EP2711438A2 - Coated leather - Google Patents

Abstract

The coated leather, especially top-grain leather with a Nubuk surface structure, carries a soft polyurethane finish layer (4) in the non-embossed regions (Bnp). It is closed towards the bonding layer (3) and the leather (2), but has open micro-recesses (42) on the upper surface, closely packed in a soapsuds structure. The recesses have an inner width (Iw) = 130 mu m and especially = 80 mu m. The recesses, divided by cross linked webs (43), have a hemispherical shape with a concave inner surface (421).

Description

• Beschichtetes Leder, insbesondere Rindspaltleder, mit beliebiger fein- bis grobnarbiger, vorzugsweise mit nubuk-artig aussehender, Oberflächenstruktur, wobei die Beschichtung mit einer mit einem mechanisch und feuchtigkeits-stabilen Polymer gebildeten Oberflächenschicht gebildet ist, welche mittels einer polymer-basierten Haftschicht an die Oberfläche des Leders oder Spaltleders gebunden ist,

dadurch gekennzeichnet,
dass die an die Oberfläche des Leders bzw. Spaltleders gebundene nubukartige, sich durch Innenglätte auszeichnende, mit weichem Polyurethan gebildete Außen-Schicht (4), im nicht geprägten Bereich (Bnp) zum Leder (2) hin im wesentlichen geschlossene, jedoch nach außen hin offene, weniger als 130 µm, insbesondere weniger als 80 µm, Innenweite (lw) aufweisende, seifenschaumzellen-artig eng, dicht an dicht aneinandergrenzend angeordnete Mikrovertiefungen (42) aufweist, und
dass die Mikrovertiefungen (42) jede für sich durch dünne, nach außen hin eine matte oder feinfaserige Feinraustruktur-Oberfläche aufweisende, miteinander vernetzte Stege (43) gegeneinander begrenzt sind und eine im wesentlichen etwa (halb-) kugelschalenartig geformte, nach außen weisende, homogen glänzend glatte, konkave Innen-Oberfläche (421) aufweisen.The present invention relates to a novel coated leather, preferably split leather, in particular cow split leather, according to the preamble of claim 1 of the parent application, having the features mentioned in the characterizing part of this claim, wherein claim 1 of the parent application is as follows:

• Coated leather, in particular cow split leather, with any fine-grained to coarse-grained, preferably nubuck-like, surface structure, wherein the coating is formed with a surface layer formed with a mechanically and moisture-stable polymer, which by means of a polymer-based adhesive layer to the surface of the leather or split leather is bound,

characterized,
that bound to the surface of the leather or split leather nubuck-like, characterized by internal smoothness, formed with soft polyurethane outer layer (4) in the non-embossed area (Bnp) to the leather (2) out substantially closed, but towards the outside has open, less than 130 .mu.m, in particular less than 80 .mu.m, inside width (lw), having lathers like narrow, close to each other densely arranged micro-recesses (42), and
that the microwells (42) each by itself by thin, outwardly a matte or fine-grained Feinraustruktur surface having, interconnected webs (43) are mutually limited and a substantially approximately (half) spherical shell-like shaped, outwardly facing, homogeneous have a smooth smooth, concave inner surface (421).

It refers to a leather which is characterized by a perfect nubuck handle and nubuck look, which is suitable for shoes, sandals and special shoes, for saddles for motorcycles and bicycles as well as for the interior equipment of boats, for medical and hospital equipment and the like. Furthermore, it is to be used for cladding vehicle interior components and has a new nubuck equivalent optical and haptic quality.

It relates in particular to such a leather, which meets the special requirements in the vehicle sector in the highest degree, and which also meets the high requirements of safety shoes of groups 1 and 2.

The model for the new coated leather is genuine nubuck leather: The same results from sanding the grain top side. It forms fine fibers and the surface is dull and fine-grained rough. Nubuck leather has an interesting and beautiful appearance in the new state and has an optimal feel.

Significant disadvantages of genuine nubuck leather, however, are that the feel and appearance changes during use and after a short time to the negative. The previously fine-grained and noble matte surface quickly becomes greasy. As a result, the pleasant handle is lost. Real nubuck leather gets dirty very fast, watery soiling leaves stains and edges that are no longer removable. The light fastness of genuine nubuck leather is insufficient to bad. The color abrasion properties are poor in the dry, but especially in the wet state.

The abrasion resistance is not sufficient especially for safety shoes and sports shoes, because even after a short use of the shoes at the stressed areas an abrasion wear, which is always associated with a color change shows.

For these reasons, genuine nubuck leather, in particular in the automotive sector, as good as not used and in shoes and other commodities leathers are impregnated with oily and waxy substances, which although the performance characteristics are improved, the appearance and feel but deteriorate significantly.

The object of the invention was to provide a leather whose surface is similar in terms of look and feel of the surface of a real Nubukleders, but without having its, as mentioned above, use-limiting disadvantages.

It has further been said that the object of the invention is that the new nubuck leather does not become soiled and that it does not become shiny under extreme conditions and does not change its surface texture and color.

It is known per se to produce nubuck-like surfaces on leather by providing the leather with a foam coating and then grinding it. This process is cumbersome and expensive. The result is sanding dust and when sanding, the surface changes in its color.

The main drawback, however, is that very soft polymeric foam coatings do not grind well on the leather. The softness of a polymer is essential for a good feel.

It has also been known to concatenate prepared, polished polyurethane films on leather in the coagulation process. These films are thermoplastic, so not abrasion resistant. Their cell structure is sponge-like open-cell, so that contamination can easily penetrate, anchor themselves in the cells and can hardly be removed.

Furthermore, it is known to provide leather with a hollow microsphere containing polyurethane coating and to produce a kind Nubukeffekt by grinding the surface. However, these surfaces do not have a good grip because they hard, which is due to the fact that the shells of the ground hollow microspheres are retained in the polyurethane. It also comes here during grinding to color changes and the grinding process is dirty and expensive. The use of very soft polymers is also impossible here.

It is also known to give leathers a nubuck-like surface by electrostatic flocking with textile fibers. The fibers tend to be less resistant to abrasion and the nubuck effect is quickly lost.

It is also known to produce a nubuck effect on leather by reversibly producing in a silicone mold a film of polyurethane from which fine hairs, which consist of the same material, protrude and connect this film with the leather. These hairs have a microscopically rough surface, a maximum diameter of 100 microns and tend due to the roughness and their arrangement also to contamination. The resulting haptic is in itself high quality, as well as the look, but the overall impression is closer to a textile suede material than a nubuck leather. Under heavy use, the fine hairs can be rubbed off and the surface becomes unsightly and loses its sympathetic grip.

It has surprisingly been found that in a leather, preferably a split leather, all the same requirements and tasks are fully met and the leather surface has the look and feel of a genuine nubuck surface when smooth, approximately hemispherical, densely arranged micro Depressions, which are surrounded only by thin web-like, interconnected edges, are present in the outer layer, if this outer layer further consists of a soft polyurethane, and if the depressions with their smooth surface or the frame surfaces of the thin, web-like sheath have a diameter of less than 130μm.

The optimal nubuck surface is therefore a hybrid. Although the smooth surfaces of the recesses are larger in area than the matte surfaces of the sheathing webs, the surface has the same languidness as a natural nubuck leather. From the unaided eye, the smooth surfaces of the microwells are not perceived, even if, as particularly preferred, they are not only smooth but even shiny. The eye only recognizes a uniformly matt surface with the look of real nubuck leather. Even when you touch the micro-wells are not perceived. Due to the matt surfaces of the borders and their softness, the thin polymer surface feels like a high quality natural nubuck leather.

In a gloss level measurement according to DIN 67530, measured at a light incidence angle of 60 °, black nubuck leathers have a gloss level between 0.1 and 0.4, as well as the leather of the invention. The same applies to measurements in other colors.

What is new and surprising is that the micro-indentations and the dullness on the bridge surfaces, like a hybrid, create a perfect nubuck effect.

It should be noted at this point that the new coated leather, preferably split leather, with coating, can have virtually any type of surface structure, namely z. B. from fine to coarsely grained or with a technical surface structure.

In the leather according to the invention, the surface, in particular of a soft crosslinked polyurethane, preferably based on or from a known solidified polyurethane dispersion, it can of course be used in the leather industry finishing additives such. As pigments and / or a silicone emulsion and / or dispersion. The surface was formed on a removable silicone rubber backing and bonded to the leather by one or more polyurethane-based adhesive layers. The adhesive layer or its layers are also crosslinked. The adhesive layers are formed from polyurethane dispersions, preferably those having a crystalline structure.

The term "total coating" includes the outer layer as well as the adhesive or adhesive layer, which may be multi-layered, e.g. has a middle and a tie layer layer.

The new leather absorbs no water from the surface, furthermore it has an excellent resistance to abrasion of paint in both dry and wet condition, it is mechanically extremely resistant to abrasion and the individual layers or layers separate under extreme loads and at Do not interact with moisture. It also provides protection against wet surface soiling.

However, what distinguishes the new leather in particular, in addition to its nubuck-like appearance and feel, is its excellent general soil repellency despite the large number of pore-like depressions containing outer layer, which is a film with novel smooth, preferably shiny, concave-spherical inner surfaces of the micro-wells is.

The significantly reduced dirt pickup results from the smooth surface of the wells as well as from the small cross section of the openings. Coarser dirt can not penetrate at all. The soft, elastic webs transport when moving dirt from the hemispherical, hollow and inside smooth depressions. Because the thin webs are endless Connecting together, that is, the fact that no bridge stands alone, results in the high abrasion resistance.

Although the microstructure of the surfaces of the new leather is in itself completely opposite to the known, dirt-repellent lotus structure with finest hairs, the new surfaces are not prone to contamination and tend to move and / or presence of water for self-emptying of dirt particles, which is completely surprising.

The depressions are smooth according to the invention, their inner surface is preferably glossy in itself. However, the overall surface of the new leather or its visual impression is always dull, similar to real nubuck leather.

Furthermore, the surface of the new leather is extremely easy to handle and has a feel, as they have only very high quality, nubuck leather.

In the new product not only the abrasion and Farbabriebeigenschaften be further improved significantly, it prevents or reduces not only unwanted pollution and creaky noises and, above all, however, as already mentioned, its feel is particularly positive. In addition, there is a new hybrid optics, which, as evidenced by the smooth, preferably shiny, light-reflecting concave inner surfaces of the micro-wells, as well as by the matt to fine-grained web surfaces.

Of a coated leather, preferably split leather, already high adhesive properties are required and this meets the new coated leather or split leather according to the invention easily. Due to the known use of polyurethane dispersions having a crystalline structure, which additionally contains a crosslinker, for the adhesive or adhesive layers or layer layers creates a nearly inseparable connection with each other and with the leather, especially when one of the adhesive or adhesive layers is still wet when brought together before pressing.

The complete coating advantageously has a maximum thickness of only 0.15 mm, so that the coated leather can be referred to as "genuine leather". The overall coating may be two or more layers. A preferably provided, very thin silicone pad remains unconsidered.

To solve the problem solved according to the invention it was further to provide a split leather, for example, parts of the dashboard of motor vehicles, which, if it is foamed, does not absorb water from the surface, to hinder or exclude the expansion and shrinkage effects usually caused by leather , The leather used in this way is of course long Time in the climate change test and hot exposure resistant and thus meets in particular the requirements of the automotive industry for all types of vehicles.

Furthermore, according to the invention, it is the task of the new leather to use the same for safety shoes of groups 1 and 2. To achieve a previously non-existent water vapor permeability, the leather may have a mechanical hole perforation, as will be explained in more detail later.

• Bei einem echten Nubukleder, also bei einem Leder, bei dem die Narbenoberfläche durch Schleifen, meist mit Schleifpapier, mit einer Körnung zwischen 180 und 450 aufgeraut worden ist, ist es notwendig, dass nach dem Schleifen die Leder-jeweils farbabhängig - wieder bzw. nochmals gefärbt werden müssen, weil beim Schleifen der Narbenschicht die vorher farbintensive Narbenoberschicht sich infolge Aufhellens stark verändert.

The difference between a real nubuck leather and the new coating is the following:

• In a real nubuck leather, so in a leather in which the grain surface has been roughened by grinding, usually with sandpaper, with a grain size between 180 and 450, it is necessary that after sanding the leather-each color-dependent - again or again must be colored, because when grinding the grain layer, the previously color-intense grain upper layer changes greatly due to whitening.

Dark-colored nubuck leathers, especially black ones, always have to be dyed again after sanding, which is cumbersome, energy-intensive and expensive.

The new coated leather, in which this re-dyeing is not necessary, shows the same or even better results than the genuine nubuck leather in a gloss level detection, measured according to DIN 67530 at 60 ° incidence angle, with the new leather in the preferred embodiment with direct Incident light and corresponding magnification recognizes the smooth, preferably shiny surface of the wells.

Results of the gloss measurement: genuine nubuck leather, black: result: 0.1 to 0.4; leather according to the invention, black, result: 0.1 to 0.4

The leathers, which are equipped with the novel nubuck-like surface layer, meet all the requirements and parameters of the vehicle and safety shoe industry. They are resistant to bending, soft and extremely abrasion resistant. Tested in accordance with DIN EN ISO 14327 with the friction wheel H22, the surface has e.g. after 30,000 cycles still no damage.

For nubuck leather, however, damage with color changes is visible after only 1,000 cycles. Also tested according to DIN EN ISO 12947-1 after 50,000 cycles, in the dry state, this finding has been confirmed, in contrast to nubuck leather, which already changes after 1000 cycles.

Even when wet, no damage to the surface could be detected after 12,000 to 15,000 cycles.

In a further test based on DIN EN ISO 12947-1 for determining the abrasion resistance under the influence of elevated temperature, specifically at 80 ° C, no damage could be detected after 10,000 cycles and therefore this test was then terminated.

The adhesion after a storage of water for 24 h in accordance with ISO 11644 is easily met with 10 N. The value is about three times higher than conventional car springs. Since no water can penetrate into the leather due to the coating surface, it is also fully suitable for motorcycle saddles as well as riding and bicycle saddles.

Also, the coating of the present invention does not alter its properties in the cyclic change test, the coating effectively acts as a seal and prevents the ingress of moisture to the leather which, if it had access, would adversely affect the stretch and shrink properties of the leather.

The new coated leathers, preferably split leather, are optimally suited for foam-backed components and for parts which come into contact with human skin, in particular for steering wheels, center consoles, shifter knobs, armrests and the like, but also for boat equipment, hospital and Sanitary products u. Like. And further for clothes, shoes and gloves and especially for safety shoes.

Although the thickness of the new overall coating of the new leather is as small as 0.15 mm at most, it not only has excellent mechanical and physical properties, but is also very soft, cuddly and comfortable to the touch, and virtually immune to any kind of soiling.

The new surface or outer layer can, as already mentioned, show any, in particular impressed, surface structure.

It should be emphasized at this point separately that the leather according to the invention, in particular split leather, optimally not only for automotive, but also for truck and bus seat covers especially in combination with textiles and furthermore especially for safety, work and sports Shoes, motorcycle, bicycle and riding saddles u. Like. Can be used.

• Leder, insbesondere nach Anspruch 1 der Stammanmeldung, dadurch gekennzeichnet, dass die Haftschicht (3) mit einer Mittelschichtlage (3') und einer Verbindungsschicht-Lage (2") ausgebildet ist und mit einer auf einer heißen, vorzugsweise mit Erhebungen od. dgl., insbesondere nubukartig, strukturierten, von Zinn bzw. zinnorganischen Verbindungen freien Siliconunterlage bzw. - matrize aus einer wässrigen, überwiegend Polyurethan enthaltenden Kunststoffdispersion vorfabrizierten Außenschicht (4), und einer auf derselben ausgebildeten, mit derselben verbundenen und letztlich unterhalb derselben angeordneten, überwiegend ebenfalls aus einer Polyurethan enthaltenden Kunststoffdispersion gebildeten Haftschicht (3) mit Mittelschicht-Lage (3') und Verbindungsschicht-Lage (3"), die ebenfalls überwiegend aus einer polyurethanhaltigen Kunststoffdispersion hergestellt, die auf das Leder appliziert worden und mit der Mittelschicht-Lage (3') verbunden ist, gebildet ist,
  • dass die mit einem zumindest ein Siliconpolymer bzw. Siliconadditiv enthaltenden Polymer, insbesondere Polyurethan, gebildete zinn-freie, vorzugsweise eine mit einer mittels im Negativ nubuk-artigen Prägung ausgebildete Außen-Oberfläche (40) aufweisende Außenschicht (4) mit einer Mehrzahl von auf ihrer der Mittelschicht-Lage (3') zugewandten Seite beginnenden und die Außenschicht (4) bis zu ihrer Außenseite bzw.
  • Oberfläche (40) voll durchdringenden und/oder noch innerhalb der Außenschicht (4) endenden, geringe Innenweite aufweisenden, Hohlräumen, Hohlgängen, Kapillaren, Poren oder Öffnungen (45) und/oder Ausnehmungen, Höhlungen oder Vertiefungen (45') ausgebildet ist,
  • welche mit in dieselben eindringenden bzw. eingedrungenen und dieselben verschließenden, an deren Innenwandungen satt gebundenen und dort gegebenenfalls verankerten, mit dem Polymer- , insbesondere Polyurethanmaterial der Mittelschichtlage (3') der Haftschicht (3) einstückigen Form- bzw. Füllkörpern (36, 36'), Stalagmiten, Zapfen, Stäben, Zylindern, Kegeln oder dgl. aufgefüllt sind.

A particularly preferred embodiment in the context of the present invention, which ensures a particularly good, virtually inseparable adhesion of the outer layer to the adhesive or adhesive layer responsible for the binding to the leather, is disclosed in claim 2 of the Stammanmeidung, which reads as follows:

• Leather, in particular according to claim 1 of the parent application, characterized in that the adhesive layer (3) with a middle layer layer (3 ') and a tie layer layer (2 ") is formed and with a on a hot, preferably with elevations od. Like. , in particular nubuck-like, structured, of tin or organotin-free silicone underlay or - matrices of an aqueous, predominantly polyurethane-containing plastic dispersion prefabricated Outer layer (4), and one formed thereon, connected to the same and ultimately arranged below the same, mainly also formed from a polyurethane-containing plastic dispersion adhesive layer (3) with middle layer layer (3 ') and tie layer layer (3 "), the also made predominantly of a polyurethane-containing plastic dispersion which has been applied to the leather and connected to the middle-layer layer (3 ') is formed,
  • in that the tin-free outer layer (4) having an outer surface (40) formed by means of a negative nubuck-type embossment and comprising a polymer comprising at least one silicone polymer or silicone additive, in particular, has a plurality of on its surface the middle layer layer (3 ') facing side beginning and the outer layer (4) to its outer side or
  • Surface (40) is formed of full penetrating cavities or hollow cavities, capillaries, pores or openings (45) and / or recesses, cavities or depressions (45 ') which terminate within the outer layer (4) and have low inner widths,
  • which with the same penetrating or penetrated and the same occlusive, on the inner walls saturated bound and possibly anchored there, with the polymer, in particular polyurethane material of the middle layer layer (3 ') of the adhesive layer (3) integral molding or packing (36, 36 ') Stalagmites, cones, rods, cylinders, cones or the like. Are filled.

• So beschreibt die DE 3720776 A ein Leder, bei dem die Beschichtung aus drei Schichten besteht, wobei als Mittelschicht und als Verbindungsschicht eine Ausgleichsschicht vorgesehen ist. Die dort beschriebenen Leder weisen bei höheren Temperaturen schlechte Hafteigenschaften der Beschichtung zum Leder hin auf. Außerdem erfüllen sie nicht die Haptik- und Griffeigenschaften, wie sie insbesondere für die Automobilindustrie gefordert sind. Ferner ist dort vorgeschrieben, in der Außenschicht Nitrocellulose zu verwenden, was in Kombination mit Polyurethanschäumen zu Verfärbungen führt.

Before discussing the advantages of this variant of the nubuck-style new leather, let us briefly turn to the state of the art in this sector:

• That's how it describes DE 3720776 A a leather in which the coating consists of three layers, wherein a leveling layer is provided as the middle layer and as the connecting layer. The leathers described therein have poor adhesive properties of the coating towards the leather at higher temperatures. In addition, they do not fulfill the haptic and grip properties, as they are particularly required for the automotive industry. Furthermore, it is prescribed there to use nitrocellulose in the outer layer, which leads to discoloration in combination with polyurethane foams.

The outer layer provided there contains no silicone additives and has no capillaries or other pores or openings.
The US 6,177,198 B1 describes a grain leather in which the coating consists of three layers. The provided there outer layer has pores, which are only partially lined by the thin middle layer. The middle layer and the tie layer together have a thickness of less than 0.03mm. The outer layer contains only about 1% of a silicone additive. The middle and tie layers provided there are unsuitable for split leather and are unable to actually close said capillaries and depressions in the outer layer. Furthermore, these leathers take according to this US 6,177,198 B1 water over its surface, which is absolutely unfavorable.

The US 4,751,116 A describes a split leather whose outer layer has been formed on a textured silicone backing. The coating described therein, however, is thick, in no way has the properties required by the automotive industry, and contains no silicone additives and, in particular, no depressions, capillaries or the like in the outer layer.

An essential aspect of the present invention is that the outer layer in a conventional manner on a warm silicone or polysiloxane underlay or -Matrize with - the pores, tubes, aisles u. Like. - From the base towering pins, pins, surveys is formed and that the surface of the outer layer, in addition to the respective surface structure has also received a degree of dullness to a certain degree, which is durable and not at high stress during rubbing under pressure changed.

Contrary to the previous procedure when creating the Siliconmatrize the same is specifically not crosslinked using tin or tin organic compounds, which is an immigration of tin in the finish layer absolutely can not occur and thus caused by tin or traces of tin or cause problems the skin of the user can not occur.

It is particularly preferred to use a matrix for the formation of the finishing layer, in which the crosslinking with platinum is carried out as a crosslinking catalyst.

Preferably, the outer layer contains between 2.5 and 20 wt .-%, based on the total weight of the outer layer, preferably between 6 and 12 wt .-%, polysiloxane.

Advantageously, the polysiloxane is embedded in the predominantly polyurethane-formed outer layer in the form of the smallest, solid particles or of solid microparticles. In addition to these solid microparticles, which preferably have properties such as a very soft silicone rubber, higher molecular weight silicones introduced via a dispersion or emulsion may also be present.

Small solid particles of polysiloxane are also particles of polysiloxane to understand, which are incorporated into the outer layer.

The main constituents of the outer layer preferably consist of a medium-hard branched polyurethane which is formed by an ultimately solidified dispersion.

The inventively fully filled cavities and capillaries, or better said, the same wall-connected or-anchored filling form-filling in the outer layer are integral with the middle layer layer components of the middle layer layer of the adhesive layer.

The middle layer layer itself also advantageously consists of an ultimately solidified, known per se polyurethane dispersion, which has exhibited thermoplastic properties before crosslinking.

In contrast to the outer layer, which advantageously already has an at least partially branched structure before crosslinking, the middle layer layer advantageously has a somewhat unbranched or linear structure and has excellent adhesive properties. By then cross-linking their mechanical properties are significantly improved and repealed the previously passed thermoplastic properties.

According to the invention, it is provided and essential that the material of the middle layer layer penetrates into the capillaries, openings, cavities, cavities, pores, hollow tubes or the like originally present in the outer layer, penetrates them completely and connects with their walls or anchors there, wherein a particularly high adhesion of the two said layers or layers to each other is achieved by the additional mechanical anchoring.

A particularly good adhesion is achieved if the outer layer to the affiliated, preferably formed as a homogeneous adhesive layer, middle layer position per cm ² between 20 and 3, in particular between 18 and 5, capillaries, tubes, pores or the like or back side depressions od. Like. Has.

The middle layer layer and the tie layer layer advantageously have a higher layer thickness together than the outer layer.

They preferably have both the almost same chemical structure, but which is deliberately different from the chemical structure of the outer layer.

In no way is it undesirable if material of the coherent watertight bonding layer layer projects into the cavities, openings, recesses, pores, passages, pipes or the like of the outer layer.

The outer layer with its inventively relatively high silicone content has due to the high proportion of polysiloxanes on the desired soft feel and a high abrasion and Farbabriebsfestigkeit.

• Leder nach Anspruch 2 der Stammanmeldung, dadurch gekennzeichnet, dass nicht nur das mit dem Polymer- , insbesondere Polyurethanmaterial der Mittelschicht-Lage (3') idente, einstückige Polymer-, insbesondere Polyurethanmaterial in die Hohlräume, Hohlgänge, Kapillaren, Poren (45), bzw. Öffnungen, Ausnehmungen oder Vertiefungen (45') der Außenschicht (4) eingedrungen ist und dieselben als Füllkörper (36) voll (auf)füllt, sondern dass in die Form-Füllkörper (36), bzw. in dort unterseitig beginnenden und innerhalb desselben endenden oder bis zur Oberfläche (40) der Außenschicht (4) durchreichenden Hohlräume (35', 35) der die Hohlräume der Außenschicht-Lage (4') füllenden Füll- bzw. Formkörper (36' 36) auch Füll-Formkörper (26' 26) aus mit dem Polymer-, insbesondere Polyurethanmaterial der Verbindungsschicht-Lage (3") identen, einstückigen Polymer-, insbesondere Polyurethanmaterial voll eingedrungen und dort wandungs-verankert ist.

Durch diesen gewissermaßen zusätzlichen "Vernietungseffekt" entsteht eine tatsächlich untrennbare Verbindung der Schichten und Schichtlagen miteinander, und dies, wie sich zeigte, im Wesentlichen unabhängig von der Art und Menge des Siliconanteils in der Außenschicht. Diese untrennbare Verbindung bleibt auch unter dem Einfluss von Feuchtigkeit und Nässe voll bestehen.Despite the high silicone content in the outer layer, which is known to have a separating effect, an inseparable connection of the layers and layer layers of the coating results from the fact that the middle layer layer and optionally also the tie layer layer penetrate into the capillaries and openings of the outer layer and anchor themselves there, as disclosed in claim 3 of the parent application, which reads as follows:

• Leather according to Claim 2 of the parent application, characterized in that not only the one-piece polymer material, in particular polyurethane material, which is identical to the polymer, in particular polyurethane material, of the middle layer layer (3 ') penetrates into the cavities, hollow passages, capillaries, pores (45), or openings, recesses or depressions (45 ') of the outer layer (4) has penetrated and the same as filling body (36) fully (up) fills, but that in the mold-filling body (36), or in there beginning underside and within the same ending or up to the surface (40) of the outer layer (4) passing through cavities (35 ', 35) of the cavities of the outer layer layer (4') filling or molding (36 '36) and filling molded body (26 '26) from the polymer, in particular polyurethane material of the tie layer layer (3 ") identical, one-piece polymer, in particular polyurethane material fully penetrated and wall-anchored there.

By virtue of this somewhat additional "riveting effect", a truly inseparable connection of the layers and layer layers with each other is produced, and this has been found to be essentially independent of the type and amount of silicone content in the outer layer. This inseparable connection remains fully intact even under the influence of moisture and moisture.

The bonding layer layer of the adhesive layer formed with the solidified polyurethane dispersion ensures that the entire coating is also firmly bonded to the ground (known) and / or milled and / or staked split leather. Not only is an inseparable adhesion of the layers and layer layers to one another achieved by the interlocking or nested structure of the coating, but all the pores, capillaries, openings or the like of the outer layer itself are fully and watertight.

Although the total thickness of the coating is at most 0.15 mm, but is better thinner than 0.15 mm, and preferably less than 0.12 mm, it is water-repellent or waterproof from the top. Water bubbles off or does not penetrate the leather.

The thickness of the outer layer is advantageously between 30 and 45% and that of the middle layer and the tie layer layer together between 70 and 55% of the overall structure of the new coating.

The coated split leather according to the invention fulfill all the parameters of the vehicle industry. They are durable, soft and extremely resistant to abrasion. The abrasion resistance of the same is about ten times that of conventional scar leather for vehicles.

The adhesion after a storage of water for 24 h in accordance with ISO 11644 is easily met with 10 N. The value is three times higher than conventional car springs

The coating according to the invention also does not change its properties during the climate change test, the coating effectively acts as a seal and prevents the ingress of moisture from the outside which, if it had access, would adversely affect the stretching and shrinking properties of the leather.

The coated split leathers are optimally suited for back-foamed components and for parts which come into contact with the human skin, such as e.g. Steering wheels, center consoles, shifter knobs, armrests and the like, as well as for boat equipment, hospital and sanitary articles etc ..

Furthermore, they are particularly suitable for work shoes that are worn in the wet area and for winter street shoes, where no more salt edges occur.

Neither the middle nor the tie layer contain silicones.

Although the overall coating of the new leather is thinner than 0.15 mm, it not only has excellent mechanical and physical properties, it is also very soft and comfortable to the touch, and virtually immune to waterborne soiling due to the high silicone content of its outer layer. This is especially important for nubuck-like surfaces.

The haptic properties can be further improved if the middle and / or tie layer layer contains per se known hollow microspheres with a volume fraction of less than 10% or contain.

The leathers according to the invention are soft if they are not only ground in a known manner prior to coating, but also, as may be provided according to the invention, have undergone a rolling and / or staking process. As a result, the adhesion is further improved because abrasive dust and loose fibers are removed from the leather surface or at least reduced there.

Although the outer layer is at most, especially less than, 45% of the total thickness of the overall thin finish, it can exhibit any surface texture.

According to the invention or its preferred embodiments, the outer layer has the look and feel of a nubuck leather. According to the invention, this is achieved by the silicone die for the outer surface of the outer layer having a negative nubuck-like, rough surface with elevations and depressions in the range between 0.0005 and 0.008 mm, which is also a consequence of the high silicone content in the outer layer.

When grinding a foamed plastic body with preferably one round cell structure round cells are opened more or less wide on the surface and open cells are formed on the plastic body. This structure is transferred to the surface of the outer layer via a warm silicone matrix.

This - as with a nubuck leather looking - surface can also be z. B. additionally have an embossed structure.

Even such a surface fully meets the requirements of the vehicle and footwear industry. Because the "open cells" acting as in the case of the nubuck effect are only arranged in the surface of the outer layer, the layer absorbs no water and, of course, does not allow water to pass through.

According to the invention, it can further be provided that the outer layer has a layer of a silicone rubber, which has a thickness of less than 0.005 mm and is formed from an aqueous silicone emulsion with a particle size in the nanometer range. This further improves the prevention of wet contamination, as well as the creaking behavior. Last but not least, this extremely thin layer also improves the fire-retardant behavior of the new coated split leather.

The split leather according to the invention according to claim 2 and claim 3 of the parent application, the wording of which is listed above, can be optimally used for truck seat covers as well as for bus seat covers, especially in combination with textiles.

• Leder nach einem der Ansprüche 1 bis 3 der Stammanmeldung, dadurch gekennzeichnet, dass in der Außenschicht (4) pro cm², durchschnittlich zwischen 28 und 3, insbesondere zwischen 18 und 5, mit Polymer-, insbesondere Polyurethanmaterial, zumindest der Mittelschicht-Lage (3') voll (auf)gefüllte Hohlräume, Hohlgänge, Kapillaren, Poren (45) und/oder Öffnungen, Ausnehmungen oder Vertiefungen (45') vorhanden sind,

und Anspruch 5 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 4 der Stammanmeldung dadurch gekennzeichnet, dass die in der Außenschicht (4) vorhandenen, bis zu deren Außen-Oberfläche (40) durchgehenden bzw. reichenden Hohlräume, Hohlgänge, Kapillaren oder Poren (45) im Wesentlichen lichte Weiten bzw. Durchmesser im Bereich von 10 bis 100µm aufweisen,

und Anspruch 6 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 4 der Stammanmeldung, dadurch gekennzeichnet, dass die in der Außenschicht (4) vorhandenen, innerhalb derselben endenden, also nicht bis zur Außen-Oberfläche (40) durchgehenden Öffnungen, Ausnehmungen oder Vertiefungen (45') im Wesentlichen lichte Weiten bzw. Durchmesser im Bereich von 10 bis 100 µm aufweisen,

und Anspruch 7 der Stammanmeldung, wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 6 der Stammanmeldung, dadurch gekennzeichnet, dass das Verhältnis von bis zur Außenoberfläche (40) der Außenschicht (4) reichenden bzw. durchgehenden Hohlräume, Hohlgänge, Kapillaren oder Poren (45) zu den noch innerhalb der Außenschicht (4) endenden Öffnungen, Ausnehmungen oder Vertiefungen (45') von 30 bis 10 %, insbesondere von 25 bis 15 %, bis 70 bis 90 %, insbesondere von 75 bis 85 % reicht.

The above-described and various embodiments and variations of the present invention or inventively obtained split leather, and in particular their coatings and their forms, in particular as regards the mutual riveting of the layers and layers, forms the subject matter of claims 4 to 7 of the parent application, wherein Claim 4 of the parent application reads as follows:

• Leather according to one of claims 1 to 3 of the parent application, characterized in that in the outer layer (4) per cm ² , on average between 28 and 3, in particular between 18 and 5, with polymer, in particular polyurethane material, at least the middle layer layer ( 3 ') are full (on) filled cavities, hollow passages, capillaries, pores (45) and / or openings, recesses or depressions (45') are present,

and claim 5 of the parent application reads as follows:

• Leather according to one of Claims 1 to 4 of the parent application, characterized in that the cavities, hollow passages, capillaries or pores (45) present in the outer layer (4) and extending up to their outer surface (40) have substantially clear widths or diameter in the range of 10 to 100 μm,

and Claim 6 of the parent application reads as follows:

• Leather according to one of Claims 1 to 4 of the parent application, characterized in that the recesses or recesses (45 ') present in the outer layer (4) and ending within the same, ie not up to the outer surface (40), substantially have clear widths or diameters in the range of 10 to 100 μm,

and claim 7 of the parent application, reads as follows:

• Leather according to one of claims 1 to 6 of the parent application, characterized in that the ratio of up to the outer surface (40) of the outer layer (4) reaching or continuous cavities, hollow passages, capillaries or pores (45) to those still within the outer layer ( 4) ending openings, recesses or depressions (45 ') of 30 to 10%, in particular from 25 to 15%, to 70 to 90%, in particular from 75 to 85%.

• Leder nach einem der Ansprüche 1 bis 7 der Stammanmeldung, dadurch gekennzeichnet,
  dass die Außenschicht (4) mit den Mikro-Vertiefungen (42) und den oberflächenmatten, dieselben umrandenden Stegen (43) aus einem weichen, vernetzten Polyurethan mit einer Härte von weniger als 75 Shore A, insbesondere von weniger als 55 Shore A, gebildet ist,

und Anspruch 9 der Stammanmeldung lautet:

• Leder nach einem der Ansprüche 1 bis 8 der Stammanmeldung, dadurch gekennzeichnet, dass die Mikro-Vertiefungen (42) in der Außenschicht (4) derselben jeweils in sich geschlossene, ineinander übergehende Umrandungen (Stege) aufweisen, und dass sie selbst gegebenenfalls polyedrische oder hexagonale Querschnitts-Gestalt aufweisen können,

und Anspruch 10 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 9 der Stammanmeldung, dadurch gekennzeichnet,
  dass die Innenweite (lw) der Mikro-Vertiefungen (42) 20 bis 100 µm, insbesondere 30 bis 80 µm,
  dass die Tiefe (tv) der Mikro-Vertiefungen (42) 5 bis 80 µm, insbesondere 10 bis 60 µm, und
  dass die Stärke (ds) der Stege (43) zwischen den Mikro-Vertiefungen (42) 1 bis 30 µm beträgt,

und Anspruch 11 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 10 der Stammanmeldung, dadurch gekennzeichnet, dass die Außenschicht (4) eine von der für die Gestaltung ihrer Außen- bzw. Oberfläche (40) und der Poren (45) vorgesehenen Siliconmatrize auf sie übertragene, beim Schleifen von geschäumtem, Kunststoffmaterial, Gummi oder dgl. gebildete, vorzugsweise rund- , insbesondere hohlkugelzellige, Oberflächenstruktur (41) aufweist,

und Anspruch 12 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 11 der Stammanmeldung, dadurch gekennzeichnet, dass in der Außenschicht (4) zwischen 1,5 und 20 Gew.-%, vorzugsweise bei Narbenleder oder Leder mit technischer Oberfläche zwischen 4 und 12 Gew.-% oder vorzugsweise bei nubuklederartiger Oberfläche zwischen 10 und 18 Gew.-%, zumindest eines Silicons bzw. Polysiloxans, jeweils bezogen auf das Gesamtgewicht der genannten Schicht (4), enthalten sind,

und Anspruch 13 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 12 der Stammanmeldung, dadurch gekennzeichnet, dass das vernetzte Polyurethan der Außenschicht (4) kleinste Polysiloxan-Partikel mit einer Partikelgröße von maximal 30 µm bis zu einem Volumenanteil von maximal 15 % enthält,

und Anspruch 14 der Stammanmeldung wie folgt lautet:

• Leder nach Anspruch 12 oder 13 der Stammanmeldung, dadurch gekennzeichnet, dass das Silicon bzw. Polysiloxan in Form von sehr kleinen kautschukartigen Feststoff-Partikeln, bevorzugt von derartigen Mikro-Partikeln, in der Außenschicht (4) eingebettet ist,

und Anspruch 15 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 12 bis 14 der Stammanmeldung, dadurch gekennzeichnet, dass die Silicon- bzw. Polysiloxan-Partikel in Form von höhermolekularen Polysiloxan-Ölen mit Molgewichten von etwa 2000 bis etwa 100000, vorzugsweise mit solchen mit Molgewichten von über 5000, vorliegen, die über eine Emulsion mit Wasser in das Polyurethan der Außenschicht (4) vor dessen Vernetzung eingebracht worden sind,

und Anspruch 16 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 15 der Stammanmeldung, dadurch gekennzeichnet, dass in die - aus einer mit einem mittelharten verzweigten Polyurethan gebildeten und danach verfestigten bzw. vernetzten Polyurethan gebildeten Dispersion gebildete - Außenschicht (4) neben den sehr kleinen festen Silicon- bzw. Polysiloxanpartikeln, bevorzugt mit Eigenschaften eines sehr weichen Siliconkautschuks, auch höhermolekulare, über eine Emulsion eingebrachte Silicone eingebracht sind,

und Anspruch 17 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 16 der Stammanmeldung, dadurch gekennzeichnet, dass das vernetzte Polyurethan der Außenschicht (4) Mikrohohlkugeln, vorzugsweise aus einem thermoplastischen Kunststoff mit einem Durchmesser von maximal 60 µm und in einer Menge von zwischen 0,3 und 8 Gew.-%, jeweils bezogen auf die Gesamtbeschichtung (5) enthält,

und Anspruch 18 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 17 der Stammanmeldung, dadurch gekennzeichnet, dass die Dicke (do) der Außenschicht (4) 0,04 bis 0,1 mm beträgt,

und Anspruch 19 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 18 der Stammanmeldung, dadurch gekennzeichnet, dass die Außenschicht (4) beliebige Oberflächen- oder Prägestruktur (41) und/oder Mattigkeit, vorzugsweise jedoch Aussehen und Griff eines Nubuk-Leders mit einer mikroskopisch rauen Oberfläche mit Erhöhungen und Vertiefungen im Bereich zwischen 0,005 und 0,02 mm, aufweist.

With respect to the various advantageous embodiments of the surface and the material of the outer layer of the new coated leather provide the claims 8 to 19 of the parent application, in more detail, where claim 8 of the parent application is as follows:

• Leather according to one of Claims 1 to 7 of the parent application, characterized in that
  in that the outer layer (4) with the micro-depressions (42) and the surface-matt, the same-bordering webs (43) is formed of a soft, cross-linked polyurethane having a hardness of less than 75 Shore A, in particular less than 55 Shore A. .

and Claim 9 of the parent application reads:

• Leather according to one of claims 1 to 8 of the parent application, characterized in that the micro-depressions (42) in the outer layer (4) of the same in each case self-contained, merging into each boundary (webs), and that they themselves optionally polyhedral or hexagonal May have cross-sectional shape,

and Claim 10 of the parent application reads as follows:

• Leather according to one of Claims 1 to 9 of the parent application, characterized in that
  the inner width (lw) of the micro-depressions (42) is 20 to 100 μm, in particular 30 to 80 μm,
  the depth (tv) of the micro-depressions (42) is 5 to 80 μm, in particular 10 to 60 μm, and
  the thickness (ds) of the webs (43) between the micro-depressions (42) is 1 to 30 μm,

and Claim 11 of the parent application reads as follows:

• Leather according to one of Claims 1 to 10 of the parent application, characterized in that the outer layer (4) transfers a silicone matrix intended for this purpose to the design of its outer surface (40) and the pores (45) when grinding having foamed, plastic material, rubber or the like, preferably round, in particular hollow spherical, surface structure (41),

and claim 12 of the parent application reads as follows:

• Leather according to one of claims 1 to 11 of the parent application, characterized in that in the outer layer (4) between 1.5 and 20 wt .-%, preferably in grain leather or leather with technical surface between 4 and 12 wt .-% or preferably in the case of a nubuck-like surface, between 10 and 18% by weight, of at least one silicone or polysiloxane, in each case based on the total weight of said layer (4),

and claim 13 of the parent application reads as follows:

• Leather according to one of claims 1 to 12 of the parent application, characterized in that the crosslinked polyurethane of the outer layer (4) contains the smallest polysiloxane particles having a particle size of not more than 30 μm up to a volume fraction of not more than 15%,

and Claim 14 of the parent application reads as follows:

• Leather according to claim 12 or 13 of the parent application, characterized in that the silicone or polysiloxane is embedded in the outer layer (4) in the form of very small rubber-like solid particles, preferably of such micro-particles,

and claim 15 of the parent application reads as follows:

• Leather according to one of Claims 12 to 14 of the parent application, characterized in that the silicone or polysiloxane particles are in the form of relatively high molecular weight polysiloxane oils having molecular weights of about 2,000 to about 100,000, preferably those having molecular weights of more than 5,000, which have been introduced via an emulsion with water into the polyurethane of the outer layer (4) before its crosslinking,

and Claim 16 of the parent application reads as follows:

• Leather according to one of Claims 1 to 15 of the parent application, characterized in that the outer layer (4) formed from a dispersion formed with a medium-hard branched polyurethane and then solidified or crosslinked polyurethane is in addition to the very small solid silicone or Polysiloxanpartikeln, preferably with properties of a very soft silicone rubber, also higher molecular weight introduced via an emulsion silicones are introduced,

and Claim 17 of the parent application reads as follows:

• Leather according to one of claims 1 to 16 of the parent application, characterized in that the cross-linked polyurethane of the outer layer (4) hollow microspheres, preferably made of a thermoplastic material having a maximum diameter of 60 microns and in an amount of between 0.3 and 8 wt. %, in each case based on the total coating (5),

and claim 18 of the parent application reads as follows:

• Leather according to one of Claims 1 to 17 of the parent application, characterized in that the thickness (do) of the outer layer (4) is 0.04 to 0.1 mm,

and claim 19 of the parent application reads as follows:

• Leather according to one of claims 1 to 18 of the parent application, characterized in that the outer layer (4) any surface or embossed structure (41) and / or fatigue, but preferably appearance and feel of a nubuck leather with a microscopically rough surface with elevations and Wells in the range between 0.005 and 0.02 mm, has.

• Leder, vorzugsweise beschichtetes Spaltleder, insbesondere Rindspaltleder, nach einem der Ansprüche 1 bis 19 der Stammanmeldung, dadurch gekennzeichnet, dass die Mittelschicht-Lage (3') aus einer schließlich verfestigten bzw. vernetzten, an sich bekannten Polyurethandispersion gebildet ist, welche vor dem Vernetzen thermoplastische Eigenschaften und eine im wesentlichen nicht verzweigte bzw. lineare Struktur und hohe Klebeeigenschaften aufgewiesen hat,

und Anspruch 21 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 20 der Stammanmeldung, dadurch gekennzeichnet, dass die Mittelschicht-Lage (3") und/oder die Verbindungsschicht-Lage (3") Mikrohohlkugeln mit einem Volumsanteil von maximal 10% enthält.

As far as the material of the adhesive layer or the same forming layer layers is concerned, reference should be made to claims 20 and 21 of the parent application, whereby claim 20 of the parent application reads as follows:

• Leather, preferably coated split leather, in particular cow split leather, according to one of claims 1 to 19 of the parent application, characterized in that the middle layer layer (3 ') is formed from a finally solidified or crosslinked, known per se polyurethane dispersion which prior to crosslinking has exhibited thermoplastic properties and a substantially non-branched or linear structure and high adhesive properties,

and claim 21 of the parent application reads as follows:

• Leather according to one of claims 1 to 20 of the parent application, characterized in that the middle layer layer (3 ") and / or the bonding layer layer (3") contains hollow microspheres with a volume fraction of at most 10%.

Another essential object of the invention is a further improvement of the essential new properties of the leather according to the invention by applying a finish layer on its outer layer. This finish layer has been mostly on a polymer or polyurethane layer and is formed for environmental reasons from aqueous polyurethane dispersions. This finish is relatively thick, usually even more than 0.01 mm. Such polyurethane finish layers are usually hard and do not have good hydrolysis properties.

To improve the feel and the color and abrasion properties, in particular for vehicle and shoe leather, the outer layers applied to the outer layers then contain leather silicone emulsions and / or dispersions or are constructed with these. These silicone emulsions are prepared, for example, from low to medium molecular weight oils with the concomitant use of emulsifiers. The emulsifiers and oils emigrate to the surface over time and are worn away in use.

It is further known to include absorbent materials, such as e.g. To impregnate fabric or leather with silicone emulsions.

A disadvantage of the conventional polyurethane-containing finish layers is that, due to their relatively high thickness of about 0.01 mm, they close the pores present in the underlying layers, which leads to the reduction of a pre-existing air and water vapor permeability. In the fresh state, so long as the silicone emulsions are still present as such, these finish layers are also slightly hydrophobic. With perforated leather, aqueous liquids penetrate unhindered through the entire finish into the leather and lead to fungal growth and bad odors. Aqueous products such as coffee, red wine or ketchup leave non-removable contaminants, especially if the silicone emulsion has emigrated in whole or in part.

A further object of the present invention is therefore to provide a natural leather with a coating or dressing in which the outer finish layer does not have these disadvantages, ie is itself resistant to hydrolysis and the underlying, formed from a solidified, polyurethane-containing dispersion Outer layer protects. In addition, the finish layer should be thin so that it does not close existing or introduced pores.

It should also be soft and have a particularly good feel, it should not contain emulsifiers, far as the wet properties are deteriorated, furthermore it should be light, scratch and abrasion resistant, permanently water repellent, transparent to colored transparent, free from VOC, heat resistant and be dirt-repellent.

Furthermore, the finishing layer should not be able to be polished and the products equipped therewith, e.g. Car seats, steering wheels, furniture covers or shoes should not change their gloss over time.

A further object of the invention is to ensure that continuous perforations in the leather and optionally provided in the dressing or coating capillaries and / or pores for improving the water vapor and air permeability are open or remain and that further also the possibility consists of eliminating the wicking of sewing threads or a water transport, eg in shoes, from the outside in, to prevent what e.g. in so-called Semianilinleder still represents a major problem.

• Leder, insbesondere nach einem der Ansprüche 1 bis 21 der Stammanmeldung, dadurch gekennzeichnet, dass es auf der Außenseite (40) seiner Außenschicht (4) eine dünne abschließende wasserabweisende Finishschicht (6) aufweist, welche mit Siliconteilchen im Nano-Bereich gebildet ist, insbesondere aus Siliconteilchen im Nano-Bereich besteht, und frei von Emulgatoren ist und mit der Polyurethanmaterial der Außenschicht (4) bzw. im wesentlichen untrennbar verbunden ist.

Finally, the applied finish layer should mechanically, physically or chemically protect the underlying polyurethane-formed outer layer and thus also the leather surface.
These objects are achieved in a leather of the type mentioned above with the features mentioned in the characterizing part of claim 22 of the parent application, Claim 22 of the parent application reads as follows:

• Leather, in particular according to one of claims 1 to 21 of the parent application, characterized in that on the outer side (40) of its outer layer (4) has a thin final water-repellent finish layer (6) which is formed with silicone particles in the nano-range, in particular consists of silicone particles in the nano-range, and is free of emulsifiers and is connected to the polyurethane material of the outer layer (4) or substantially inseparable.

The invention thus provides that an emulsifier-free, extremely finely divided, almost water-clear, transparent aqueous silicone emulsion having particle sizes in the nanometer range and having a solids content of less than 5%, preferably less than 2.5%, and a viscosity similar to water on the polyurethane layer applied and firmly connected to this. On the polyurethane outer layer, a hydrophobic finish layer is formed which, in the solidified state, is thinner than 0.009 mm, preferably thinner than 0.007 mm.

This finish layer is advantageously colorless transparent and also penetrates into capillaries, hair pores, as well as in perforations and pores in the polyurethane coating of the leather, in particular in its outer opening area and prevents even with perforated leather that a drop of water under static conditions through the perforations, etc Does not penetrate into the leather, even if the perforations od. Like. Have a diameter of 0.5 mm. The surface tension of the water on this finish layer is so great that a droplet stops on the hydrophobic surface and can not penetrate into a perforation or capillary.

A previously existing air and water vapor permeability of natural leather is not or not significantly changed by the applied finish layer. The finish layer is so thin that, for example, 1m ^{2 of} leather with the finishing layer only weighs about 4 grams more than the leather without the layer.

It has been found that the hydrolysis behavior of the polyurethane outer layer has been substantially improved by the application of the described finish layer, since the latter is resistant to hydrolysis and makes the access of water to the outer layer more difficult, which is of particular importance for vehicle seats in hot and humid climates.

Furthermore, it was surprisingly found that the leather provided with the silicone finish layer according to the invention is not only water-repellent, but also has outstanding properties with respect to its creaking behavior.

If a water-resistant polyurethane outer layer without a silicone finishing layer as described previously comes into contact with water, where it is wetted and the water remains on it without penetrating, but if there is a finish layer, the water will roll off from it.

Finally, the finish layer penetrates water, aqueous soil and other water-containing liquids, such as water. Milk, red wine, e.g. in perforated leather car seats, prevented or permanently difficult. Rain showers leave no damage on the seats of a cabriolet, especially not because the wicking effect of the suture can be eliminated by means of the material of the finish layer in the region of the seams.

The finish layer, which advantageously has a density of less than 1, gives the leather a particularly pleasant feel and a "silky" feel, which does not change its properties even during long use. The thin, transparent "silky-glossy" finish layer reflects the color depth of the pigmented underlying polyurethane outer layer well.

The leather provided with the finish layer according to the invention has a particularly good flex life. Especially at low temperatures, it is far superior to a leather with conventional finishes. Thus, at temperatures of -20 ° C, 50,000 flexes are achieved, whereas with conventional leathers the surface already shows damage at 5,000 flexes.

Silicone emulsions in the polyurethane outer layer, which otherwise tend to emigrate and, because of their separating action, have an adhesive effect, even have a positive effect because they have an affinity for the silicone nanoparticles, resulting in a good bond between the solidified, polyurethane-containing aqueous dispersion outer layer and the finish layer leads. The finish layer even largely prevents emigration of the oily constituents of a silicone emulsion present in the polyurethane layer coating or in its outer layer.

• Leder nach einem der Ansprüche 1 bis 22 der Stammanmeldung, dadurch gekennzeichnet, dass die vorwiegende Größe der Silicon-Nanoteilchen in der einen zusammenhängenden Film bildenden Finishschicht (6) in einem Bereich von 1 bis 25 nm, vorzugsweise 8 bis 16 nm, liegt,

und Anspruch 24 der Stammanmeldung wie folgt lautet:

• Leder nach Anspruch 1 bis 23 der Stammanmeldung, dadurch gekennzeichnet, dass die Dicke der Finishschicht (3) 0,0005 bis 0,009 mm, insbesondere 0,003 bis 0,007 mm, und vorzugsweise 0,001 bis 0,004 mm, beträgt, und/oder dass die Finishschicht (6) eine Dichte kleiner 1 besitzt,

und Anspruch 25 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 24 der Stammanmeldung, dadurch gekennzeichnet, dass die, insbesondere offenporig ausgebildete, Polyurethan-Beschichtung (5) Kapillaren, Perforationen und/oder Poren (7) enthält, die in bzw. an ihren Innenwandflächenbereichen bzw. auf ihren Oberflächen mit der Finishschicht (6) ausgekleidet bzw. beschichtet sind,

und Anspruch 26 der Stammanmeldung, wie folgt lautet:

• 26. Leder nach einem der Ansprüche 1 bis 25 der Stammanmeldung, dadurch gekennzeichnet, dass die Nanoteilchen in der Finishschicht (6) mit Polydimethylsiloxan gebildet sind,

und Anspruch 27 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 26 der Stammanmeldung, dadurch gekennzeichnet, dass in der Finishschicht (6) die Nanoteilchen in einer ersten Form, nämlich als Poly[3-((2_-aminoethyl)amino)propyl]methyl(dimethyl)siloxan, insbesondere 2-hexyloxyethoxy-terminiert, und/oder in einer zweiten Form, nämlich als Poly[3-((2-aminoethyl)amino)propyl]methyl(dimethyl)siloxan, insbesondere methoxy-terminiert, vorliegen, wobei gegebenenfalls das Verhältnis der ersten Form zur zweiten Form zwischen 7:1 und 3:1, vorzugsweise zwischen 6:1 und 4:1, liegt,

und Anspruch 28 der Stammanmeldung, wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 27 der Stammanmeldung, dadurch gekennzeichnet, dass die Finishschicht (6) transparent ist und aus einer transparenten, verfestigten Siliconemulsion gebildet ist,

und Anspruch 29 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 28 der Stammanmeldung, dadurch gekennzeichnet, dass die Finishschicht (6) einen zusammenhängenden, dünnen Film bildet, der frei von flüchtigen Bestandteilen ist,

und Anspruch 30 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 29 der Stammanmeldung, dadurch gekennzeichnet, dass die Finishschicht (6) Diethylen-Glykolmonobutylether in einer Menge von weniger als 1 Gew.-% enthält,

und Anspruch 31 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 30 der Stammanmeldung, dadurch gekennzeichnet, dass die Finishschicht (6) einen Polyisocyanat-Anteil zwischen 1 und 15 Gew.-%, vorzugsweise einen Anteil zwischen 1 und 7 Gew.-%, insbesondere zwischen 1 und 5 Gew.-%, jeweils bezogen auf den Anteil der Silicon-Nanopartikel besitzt,

und Anspruch 32 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 31 der Stammanmeldung, dadurch gekennzeichnet, dass im Leder (2) vorhandene Nähte und/oder deren Nahtloch-Wandflächen mit der emulgatorenfreien Finishschicht (6) beschichtet sind,

Die Ansprüche 33 bis 38 der Stammanmeldung betreffen nähere Einzelheiten der Haftschicht, bzw. von deren Mittelschicht-Lage und Verbindungsschicht-Lage der erfindungsgemäßen Leder, wobei Anspruch 33 der Stammanmeldung, wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 32 der Stammanmeldung, dadurch gekennzeichnet, dass die Polymer- , insbesondere Polyurethanmaterialien, sowohl der Mittelschicht-Lage (3') als auch der Verbindungsschicht-Lage (3") von Silicon- und Fluorpolymer(en) frei sind,

und Anspruch 34 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 33 der Stammanmeldung, dadurch gekennzeichnet, dass die Polymer- , insbesondere Polyurethanmaterialien der Mittelschicht-Lage (3') und der Verbindungsschicht-Lage (3") im wesentlichen einander ähnliche oder fast gleiche Zusammensetzungen und/oder Ausgangsmolekülgrößen aufweisen,

und Anspruch 35 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 34 der Stammanmeldung, dadurch gekennzeichnet, dass dessen wasserabweisende Beschichtung (5) maximal 0,15 mm, vorzugsweise weniger als 0,15 mm, und besonders bevorzugt weniger als 0,12 mm Schichtdicke aufweist und über keine nennenswerte oder eine beabsichtigte Wasserdampfdurchlässigkeit verfügt,

und Anspruch 36 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 35 der Stammanmeldung, dadurch gekennzeichnet, dass die Mittelschicht-Lage (3') und die mit ihr und mit der Lederoberfläche (20) verbundene Verbindungsschicht-Lage (3") gemeinsam eine höhere Schichtdicke (dmv) aufweisen als die Außenschicht (4),

und Anspruch 37 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 36 der Stammanmeldung, dadurch gekennzeichnet, dass die Dicke (df) der Außenschicht (4) zwischen 30 und 45% und die gemeinsame Dicke (dmv) von Mittelschicht-Lage (3') und Verbindungsschicht-Lage (3") zwischen 70 und 55 %, jeweils bezogen auf die Gesamtdicke (db) der Beschichtung (5), beträgt,

und Anspruch 38 der Stammanmeldung, wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 37 der Stammanmeldung, dadurch gekennzeichnet, dass jede der die Beschichtung (5) des Spaltleders (1) bildenden Schichten und Schichtlagen (3; 3', 3", 4) von Zinn bzw. von jeglicher Zinn-Verbindung freigehalten ist.

Die Ansprüche 39 bis 42 der Stammanmeldung beschäftigen sich mit dem in den Ledern in den verschiedenen bisher beschriebenen Ausführungsformen z.B. herstellungstechnisch vorhandenen und insbesondere in deren Beschichtungen eingebrachten Porenkanälen und Perforationen, wobei Anspruch 39 der Stammanmeldung, wie folgt lautet:

• Leder, insbesondere nach einem der Ansprüche 1 bis 38 der Stammanmeldung, dadurch gekennzeichnet, dass dessen Beschichtung (5) bzw. Außenschicht (4), bis in das Leder (2) hinein von auf mechanischem Wege, beispielsweise mittels Lochpfeifen oder -nadeln hergestellten Loch-Perforationen durchdrungen ist, wobei bevorzugterweise vorgesehen ist, dass sowohl die Beschichtung (5) bzw. Außenschicht (4) als auch die Innen-Oberflächen der Loch-Perforationen (7) sowohl in der Beschichtung (5) bzw. Außenschicht (4) als auch im Leder (2) mit der wasserabweisenden Nano-Ausrüstungsschicht (6) aus dem Siliconpolymer, vorzugsweise mit einer Dicke von 0,001 bis 0,004 mm, versehen ist,
  und Anspruch 40 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 39 der Stammanmeldung, dadurch gekennzeichnet, dass dessen Außenschicht (4) und die Haft- bzw. Klebeschicht (3), also die Beschichtung (5), bis in das Leder (2) hinein zur Verbesserung einer Wasserdampfdurchlässigkeit von, insbesondere mittels Funkenerosion (Coronartechnik) hergestellten, Loch-Perforationen (7) durchdrungen ist,

und Anspruch 41 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 40 der Stammanmeldung, dadurch gekennzeichnet, dass die Loch-Perforationen (7) bis in eine Tiefe von maximal 60% der Summe der Stärke bzw. Dicke des Leders (2) plus der Stärke bzw. Dicke der Beschichtung (5) bzw. Außenschicht (4) eingebracht sind,

und Anspruch 42 der Stammanmeldung wie folgt lautet:

• Leder nach einem der Ansprüche 1 bis 41 der Stammanmeldung, dadurch gekennzeichnet, dass es mit 3 bis 65, insbesondere mit 8 bis 18, Loch-Perforationen (7) pro cm² versehen ist, wobei die Lochperforationen, bevorzugterweise eine innere Weite von 0,01 bis 0,8 mm aufweisen.

Further details on advantageous embodiments of the leather according to the invention with the new finish layer can be found in claims 23 to 32 of the parent application, wherein claim 23 of the parent application reads as follows:

• Leather according to one of Claims 1 to 22 of the parent application, characterized in that the predominant size of the silicone nanoparticles in the one continuous film-forming finish layer (6) is in a range from 1 to 25 nm, preferably 8 to 16 nm,

and Claim 24 of the parent application reads as follows:

• Leather according to claims 1 to 23 of the parent application, characterized in that the thickness of the finish layer (3) is 0.0005 to 0.009 mm, in particular 0.003 to 0.007 mm, and preferably 0.001 to 0.004 mm, and / or that the finish layer (6 ) has a density less than 1,

and Claim 25 of the parent application reads as follows:

• Leather according to one of claims 1 to 24 of the parent application, characterized in that the, in particular porous, polyurethane coating (5) contains capillaries, perforations and / or pores (7) in or on their inner wall surface areas or on their Surfaces are lined or coated with the finish layer (6),

and Claim 26 of the parent application reads as follows:

• 26. Leather according to one of claims 1 to 25 of the parent application, characterized in that the nanoparticles are formed in the finish layer (6) with polydimethylsiloxane,

and Claim 27 of the parent application reads as follows:

• Leather according to one of claims 1 to 26 of the parent application, characterized in that in the finish layer (6) the nanoparticles are in a first form, namely as poly [3 - ((2 _- aminoethyl) amino) propyl] methyl (dimethyl) siloxane, in particular 2-hexyloxyethoxy-terminated, and / or in a second form, namely as poly [3 - ((2-aminoethyl) amino) propyl] methyl (dimethyl) siloxane, in particular methoxy-terminated, be present, where appropriate, the ratio of the first Form to the second form is between 7: 1 and 3: 1, preferably between 6: 1 and 4: 1,

and Claim 28 of the parent application reads as follows:

• Leather according to one of claims 1 to 27 of the parent application, characterized in that the finish layer (6) is transparent and is formed from a transparent, solidified silicone emulsion,

and Claim 29 of the parent application reads as follows:

• Leather according to one of Claims 1 to 28 of the parent application, characterized in that the finish layer (6) forms a coherent, thin film which is free of volatiles,

and Claim 30 of the parent application reads as follows:

• Leather according to one of Claims 1 to 29 of the parent application, characterized in that the finish layer (6) contains diethylene glycol monobutyl ether in an amount of less than 1% by weight,

and Claim 31 of the parent application reads as follows:

• Leather according to one of claims 1 to 30 of the parent application, characterized in that the finishing layer (6) has a polyisocyanate content of between 1 and 15% by weight, preferably a proportion of between 1 and 7% by weight, in particular between 1 and 5 Wt .-%, in each case based on the proportion of silicone nanoparticles,

and claim 32 of the parent application reads as follows:

• Leather according to one of Claims 1 to 31 of the parent application, characterized in that seams present in the leather (2) and / or their seam-hole wall surfaces are coated with the emulsifier-free finish layer (6),

Claims 33 to 38 of the parent application relate to further details of the adhesive layer, or of its middle layer layer and tie layer layer of the leather according to the invention, wherein claim 33 of the parent application reads as follows:

• Leather according to one of Claims 1 to 32 of the parent application, characterized in that the polymer materials, in particular polyurethane materials, both the middle layer layer (3 ') and the tie layer layer (3 ") are free of silicone and fluoropolymer (s) are,

and Claim 34 of the parent application reads as follows:

• Leather according to one of Claims 1 to 33 of the parent application, characterized in that the polymer materials, in particular polyurethane materials, of the middle layer layer (3 ') and the tie layer layer (3 ") have substantially similar or almost identical compositions and / or starting molecular sizes exhibit,

and Claim 35 of the parent application reads as follows:

• Leather according to one of claims 1 to 34 of the parent application, characterized in that its water-repellent coating (5) has a maximum of 0.15 mm, preferably less than 0.15 mm, and more preferably less than 0.12 mm layer thickness and no significant or has an intended water vapor permeability,

and Claim 36 of the parent application reads as follows:

• Leather according to one of claims 1 to 35 of the parent application, characterized in that the middle layer layer (3 ') and the connecting layer layer (3 ") connected to it and to the leather surface (20) together have a higher layer thickness (dmv) as the outer layer (4),

and Claim 37 of the parent application reads as follows:

• Leather according to one of Claims 1 to 36 of the parent application, characterized in that the thickness (df) of the outer layer (4) is between 30 and 45% and the common thickness (dmv) of the middle layer layer (3 ') and the tie layer layer (3). 3 ") is between 70 and 55%, in each case based on the total thickness (db) of the coating (5),

and Claim 38 of the parent application reads as follows:

• Leather according to one of Claims 1 to 37 of the parent application, characterized in that each of the layers (5; 3 ', 3 ", 4) of the split leather (1) forming the coating (5) of tin or of any tin Connection is kept.

Claims 39 to 42 of the parent application are concerned with the pore channels and perforations present in the leathers in the various embodiments described hitherto, for example, and in particular in their coatings, claim 39 of the parent application being as follows:

• Leather, in particular according to one of claims 1 to 38 of the parent application, characterized in that its coating (5) or outer layer (4), up into the leather (2) of by mechanical means, for example by means of perforated pipes or needles produced hole -Perforationen is, wherein it is preferably provided that both the coating (5) or outer layer (4) and the inner surfaces of the hole perforations (7) in both the coating (5) and outer layer (4) as also provided in the leather (2) with the water-repellent nano-finishing layer (6) of the silicone polymer, preferably with a thickness of 0.001 to 0.004 mm,
  and claim 40 of the parent application reads as follows:

• Leather according to one of claims 1 to 39 of the parent application, characterized in that its outer layer (4) and the adhesive or adhesive layer (3), ie the coating (5), into the leather (2) in order to improve a water vapor permeability penetrated by, in particular by means of spark erosion (corona technology), hole perforations (7),

and Claim 41 of the parent application reads as follows:

• Leather according to one of Claims 1 to 40 of the parent application, characterized in that the perforations (7) extend to a maximum depth of 60% of the sum of the thickness of the leather (2) plus the thickness of the coating (5) or outer layer (4) are introduced,

and Claim 42 of the parent application reads as follows:

• Leather according to one of claims 1 to 41 of the parent application, characterized in that it is provided with 3 to 65, in particular with 8 to 18, perforations (7) per cm ² , the perforations, preferably an inner width of 0, 01 to 0.8 mm.

If, for certain applications, in particular in the shoe or vehicle sector, a certain water vapor permeability of the new leather is additionally required, the coating of the leather can be perforated mechanically or physically, preferably so that only the coating in its entirety - ie through the coating throughout - Is perforated, and the perforations from the top or surface of the outer layer her only partially penetrated into the leather is, for example, up to about 50% or 60%.

By perforating, e.g. understood the piercing with blunt needles with a diameter of less than 0.3 and 1.6 mm.

Preferably, between 4 and, for example, 72 fine channels per cm ² are arranged. After perforating, the thin coating is coated with the silicone nanoparticle dispersion forming the finish layer in a thickness as disclosed, but such that the walls of the perforations are also lined, but the perforations are not clogged thereby and are thus water vapor permeable to the outside are.

According to the invention, the mechanical or physical perforation may be applied to the entire split leather piece or to a size part, e.g. a shoe or saddle done. According to the invention, the thin silicone nanoparticle coating can also be applied to the finished shoe or the finished part of a vehicle seat.

• Vor allem bei der nubuk-artigen Beschichtung entstehen produktionsbedingt sehr wenige, sehr feine Kapillaren, welche die gesamte Beschichtung durchdringen. Diese Kapillare sind aber so klein bzw. eng, nämlich im Mittel weniger als 0,03 mm, dass sie optisch nicht wahrgenommen werden können und im Verhältnis zu den Halbkugelvertiefungen an der Außenseite, die nach innen hin geschlossen sind beträgt zum Oberflächenanteil in diesen geschlossenen Halbkugelvertiefungen zwischen 1 und maximal 10 %.

In addition, it should be noted that:

• Especially with the nubuck-type coating, very few, very fine capillaries, which penetrate the entire coating, are produced due to the production. However, these capillaries are so small or narrow, namely on average less than 0.03 mm that they can not be visually perceived and in relation to the hemispherical recesses on the outside, which are closed inwards to the surface portion in these closed hemispherical recesses between 1 and a maximum of 10%.

For certain applications, e.g. for safety shoes of group 2, it may be possible that the intended steam pressure liquid and the required water vapor number will not be reached.

In this case, the coating can additionally be mechanically perforated. The silicone nano-coating not only improves soiling behavior, it also prevents water from penetrating from the outside to and into the leather.

• Leder nach einem der Ansprüche 1 bis 42 der Stammanmeldung, dadurch gekennzeichnet, dass das vernetzte Polyurethan der Verbindungsschicht-Lage (3") mit sehr feinteiligen anorganischen Pulvern, insbesondere Keramik-Pulvern oder Quarz-Pulvern, mit einer Teilchengröße von maximal 60µm in einer Menge von 0,3 bis 10 Gew.- %, jeweils bezogen auf den Anteil an vernetztem Polyurethan, versetzt ist.

It has been found, see claim 43 of the parent application, that by the addition of finely divided ceramic (Ceramic) powder having a particle size of max. 60 microns, especially in an amount between 0.3 and 10 wt .-%, each based on the total coating, the temperature is dissipated more rapidly to the chrome-tanned substrate (split) leather, claim 43 of the parent application is as follows:

• Leather according to one of claims 1 to 42 of the parent application, characterized in that the crosslinked polyurethane of the tie layer layer (3 ") with very finely divided inorganic powders, in particular ceramic powders or quartz powders, having a particle size of not more than 60 μm in an amount from 0.3 to 10% by weight, in each case based on the proportion of crosslinked polyurethane, is added.

In place of ceramic powders, other inorganic powders, e.g. Quartz powder, used. This is very beneficial for safety shoes worn in a warm environment.

• Leder nach einem der Ansprüche 39 bis 43 der Stammanmeldung, dadurch gekennzeichnet, dass, insbesondere für Sicherheitsschuhe oder Teile derselben, zwischen dem Substrat-Leder (2) und der Oberflächen- bzw. Außenschicht (4) ein Gewebe oder Gewirke aus Fasern eines schnittwiderstandsfähigen Materials, insbesondere aus Polyaramidfasern, vorzugsweise mit einem Flächengewicht von 40 bis 85 g/m², angeordnet ist.

In safety shoes for use in industry and commerce, in which sharp or sharp-edged objects are to be manipulated, and where cut resistance is important, such as in particular in the field of glass production and processing, leather according to the invention have proven to claim 44 parent application which between the provided with micro-wells polyurethane outer layer and the substrate leather, eg in the adhesive layer, a woven or knitted fabric of a highly resistant yarn material, in particular based on polyaramid fibers or filaments, preferably with a basis weight of 40 to 85 g / m ² , wherein claim 44 of the parent application reads as follows:

• Leather according to one of claims 39 to 43 of the parent application, characterized in that, in particular for safety shoes or parts thereof, between the substrate leather (2) and the surface or outer layer (4) a woven or knitted fabric of fibers of a cut-resistant material , in particular of polyaramid fibers, preferably with a basis weight of 40 to 85 g / m ² , is arranged.

By itself, the total coating without tissue insert should be a maximum of 0.15 mm. When embedding a woven or knitted fabric, in particular of polyaramid fibers, the coating will increase approximately by the thickness of the fabric or knitted fabric, with the result that the thickness of the overall coating increases to approximately at least 0.30 mm.

To determine the total coating thickness, the polymer coating is separated from the leather separately from leather fibers and determined with a starch meter at a contact pressure of 1000 g per 1 cm ² . Without fabric insert, the thickness is between 0.09 and 0.15 mm.

• Leder nach einem der Ansprüche 1 bis 44 der Stammanmeldung, dadurch gekennzeichnet, dass die Innenseite des Substrat-Leders (2) mit Silicon-Emulsion beschichtet ist und/oder dass die Rückseite des Leders (2) zur Reduzierung einer Wasseraufnahme mit einer verfestigten Silicondispersion oder Siliconemulsion, welche feste Polysiloxanpartikel im Nano- und/oder Mikrobereich enthält, beschichtet bzw. imprägniert ist.

If in safety shoes in addition, the leather back is impregnated with the silicone nano-dispersion, as provided according to claim 45 of the parent application, water, which penetrates, for example by a damaged coating to the leather, not spread on the leather back and this Skin of the wearer near layer remains dry and thus comfortable, whereby claim 45 of the parent application reads as follows:

• Leather according to one of claims 1 to 44 of the parent application, characterized in that the inside of the substrate leather (2) is coated with silicone emulsion and / or that the backside of the leather (2) reduces water absorption with a solidified silicone dispersion or silicone emulsion, which polysiloxane solid particles in the nano and / or micro range contains, coated or impregnated.

The thin monolayer on the surface and the nano-impregnation on the leather backside practically do not affect the water vapor permeability. The leathers are and therefore remain waterproof from the outside, but they are water vapor permeable from the inside.

This back impregnation with the nano-silicone dispersion or emulsion not only prevents or not only reduces the water absorption from the back of the leather, it also has a very positive effect on the fire behavior of the leather according to the invention. Especially if this thin nano-layer is on the top of the finish and on the back of the leather and as impregnation, which has penetrated about 0.2 mm into the leather.

Even with the most stringent fire test tests, the leather does not burn or extinguish within a very short time. Such leathers even meet stringent fire performance tests for the aircraft industry.

• Sicherheitsschuh, dadurch gekennzeichnet, dass zumindest dessen Schaftmaterial zumindest teilweise mit einem Leder gemäß einem der Ansprüche 1 bis 45 der Stammanmeldung, insbesondere gemäß einem der Ansprüche 22 bis 45 der Stammanmeldung, gebildet ist.

The claim 46 of the parent application, refers to a safety shoe, which is at least partially made with a leather according to the invention, wherein claim 46 of the parent application, reads as follows:

• Safety shoe, characterized in that at least its shaft material is at least partially formed with a leather according to one of claims 1 to 45 of the parent application, in particular according to one of claims 22 to 45 of the parent application.

• Verfahren zur Herstellung eines beschichteten Leders mit einer Beschichtung (5) gemäß einem der Ansprüche 1 bis 46 der Stammanmeldung, dadurch gekennzeichnet, - dass eine Schar bzw. Anhäufung von eng bzw. dicht an dicht aneinander liegend angeordneten Mikrohohlkugeln in einen Polymermatrix-Block eingebettet bzw.eingebunden wird,
  • dass nach dessen Verfestigung der Polymermatrix-Block von seiner Oberfläche her im wesentlichen eben angeschliffen wird, wobei die Mikrohohlkugeln geöffnet werden und deren konkaven Innen-Oberflächen freigelegt werden,
  • dass dann unter Einsatz dieses, die angeschliffenen, etwa kugelschalenartige Innen-Oberflächen aufweisenden Mikrohohlkugeln enthaltenden Blocks durch Ver- bzw. Ausgießen mit einem Polymer, insbesondere mit einem Silikonpolymer, ein der Hohlkugelschalen-Struktur entsprechende glatte Erhebungen aufweisendes Negativ hergestellt wird, und,
  • dass auf dieses Negativ eine Dispersion des Außenschicht-Polymers, insbesondere - Polyurethans, aufgetragen wird, das nach Aushärtung mittels der Haftschicht mit der, vorzugsweise angeschliffenen, Oberfläche des Leders, insbesondere Spaltleders, nach Aufbringung der Haftschicht verbunden wird,
  und Anspruch 48 der Stammanmeldung wie folgt lautet:
  • Verfahren nach Anspruch 47 der Stammanmeldung, zur Herstellung eines beschichteten Leders mit einer Oberflächenschicht gemäß einem der Ansprüche 1 bis 46 der Stammanmeldung, dadurch gekennzeichnet,
    • dass eine Schar bzw. Anhäufung von eng bzw. dicht an dicht aneinander liegend angeordneten Mikrohohlkugeln in einen Polymermatrix-Block eingebettet bzw. eingebunden wird,
    • dass nach dessen Verfestigung der Polymermatrix-Block von seiner Oberfläche her im wesentlichen eben angeschliffen wird, wobei die Mikrohohlkugeln geöffnet werden und deren konkaven Innen-Oberflächen freigelegt werden,
    • dass dann unter Einsatz dieses, die angeschliffenen, etwa kugelschalenartige Innen-Oberflächen aufweisenden Mikrohohlkugeln enthaltenden Blocks durch Ver- bzw. Ausgießen mit einem Polymer, insbesondere mit einem Siliconpolymer, ein der Hohlkugelschalen-Struktur entsprechende glatte Erhebungen aufweisendes Negativ hergestellt wird, und,
    • dass auf dieses Negativ zur Bildung der Beschichtung zumindest eine Polyurethan-Dispersionschicht als Außenschicht aufgetragen wird, und dass auf diese Schicht nach ihrer Verfestigung eine weitere andere Polyurethan-Dispersionsschicht als Haftschicht oder Teillage der Haftschicht aufgetragen wird,
    • dass auch diese Schicht durch Wasserentzug verfestigt wird und dass darauf ein Leder, vorzugsweise ein Spaltleder, auf welches unmittelbar vorher die gleiche Polyurethan-Dispersion aufgetragen worden ist, mit der noch nassen Polyurethan-Dispersion aufgelegt und verpresst wird und dass nach dem Verpressen das Leder von der Unterlage entfernt
    wird und gegebenenfalls von der Außenseite der Beschichtung bzw. der Außenschicht her perforiert wird,
  während die Ansprüche 49 bis 61 der Stammanmeldung, sich auf verschiedene bevorzugte Ausführungsformen der mit Silicon-Nanopartikeln gebildeten Finishschicht beziehen, wobei Anspruch 49 der Stammanmeldung wie folgt lautet:
  • Verfahren, insbesondere nach Anspruch 47 oder 48 der Stammanmeldung zur Herstellung eines Leders insbesondere nach einem der Ansprüche 1 bis 45 der Stammanmeldung, das auf seiner Außen- bzw. Gebrauchsseite mit einer auf Polyurethandispersion basierenden Außenschicht versehen ist, dadurch gekennzeichnet, dass auf diese Außenschicht zur Ausbildung einer wasserabweisenden bzw. hydrophoben Finishschicht eine emulgatorfreie, feinteilige, wässrige Siliconemulsion aufgebracht wird, in der die Siliconteilchen als Nanoteilchen vorliegen und damit die einen zusammenhängenden Film ausbildende, und mit der Beschichtung bzw. mit der Poylurethan-Außenschicht untrennbar verbundene, hydrophobe Finishschicht ausgebildet wird,
  und Anspruch 50 der Stammanmeldung, wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 49 der Stammanmeldung, dadurch gekennzeichnet, dass zur Bildung der Finishschicht eine Siliconemulsion aufgebracht wird, in der Nanoteilchen mit einer Größe in einem Bereich von 1 bis 25 nm, vorzugsweise 8 bis 16 nm, enthalten sind,
  und Anspruch 51 der Stammanmeldung, wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 50 der Stammanmeldung, dadurch gekennzeichnet, dass die Siliconemulsion mit einer Dicke aufgebracht wird, dass die Dicke der aufgetrockneten Finishschicht (6) 0,0005 bis 0,009 mm, vorzugsweise 0,003 bis 0,007 mm, beträgt,
  und Anspruch 52 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 51 der Stammanmeldung, dadurch gekennzeichnet, dass im Leder, und gegebenenfalls in der Beschichtung bzw. Zurichtung ausgebildete bzw. vorhandene Kapillaren, Perforationen und/oder Poren auf ihren Innenwandflächenbereichen und auf ihrer Oberfläche mit der Finishschicht, beschichtet werden,
  und Anspruch 53 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 52 der Stammanmeldung, dadurch gekennzeichnet, dass eine Siliconemulsion auf die Beschichtung bzw. Außenschicht aufgesprüht wird, welche Nanoteilchen aus Polydimethylsiloxan enthält,
  und Anspruch 54 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 53 der Stammanmeldung, dadurch gekennzeichnet, dass eine Siliconemulsion auf die Beschichtung bzw. Außenschicht aufgesprüht wird, die Poly[3-((2-aminoethyl)amino)propyl]methyl(dimethyl)siloxan, insbesondere 2-hexyloxyethoxy-terminiert, und/oder Poly[3-((2-aminoethyl)amino)propyl]methyl(dimethyl) siloxan, insbesondere methoxy-terminiert, enthält,
  und Anspruch 55 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 54 der Stammanmeldung, dadurch gekennzeichnet, dass auf die Oberflächenschicht (4) eine emulgatorfreie, wässrige Siliconemulsion aufgesprüht wird, deren Feststoffanteil an Nanopartikel zwischen 0,8 und 5 Gew.-%, vorzugsweise zwischen 0,8 und 2,5 Gew.-%, liegt und/oder dass die Siliconemulsion eine Viskosität ähnlich Wasser besitzt,
  und Anspruch 56 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 55 der Stammanmeldung, dadurch gekennzeichnet, dass die Siliconemulsion in einer Menge von 10 bis 200 g/m², insbesondere von 20 bis 120 g/m², auf die Oberflächenschicht (2) aufgesprüht wird,
  und Anspruch 57 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 56 der Stammanmeldung, dadurch gekennzeichnet, dass die Siliconemulsion Isopropanol in einer Menge von 0,5 bis 8 Vol.- %, vorzugsweise 1 bis 5 Vol.-%, enthält,
  und Anspruch 58 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 57 der Stammanmeldung, dadurch gekennzeichnet, dass die Siliconemulsion bis zu 12 Vol.-%, vorzugsweise jeweils bis zu 6 Vol.-%, Diethylenglykolmonobutylether und/oder Ethylenglykolmonohexylether enthält,
  und Anspruch 59 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 58 der Stammanmeldung, dadurch gekennzeichnet, dass die eingesetzte Siliconemulsion wässriges, Polyisocyanat in einer Menge von 1 bis 15 Gew.-%, vorzugsweise 1 bis 7 Gew.-%, jeweils bezogen auf das Gewicht der Nanoteilchen, enthält,
  und Anspruch 60 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 59 der Stammanmeldung, dadurch gekennzeichnet, dass als Siliconemulsion eine Siliconöl-in-Wasser-Emulsion eingesetzt wird, in welcher die Siliconteilchen als Nanopartikel vorliegen,
  und Anspruch 61 der Stammanmeldung wie folgt lautet:
  • Verfahren nach einem der Ansprüche 47 bis 60 der Stammanmeldung, dadurch gekennzeichnet, dass nach dem Aufsprühen der Siliconemulsion ein Ablüften und/oder Trocknen bei Temperaturen bis 100°C erfolgt, bis die aufgebrachte hydrophobe Finishschicht (6) vollständig getrocknet an der Beschichtung bzw. Außenschicht (5) anhaftet bzw. abgetrocknet ist bzw. einen zusammenhängenden Film ausbildet.

Furthermore, the processes for producing the new leather constitute essential objects of the invention, wherein claims 47 and 48 of the parent application relate in particular to the formation of the nubuck-like surface of the leather coating or its outer layer, wherein claim 47 of the parent application, as follows is:

• A process for producing a coated leather having a coating (5) according to one of claims 1 to 46 of the parent application, characterized in that - a group or cluster of hollow microspheres arranged closely adjacent to one another is embedded in a polymer matrix block is included,
  • after its solidification, the surface of the polymer matrix block is ground essentially flat, whereby the hollow microspheres are opened and their concave inner surfaces are uncovered,
  • that then using this, the ground, containing approximately spherical shell-like inner surfaces having hollow microspheres block produced by pouring or pouring with a polymer, in particular with a silicone polymer, a hollow spherical shell structure corresponding smooth elevations having negative, and
  • a dispersion of the outer-layer polymer, in particular polyurethane, is applied to this negative, which after curing by means of the adhesive layer is bonded to the, preferably sanded, surface of the leather, in particular split leather, after application of the adhesive layer,
  and Claim 48 of the parent application reads as follows:
  • Process according to Claim 47 of the parent application, for the production of a coated leather having a surface layer according to one of Claims 1 to 46 of the parent application, characterized in that
    • a group or accumulation of hollow microspheres arranged closely or close to one another is embedded in a polymer matrix block,
    • after its solidification, the surface of the polymer matrix block is ground essentially flat, whereby the hollow microspheres are opened and their concave inner surfaces are uncovered,
    • that then using this, the sanded, about spherical shell-like inner surfaces containing hollow microspheres containing block by pouring or pouring with a polymer, in particular with a silicone polymer, a hollow spherical shell structure corresponding smooth elevations having negative is prepared, and
    • in that at least one polyurethane dispersion layer is applied as outer layer to this negative for the formation of the coating, and that a further, different polyurethane dispersion layer is applied to this layer after its solidification as an adhesive layer or partial layer of the adhesive layer,
    • that this layer is solidified by dehydration and that thereon a leather, preferably a split leather, on which immediately before the same polyurethane dispersion has been applied, is placed and pressed with the still wet polyurethane dispersion and that after pressing the leather of the pad removed
    is optionally perforated from the outside of the coating or the outer layer,
  while claims 49 to 61 of the parent application relate to various preferred embodiments of the finish layer formed with silicone nanoparticles, claim 49 of the parent application being as follows:
  • A method, in particular according to claim 47 or 48 of the parent application for the production of a leather, in particular according to one of claims 1 to 45 of the parent application, which is provided on its outer or use side with a polyurethane dispersion based on outer layer, characterized in that on this outer layer to Forming a water-repellent or hydrophobic finish layer an emulsifier-free, finely divided, aqueous silicone emulsion is applied, in which the silicone particles are present as nanoparticles and thus a continuous film forming, and inextricably linked to the coating or with the Poylurethan outer layer, hydrophobic finish layer is formed .
  and claim 50 of the parent application, as follows:
  • Method according to one of claims 47 to 49 of the parent application, characterized in that for the formation of the finish layer a silicone emulsion is applied, in which nanoparticles with a size in a range from 1 to 25 nm, preferably 8 to 16 nm, are contained,
  and Claim 51 of the parent application reads as follows:
  • Method according to one of claims 47 to 50 of the parent application, characterized in that the silicone emulsion is applied with a thickness such that the thickness of the dried finish layer (6) is 0.0005 to 0.009 mm, preferably 0.003 to 0.007 mm,
  and claim 52 of the parent application reads as follows:
  • Method according to one of claims 47 to 51 of the parent application, characterized in that in the leather, and optionally in the coating or dressing formed or existing capillaries, perforations and / or pores on their inner wall surface areas and on its surface with the finish layer coated become,
  and claim 53 of the parent application reads as follows:
  • Method according to one of claims 47 to 52 of the parent application, characterized in that a silicone emulsion is sprayed onto the coating or outer layer containing nanoparticles of polydimethylsiloxane,
  and claim 54 of the parent application reads as follows:
  • Process according to one of Claims 47 to 53 of the parent application, characterized in that a silicone emulsion is sprayed onto the coating or outer layer which comprises poly [3 - ((2-aminoethyl) amino) propyl] methyl (dimethyl) siloxane, in particular 2- hexyloxyethoxy-terminated, and / or poly [3 - ((2-aminoethyl) amino) propyl] methyl (dimethyl) siloxane, in particular methoxy-terminated, contains,
  and Claim 55 of the parent application reads as follows:
  • Method according to one of claims 47 to 54 of the parent application, characterized in that on the surface layer (4) an emulsifier-free, aqueous silicone emulsion is sprayed, the solids content of nanoparticles between 0.8 and 5 wt .-%, preferably between 0.8 and 2.5% by weight, and / or that the silicone emulsion has a viscosity similar to water,
  and Claim 56 of the parent application reads as follows:
  • Method according to one of claims 47 to 55 of the parent application, characterized in that the silicone emulsion is sprayed in an amount of 10 to 200 g / m ^2, in particular from 20 to 120 g / m ² on the surface layer (2),
  and claim 57 of the parent application reads as follows:
  • Process according to one of Claims 47 to 56 of the parent application, characterized in that the silicone emulsion contains isopropanol in an amount of 0.5 to 8% by volume, preferably 1 to 5% by volume,
  and Claim 58 of the parent application reads as follows:
  • Process according to one of Claims 47 to 57 of the parent application, characterized in that the silicone emulsion contains up to 12% by volume, preferably in each case up to 6% by volume, of diethylene glycol monobutyl ether and / or ethylene glycol monohexyl ether,
  and claim 59 of the parent application reads as follows:
  • Process according to one of Claims 47 to 58 of the parent application, characterized in that the silicone emulsion used comprises aqueous, polyisocyanate in an amount of 1 to 15% by weight, preferably 1 to 7% by weight, in each case based on the weight of the nanoparticles, contains
  and Claim 60 of the parent application reads as follows:
  • Process according to one of Claims 47 to 59 of the parent application, characterized in that a silicone oil in water emulsion in which the silicone particles are present as nanoparticles is used as silicone emulsion,
  and Claim 61 of the parent application reads as follows:
  • Method according to one of claims 47 to 60 of the parent application, characterized in that after the spraying of the silicone emulsion, a drying and / or drying takes place at temperatures up to 100 ° C until the applied hydrophobic finish layer (6) completely dried on the coating or outer layer (5) adheres or dries or forms a coherent film.

• Verfahren nach einem der Ansprüche 47 bis 61 der Stammanmeldung, dadurch gekennzeichnet, dass eine Polysiloxandispersion oder -emulsion, welche kleinste feste Teilchen im Nano- und/oder Mikrobereich enthält, zur Reduzierung der Wasseraufnahme, insbesondere bei Sicherheitsschuhen, auf die Lederrückseite (2) aufgesprüht und getrocknet wird,

und Anspruch 63 der Stammanmeldung wie folgt lautet:

• Verfahren nach einem der Ansprüche 47 bis 62 der Stammanmeldung, dadurch gekennzeichnet, dass in der Silicondispersion bzw. -emulsion bzw. in der Finishschicht (6) Nano- und/oder Mikropartikel enthalten sind, wobei 40 bis 60 % Vol.- oder Gew.-%, insbesondere 50 % Vol.- oder Gew.-%, Mikropartikel und Nanopartikel in der Finishschicht (6) enthalten sind,

und Anspruch 64 der Stammanmeldung wie folgt lautet:

• Verfahren nach einem der Ansprüche 47 bis 63 der Stammanmeldung, dadurch gekennzeichnet, dass der kristallinen Polymerdispersion für die Verbindungsschicht (3) oder -schichten (3', 3") 10 bis 45 Vol.-% einer Acrylatdispersion zugesetzt werden bzw. sind, die für sich allein zu weichen klebrigen Filmen führen würden, wie sie bei Holzklebstoffen bekannt sind,

und Anspruch 65 der Stammanmeldung wie folgt lautet:

• Leder für Sicherheitsschuhe, vorzugsweise aus Spaltleder in einer Stärke zwischen 1,7 und 2,2 mm, insbesondere nach einem der Ansprüche 1 bis 64 der Stammanmeldung, dadurch gekennzeichnet, dass die Polysiloxanimprägnierung maximal 0,6 mm in die Lederrückseite eingesogen bzw. eingezogen wird, und dass der restliche Teil des Leders bis zur Verbindungsschicht frei von Polysiloxan ist, und dass auch dieser Teil von der Schnittkante her gesehen wenig Wasser aufnimmt, sodass der Wikingtest erfüllt ist.

Further objects of the invention are set out in claims 62 to 65 of the parent application, claim 62 of the parent application being as follows:

• Method according to one of claims 47 to 61 of the parent application, characterized in that a polysiloxane dispersion or emulsion containing smallest solid particles in the nano- and / or micro-range, sprayed on the leather back (2) to reduce water absorption, especially in safety shoes and dried,

and claim 63 of the parent application reads as follows:

• Method according to one of claims 47 to 62 of the parent application, characterized in that nano and / or microparticles are contained in the silicone dispersion or emulsion or in the finish layer (6), with 40 to 60% by volume or by weight, in particular 50% by volume or by weight. %, Microparticles and nanoparticles are contained in the finish layer (6),

and Claim 64 of the parent application reads as follows:

• Method according to one of claims 47 to 63 of the parent application, characterized in that the crystalline polymer dispersion for the bonding layer (3) or layers (3 ', 3 ") are added 10 to 45 vol .-% of an acrylate dispersion, the would lead to soft, sticky films on their own, as they are known in wood adhesives,

and Claim 65 of the parent application reads as follows:

• Leather for safety shoes, preferably made of split leather in a thickness between 1.7 and 2.2 mm, in particular according to one of claims 1 to 64 of the parent application, characterized in that the polysiloxane impregnation is sucked in or drawn in a maximum of 0.6 mm into the leather back and that the remaining part of the leather is free of polysiloxane up to the bonding layer, and that also this part absorbs little water from the cutting edge, so that the viking test is fulfilled.

• Verwendung einer emulgatorfreien, wässrigen, feinteilige Nanopartikel enthaltende Siliconemulsion für die Hydrophobierung von Leder durch direktes Aufbringen auf die eine Polyurethan-Außenschicht (4) aufweisende Oberfläche eines Lederkörpers (2) in Form einer an dieser Schicht (4) fest anhaftenden Finishschicht (6),

und Anspruch 67 der Stammanmeldung wie folgt lautet:

• Produkte aus einem Leder gemäß einem der Ansprüche 1 bis 46 der Stammanmeldung, hergestellt nach einem Verfahren gemäß einem der Ansprüche 49 bis 65 der Stammanmeldung, insbesondere in Form von Schuhen, Sicherheitsschuhen, Handtaschen, Lederbekleidung, Oberflächen und Überzügen in Fahrzeugen, Schutzbekleidungen aus Leder, Koffern und Sitz- und /oder Liegemöbeln.

Anhand der Zeichnung wird die Erfindung näher erläutert:

• Es zeigen die Fig. 1 die Ansicht eines Schnittes durch das neue Leder, wie es grundsätzlich dem Anspruch 1 entspricht, die Fig. 2 eine Detail-Schnittansicht der Oberflächenschicht dieses neuen Leders und die Fig. 3 und 4 REM-Aufnahmen der Oberflächen dieses Leder mit unterschiedlichen Vergrößerungen.

Finally, the use of the silicone nanoparticle emulsion according to claim 66 of the parent application and the typical products of the new leather according to claim 67 of the parent application are important subject matter of the invention, wherein claim 66 of the parent application reads as follows:

• Use of an emulsifier-free, aqueous, finely divided nanoparticle-containing silicone emulsion for the hydrophobization of leather by direct application to the surface of a leather body (2) having a polyurethane outer layer (4) in the form of a finish layer (6) firmly adhering to this layer (4),

and Claim 67 of the parent application reads as follows:

• Products made of a leather according to one of claims 1 to 46 of the parent application, produced by a process according to one of claims 49 to 65 of the parent application, in particular in the form of shoes, safety shoes, Handbags, leather clothing, surfaces and coverings in vehicles, protective clothing of leather, suitcases and seating and / or reclining furniture.

Reference to the drawing, the invention is explained in more detail:

• It show the Fig. 1 the view of a section through the new leather, as it basically corresponds to claim 1, the Fig. 2 a detail sectional view of the surface layer of this new leather and the 3 and 4 SEM images of the surfaces of this leather with different magnifications.

The Fig. 5 to 8 show schematic views of the cross sections through the near-surface region of the new, provided with coating leather or split leather according to the invention and the Fig. 9 and 10 enlarged photographs of the outer surface of the finish layer, the structure of which has been formed here using a foamed polymer.

The Fig. 11 and Fig. 12 Finally, show enlarged schematic sections through the surface structure of a provided with a already as mentioned finish layer new leather.

The Fig. 1 shows how, for example, the ground, surface 20 of the substrate forming split leather 2 a coating 5 - here single-layer adhesive layer 3, for example, based on polyurethane surface is bound, to which in turn or to its surface 30, the novel, nubuck character having outer layer 4 is bound surface.

Said outer layer 4, which has a thickness do, has on its surfaces, in the regions Bnp not embossed 41, a multiplicity of micro-indentations 42 with inner widths lw, which are recessed into them, close to the surface and open to the surface, in the manner of hemispherical-shell-like concavities. preferably in the range of 20 to 80 microns, on.

The inner surfaces 421 of the spherical shell or dome-like micro-recesses 42 are at least microscopically smooth and therefore have a high light-reflecting capacity, they shine so, however, which is hidden from the unaided eye, however, when viewed with the microscope is quite visible.

On the other hand, the surfaces 431 of the webs 43 which surround the micro-depressions 42, in each case delimiting and mutually interconnected, are substantially rougher, they are matt to extremely fine-fibrous, which surface finish is e.g. from the ground surfaces of the negatives used to make the micro-wells 42.

The thickness or width ds of the webs 43 is a fraction of the inner width Iw of about halbkugelschalen-like concave micro-wells 42. The same are all the adhesive layer 3 towards the bottom closed and guarantee in addition to the full moisture resistance of the new coated leather 100, in particular its high Schmutzabweisevermögen.

The depth tv of the microwells 42 is of course related to their inner width lw and is for example 5 to 60 microns.

The narrow surfaces 431 of the borders or webs 43 are matt to extremely fine-fiber soft and flexible and convey the typical nubuck handle and the nubuck-like appearance in combination with the dirt-repellent smooth microwells 42.

When the surface of the new leather 100 formed by the narrow webs 43 is touched, only the soft, dull surface texture which mediates a perfect nubuck feeling is felt, whereby the micro-depressions 42 as such can not be perceived.

The micro-recesses 42 have, as already mentioned, a very smooth, homogeneous, that is, in themselves shiny, light-reflecting concave surface 421, which is under a light microscope at e.g. 50x magnification is clearly visible. The mentioned micro-depressions 42 or their surfaces 421 are smooth, homogeneous and liquid-tight on all sides.

The often even better than nubuck leather-looking, also so appealing new surface, consists in all parts in one piece of a soft cross-linked polyurethane.

The polyurethane has a hardness of at least less than 75 Shore A. The outer layer 4 can of course also pigments and other additives known per se in finishing layers, such as in particular handle, lubricants od. Like. Contain. The soil-repellent effect is also improved by the outer layer 4 contains per se known silicone particles, which are added to the polyurethane dispersion prior to solidification as a silicone dispersion or silicone emulsion.

The Shore hardness is determined after solidification of the polyurethane dispersion mixture into a film with a thickness of 5 mm.

The novel nubuck-like top or outer layer is preferably formed by evaporation of water from a polyurethane dispersion applied to a silicone rubber negative support having a multiplicity of positive spherical caps on the surface.

In the Fig. 1 It is further shown that, for example, for leather for safety shoes 5 perforations 7 can be introduced into the coating, which extend into the leather 2 inside. In this case, it is favorable if a silicone finish layer 6 is applied to the outer layer 4, which ultimately also covers the walls of the perforations 7 and optionally impregnates the leather 2. The beginning of the perforation 7 is in the Fig. 2 shown closer.

From the Fig. 1 is still evident, as the micro-wells 42 only in the not embossed areas Bnp of the finish layer 4, and the embossment 41 in the embossed area Bp.

The Fig. 2 illustrates - with otherwise constant reference numerals - the ratios described in the novel outer layer 4. There is the difference between the matte to fine-grained outer surface 431 of the micro-wells 42 surrounding ridges 43 and the light-reflecting smooth concave inner surface 421 of approximately hemispherical micro-wells 42 made clear.

With otherwise constant reference numerals, the two show 3 and 4 Scanning electron micrographs SEM images with 50 and 100 times magnification of the surface 40 of the novel outer layer 4 of the new coated leather 100 with the large number of - here dark - close together micro-wells 42 with their outwardly open, essentially hemispherical-like smooth inner surfaces 421 and the - here bright-webs 43 with relatively rough or matte surface 431 in those areas Bnp, where no embossment 41 has been made.

It is from the 3 and 4 Furthermore, it can be seen that the micro-depressions 42, which have self-contained borders, are not quite regular, and it should not go unmentioned that in extreme cases, for example, they may also have polyhedral, in particular hexahedral, shape or cross-sectional shape.

The Fig. 5 again shows the base forming split leather 2, the surface 20 is freed from its grain layer. At this surface 20, the bonding to the same surface, formed from a solidified, predominantly polyurethane-containing dispersion layer layer 3 "of the adhesive layer 3, whose top-side outer surface 30" to a preferably similar compound and with the same, possibly even partially chemically, connected middle layer layer 3 'of the adhesive layer 3 is adjacent.

This middle-layer layer 3 'is provided on its surface 30' with the silicone- or polysiloxane-containing, on its surface 40 a e.g. connected about hill-like structure 41 having outer layer 4.

Overall, the three layers or layers 3 and 3 ", 3 'and 4 just described form the db thick coating 5 of the leather 100 coated according to the invention, the common thickness dvm of the layer layers 3' and 3" being higher than the thickness df of the outer layer 4.

It is essential that in the z. B. produced on a hot die outer layer 4 formed there by surveys of the die, from its lower boundary surface 40 'of the outer layer 4 either to the surface 40 out full continuous tubes, passages, pores, cavities 45 or the like extend and / or recesses, depressions 45 'or the like, at least in the outer layer, but which still terminate within the outer layer 4.

In these initially existing tubes, passages 45 or the like and / or recesses, "depressions" 45 'or the like, protrude -with the polymer material of the middle-layer layer 3 and formed integrally therewith, here schematically as an approximately cylindrical pin 36'. and the recesses, recesses 45 'or the like, and the recesses, depressions 45' or the like, which are always fully filled and formally bound to the side walls of the filling or filling projections 36 'or 360, which in the case of continuous pores 45 od. Like. There to the surface 40 of the outer layer 4 range.

The mold-filling bodies 36 ', 360 are formed from a high-tack prior to solidification polymer dispersion, which in the same way as the rest of the middle layer layer 3' z. B. by crosslinking, has been solidified to the middle layer layer 3 '.

For example, an average of about 5 to 10 pores or recesses 45, 45 'which are present on the outer layer 4 and / or are not fully penetrating per cm ^{2 of} finish layer surface 40 are present.

Also in this Fig. 5 is schematically shown one of the introduced into the coating 5 hole perforations 7, as well as a bonded to the outer surface 40 nano-silicone finish layer 6, which also covers the wall of the perforation 7 and the leather 2 at least slightly impregnated at its bottom.

For otherwise constant reference numerals is from the Fig. 6 It can be seen that the here shown, fully outwardly through passages, tubes 45 or the like are filled approximately with frustoconical protuberances 36 'of the middle layer layer 3', which extend to the outer surface 40 of the outer layer 4.

Within one of these protuberances 36 'of the middle layer layer 3' forth here also approximately conical recess 35 'is formed, which in turn with a penetrated into it, about conical form-filling body 36 "from the polymer material of the bonding layer layer 3" filled is.

Of course, in this coating 5 perforations 7 analogous to Fig. 5 be introduced.

Furthermore, the shows Fig. 7 with otherwise constant reference numerals, a further embodiment of the leather 100 according to the invention with a frustoconical pore 45 extending to the outer surface 40 of the outer layer 4 or the like, which is provided with a continuous peg 36 'or the like from the polymer material of the middle layer 3'. fully satisfied.

Here, the pin 36 'od. Like. Also a full to the surface 40th the outer layer 4 passing pore 35 ', which in turn with an inner pin 36 "od. The like. From the polymer material of the bonding layer layer 3" is fully filled, which also only at the outer layer surface 40, there exposed ends. In this embodiment of the leather coating 5, a particularly high adhesion is ensured between the outer layer 4 and the layered bearings 3 'and 3 ".

The Fig. 8 shows - with otherwise constant reference numerals - a section through an inventive coated split leather 100, where there the anchoring pores 45 'od. Like. In the outer layer 4 does not go to the outer surface 40 and thus not the same filling layer anchoring pins 36' od. Like. From the polymer material of the middle layer layer 3 '.

In the Fig. 8 It can be clearly seen how the outer surface 40 of the outer layer 4 is formed by the "multi-spherical" surface, eg a spherically foamed polymer, having a hemispherical structure 41 and has a nubuck-like appearance.

The Fig. 9 and 10 show - with otherwise constant reference numerals - in 100x magnification - each have a plan view of the just mentioned, many approximately hemispherical depressions having, outer surface 40 of the outer layer 4 of the in the Fig. 8 coated split leather 100 shown.

In the finish layer, a total of 1.5 to 20 wt .-% polysiloxanes contained in grain leather or leather with a technical surface, this content of polysiloxanes is preferably 4 to 12 wt .-%, in leather with nubuck-like surface preferably 10 to 18 wt. %.

In the Fig. 11 , which explains the finish coating of the leather in more detail, is an enlarged section through a leather 100, that represented by a natural leather. On the leather body 2, a dressing 5 here with only one outer layer 4, which is optionally bonded to the leather 2 with an adhesive layer 3 and in the form of at least two polymer layer layers 4 ', 4 "formed with aqueous polymer dispersions, in particular polyurethane dispersion. At least two polyurethane layers 4, 4 "are expediently applied to the leather 2 as finish or coating 5. The inner (s) polyurethane layer (s) 4 'may be somewhat softer, in particular in order to improve the adhesion to the leather 2. The outboard (s) outer layer 4 'based on polyurethane can be made somewhat harder. Micro hollow spheres may be arranged or contained in at least one of these polymer layers.

6 denotes a finish layer applied to the polyurethane layer or to the outermost polyurethane layer, that is to say outer layer 4. This finish layer 6 is a thin, emulsifier-free, finely divided silicone finishing layer which comprises silicone particles in the nanometer range, in particular in the range from 1 to 25 nm, preferably 8 to 16 nm.

The thickness of the finish layer 6 applied to the outer layer 4 is about 0.0005 to 0.009 mm, preferably 0.003 to 0.007 mm.

In the near-surface inner wall region of capillaries 7, which are formed in the leather body 2 or in the outer and in the adhesive layer 4, 3, a finish layer 6 is also formed and the silicone emulsion also penetrates into the capillaries 7, but does not clog them, but forms at least in the upper or outer end of the capillaries 7, as from Fig. 11 it can be seen on the wall of a surface finishing or protective layer 6 from.

It can be seen that even under dynamic conditions, a water droplet 8 can not penetrate or penetrate to or into the leather 2 due to its surface tension with respect to the applied outer layer 4, the finisher 6 and the in-mold Fig. 6 At the bottom of the capillaries 7 trained impregnation of the leather 2, which substantially complicates the spread and penetration of water into the leather. Since the finish layer 6 is made extremely thin everywhere, it can line and thus protect the inner surfaces of the perforation openings 5. The same applies to pores and capillaries present in the outer and adhesive layer 4, 3, which are coated on their wall surfaces with the silicone emulsion of the finish layer 6.

Fig. 12 shows a full-grain leather, the surface of which was at best polished with a very fine-grained sandpaper (finer than 350 grit) before applying the polyurethane outer layer 4. The outer layer 4 containing, in particular, pigments, a crosslinker and a silicone emulsion with a thickness of, for example, about 0.015 mm is applied by spraying directly onto the grain surface of a, preferably colored, leather 2.

According to the invention, it is provided that in the finish layer 6, the nanoparticles in a first form, namely poly [3 - ((2-aminoethyl) amino) propyl] methyl (dimethyl) siloxane, in particular 2-hexyloxyethoxy-terminated, and / or in a second Form, namely poly [3 - ((2-aminoethyl) amino) propyl] methyl (dimethyl) siloxane, in particular methoxy terminated.

By "predominant size" is meant that at least 50 to 80%, in particular 60 to 95%, of the nano-particles present have the size specified in the characterizing portion of claim 23.

The inventively provided finish layer 6 adapts perfectly to the surface structure of the polyurethane-containing outer layer 4. The outer layer 4 can be so thin that you can see the hair pores of a full-grain leather. It can also be thicker and have an embossing; she may have a fantasy or manmade interface; it may have been applied indirectly or directly to the natural leather 2. Particularly preferred is their application to the new leather with nubuck-like outer surface.

In contrast to conventional finish layers which contain emulsions containing silicone emulsions, the finish layer 6 leads to unadulterated test results, in particular in the determination of abrasion resistance, whereas hitherto known ablatable silicone emulsions deposit on the test specimen and falsify the test result.

The finish layer 6 may also contain minor amounts of organic components such as e.g. Contain ethylene glycol monobutyl ether, with which the nanoparticles are connected to each other and with the polyurethane-containing outer layer 2. These crosslinked or compound components have so far been disregarded except polysiloxane, in the enumeration of the constituents of the finish layer 6.

According to the invention, in the seam area of e.g. Shoes or car seats, the wicking of the suture can be eliminated by a subsequent application of thin, transparent nano-silicone dispersion. An existing finish layer 6 does not interfere with this.

The polyurethane-containing, solidified aqueous or applied as aqueous dispersion outer layer 4 contains pigments and is in particular crosslinked with a modified Polyisocyannat. Preferably, it can also coarser silicone particles with sizes between 1 and 100 microns and / or liquid silicone, which is added via an emulsifier containing aqueous silicone emulsion of the polyurethane dispersion.

It has been found that even with a so-called semi-aniline leather - which means full-grain dyed leather with a polymer finish of less than 0.03 mm thickness, this dressing has continuous capillaries, - watery no longer removable contaminants neither on their surface 3 nor in the leather 1 arise because, as in Fig. 11 Even the leather 2 itself is partially hydrophobic and the setting and sticking of dirt in the leather itself is prevented or hindered. The dirt-repellent effect is achieved by a nubuck-like formation of the outer surface 40 of the outer layer 4, as shown in the Fig. 11 is implied, much reinforced.

The thin, extremely finely divided silicone emulsion penetrates the finest capillaries 7 in the case of full-grain leather 2 and partially penetrates into the leather 2 at the end of the capillaries 7 in the region 4. As a result, leather coated in this way behaves in a similar manner to water-repellent leather as fully waterproofed leather in barrels, but without the disadvantages that these leathers have.

The outer layer 4 as well as any existing in this layer 4 silicone emulsions, which always complicate the application of new layers due to their release properties, lead here to an improved connection of the layer layers 4 and 6, obviously in that the nano-particles of the Layer 6 with the microparticles in the outer layer 4 connect.
The hitherto regarded as negative feature that the dressing or coating 5 contains no nano-particle silicones, but silicones, which were introduced by means of emulsifiers and water in the dressing 5, as previously formed the finishing layer, according to the invention leads to a good Compounding the dressing 5 or the outer layer 4 with the finish layer 6 and improved in all respects properties.

Above all, the interaction of the layers 4 and 6, which each consist of different materials, results in these substantially improved properties of the leather 100.

The extremely fine polysiloxane nanoparticles of the layer 6 also penetrate into the microscopically rough surface depressions of the polyurethane outer layer 4.

The microscopic roughness of the outer layer 4 is unavoidable, because it results solely from the fact that the particles of the polyurethane dispersion forming them are greater than 2 microns and often greater than 5 microns. This allows the nano-particles of the finish layer 6 to deposit in these microscopically rough depressions.

As a result of this arrangement of the layer 6 on and, as it were, in the surface of the outer layer 4, substantial product improvements result, above all, in the mechanical / physical area, and in particular also in the feel of the new leather 100, because the finish layer 6 in contrast to a conventional one Ppolyurethan finish layer has no microscopic roughness or only to a much lesser extent.

Another advantage is the high temperature resistance, which shows no changes in the temperature range between - 30 ° C and + 200 ° C.

Through the interaction, namely that the extremely fine silicone nanoparticles of the finish layer 6 penetrate into the microscopically fine depressions or in the nubuck effect causing micro-depressions 41 of the polyurethane outer layer 4 and can not be removed from this position , causes layer 3 to be extremely resistant to abrasion and water repellency. An attempt to grind nano-layer 6 20 times with 220 grit abrasive paper at a pressure of 500 g / cm ² showed the surprising result that in the end the hydrophobic properties are still fully preserved.

The test was carried out in accordance with VESLIC according to DIN 11640.

After this test, the surface showed no change even at 6x magnification.

In general, it is noted that the outer layer 4 or the polyurethane coating advantageously coarser silicone particles between 1 and 100 μ contains. These solid particles are to be understood as meaning polysiloxane particles or polysiloxane resin particles.

Further, it has been found that a silicone dispersion applied to the surface of the outer layer 4 - as well as the finish layer 6 - is still more hydrophobic if not only nanoparticles but also microparticles are included in it, i. when nanoparticles and microparticles form this layer 6. It is also expedient to use a dispersion which forms the layer 6 only with microparticles. Advantageously, 40 to 60% by weight or by volume of microparticles and 40 to 60% by volume or by weight of nanoparticles are used. In particular, equal amounts can be used.

In order to achieve the high requirements for safety shoes of group S 2 (corresponds to DIN EN ISO 20345 - 20347) and only a certain water absorption of the leather, as well as to achieve little or no water passage at a given water vapor permeability, it makes sense according to the invention Leather, preferably split leather, to use, which are not hydrophobic equipped, because this could lead to a possibly insufficient adhesion with the aqueous coatings, but to use leather that meet the Wikingtest, in combination with the outer layer 4 according to the invention with its hydrophobic surface layer. 6 which meet these requirements perfectly, especially if the leather from the back with the nano- and / or microparticles containing polysiloxane or emulsion are coated or impregnated. The leathers then not only take from the top, even if they have there pores for the water vapor permeability, but also from the back little or no water.

Especially if the leather or the outer layer should have the appearance of nubuck, it is important that the adhesive layer is soft in use, to improve the feel.

According to the invention, acrylates are added to the crystalline polyurethane-containing dispersion or the polyurethane dispersions as softening components, namely those which would lead to extremely soft, sticky films having a hardness of less than 15 Shore A alone, in an amount such that the connecting layer 3 or connecting layers 3 ', 3 "are formed with 10 and 45 vol .-% acrylate, based on the polyurethane content of the bonding layer or layers.

For the purposes of the invention goat leather can also be provided or used with the coating according to the invention. Above all, the nubuck optics is of special interest for this purpose.

According to the invention, silicone resin particles having a size of less than 20 μ, preferably less than 6 μ, in the outer layer 4 alone or in addition to the other Silicone rubber particles and / or higher molecular weight silicone particles may be present with a volume fraction up to 7%. Advantages arise when the silicone resin particles in combination with the silicone micro and / or nanoparticles form the thin finish layer 6, especially in leather with a nubuck-like surface finish. The silicone resin particles can also form layer 6 on nubuck leather alone. The resin particles are applied to the coated leather as dispersion or emulsion at the end of the manufacturing process.

It should be noted that the surface layer 4 may have production-related pores and capillaries. These openings can be closed again; such a surface is considered waterproof, but not necessarily water vapor-tight and airtight.

Water resistance thus does not mean that no steam passes. A water vapor permeability from the leather side is always present. If the case occurs that the water vapor permeability for safety shoes is too small, perforations could be formed. Even if there are pores and capillaries in the outer layer 4, however, this layer does not absorb water because it contains considerable amounts of silicone and because it is additionally hydrophobic due to the hydrophobic layer 6.

Claims (15)

A process for producing a coated leather, in particular cow split leather, of any fine-grained to coarse-grained, preferably nubuck-like, surface structure, with a coating (5), wherein the coating is formed with a surface layer formed with a mechanically and moisture-stable polymer , which is bound by means of a polymer-based adhesive layer to the surface of the leather or split leather, and bound to the surface of the leather or split leather nubuck-like, characterized by internal smoothness, formed with soft polyurethane outer layer (4), in the unembossed Area (Bnp) to the leather (2) towards substantially closed, but outwardly open, less than 130 .mu.m, in particular less than 80 .mu.m, inner width (Iw), having lathers like tight, close to each other densely arranged microwells (42 ), and
the microwells (42) each by itself by thin, outwardly a matte or fine-grained Feinraustruktur surface having, interconnected webs (43) are mutually limited and a substantially approximately (half) spherical shell-like shaped, outwardly facing, homogeneous gloss have a smooth, concave inner surface (421),
, characterized - that a band or accumulation of closely or densely embedded at close to each other horizontally arranged hollow microspheres in a polymer matrix block is bzw.eingebunden, that after its solidification, the polymer matrix block is ground substantially flat from its surface, whereby the hollow microspheres are opened and their concave inner surfaces are exposed, - That then using this, the ground, containing approximately spherical shell-like inner surfaces containing hollow microspheres block by pouring or pouring with a polymer, in particular with a silicone polymer, a hollow spherical shell structure corresponding smooth elevations having negative is prepared, and - that a dispersion of the outer layer polymer, and in particular this negative - polyurethane which is connected by means of curing the adhesive layer with the, preferably sharpened, surface of the leather, in particular split leather, after application of the adhesive layer is applied. A method according to claim 1 for producing a coated leather having a Surface layer, characterized - that a band or accumulation is closely or tightly embedded at close to each other horizontally arranged hollow microspheres in a polymer matrix block or integrated, - that the polymer matrix block is newly sanded on its surface thereof substantially after its solidification, wherein the hollow microspheres are opened and their concave inner surfaces are exposed, - That then using this, the ground, containing approximately spherical shell-like inner surfaces containing hollow microspheres block by pouring or pouring with a polymer, in particular with a silicone polymer, a hollow spherical shell structure corresponding smooth elevations having negative is prepared, and that at least one polyurethane dispersion layer is applied to this negative for forming the coating as the outer layer, and that a further different polyurethane dispersion layer is applied to this layer after its solidification as an adhesive layer or partial layer of the adhesive layer, - That this layer is solidified by dehydration and that thereon a leather, preferably a split leather, on which immediately before the same polyurethane dispersion has been applied, is placed with the still wet polyurethane dispersion and pressed and that after pressing the leather is removed from the pad and optionally perforated from the outside of the coating or the outer layer ago. A method according to claim 1 or 2 for producing a leather, which is provided on its outer or use side with a polyurethane dispersion based outer layer, characterized in that on this outer layer to form a water-repellent or hydrophobic finish layer, an emulsifier-free, finely divided, aqueous silicone emulsion is applied, in which the silicone particles are present as nanoparticles and thus the forming a continuous film, and inseparably connected to the coating or with the Poylurethan outer layer, hydrophobic finish layer is formed. Method according to one of claims 1 to 3, characterized in that in the leather, and optionally in the coating or dressing formed or existing capillaries, perforations and / or pores are coated on their inner wall surface areas and on its surface with the finish layer. Method according to one of claims 1 to 4, characterized in that the crystalline polymer dispersion for the bonding layer (3) or layers (3 ', 3 ") are added 10 to 45 vol .-% of an acrylate dispersion, which are alone alone would lead to soft sticky films, as they are known in wood adhesives. A method according to any one of claims 1 to 5, characterized in that the adhesive layer (3) having a central layer (3 ') and a compound layer sheet (2 ") is formed and od with a hot on a preferably having elevations. Like. , in particular nubuck-like, structured, of tin or organotin-free silicone underlay or - matrices of an aqueous, predominantly polyurethane-containing plastic dispersion prefabricated outer layer (4), and one formed on the same, connected to the same and ultimately arranged below the same, predominantly also from Adhesive layer (3) with a middle layer layer (3 ') and a bonding layer layer (3 "), which is likewise produced predominantly from a polyurethane-containing plastic dispersion which has been applied to the leather and which has the middle layer layer (3). 3 ') is formed, is formed, - That with at least one silicone polymer or silicone additive-containing polymer, in particular polyurethane, formed tin-free, preferably one with a formed by means of negative nubuck-like embossing outer surface (40) having outer layer (4) with a plurality of their the middle layer layer (3 ') facing side beginning and the outer layer (4) to its outer side or - Surface (40) is fully penetrating and / or within the outer layer (4) ending, low inner-width, cavities, hollow passages, capillaries, pores or openings (45) and / or recesses, cavities or depressions (45 ') is formed, - Which with the same penetrating or penetrated and the same occlusive, on the inner walls saturated bound and optionally anchored there, with the polymer, in particular polyurethane material of the middle layer layer (3 ') of the adhesive layer (3) integral molding or packing (36, 36 '), stalagmites, cones, rods, cylinders, cones or the like are filled. Method according to one of claims 1 to 6, characterized in that not only with the polymer, in particular polyurethane material of the middle layer layer (3 ') identical, one-piece polymer, in particular polyurethane material in the cavities, hollow passages, capillaries, pores (45 ), or openings, recesses or recesses (45 ') of the outer layer (4) has penetrated and fills them as filler (36) fully (up), but that in the mold-filling body (36), or in there beginning underside and within the same or up to the surface (40) of the outer layer (4) passing through cavities (35 ', 35) of the cavities of the outer layer layer (4') filling or molding (36 '36) and filling molded body (26 '26) from the polymer, in particular polyurethane material of the tie layer layer (3 ") identical, one-piece polymer, in particular polyurethane material fully penetrated and wall-anchored there. Method according to one of claims 1 to 7, characterized
in that the outer layer (4) with the micro-depressions (42) and the surface-matt, the same-bordering webs (43) is formed of a soft, cross-linked polyurethane having a hardness of less than 75 Shore A, in particular less than 55 Shore A. and or in that the inside width (Iw) of the micro-depressions (42) is 20 to 100 μm, in particular 30 to 80 μm, - That the depth (tv) of the micro-wells (42) 5 to 80 .mu.m, in particular 10 to 60 .mu.m, and - That the thickness (ds) of the webs (43) between the micro-wells (42) is 1 to 30 microns. Method according to one of Claims 1 to 8, characterized in that the outer layer (4) has a silicone matrix applied to it, for the shaping of its outer surface (40) and the pores (45), when it is foamed, Plastic material, rubber or the like. Formed, preferably round, in particular hollow spherical cell surface structure (41) and / or - That in the outer layer (4) between 1.5 and 20 wt .-%, preferably in grain leather or leather with technical surface between 4 and 12 wt .-% or preferably at Nubuklederartiger surface 10 to 18 wt .-%, at least of a silicone or polysiloxane, in each case based on the total weight of said layer (4). Method according to one of claims 1 to 9, characterized in that the crosslinked polyurethane of the outer layer (4) hollow microspheres, preferably of a thermoplastic material having a diameter of not more than 60 microns and in an amount of between 0.3 and 8 wt .-% , in each case based on the total coating (5) contains and / or the outer layer (4) has any surface or embossing structure (41) and / or mattness, but preferably the look and feel of a nubuck leather with a microscopically rough surface with elevations and depressions in the region between 0.005 and 0.02 mm. Method according to one of claims 1 to 10, characterized in that the middle layer layer (3 ') is formed from a finally solidified or crosslinked, known per se polyurethane dispersion, which prior to crosslinking thermoplastic properties and a substantially non-branched or linear structure and high adhesive properties. Method according to one of claims 1 to 11, characterized in that the, in particular open-pored trained, polyurethane coating (5) capillaries, perforations and / or pores (7) containing in or at their Innanwandflächenbereichen or on their surfaces with the finish layer (6) are lined or coated Method according to one of claims 1 to 12, characterized in that the polymer, in particular polyurethane materials of the middle layer layer (3 ') and the tie layer layer (3 ") have substantially similar or almost identical compositions and / or starting molecular sizes. Method according to one of Claims 1 to 13, characterized in that its coating (5) or outer layer (4) is penetrated into the leather (2) by perforated perforations produced by mechanical means, for example by means of perforated pipes or needles , wherein it is preferably provided that both the coating (5) or outer layer (4) and the inner surfaces of the hole perforations (7) in both the coating (5) and outer layer (4) and in leather ( 2) is provided with the water-repellent nano finishing layer (6) of the silicone polymer, preferably with a thickness of 0.001 to 0.004 mm. A method according to any one of claims 1 to 14, characterized in that, in particular for safety shoes, or portions thereof, between the substrate-leather (2) and the surface or outer layer (4) is a woven or knitted fabric of fibers of a cut resistant material, in particular of polyaramid fibers, preferably with a basis weight of 40 to 85 g / m ² , is arranged, and / or - That the inside of the substrate leather (2) is coated with silicone emulsion and / or that the back of the leather (2) to reduce water absorption with a solidified silicone dispersion or silicone emulsion, which contains polysiloxane solid particles in the nano and / or micro range , coated or impregnated.

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