.5 are emulsified with 200 g of a polyoxypropylene ether started on trimethylolpropane and 8 g of the emutifier mentioned in Example 1.8 to form a 22% emulsion in water.
  • 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) are added and let run for 30 minutes.
  • the liquor is drained, washed and again 200% water (45 ° C.) and 1.5% of a neutralizing syntan (Tanigan PC O , Bayer AG, Leverkusen) and 0.5% sodium bicarbonate are added.
  • a pH of 4.6 is established. After 45 minutes, the water is removed.
  • 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.
  • 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.
  • the leather was molded directly without roughening.
  • the separating force of the PU sole mixture on the leather was determined on a tearing machine in accordance with DIN 53 328.
  • 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.
  • the color depth that can be achieved on the comparison leather with bold 1 is only slight (light) with only a moderate level.
  • 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:
  • the separating forces between the molded-on sole and 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

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

Die Erfindung betrifft ein Verfahren zur Fettungsbehandlung von Leder, insbesondere zur Vorbereitung des Direktanspritzens von Polyurethan-Reaktivmassen unter Erhöhung der Trennkräfte zwischen Leder und Polyurethan innerhalb der Verbunde, insbesondere innerhalb Lederschaft-Polyurethan-Sohlen-Verbunden, dadurch gekennzeichnet, daß man die gegerbten Leder mit wäßrigen Flotten von Fettungsmittein, die in Form wäßriger, gegebenenfalls Lösungsmittel enthaltender Lösungen, Emulsionen oder Dispersionen

  • a) mindestens zwei Hydroxylgruppen aufweisenden Hydroxypolyestern mit einem Molekulargewicht von 200 bis 20.000, vorzugsweise 400-10.000, insbesondere 800 bis 3000, und/oder
  • b) mindestens zwei Hydroxylgruppen enthaltendenden Polycarbonaten mit einem Molekulargewicht von 200 bis 20.000, vorzugsweise 400-10.000, insbesondere 800 bis 3000, bzw.
  • c) Gemischen von Komponenten der Kategorien a) oder b) 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.
The invention relates to a process for the oil treatment of leather, in particular to prepare 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, characterized in that the tanned leather with aqueous liquors of fatliquor in the form of aqueous solutions, emulsions or dispersions which may contain solvents
  • a) at least two hydroxyl groups containing hydroxypolyesters with a molecular weight of 200 to 20,000, preferably 400-10,000, in particular 800 to 3000, and / or
  • b) at least two polycarbonates containing hydroxyl groups and having a molecular weight of 200 to 20,000, preferably 400-10,000, in particular 800 to 3000, or
  • c) mixtures of components of categories a) or b) instead of conventional release agents or together with conventional fatliquoring agents, up to the absorption of 0.1 to 20% by weight, preferably 0.2 to 10% by weight, of the fatliquor products, based on the fold weight of the leather.

Erfindungsgemäß ist weiterhin die Verwendung von mit Fettungsmitteln vorbereitetem Leder zum Direktanspritzen von Polyurethan-Reaktivmassen zu Leder-Polyurethanverbunden mit erhöhter Trennfestigkeit, insbesondere die Verwendung in Form von Schäften mit Polyurethan-Reaktivmassen in Anspritzautomaten unter Ausbildung von klebemittelfreien Schafleder-PU-Sohlenverbunden, dadurch gekennzeichnet, daß man die Fettungsbehandlung von gegerbtem Leder mit wäßrigen Flotten von Fettungsmitteln, die in Form einer wäßrigen, gegebenenfalls Lösungsmittel enthaltenden Lösung, Emulsion oder Dispersion

  • a) mindestens 2 Hydroxylgruppen enthaltende Hydroxypolyether mit einem Molekulargewicht von 200 bis 20.000 und/oder
  • b) mindestens 2 Hydroxylgruppen enthaltende Hydroxypolyester mit einem Molgewicht von 200 bis 20.000 und/oder
  • c) mindestens 2 Hydroxylgruppen enthaltende Hydroxypolycarbonate mit einem Molekulargewicht von 200 bis 20.000 bzw.
  • d) Gemische aus Komponenten der Kategorien a), b) oder c) anstelle von üblichen Fettungsmitteln oder aber zusammen mit üblichen Fettungsmitteln enthalten, bis zur Aufnahme von 0,1 bis 20 Gew.-% der Fettungsmittelprodukte, bezogen auf das Falzgewicht des Leders vornimmt.
According to the invention, the use of leather prepared with fatliquoring agents for the direct injection of polyurethane reactive compositions to give leather-polyurethane composites with increased separation resistance, in particular the use in the form of shafts with polyurethane reactive compositions in automatic sprayers with the formation of adhesive-free sheep leather-PU sole composites, characterized in that that the fatliquoring treatment of 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 hydroxypolyethers 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) contains mixtures of components of categories a), b) or c) instead of conventional fatliquoring agents or together with conventional fatliquoring agents, up to 0.1 to 20% by weight of the fatliquoring products, based on the shaved weight of the leather .

Es hat sich ferner gezeigt, daß die verfahrensgemäß mit den Fettungsmitteln nachbehandelten Leder einer ausgezeichnete, sehr farbtiefe und sehr gleichmäßige Färbung ergeben.It has also been found that the leather aftertreated in accordance with the process with the fatliquoring agents gives an excellent, very deep and very uniform color.

Aus der FR-A-1 573 918 ist ein Verfahren zur Lederbehandlung mit wäßrigen Emulsionen bestimmter Polyoxyalkylenglykole, z.B. Polyoxyethylenglykol, Polyoxypropylenglykol, bekannt.FR-A-1 573 918 describes a process for treating leather with aqueous emulsions of certain polyoxyalkylene glycols, e.g. Polyoxyethylene glycol, polyoxypropylene glycol, known.

Die Verarbeitung von Ledern zu Schuhen mit direkt angespritzter PUR- oder PVC-Sohle, d.h. ohne zusätzliche Klebeverbindung zwischen Sohlen- und (Schaft)Ledermaterial, hat in den letzten Jahren, insbesondere auf den Sportschuhsektor, zunehmend an Bedeutung gewonnen. Dabei zieht man z.B. auf geeigneten Automaten einen Schuhschaft über einen (metallenen) Leisten, fährt die Schäfte in eine relativ dicht schließende Form ein und spritzt die Sohle - ohne zusätzliches Verkleben - mit einer Polyurethan-Reaktivmischung oder gegebenenfalls einer PVC-Mischung direkt an. Damit spart man einen sonst nötigen Verklebungsvorgang zwischen Schaft und Sohle.The processing of leather into shoes with directly molded PU or PVC sole, i.e. Without additional adhesive connection between sole and (shaft) leather material, has become increasingly important in recent years, especially in the sports shoe sector. You pull e.g. on a suitable machine a shoe upper over a (metal) last, the upper moves into a relatively tight-fitting shape and the sole is injected - 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.

Dieses Verfahren ist in wirtschaftlicher Weise dann durchführbar, wenn die verwendeten Leder mit Produkten zugerichtet werden, die unter den Verarbeitungsbedingungen mit Polyurethanen eine gute Haftung eingehen, wie dies z.B. mit PU-beschichteten Spaltledern der Fall ist. Probleme bereitet dieses Direktanspritzen jedoch dann, wenn die Leder naturell verarbeitet werden sollen, weil die für die übliche Fettung der Leder notwendigen Produkte meist nur oberflächlich aufziehen und somit wie ein Trennmittel zwischen Leder und PUR-Material wirken. Hohe Haftung, wie sie insbesondere für Sportschuhe gefordert werden müssen, ist nicht zu erzielen, weil sich das Polyurethan unter der beim Anspritzvorgang entstehenden Hitzeeinwirkung nicht an das an die Oberfläche des Leders diffundierte Fettungsmaterials und damit auch nicht an das Leder selbst hinreichend fest zu binden vermag.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. However, this direct injection creates problems 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 separating agent between leather and PUR material. A high level of adhesion, as required in particular for sports shoes, cannot be achieved because the polyurethane cannot bond sufficiently to the greasing material that has diffused to the surface of the leather and therefore not to the leather itself under the heat generated during the injection process .

Eine Möglichkeit zur Umgehung dieses Effektes besteht darin, daß man nach der Fettung das Leder mit polykationaktiven Substanzen behandelt, um das Fettungsmittel an das Leder zu fixieren. Diese Methode führt jedoch nicht zum gewünschten Erfolg, weil sich die polykationaktiven Substanzen anschleinend ebenfalls - zusammen mit den Fettungsmitteln - pigmentartig oberflächlich niederschlagen und die Haftung der später aufgebrachten PUR-Sohle vermindern.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 on the surface - together with the fatliquoring agents - in pigment-like form and reduce the adhesion of the PUR sole applied later.

Weitere Möglichkeiten zur Verbesserung einer Haftung zwischen Leder und PUR-Material wurden im Einsatz von Fettungsmitteln, die sowohl eine Affinität zu Leder aufweisen, als auch mit den Isocyanat-Gruppierungen des PUR-Materials reagieren können, gesucht. Fettsäurederivate, wie sie z.B. in SU-PS 840 220 beschrieben werden, weisen diese Fähigkeiten zwar theoretisch auf, wirken jedoch wegen ihrer C10 bis C16-Fettsäurereste ebenfalls wie ein Trennmittel.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 which can 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.

Die prinzipiell in gleicher Weise einsetzbaren, auf Nonylphenol basierenden Mannich-Basen, bzw. deren Alkoxylierungsprodukte (nach US-PS 3720606) wirken katalytisch auf andere Isocyanat-Reaktionen, z.B. auf die NCO-OH-Reaktionen oder die NCO-Trimerisierung und verbessern die Haftung ebenfalls nicht. Ähnlich verhalten sich Polyglykoletheramine entsprechend DE-OS 2 539 671).The Mannich bases based on nonylphenol, or their alkoxylation products (according to US Pat. No. 3,720,606), which can in principle be used in the same way, have a catalytic effect on other isocyanate reactions, for example on the NCO-OH reactions or the NCO trimerization, and improve the adhesion not either. Polyglycol etheramines behave similarly in accordance with DE-OS 2 539 671).

Die einzigen erfolgreichen Verfahren, beliebige Oberleder für die Sohlen-Direktanspritzung herzustellen, bestehen bisher darin, entweder die Leder vor dem Anspritzvorgang mechanisch durch Schleifen aufzurauhen oder die Leder vor dem Anspritzen der PUR-Sohle oder PVC-Sohle mit einem Haftungsvermittler zu versehen, der die Haftung zwischen Leder und PUR-Material verstärkt. Beide Verfahren stellen zusätzliche und darüber hinaus aufwendige Arbeitsvorgänge dar.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.

Beispielsweise ist es sehr schwierig, beim mechanischen Aufrauhen des Leders den Schleifvorgang exakt auf die spätere Kontaktfläche zur PUR-Sohle zu begrenzen. Wird über die Grenze hinaus geschliffen, entstehen unschöne, rauhe Stellen auf dem Oberleder. Bleibt man dagegen unter dieser Grenze, ist an den nicht aufgerauhten Stellen die Haftung zwischen Sohle und Schaft stark herabgesetzt.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 in the areas that are not roughened.

Das gleiche Problem, nämlich das überaus exakte Einhalten vorgegebener Maße ist bei der zweiten Möglichkeit zur Nachbehandlung des Oberleders vor dem Anspritzvorgang, nämlich dem Aufbringen eines geeigneten Primers oder Haftvermittlers, gegeben, wenn unschöne Streifen auf dem Obermaterial einerseits bzw. verringerte Haftung der Sohle andererseits vermieden werden sollen. Solche Primer sind z.B. aromatische Oligourethane, die im allgemeinen stark zur Vergilbung neigen.The same problem, namely the extremely exact adherence to specified dimensions, is given in the second possibility for 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.

Leider sind bisher alle Versuche erfolglos geblieben, die verwendeten Oberleder selbst so herzustellen, daß ein PUR-Sohlenmaterial ohne die oben erwähnten, arbeitsaufwendigen Schritte des Anrauhens oder des Vorbehandelns mit einem Primer an diesem Leder zuverlässig haftet.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.

Überraschenderweise wurde nun gefunden, daß man gut an Polyurethanen haftende, für die Direktanspritzung von PUR-Reaktivmassen geeignete Leder erhält, wenn man das Leder, gegebenenfalls nach üblicher Nachgerbung, zusammen mit oder anstelle der normalen Lederfettungsmittel mit mindestens 2, vorzugsweise aliphatische oder cycloaliphatische gebundene Hydroxylgruppen enthaltenden Polyestern und Polyethern, deren Molekulargewichte zwischen 200 und 20.000, vorzugsweise 400 bis 10.000, betragen, und die als solche oder gegebenenfalls unter Einsatz von Emulgatoren und/oder wassermischbaren Lösungsvermittlern in die wäßrige Phase transferierbar sind, behandelt. Es wurde ferner gefunden, daß derartig behandelte Leder überraschenderweise eine ausgezeichnete Farbtiefe und Egalität aufweisen, wenn sie mit üblichen Lederfarbstoffen gefärbt werden. Farbtiefe und Egalität ist viel günstiger als bei der Behandlung von Ledern mit üblichen Fettungsmitteln.Surprisingly, it has now been found that leather which adheres well to polyurethanes and is suitable for the direct injection of PUR reactive compositions is obtained if the leather, optionally after customary retanning, together with or instead of the normal leather greasing agent with at least 2, preferably aliphatic or cycloaliphatic, bonded hydroxyl groups containing polyesters and polyethers, the molecular weights of which 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.

Die erfindungsgemäß zu verwendenden Verbindungen können, sofern sie nicht von sich aus wasserlöslich sind, auch durch Verwendung eines geeigneten Emulgators als Dispersion oder Emulsion oder durch Verwendung eines mit Wasser mischbaren Lösungsmittels als Lösungsvermittler in die wäßrige Phase transferiert werden.The compounds to be used according to the invention, if they are not inherently water-soluble, can also be transferred into the aqueous phase by using a suitable emulsifier as a dispersion or emulsion or by using a water-miscible solvent as solubilizer.

Zur Herstellung der Hydroxypolyether eignen sich Oxirane wie Ethylenoxid, 1,2-Propylenoxid, 2,3-Butylenoxid, 1,2-Butylenoxid, Epichlorhydrin oder Styroloxid, ferner Oxetane wie 1,3-Propylenoxid, sowie Oxolane wie Tetrahydrofuran. Diese werden im allgemeinen mit zwei- oder mehrwertigen, hydroxyl- und/ oder aminofunktionellen Startkomponenten zu den Polyethern a) nach an sich wohlbekannten Verfahren umgesetzt. Die Polyether sollen mehr als 3 Oxyalkylengruppen enthalten.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 preparation 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.

Als hydroxylfunktionelle (bevorzugte) oder aminofunktionelle (weniger bevorzugte) Startkomponenten können eingesetzt werden:The following can be used as hydroxyl-functional (preferred) or amino-functional (less preferred) starting components:

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 Polymerisationsprodukte 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 überraschend, daß Polyether auf Basis von hydroxyfunktionellen Startern Fettungsmittel ergeben, die eine wesentlich verbesserte Färbung und Farbegalität bei hoher Abriebechtheit der Färbungen ergeben.Hydroxyl functional initiators such as water, diols, e.g. 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 result in at least bifunctional polyethers. Polymerization products of ethylene oxide and propylene oxide based on starting components with two or three hydroxyl groups are preferred. 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 produce fatliquoring agents which result in significantly improved coloring and color levelness with high dyeing fastness to rubbing.

Aminofunktionell gestartete Hydroxypolyether ergeben dagegen oftmals mit Säurefarbstoffen Komplexe, die sich auf der Lederoberfläche (in Form von Farbsalzen) niederschlagen und gering abriebbeständige Färbungen ergeben. Außerdem fällt das Absäuern der gefärbten Leder schwer (schlechte Badauszehrung) und die Fixierung der Farbstoffe auf der Lederoberfläche ist bisweilen schwierig. Bei Polyetherpolyolen, die auf längerkettigen Aminen (mit z.B. &10 C-Atomen) gestartet sind, tritt bei der Färbung (infolge der Seitenwirkung) viel Schaum auf, was letztlich unegale Färbungen ergibt.In contrast, amino-functional hydroxypolyethers often give rise to complexes with acid dyes, which are deposited on the leather surface (in the form of color salts) and give low-abrasion-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. With polyether polyols that have started on longer-chain amines (e.g. with & 10 C atoms), a lot of foam occurs during the coloring (due to the side effect), which ultimately results in uneven coloring.

Die in Frage kommenden, erfindungsgemäß anzuwendenden, Hydroxypolyester können in an sich bekannter Weise hergestellt werden und sind z.B. Umsetzungsprodukte von mehrwertigen, vorzugsweise zweiwertigen Carbonsäuren oder ihren Gemischen. Anstelle der freien Polycarbonsäuren können auch die entsprechenden Polycarbonsäureanhydride oder entsprechende Polycarbonsäureester niedriger, einwertiger Alkohole oder deren Gemische zur Herstellung der Polyester verwendet werden. Die Polycarbonsäuren können aliphatischer, cycloaliphatischer, aromatischer, araliphatischer und/oder heterocyclischer Natur sein und gegebenenfalls substituiert, z.B. durch Halogenatome wie Chlor oder Brom und/oder ungesättigt sein.The suitable hydroxypolyesters to be used according to the invention can be prepared in a manner known per se and are e.g. Reaction products of polyvalent, 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 can be aliphatic, cycloaliphatic, aromatic, araliphatic and / or heterocyclic in nature and optionally substituted, e.g. by halogen atoms such as chlorine or bromine and / or unsaturated.

Als Beispiele für solche Carbonsäuren und deren Derivate werden genannt: Bernsteinsäsure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure, Phthalsäure, Isophthalsäure, Trimellitsäure, Phthalsäureanhydrid, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäureanhydrid, Tetrachlorphthalsäureanhydrid, Indomethylentetrahydrophthalsäureanhydrid, Glutarsäureanhydrid, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, dimerisiert und trimerisierte ungesättigte Fettsäure, gegebenenfalls in Mischung mit monomeren ungesättigten Fettsäuren, wie Ölsäure, Terephthalsäuredimethylester und Terephthalsäure-bis-glykolester.Examples of such carboxylic acids and their derivatives are: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, indomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized unsaturated fatty acid, such as a mixture of fatty acids, unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of fatty acids and unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of acids

Als mehrwertige Alkohole kommen, gegebenenfalls im Gemisch miteinander z.B. Ethylenglykol, Propandiol-1,2 und -1,3,Butandiol-1,4 und -2,3 Hexandiol-1,6, Octandiol-1,8, Neopentylglykol, 1,4-Bishydroxymethylcyclohexan, 2-Methyl-1,3-propandiol, N,N-Bis-(2-hydroxypropyl)-N-methylamin, Glycerin, Trimethylolpropan, Hexantriol-1,2,6, Butantriol-1,2,4, Trimethylolethan, Pentaerythrit, Chinit, Mannit, Sorbit, Formit, Methylglykosid, Dianhydrohexite,°ferner insbesondere Di-, Tri-, Tetra-ethylenglykole und höhere Polyethylenglykole, ferner Di-, Tri- und höhere Polypropylenglykole sowie Di-butylenglykol und höhere Polybutylenglykole in Frage.As polyhydric alcohols, optionally in a mixture with one another, for example Ethylene glycol, 1,2-and 1,3-propanediol, 1,4-butanediol and 2,3-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3 -propanediol, N, N-bis- (2-hydroxypropyl) -N-methylamine, glycerin, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4, 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 and also di-butylene glycol and higher polybutylene glycols.

Die niedermolekularen Polyole können auch in beliebigen Mischungen durch Veresterung gesetzt werden. Die zu verwendenden Polyester können anteilig auch Carboxylgruppen als Endgruppen aufweisen.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.

Ebenfalls verwendbar sind Polyester aus Lactonen, z.B. Caprolacton bzw. Hydroxycarbonsäuren, z.B. e-Hydroxycapronsäure, wobei diese Verbindungen entweder alleine oder im Gemisch mit Polyhydroxylverbindungen zur Herstellung der Polyester eingesetzt werden. Bevorzugte Polyester sind hydrophile Polyester oder auch hydrophile Polycarbonate, die unter Verwendung von Di-, Tri-, Tetra- oder Polyethylenglykolen hergestellt wurden.Lactone polyesters, e.g. Caprolactone or hydroxycarboxylic acids, e.g. e-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.

Die ebenfalls anwendbaren Polycarbonate können in an sich bekannter Weise hergestellt werden und sind z.B. Umsetzungsprodukte von mehrwertigen, vorzugsweise zwei und gegebenenfalls drei oder vierwertigen Alkoholen, mit bestimmten Kohlensäurederivaten wie Phosgen, Chlorameisensäurephenylester, Chlorameisensäureethylester, insbesondere aber Diphenylcarbonat, Diethylcarbonat, Ethylencarbonat, Propylencarbonat oder Pyrokohlensäuredimethylester.The polycarbonates which can also be used can be prepared in a manner known per se and are e.g. Reaction products of polyhydric, preferably two and optionally three or tetravalent alcohols, with certain carbonic acid derivatives such as phosgene, phenyl chloroformate, ethyl chloroformate, but especially diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate or dimethyl pyrocarbonate.

Es können auch Mischester aus Polylactonen und Estern oder Polycarbonaten oder Mischungen von Polyestern, Polylactonen und/oder Polycarbonaten eingesetzt werden. Die erfindungsgemäßen Polyether, Polyester oder Polycarbonate können, sofern sie nicht von sich aus in Wasser löslich, emulgierbar oder dispergierbar sind, durch Zugabe von üblichen Emulgatoren in die wäßrige Phase transferiert werden. Die Emulgierbarkeit von Polyestern, Polylactonen, Polycarbonaten oder Polyethern wird auch durch Einbau von geringen Mengen an ionisierbaren Gruppen (kationische oder anionischer Art bzw. von tertiären Aminen, die Salze bilden können) vereinfacht.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).

Als externe Emulgatoren kommen in Frage: langkettige Alkylsulfate bzw. Alkylsulfonate, Ethoxylierungsprodukte von Alkylphenolen, z.B. para-Nonylphenol oder von aromatisch substituierten Phenolen wie Phenylphenol bzw. von Alkylierungs- oder Benzylierungsprodukten von Phenylphenol; langkettige Alkylcarbonsäuren oder quaternierte langkettige Alkylammoniumsalze.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.

Die erfindungsgemäßen einsetzbaren Produkte werden zusammen mit oder anstelle der normalen Lederfettungsmittel eingesetzt. Die Menge der an sich bekannten, normalen Lederfettungsmittel ist dabei im allgemeinen auf Mengen von weniger als 80 Gew.-% eingeschränkt.The products which can be used 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.

Die Lederfettung dient bekanntlich dazu, vor und vor allem nach der Färbung den Ledern die endgültige Weichheit zu vermitteln. Häufig ziehen die Fettungsmittel so oberflächlich auf, daß spätere Arbeitsgänge wie das Zurichten oder insbesondere auch das direkte Anspritzen von Polyurethansohlen durch die in diesem Fall als Trennmittel wirkenden Fettungsmittel stark behindert werden. Die erfindungsgemäß zu verwendenden Produkte zeigen diese Nachteile nicht. Ihre Anwendung stellt somit eine deutliche Verbesserung bei der Weiterverarbeitung der mit ihnen behandelten Leder dar. Außerdem lassen sich die so erfindungsgemäß behandelten Leder ausgezeichnet mit tiefen Farbtönen mit hoher Egalität färben. Nach der Fettungsbehandlung werden die Leder der üblichen Nachbehandlung unterzogen, z.B. getrocknet, gestollt und gegebenenfalls nach bekannten Methoden zugerichtet.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 products to be used according to the invention do not show 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 greasing treatment, the leathers are subjected to the usual post-treatment, e.g. dried, pounded and optionally prepared by known methods.

Auf die so vorbereiteten, erfindungsgemäß gefetteten Leder werden nun die Polyurethan-Reaktivmassen direkt angespritzt. Es hat sich auch gezeigt, daß - allerdings abhängig von den verwendeten Weichmachern - diese Leder auch gut für das Anspritzen von PVC geeignet sind oder nach klassischen Methoden, z.B. nach der Zurichtung, verarbeitet werden können.The polyurethane reactive compositions are now sprayed directly onto the leather which has been greased in accordance with the invention and has been prepared in this way. It has also been shown that - depending on the plasticizers used - these leathers are also well suited for the injection of PVC or using classic methods, e.g. after preparation, can be processed.

An sich ist es belanglos, ob auf die mit den erfindungsgemäß behandelten Leder ein Polyurethanreaktivgemisch auf Polyether- oder Polyesterbasis angespritzt wird. Es hat sich aber gezeigt, daß höchste Haftungswerte dann erreicht werden, wenn das erfindungsgemäße Fettungsmittel und das Polyurethanreaktivgemisch aus der gleichen Produktklasse besteht (z.B. eine Kombination von Polyetherfettungsmitteln mit Polyetherpolyurethanreaktivmischungen, vorzugsweise aber Polyesterfettungsmittel mit Polyester-Polyurethanreaktivmischungen, wobei die Polyester die Polylactone bzw. die Polycarbonate mit einschließen).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).

Besonders hohe Haftungen erhält man bei Verwendung von Hydroxyl-Polycarbonat-Fettungsmitteln, insbesondere Hydroxy-Polyalkylenoxid- Polycarbonaten als Fettungsmittel. Bei diesen Polycarbonaten ist der Unterschied der Haftfestigkeit, die mit den angespritzten Polyurethanreaktivmassen erzielt werden nahezu unabhängig von der angewandten Reaktionsmasse. Die erfindungsgemäßen Fettungsmittel a) bis d) werden im allgemeinen in dem Bereich der Lederherstellung eingesetzt, der mit "Naßzurichtung" gekennzeichnet wird, d.h. im Bereich der Nachgerbung/Fettung. Beispielhafte Anwendungen können der Beschreibung in den Beispielen entnommen werden.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 fatliquoring agents a) to d) according to the invention are generally used in the field of leather production which is carried out with "wet finishing". is marked, ie in the area of retanning / greasing. Exemplary applications can be found in the description in the examples.

Die nach dem erfindungsgemäßen Verfahren bzw. der erfindungsgemäßen Verwendung erzielbaren Resultate hängen von der Art des Leders und von der Art der Gerbung, sowie der Art des Fettungsmittels und der Polyurethanreaktiv-Anspritzmischung ab.The results that 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.

Chromgegerbte Leder werden z.B. gewaschen, dann neutralisiert (auf pH 4,5 bis 6,0) mit 2 bis 20 Gew.- % vegetabilischen, mineralischen oder organisch-synthetischen Nachgerbstoffen behandelt sowie gegebenenfalls gefärbt. Dann werden 0,1 bis 20 Gew.-% der erfindungsgemäßen Produkte und gegebenenfalls zusätzlich handelsübliche Fettungsmittel eingesetzt und wie üblich fertiggestellt. Die Verarbeitung der Leder erfolgt in Automaten, wie sie in der Schuhindustrie üblich sind.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% by weight of the products according to the invention and, if appropriate, additional commercially available fatliquoring agents are used and finished as usual. The leather is processed in machines that are common in the shoe industry.

Wie oben beschrieben, werden aus den Ledern die Schäfte hergestellt, ein Boden (zumeist aus Textil) eingenäht, die Schäfte über einen (metallenen) Leisten gezogen und dann in geeigneten Automaten die Polyurethanmassen (Sohlen) angespritzt.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.

Die Polyurethan-Reaktivmischungen enthalten die üblichen Ausgangskomponenten, z.B. höhermolekulare Verbindungen mit mindestens 2, vorzugsweise 2 bis 4, gegenüber NCO reaktiven Endgruppen wie OH-, NH2-, NHR-, COOH oder-CONHNH2-Endgruppen, bei einem Molekulargewicht von etwa 400 bis 10.000, die üblichen aliphatischen, cycloaliphatischen, aromatischen oder heterocyclischen Polyisocyanate, wie sie im Stand der Technik bekannt sind, und gegebenenfalls niedermolekulare Kettenverlängerungsmittel mit den genannten Endgruppen und Molekulargewichten von 18, 32 bis 399, z.B. Wasser, Di-Polyole oder Di-/Polyamine oder andere bekannte Verbindungen. Die Polyhydroxylverbindungen können auch kompliziertere natürliche Stoffe wie Rizinusöl oder modifiziertes Leinöl sein. Die Reaktivmischungen können darüber hinaus die üblichen PU-Katalysatoren, sowie sonstige, übliche Hilfs- und Zusatzstoffe aufweisen, z.B. Pigmente, Füllmittel, Fasern, Glasrohrkugeln, Treibmittel, Stabilisatoren, Farbstoffe und ähnliches. Es können anstelle der Polyisocyanate auch NCO-Prepolymere oder Semiprepolymere eingesetzt werden. Die NCO-Kennzahlen können in üblicher Breite variiert werden, z.B. von Kennzahlen 60 bis Kennzahl 125, vorzugsweise Kennzahlen 90 bis 115. Der Spritzprozeß kann durch automatische Dosierung und Vermischung der Reaktionskomponenten, vorzugsweise taktmäßig, erfolgen. Die Dichte der sich aus den Polyurethanreaktivmassen bildenden Polyurethanelastomeren kann 800 kg/m (zellige Elastomere) bis zur homogenen Dichte der Polyurethanelastomermasse betragen.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 up to 10,000, the usual aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates as known in the prior art, and optionally low molecular weight chain extenders with the end groups mentioned and molecular weights from 18, 32 to 399, for example water, di-polyols or di- / 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 semi-prepolymers can also be used. The NCO key figures can be varied in a customary range, for example from key figures 60 to key figure 125, preferably key figures 90 to 115. The spraying process can be carried out by automatic metering and mixing of the reaction components, preferably in cycles. The density of the polyurethane elastomers formed from the polyurethane reactive compositions can be 800 kg / m (cellular elastomers) up to the homogeneous density of the polyurethane elastomer composition.

Geeignete Polyurethan-Reaktivmassen für anspritzbare Sohlen bestehen z.B. aus folgenden Mischungen:

  • a) Polyetherurethan-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. Erfindungsgemäß zu verwendende Fettungsmittel auf Hydroxy-polyether-polyester oder -polycarbonatbasis1. Hydroxy-polyether-polyester or polycarbonate-based fatliquor to be used according to the invention Beispiel 1.1Example 1.1

6 kg eines handelsüblichen, linearen Polyethers (Molekulargewicht 2000) auf Basis eines Polyoxypropylen/Oxyethylen-diols mit 15 Gew.-% endständigen Oxyethylengruppen werden in 4kg warmen Wasser gelöst.6 kg of a commercially available, linear polyether (molecular weight 2000) based on a polyoxypropylene / oxyethylene diol with 15% by weight of terminal oxyethylene groups are dissolved in 4 kg of warm water.

Beispiel 1.2Example 1.2

3,6 Kg des Oxyethylenendgruppen enthaltenden Polyethers von Beispiel 1.1 und 0,4 kg eines handelsüblichen, linearen Polyoxypropylenetherdiols vom Molekulargewicht 2000 werden miteinander vermischt.3.6 kg of the oxyethylene end group-containing polyether from Example 1.1 and 0.4 kg of a commercially available, linear polyoxypropylene ether diol of molecular weight 2000 are mixed together.

Beispiel 1.3Example 1.3

500 g eines Hydroxy-polycarbonats auf Basis von Hexandiol-Polycarbonatvom Molekulargewicht 1800 werden mit Hilfe von 10 g eines Emulgators auf Basis 3-Benzyl-4-hydroxy-biphenyl-polyglykolether in 600 g Wasser dispergiert. Es bildet sich eine Emulsion.500 g of a hydroxy polycarbonate based on hexanediol polycarbonate of molecular weight 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.

Beispiel 1.4Example 1.4

500 g eines bifunktionellen Polydiethylenglykol-adipats, Molekulargewicht 2000, werden in 100 g Diacetonalkohol gelöst und mit 10 g eines Emulgators auf der Basis von Stearylamin + 8 Mol Ethylenoxid und 500 g Wasser in eine Emulsion überführt.500 g of a bifunctional polydiethylene glycol adipate, molecular weight 2000, are dissolved in 100 g of diacetone alcohol and converted into an emulsion with 10 g of an emulsifier based on stearylamine + 8 moles of ethylene oxide and 500 g of water.

Beispiel 1.5Example 1.5

500 g eines difunktionellen Mischesters aus Adipinsäure, Hexandiol/Neopentylglykol (im Verhältnis 5:7), Molekulargewicht 1700, wurden mit 10 g eines Emulgators auf Stearylamin + 8 Mol Ethylenoxid und 500 g Wasser in die wäßrige Phase überführt.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.

Beispiel 1.6Example 1.6

500 g eines linearen Polyethers auf Basis Oxyethylen/Oxypropylen-Mischethers des Molekulargewichts 4000 und 18 Gew.-% endständigen Oxyethylengruppen werden mit Hilfe von 10 g des vorbeschriebenen Emulgators sowie 100 g Ethylglykol in 500 g Wasser dispergiert.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.

Beispiel 1.7Example 1.7

200 g eines Polyesters aus Adipinsäure, Hexandiol und Neopentylglykol von Beispiel 1.5 werden mit Hilfe von 200 g eines Polyethers wie in Beispiel 1.1 (Molekulargewicht 4000) in 592 g Wasser dispergiert.200 g of a polyester of adipic acid, hexanediol and neopentyl glycol from Example 1.5 are dispersed in 592 g of water using 200 g of a polyether as in Example 1.1 (molecular weight 4000).

Beispiel 1.8Example 1.8

200 g des Polyesters wie in Beispiel 1.5 und 200 g des Polyethers wie in Beispiel 1.1 werden mit 8 g 3-Benzyl-4-hydroxy-diphenyl-polyglykolether als Emulgator in Wasser zu einer 25%igen Feststoff enthaltenden Emulsion emulgiert.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.

Beispiel 1.9Example 1.9

200 g eines Polyesters wie in Beispiel 1.5 werden mit 200 g eines auf Trimethylolpropan gestarteten Polyoxypropylenethers und 8 g des in Beispiel 1.8 genannten Emutgators.zu einer 22%igen Emulsion in Wasser emulgiert.200 g of a polyester as in Example 1.5 are emulsified with 200 g of a polyoxypropylene ether started on trimethylolpropane and 8 g of the emutifier mentioned in Example 1.8 to form a 22% emulsion in water.

Beispiel 1.10Example 1.10

Ein bifunktionelles Triethylenglykol-polycarbonat vom Molekulargewicht 2000 wird unter Zusatz von 2% Emulgator, wie in Beispiel 1.8, mit einer 50%igen Emulsion verrührt.

  • 2. Anwendungsbeispiele
  • 2.1 Chrom-Oberleder mit Polymerisat-Nachgerbung
A bifunctional triethylene glycol polycarbonate with a molecular weight of 2000 is stirred with a 50% emulsion with the addition of 2% emulsifier, as in Example 1.8.
  • 2. Examples of use
  • 2.1 Chrome upper leather with polymer retanning

Ein chromgegerbtes Leder wird mit 200% Wasser (45°C) versetzt und 0,2% 10%ige Essigsäure und 2,5% eines hochlichtechten Austauschgerbstoffes (Tanigan-3LN@, Bayer AG, Leverkusen) zugefügt und 30 Minuten laufen lassen. Man läßt die Flotte ab, wäscht und gibt erneut 200% Wasser (45°C) sowie 1,5% eines neutralisierenden Syntans (Tanigan PCO, Bayer AG, Leverkusen) sowie 0,5% Natriumbicarbonat zu. Es stellt sich ein pH von 4,6 ein. Nach 45 Minuten wird entflottet. Ohne Flotte setzt man jetzt 3% einer (1:4 mit Wasser verdünnten) 40%igen, teilneutralisierten Polymethacrylsäure (Baytigan AR@, Bayer AG, Leverkusen) und 2% eines 1:4 mit Wasser verdünnten Nachgerbstoffs auf Basis einer 40%igen Polyestercarbonsäure (LevotanO-C, Bayer AG, Leverkusen) zu, fügt nach 30 Minuten (pH = 4,7) 0,5% eines 1:4 mit Wasser verdünnten, 60%igen kationischen Fettungsmittels auf Basis synthetischer Fettstoffe (Produkt EucoriolO-KSP, Firma Stockhausen, Krefeld) zu, und nach weiteren 20 Minuten 2% eines lichtechten Dispergators auf Sulfosäurebasis (Baykanol®―HLX, Bayer AG, Leverkusen) zu. Nach 10 Minuten werden 9% eines lichtechten Austauschgerbstoffes (TaniganO-LD) zugegeben, 45 Minuten laufen lassen, entflottet und schließlich zweimal mit je 100% Wasser von 50°C gewaschen.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) are added and let run for 30 minutes. The liquor is drained, washed and again 200% water (45 ° C.) and 1.5% of a neutralizing syntan (Tanigan PC O , 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 O- 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 O- 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 replacement tanning agent (Tanigan O- LD) is added, left to run for 45 minutes, deflottled and finally washed twice with 100% water at 50 ° C.

Vergleichbare Hälften wurden einerseits mit einer als gut wirksam nach Stand der Technik bekannten Fettungsmittelmischung behandelt (Coripol-DX-902, Fa. Stockhausen, Spermöl-Austauschprodukt Chromopol-UFB/W + Chlorparaffin Coripol-ICA, Firma Stockhausen, Krefeld - 8% Rückfett), bzw. (erfindungsgemäß) mit 4% der Fettungsmischung aus Beispiel 1.1.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.

Beide Proben wurden jeweils mit einer handelsüblichen Polyether (PÄ)-PU-Reaktiv-Sohlenmischung bzw. einer Polyesterurethan-Reaktivmischung (PES) angespritzt. Die Verbindung der gefetteten Leder mit den PU-Reaktivmischungen erfolgte auf einem der bereits geschilderten Automaten in Form von Schaftleder + Sohle.Both samples were injected with a commercially available polyether (PA) -PU reactive sole mixture or a polyester urethane reactive mixture (PES). The greased leather was combined with the PU reactive mixtures on one of the machines already described in the form of leather and sole.

Die Ergebnisse waren:

Figure imgb0001
The results were:
Figure imgb0001

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.

Beispiel 2.2Example 2.2

Gemillte Schuhnappa/chromfreie Nachgerbung

Figure imgb0002
Milled shoe appa / chrome-free retanning
Figure imgb0002

Fettung der Leder:Greasing the leather:

Fettung 1 (Vergleich)

Figure imgb0003
Fettung 2 (erfindungsgemäß)Bold 1 (comparison)
Figure imgb0003
 Bold 2 (according to the invention)

auf Vergleichsleder mit 12,5% des Produktes von Beispiel 1.3.on comparison leather with 12.5% of the product from Example 1.3.

Fettung 3 (erfindungsgemäß)Bold 3 (according to the invention)

auf Vergleichsleder mit 12% des Produktes aus Beispiel 1.4.on comparison leather with 12% of the product from example 1.4.

Die Leder lassen sich mit Lederfarbstoffen anfärben. Dabei wird mit den erfindungsgemäß gefetteten Ledern (Fettung 2 oder 3) eine sehr volle bzw. volle Färbung des Leders erzielt, bei einer guten bis sehr guten Egalität der Färbung. Dagegen ist die erzielbare Farbtiefe auf dem Vergleichs-Leder mit Fettung 1 nur gering (hell) bei nur einer mäßig einzustufenden Egalität.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.

Auf einem üblichen Anspritzautomaten wurden die Leder mit Fettung 1, 2 bzw. 3 jeweils mit Reaktiv-PU-Mischungen angespritzt. Die Ergebnisse der Anspritzversuche waren:

Figure imgb0004
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:
Figure imgb0004

Die Trennkräfte zwischen angespritzter Sohle und gefettetem 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.According to the invention, the separating forces between the molded-on sole and 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.

Beispiel 2.3Example 2.3 Weiches Oberleder/vollnarbig oder geschliffenSoft upper leather / full-grain or sanded

Figure imgb0005
Figure imgb0005

Fettung 2Bold 2

10% produkt gemäß Beispiel 1.4.10% product according to example 1.4.

Fettung 3Bold 3

10% Produkt gemäß Beispiel 1.6.10% product according to example 1.6.

Fettung 4Bold 4

10% Produkt entsprechend Beispiel 1.5.

Figure imgb0006
Beispiel 2.410% product according to example 1.5.
Figure imgb0006
 Example 2.4

Die Beispiele 2.1 und 2,2 wurden wiederholt und die erfindungsgemäßen Fettungsprodukte wie folgt variiert: (als Emulsionen, unter Emulgatorzusatz eingesetzt). Die Ergebnisse sind in der Tabelle zusammengestellt.

Figure imgb0007
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.
Figure imgb0007

Claims (7)

1. Use of fat-liquored leather for the direct moulding-on of polyurethane reactive compositions to give leather/polyurethane composites which have increased resistance to separation, characterized in that the fat-liquoring treatment of tanned leather is carried out by means of aqueous liquors of fat-liquoring agents which contain, in the form of an aqueous solution, emulsion or dispersion which may contain solvents,
a) hydroxypolyethers which contain at least 2 hydroxyl groups and have a molecular weight of 200 to 20,000 and/or
b) hydroxypolyesters which contain at least 2 hydroxyl groups and have a molecular weight of 200 to 20,000 and/or
c) hydroxypolycarbonates which contain at least 2 hydroxyl groups and have a molecular weight of 200 to 20,000 or
d) mixtures of components of categories a), b) or c) instead of conventional fat-liquoring agents or, alternatively, together with conventional fat-liquoring agents up to a liquor pick up of 0.1 to 20% by weight of the fat-liquoring products, relative to the shaved weight of the leather.
2. Use according to Claim 1, characterized in that the pretreated leathers are used in conventional moulding-on machines in the form of leather shafts together with polyurethane reactive compositions with the formation of adhesive-free shaft leather/PU sole composites.
3. Use according to Claim 1 characterized in that fat-liquoring agents based on hydroxypolyesters and/ or hydroxypolycarbonates are used for the treatment of the leathers, and the polyurethane reactive compositions based on polyesters or polycarbonates are used for the moulding-on.
4. Use according to Claim 1, characterized in that fat-liquoring agents based on hydroxypolyethers are used for the treatment of the leathers and polyurethane reactive compositions based on polyethers are used for the moulding-on.
5. Process for the fat-liquoring treatment of leather, characterized in that the tanned leathers are treated with aqueous liquors of fat-liquoring agents which contain, in the form of an aqueous solution, emulsion or dispersion which may contain solvents,
a) hydroxypolyesters which contain at least two hydroxyl groups and having a molecular weight of 200 to 20,000 and/or
b) hydroxypolycarbonates which contain at least two hydroxyl groups and have a molecular weight of 200 to 20,000 or
c) mixtures of components of categories a) or b) instead of conventional fat-liquoring agents or, together with conventional fat-liquoring agents up to a liquor pick up of 0.1 to 20% by weight of the fat-liquoring products, relative to the shaved weight of the leather.
6. Process according to Claim 5, characterized in that the hydroxypolyesters or hydroxypolycarbonates have been synthesized from di-, tri-, tetra- or polyethyleneglycols.
7. Process according to Claim 5, characterized in that the hydroxypolyesters and/or hydroxypolycarbonates have a molecular weight of 400 to 10,000.
EP86106114A 1985-05-17 1986-05-05 Method of fat liquoring leather and its use in direct spraying polyurethane for leather/polyurethane bonding Expired - Lifetime EP0204162B1 (en)

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US5061517A (en) * 1989-11-22 1991-10-29 Speer Lawrence L Brush-on finish for footwear and similar articles
US5284568A (en) * 1992-07-17 1994-02-08 E. I. Du Pont De Nemours And Company Disposable cartridge for ion selective electrode sensors
US5503754A (en) * 1993-11-10 1996-04-02 Henkel Corporation Wet treatment of leather hides
DE19707713A1 (en) * 1997-02-26 1998-08-27 Basf Ag Composition for the treatment of tanned leather and its manufacture
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FR1573918A (en) * 1968-01-29 1969-07-11
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DE3048159A1 (en) * 1979-12-21 1981-09-03 Toyo Boseki K.K., Osaka AQUEOUS POLYESTER RESIN DISPERSION
NL8304021A (en) * 1983-11-23 1984-12-03 Akzo Nv Aq. polymer dispersion stabilised with ionised carboxylic polyester - from acid anhydride and polyester

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