权利要求：
1. Method for producing a surface-structured layered material which has a carrier layer (1) and a layer (2) made of polyurethane connected thereto, wherein as a carrier layer (1), present in particular in piece form, a leather, preferably a buffed grain leather or a cowhide split leather, a textile material, preferably a woven fabric or a knitted fabric, a cellulose fibre material, a split foam, a leather fibre material or a microfibre fleece, is used and is connected with the layer (2), wherein on the carrier layer (1) is applied as a layer (2) at least one, preferably one single, layer made of a thermoplastic polyurethane foam particularly containing gas bubbles, preferably a polyurethane impact foam containing hollow microspheres and/or a polyurethane foam containing hollow microspheres, characterised in - that the polyurethane foam containing in particular gas bubbles is produced with a polyurethane dispersion mixture, wherein the individual polyurethane dispersion used for the production of the polyurethane dispersion mixture display different softening points in a dry state, - but for producing the polyurethane dispersion mixture one or several polyurethane dispersions with heat-activatable melting or contact adhesive properties and with a softening point in dry state higher than 40°C, preferably higher than 45°C, in the amount of 18 to 52 wt% of the finished polyurethane dispersion mixture and one or more polyurethane dispersions without melting or contact adhesive properties and having a softening point however 95°C, preferably higher than 125°C, and the amount of 39 to 73 wt% of the finished polyurethane dispersion mixture are mixed, - that the polyurethane dispersion mixture for the layer (2) is applied with a thickness onto the carrier layer (1) such that in the dried state it has a thickness of 0.075 to 0.450 mm, preferably of 0.150 to 0.280 mm, - that prior to or simultaneously with a structuring of the polyurethane foam a further layer (3), consisting of a non-foamed polyurethane dispersion constituting a mixture of several polyurethane dispersions is applied onto the layer (2), - wherein the further layer (3), which is constructed with, where appropriate aliphatic, polyether, polyester and/or polycarbonate polyurethane, has a thickness after the solidifying or drying of 0.015 to 0.060 mm, preferably 0.020 to 0.045 mm, has a hardness of greater than 70 Shore A, is not sticky at temperatures of 125 to 165°C and, where appropriate, is not thermoplastic, - that the layer (2) with the layer (3) for the structuring taking place by means of a matrix (4) is brought up to a temperature of 110 to 165°C, preferably 120 to 155°C, - that during structuring, the format and punching parts (30) or the carrier layer (1) are loaded by means of a pressure-elastic supporting part (10), which is at least as great as the part to be structured, in particular to compensate for fluctuations in thickness in the carrier layer (1) and for the pressing across the entire surface of the polyurethane foam into the indentations of the matrix (4) and for its anchoring in the carrier layer (1), and - that the carrier layer (1), the further layer (3) and the layer (2) are pressed with one another with the application of a contact pressure of 4 to 48 kg/cm2, preferably of 18 to 25 kg/cm2, and are structured with the matrix (4), wherein the dried layer (2) is applied with pressure simultaneously or together with the further layer (3) with the structured matrix (4) and a structuring is formed or embossed onto the surface of the layer (2) and the further layer (3) applied onto the layer (2), - wherein following the completed three-dimensional structuring, the layer (2) remains thermoplastic and the layer (2) and the further layer (3), which is thinner and harder than the layer (2), cannot be separated, but can still be multiply embossed or can in addition be structured with other embossments.
2. Method according to claim 1, characterised in - that the polyurethane dispersions are selected such that, following the drying and also following any sub-cross-linking which may take place, the polyurethane dispersion mixture has thermoplastic properties, and/or - that the composition of the polyurethane dispersion mixture is selected such that after the drying and structuring, the layer (2) has a hardness of 28 to 75 Shore-A, preferably of 28 to 68 Shore-A, in particular of 30 to 60 Shore-A, and/or - that the polyurethane of the employed polyurethane dispersions, which have thermally activatable adhesive properties, has at least in part linear and/or at least partially crystalline structure and/or is thermoplastic, and/or that a polyurethane foam is created from the polyurethane dispersions or is employed, which is thermoplastic surface structurable after its drying, and/or - that cuttings are shaped or punched out from the coated carrier layer (1) and these cuttings are subjected to the embossing or structuring procedure after an intermediate storage.
3. Method according to claim 1 or 2, characterised in that the polyurethane foam is created in that a gas or gas bubbles, preferably or nitrogen, are introduced into the polyurethane dispersion or the polyurethane dispersion mixture, wherein so much gas is introduced or incorporated into one litre of the polyurethane dispersion or polyurethane dispersion mixture that one litre assumes a volume of 1.10 to 1.70 I, preferably 1.20 to 1.50 l.
4. Method according to any of claims 1 to 3, characterised in - that as matrices (4), matrices of textile material, preferably woven, knitted and crocheted fabrics, or net-like materials or matrices with matrix surfaces of metallic fibres and/or threads or matrices of paper coated with plastic having a structured surface or matrices produced in 3D printing processes or of low-melting metal alloys or surface-structured matrices of silicone rubber masses or silicone resin are used, which have a Shore-A hardness of 25 to 98, the density of which is, where appropriate, more than 1.15 g/cm3 and which, where appropriate, are condensation or addition cross-linked, and/or - that as material for a matrix (4), silicone rubber or textile material is used which is applied to or fastened on a metal plate (20), wherein, where appropriate the, preferably 0.5 to 1.2 mm long, preferably with tapering cross-sectional surface, needle-like or mandrel-like continuations or webs with a diameter or a width of 0.8 to 1.5 mm penetrating the silicone rubber material or the textile woven fabric or protruding into its structural hollow spaces protrude from the metal plate (20).
5. Method according to any of claims 1 to 4, characterised in - that the polyurethane foam is applied onto the carrier layer (1) in particular in an airless manner, sprayed on or applied in a screen-press method or with at least one roller or a squeegee with a consistent thickness, wherein prior to or after the application of the polyurethane foam, in particular after its drying, the carrier layer (1) is divided punched to form cuttings or format parts (30) and the layered cuttings or format parts (30) are subjected to the embossing or structuring under the influence of pressure and temperature.
6. Method according to any of claims 1 to 5, characterised in that when a microfibre nonwoven is used as a carrier layer (1), the interspaces between the fibres of the nonwoven are at least partially filled with coagulated or phoned plastic foam, preferably on a polyurethane basis.
7. Method according to any of claims 1 to 6, characterised in that prior to the structuring of the surface, the layer (2) of polyurethane foam on the structure-providing matrix (4) the further layer (3), possibly having another colour than the layer (2) is formed of a non-foamed polyurethane dispersion, preferably a polyurethane dispersion on polyether polycarbonate or polyester basis, or polyurethane dispersion mixture of this sort is formed in a thickness of 0.015 to 0.060 mm, preferably 0.020 to 0.045 mm, which contains a maximum of 1.5 wt%, preferably maximum 0.5 wt % water, in particular is dried to be free of water, has, at least at a temperature of 110°C, no adhesive properties and is so far solidified and/or interconnected that it can be drawn off and the structured matrix (4) without sticking, and that this layer (3) located on the matrix (4) heated to a temperature of 90 to 145°C is brought into contact with the layer (2), is applied with pressure and, in the course of the structuring which takes place at the same time, is connected to the layer (2), wherein advantageously this layer (3) has a Shore-A hardness of 45 to 95 after the structuring.
8. Method according to any of claims 1 to 7, characterised in that the further layer (3) is applied to the layer (2) in that prior to the structuring of the layer (2) with a matrix (4) the further layer (3) consisting of a polyurethane dispersion or polyurethane dispersion mixture, possibly having a different, preferably greater hardness and/or colour, is applied onto the layer (2) and in the course of the structuring is bonded thereto, wherein the further layer (3) is formed from a non-foamed polyurethane dispersion or polyurethane dispersion mixture and is supplied in a thickness such that after the drying it has a thickness of 0.015 to 0.060 mm, preferably 0.020 to 0.045 mm, wherein, where appropriate, it is dried to a water content of maximum 1.5 wt%, preferably maximum 0.5 wt% water, in particular to be free of water.
9. Method according to any of claims 1 to 8, characterised in - that the matrix (4) is heated for the structuring to a temperature of 110 to 165°C, wherein for a heated matrix (4) a press or contact duration of 2 to 18 s is complied with, and/or the layer (2), with the layer (3) is brought up to a temperature of 110 to 165°C, in particular 120 to 155°C, e.g. using infrared radiation, and has pressure applied and is structured with a matrix (4) which is possibly heated to 110 to 145°C.
10. Method according to any of claims 1 to 9, characterised in - that in the course of structuring, perforations are formed in the layer (2) and the further layer (3) which reach as far as or into the carrier layer (1), but do not penetrate this, and/or - that a structuring and simultaneous perforation or a structuring and subsequent perforation with a matrix or a plate bearing needles is carried out at temperatures of between 110 and 160°C, and/or that when drawing off a metal plate (20) equipped with the webs (19), its tips, which penetrates through the layer (2) and the further layer (3) leave visible indentations in the layer material, and/or - that the perforations are undertaken with a plate or a matrix from which sharp needles or mandrels protrude which are up to 2.8 mm long, wherein the structuring and a simultaneous or subsequent perforation of the layer material (1) takes place at a temperature of between 110 and 160°C.
11. Method according to any of claims 1 to 10, characterised in that to the polyurethane dispersion mixture is added cross-linkers in the amount of up to 4.2 wt%, preferably from 0.9 to 3.2 wt%, in relation to the total weight of the polyurethane foam, and remains thermoplastic also after a structuring which has taken place under the influence of pressure and temperature, and/or - that to the polyurethane dispersion mixture is added 8 to 25 wt% of a 40 to 60% acrylate dispersion, related to the total weight of the polyurethane foam.
12. Method according to any of claims 1 to 11, characterised in that format parts or punching parts are separated out from and embossed from a large-scale carrier layer (1) coated with polyurethane foam, and/or - that the layer (2) and the further layer (3) are formed with differing composition and/or pigmentation or colour, in particular with differing content of cross-linkers, and display thermoplastic behaviour, and/or - that a colouring or finish layer (6) is applied to the further layer (3) prior to the structuring, wherein this colouring or finish layer is advantageously pressed on and is, where appropriate, formed by a colour or colour layer or coloured plastic film or plastic film having a colour pattern which adheres to the layer (3) or can be connected thereto, and/or - that punching parts or format parts (30) worked out of the layer material, where appropriate after a longer storage time, e.g. in a shoe factory, are structured under the predetermined pressure and in the presence of the predetermined temperature without adversely affecting the consistency of the carrier layer through the application of pressure or without substantially changing the foam structure.
13. Method according to any of claims 1 to 12, characterised in that for the embossing or structuring procedure, a layer or a plate or a supporting part (10) made of pressure-elastic material is arranged between a pressing stamp (12) and the punching part (30) or the carrier layer (1) of the layer material (1), wherein the pressure-elastic material is an elastomer foam, a pressure that filled with the gas or a liquid with flexible walls or a felt or nonwoven impregnated with elastomers, e.g. silicone rubber.
14. Method according to any of claims 1 to 13, characterised in that the pressure-elastic support part (10) is fastened to a pressure stamp (12), advantageously in the form of a pressure plate, wherein the pressure-elastic material of the supporting part (10) is per se compressible by more than 4% at a pressure of 10 kg/cm2 and has a thickness of 1.5 to 12 mm, preferably 1 to 8 mm, and where appropriate retains its form after a removal of pressure in less than 4 s, and/or - that the Shore A hardness of the supporting part (10) is comparable with the Shore A hardness of the matrix (4).
15. Method according to any of claims 1 to 14, characterised in that for the structuring the carrier layer (1) contacted with the matrix (4) is pressed through between two rollers, wherein one of the rollers has a pressure-elastic coating which presses the layout material with a predetermined pressure onto the metal matrix (4) with its structuring surface made of silicon rubber or textile material, and/or - that the application of the pressing pressure is carried out with a metal roller, which moves from the one side to the other side across the plate or matrix, which is coated with a pressure-elastic material corresponding to a supporting part (10).
16. Method according to any of claims 1 to 15, characterised in that prior to the application of the layer (2) of the polyurethane foam onto a carrier layer (1) formed by a textile material, e.g. woven material or knitted material onto the surface of the textile material, a thin layer (5) of, where appropriate, foamed soft PVC or of a foamed or non-foamed, cross-linkable polyurethane dispersion or a non-foamed, cross-linkable polyurethane dispersion mixture of aliphatic and/or aromatic polyurethane on a polyester or polyether basis of a cross-linkable polyacrylate dispersion is applied, which constitutes a connecting layer for the layer (2) of polyurethane foam to be applied onto the layer 1, and, after the drying, has a thickness of 0.25 to 0.40 mm.
17. Layered material comprising a carrier layer (1) and a layer (2) of polyurethane connected thereto, wherein the carrier layer (1), present in particular in piece form, is a leather, preferably a grain leather, in particular a buffed grain leather or a cowhide split leather, a textile material, preferably a woven fabric or a knitted fabric, a cellulose fibre material, a split foam, a leather fibre material or a microfibre fleece, produced according to a method according to any of claims 1 to 16, characterised in - that the layer (2), is formed from at least one, preferably one single, layer of a non-cross-linked or sub-cross-linked polyurethane foam particularly containing gas bubbles, preferably a, where appropriate, polyurethane impact foam containing hollow microspheres or a polyurethane foam containing hollow microspheres, which where appropriate has a maximum water content of 1.5 wt%, preferably 0.5 wt%, is in particular free of water, wherein the layer (2) has a softening point of above 90°C and is sticky at a temperature of 110 to 165°C, has thermoplastic properties, and is flowable and deformable under pressure, - that a further layer (3) of a non-foamed polyurethane dispersion is applied to the layer (2) and is bonded with this layer (2), and - that a structuring is formed or embossed on the surface of the layer (2) and the further layer (3) applied to the layer (2).
18. Layered material according to claim 17, characterised in - that the polyurethane foam of the layer (2) has a specific weight of 0.800 to 1.050 g/cm3 and/or - that the layer (2) of polyurethane foam has a thickness of 0.075 to 0.450 mm, preferably of 0.150 to 0.280 mm, and/or - that the layer (2) of solidified, dried polyurethane foam has a Shore-A hardness of 28 to 68, and/or - that the layer (2) contains between 0 to 4.2 wt% cross-linkers, in relation to the total weight of the layer (2), and/or - that the layer (3) is not or is not yet sticky at temperatures of 125 to 165°C, and/or - that the further layer (3) is 0.015 to 0.060 mm thick and is thinner and harder than the layer (2) and is not sticky at temperatures of 125 to 165°C.
19. Layered material according to any of claims 17 or 18, characterised in that perforations are formed in the layer (2) and in the further layer (3) of the layered material things
20. Layered material according to any of claims 17 to 19, characterised in that in the case of a carrier layer (1), formed of a textile material, between the textile material and the layer (2) is formed a thin layer (5) of foamed soft PVC or of a cross-linked foam layer made of a polyurethane dispersion or of a polyacrylate dispersion, which layer (5) has a thickness of 0.25 to 0.45 mm and constitutes a connecting layer for the layer (2) of polyurethane foam to be applied, wherein, where appropriate, the two layers (2, 5) form a total thickness of 0.30 to 0.60 mm.
21. Layers material according to any of claims 17 to 20, characterised in that the thin, heat-structurable, non-foamed layer (3), applied or bonded to the layer (2), made of a polyurethane dispersion or polyurethane dispersion mixture on aliphatic polyether polycarbonate and/or polyester basis, has a thickness of 0.0150 to 0.060 mm, preferably 0.020 to 0.0350 mm, wherein in the layer (2) of polyurethane foam is formed or embossed a structure corresponding to the structure embossing in the layer (3) and wherein the layer (3) advantageously has a greater Shore-A hardness than the layer (2) for a hardness of more than 70 Shore-A, preferably between 78 to 98 Shore-A, and, where appropriate, contains 1 to 4 wt% polysiloxane.
22. Layered material according to any of claims 17 to 21, characterised in - that the grain leather is a full-grain cowhide leather, preferably cowhide split leather, calf leather, goat leather, lamb leather, water buffalo leather, pig leather, sheep leather or kangaroo leather, in the case of which leather up to at least 5% of the grain layer is advantageously mechanically removed, and/or - that the fibres of the micro-fibre nonwoven consist of polyester or polyamide, wherein the hollow spaces between the fibres, impregnated or filled with a plastic, preferably on polyurethane polyester basis, which has a foam structure or a coagulated micro cell structure, and/or - that the leather fibre material contains between 13 and 48 wt% synthetic fibres, and/or - that the layered material is present in the form of a punched part or cutting (30).
23. Layered material according to any of claims 17 to 22, characterised in - that the polyurethane foam has a micro-cellular structure and/or is air permeable and/or has a water vapour permeability of more than 0.50 mg/cm2/h, preferably of more than 0.12 mg/cm2/h, according to DIN EN ISO 14268, and/or - that the carrier layer (1) is formed to be air permeable, in particular in directions parallel to its surface, and is formed advantageously with textile material or fibres or threads.
24. Layered material according to any of claims 17 to 23, characterised in - that when 1g MEK is applied directly onto a surface of 100 by 100 mm of the layer (2), the MEK penetrates into the layer (2) and causes a swelling which retracts after the MEK evaporates, and - that when MEK supplied under the same conditions onto the further layer (3) bonded inseparably with the layer (2), after the evaporation of the applied MEK the surface remains undamaged.
25. Objects produced by using a layered material according to any of claims 17 to 24, such as sheet goods, cut-to-size parts, stamped parts, shoe parts, sports and work shoes, shoe insoles, bags, leather goods, steering wheel covers, upholstery covers, interior wall linings for vehicles and seat covers for motor vehicles, wherein the surface of the objects and the layer (2) and the layer (3) have an embossed structuring.
26. Objects according to claim 25, characterised in - that the layer (2) is thermoplastic or deforms under the influence of heat and pressure or is structured and deformable and structurable, and/or - that the layer (2) is thermoplastic and the layer (2) and the further layer (3), which is thinner and harder than the layer (2) are not separable after they completed three-dimensional structuring, but can still be embossed many times or can be structured additionally with other embossings.