WO2020119961A1 - Matériau stratifié et procédé de production d'un matériau stratifié - Google Patents

Matériau stratifié et procédé de production d'un matériau stratifié Download PDF

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Publication number
WO2020119961A1
WO2020119961A1 PCT/EP2019/069529 EP2019069529W WO2020119961A1 WO 2020119961 A1 WO2020119961 A1 WO 2020119961A1 EP 2019069529 W EP2019069529 W EP 2019069529W WO 2020119961 A1 WO2020119961 A1 WO 2020119961A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
foam
dispersion
structuring
leather
Prior art date
Application number
PCT/EP2019/069529
Other languages
German (de)
English (en)
Inventor
Schaefer PHILIPP
Original Assignee
Schaefer Philipp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from ATA50354/2019A external-priority patent/AT521907A1/de
Priority claimed from DE102019110290.1A external-priority patent/DE102019110290A1/de
Application filed by Schaefer Philipp filed Critical Schaefer Philipp
Priority to CA3122879A priority Critical patent/CA3122879A1/fr
Priority to EP19742584.6A priority patent/EP3894624B1/fr
Priority to US17/312,338 priority patent/US20220040946A1/en
Priority to CN201980091647.0A priority patent/CN113423886A/zh
Publication of WO2020119961A1 publication Critical patent/WO2020119961A1/fr

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Classifications

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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2601/00—Upholstery
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/12—Permeability or impermeability properties
    • D06N2209/121—Permeability to gases, adsorption
    • D06N2209/123—Breathable
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2213/00—Others characteristics
    • D06N2213/04—Perforated layer
    • D06N2213/045—Perforated layer the coating layer does not completely close the openings between the fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using knitted fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0045—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by applying a ready-made foam layer; obtained by compressing, crinkling or crushing a foam layer, e.g. Kaschierverfahren für Schaumschicht
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by incorporating air, i.e. froth
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0054—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by mechanical perforations
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0079—Suction, vacuum treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other

Definitions

  • the invention relates to a method for producing a layer material according to the preamble of patent claim 1.
  • EP 1644539-B1 describes continuous capillaries through a PU coating.
  • the coating is structured on a matrix made of silicone rubber.
  • the polyurethane dispersion or mixture for the structuring layer is applied to the negatively structured matrix and dried and solidified by means of heat.
  • the die itself does not absorb any water, so that the water can only be removed via and / or through the surface of the coating.
  • the structuring takes place in-situ during the drying and solidification of the polyurethane dispersion top layer.
  • An essential object of the invention is the saving of energy and the associated reduction in emissions.
  • capillaries are only possible with thin coatings. Their number per unit area and their diameter are difficult to control because they form as holes in the coating when the PU dispersion solidifies on the die, which holes have to communicate with holes or thin spots in the adhesive layer.
  • the coating is cross-linked and cannot be restructured, and even if this were possible, the capillaries would close under the high pressure required for embossing. These coatings show a uniform structure in the surface. The same applies to so-called corrected scar liver with a foamed polyurethane coating.
  • the invention has among others the Task to avoid these disadvantages and to create format blanks and stamped parts for the processing industry, namely the formation of individual surfaces, which can also have technical functions, for example the formation of stamped parts for shoes, which have different structures in one piece and possibly also have evenly distributed or precisely formed capillaries.
  • a layer material is created which does not have these defects and forms the prerequisite for creating format blanks which can be structured inexpensively and with any surface in the processing industry.
  • the invention enables technicians and product designers, for example in a shoe factory, to individually design the surface.
  • the production of the matrices in the 3D process is digitally simple and can be carried out quickly with small matrices.
  • a further object of the invention is to coat a leather in such a way and to structure the cut-out parts in such a way that only die-related waste arises, because the parts of the skin of small thickness and loose grain, which normally represent waste, also match the material Structure can be provided. This is achieved primarily through the embossing parameters, pressure and temperature as well as the pressing or embossing tools which have pressure-elastic materials.
  • the residence time of the dispersion or of the dispersion mixtures for the structuring surface is between 2 and 5 minutes. According to the task, this time should be reduced to a few seconds.
  • Known materials or coatings, which were produced on reversing matrices, consist of several layers. Layer separations are therefore preprogrammed. A layered structure also creates a so-called plywood effect, ie the substrate materials automatically become stiffer after coating. The known layer materials are relatively hard.
  • soft layer materials are to be created with a homogeneous-looking surface which, during hot stamping, because of their foam structure provided according to the invention, prevents the full temperature of the die from being passed on to the carrier layer during pressing. Higher temperatures are perceived as stress in both microfiber fleece and leather, and the carrier materials harden and lose strength, especially when moisture, heat and pressure act together on the carrier layer.
  • the essential task of the invention is to create a layered material which is easy to manufacture and store, which permits exact surface structuring, in particular of format blanks and stamped parts, which has the best mechanical or physical properties and which can be produced and processed economically.
  • the layer should be built up from a single layer of aqueous PU dispersions and should not have any voids, sink marks, bubbles or cracks that arise during drying, even with a thickness of more than 0.4 mm. Furthermore, the wet coating should not lose its full water content in thickness when drying or water removal.
  • Another essential object of the invention is to provide a layer material with a flat, structureless, two-dimensional coating surface in such a way that the coating can be shaped economically with any individual structuring even after a storage period of more than six months without loss of quality and a three-dimensional structure accepts or maintains.
  • the embossing of the layer material should therefore be possible after a longer period of time after the layers have been created. This is mainly achieved with the special type of PU foam used, in particular its thermoplasticity and composition.
  • Another object of the invention is to create a layer material, the layers of which can be created with PU dispersions on a purely aqueous basis.
  • a layer material is obtained in which a carrier layer carries a surface-structurable layer, which can be optimally processed even after long storage. It is only necessary to thermally activate the surface-structurable layer and thermoplastic above its softening point with a die under heat and
  • the layer and the further layer retain their structure after deduction from the matrix.
  • the pressurization results in a practically inseparable layer material, which reproduces the die faithfully, above all due to the layer thickness and the chosen embossing pressure.
  • the layer of PU foam applied to the carrier layer and the further, non-foamed layer are structured.
  • the consistency of the backing is not adversely affected by the pressurization.
  • the pressure range according to the invention takes into account the consistency of the PU foams used and structured, without significantly changing the foam structure.
  • the embossing process can be carried out economically for smaller cuts and stamped parts.
  • the layer is dried after application to the carrier layer before structuring to a water content of less than 1.5% by weight, preferably less than 0.5% by weight, in particular until it is water-free.
  • aqueous PU Dispersion mixture based on aliphatic and / or aromatic polyether and / or polyester and / or polycarbonate polyurethane used.
  • the PU foam is also produced with a PU dispersion mixture, in which the individual readily miscible PU dispersions used to produce the PU dispersion mixture show different temperatures of their softening point in the dried state.
  • the PU dispersions are selected so that the PU dispersion mixture has or maintains thermoplastic contact adhesive properties after it has dried and any crosslinking, but this is only a subcrosslinking, and also after it has been embossed or structured.
  • a foamable PU dispersion mixture contains between 65 and 91% by weight polyurethane dispersions based on the total weight of the PU foam with all additives. These additives are e.g. Polyacrylate dispersions, thickeners, pigments, flame retardant additives, foaming agents, crosslinkers. PU dispersion mixtures are used which each contain between 35 and 52% by weight, based on the total weight of the respective PU dispersion, of solids.
  • the softening point and the adhesive properties of the PU foam can not only be determined by choosing the softening point of the individual PU dispersions, but can also be controlled by adding crosslinking agents. 0 to 4.2% by weight of crosslinking agent, based on the total weight of the PU foam, is advantageously used.
  • a crosslinker of this type is, for example, the crosslinker XL80 from Lanxess AG. It is advantageous to use PU dispersions which have a softening point in the dried, uncrosslinked or undercrosslinked state which is above 45 ° C. and which thus become soft and sticky above this temperature. The softening point can also be above 95 ° C. when using crosslinking agents to the extent according to the invention.
  • the dried PU dispersion mixture Before and after the crosslinking, the dried PU dispersion mixture should have thermoplastic properties and the PU dispersion mixture is flowable under pressure above the softening point and can be permanently deformed.
  • the layer of PU foam should be honey-like, viscous but not thin, in order to be able to adopt the structure of the die quickly and precisely.
  • the softening point and the adhesive properties can be set or selected.
  • Multiple PU dispersions can also be used to produce the proportion of the PU dispersion mixture with hot melt or contact adhesive properties and for the proportion of the PU dispersion mixture without such properties, which two proportions are mixed to produce the PU foam that each have or develop desired properties.
  • thickeners based on water-free polyacrylate with a viscous consistency or foam additives containing ammonia, such as e.g. Millio shape used.
  • Polyacrylate-based thickeners which stabilize the PU foam are used to an extent of 1.5 to 5% by weight of the total weight of the PU foam.
  • PU dispersions based on aliphatic polyether and / or polyester and / or polycarbonate polyurethanes are used to create the PU foam.
  • the PU dispersions used for the preparation of PU dispersion mixtures can have different temperatures for their respective softening points or are selected or mixed according to this point of view. It is thus possible to specifically set different softening points or softening ranges for the dried PU foam. By heating to this desired softening point or above it or to a softening area that allows embossing, it is possible to permanently impart a desired surface structure to the surface of the water-free or almost water-free, thermoplastic or thermoplastic structurable PU foam.
  • Different PU dispersions are mainly used to adjust or optimize the hydrolysis resistance, adhesion, softness and embossability of the PU foam and to adapt it to different applications.
  • the PU dispersions used to produce the PU foam advantageously each contain 35 to 52% by weight PU solid, based on the respective weight of the PU dispersion used, including its additives.
  • the individual PU dispersions are then mixed or mixed into the PU dispersion mixture and the PU dispersion mixture used to produce the PU foam contains 65 to 91% by weight of such PU dispersions, based on the total weight of the PU foam together all aggregates.
  • a PU dispersion mixture which contains between 18 and 52% by weight, based on the finished PU dispersion mixture, of a commercially available PU dispersion based on polyester with a solids content of approx. 40%, such as that offered by BASF as a heat-activated industrial contact adhesive under the name Luphen.
  • the remaining 39 to 73% by weight are formed from a PU dispersion which likewise contains about 40% solids and has a softening point of above 125 ° C., for example a PU dispersion with the designation DLV-N from Lanxess AG.
  • This mixture leads to exceptionally high adhesion properties, especially in the case of microfiber nonwovens and sanded grain leather, without significantly hardening the finished product.
  • the heat-activatable polyurethane of PU dispersions which can be used advantageously has at least a partially linear and / or at least partially crystalline structure and can be thermoformed in the dried state and can also be compressed as PU foam.
  • the PU dispersions for the PU dispersion mixture for creating the PU foam have a pH of 6 to 9.5.
  • the dried PU foam is water-free and not cross-linked or under-cross-linked and softens or becomes sticky at a temperature of 110 to 160 ° C or melts with high viscosity and flows under the intended pressure to be able to adopt the structure of the matrix.
  • the PU foam is created by introducing a gas, preferably air or nitrogen, into or the PU dispersion mixture, with so much gas and / or hollow microspheres being introduced or hammered into one liter of the PU dispersion mixture that one liter of the Starting material assumes a volume of 1, 10 to 1, 70 I, preferably 1, 20 to 1, 50 I.
  • a gas preferably air or nitrogen
  • the procedure according to the invention is simple and economical. It is possible that the PU foam is sprayed onto the carrier layer, in particular airless, or is applied using the screen printing process or with at least one roller or doctor blade in the same thickness. In this way, it is easy to set the desired thickness of the layer of PU foam to be applied, which thickness is ultimately also important for the properties of the layer material. For special applications, it can be advantageous if, prior to or simultaneously with the structuring of the PU foam with the die, a further layer of a PU dispersion, possibly of a different color, is applied or bonded directly onto the layer. After solidification or drying, this layer has a thickness of 0.015 to 0.060 mm, preferably 0.020 to 0.045 mm.
  • the further layer can be applied directly to the PU foam, which is advantageously already dried and is already on the carrier layer.
  • this additional thin layer it is also possible to apply this additional thin layer to the die before embossing the PU foam and, in the course of embossing the PU foam, to apply the additional layer on the die directly to the surface of the PU foam with the die to connect under pressure or to transfer to this.
  • the carrier layer or the layer material provided with the layer of dried PU foam can be produced in sheets or in the form of blanks and can be stored well after the PU foam has dried.
  • the dried layer in order to produce a surface-structured layer material, is pressurized with a structured die and, if necessary, reduced in thickness.
  • the connection of the layer with the carrier layer is thus further improved. This is advantageously done at a temperature of 110 to 160 ° C.
  • a contact time of 2 to 28 s, preferably 6 to 18 s, and a contact pressure of 4 to 48 kg / cm 2 are maintained.
  • the layer made of PU foam can be brought to a temperature of 110 to 160 ° C., for example with IR radiation, for pressure, structured and optionally reduced in thickness for the structuring, if necessary simultaneously or together with the further layer.
  • the carrier layer, the further layer and the layer with the application of a contact pressure of 0.8 to 48 kg / cm 2 , preferably 4 to 48 kg / cm 2 , in particular 18 to 25 kg / cm 2 , pressed together and connected and structured with a die.
  • the PU foam contains additives, for example pigments and / or polyacrylate dispersions and / or silicones and / or matting agents and / or thickeners and / or crosslinking agents and / or flame retardants.
  • PU foam Based on the total weight of the PU foam, 1.5 to 3.5% by weight of hollow microspheres or 2 to 12% by weight of pigments or 1.8 to 4.5% by weight of polyacrylates can be used as a thickener and foam stabilizer or 1 to 4 wt .-% silicones are added.
  • the PU foam is created in such a way that the layer after structuring with the die has a density of 0.80 to 1.05 g / cm 3 or from 0.89 to 1.05 g / cm 3 owns.
  • the density depends largely on the type and amount of pigments.
  • a PU foam colored white with titanium dioxide naturally has a higher density than a black PU foam.
  • the thickness also has a certain influence on the viscosity and embossability of the PU foam.
  • the weight specifications relate to the total weight of the PU foam.
  • the PU foam is not or not completely crosslinked and remains thermoplastic after a first structuring process.
  • the additional layer applied to the surface of the dried PU foam does not have to be thermoplastic, but is advantageously heat-resistant and resistant to MEK and isopropanol.
  • the further layer even if it is not thermoplastic, takes on the structure of the PU layer and that of the die. Above all, however, the color pigments used with the further layer can have different colors than the layer.
  • carrier layer formed on the surface of the textile material as a pre-coating consists of a thin layer of PU impact foam or of optionally foamed soft PVC, each with a thickness of 0.25 to 0.40 mm, or of an equally strong, crosslinked PU dispersion foam layer or a polyacrylate foam layer.
  • the carrier layer is thus coated with a layer of foamed soft PVC or a cross-linked PU foam or a polyacrylate layer.
  • a layer material according to the invention is characterized by the features stated in the characterizing part of claim 11.
  • Such a layered material can also be surface-structured after a long storage period at elevated temperature and simultaneous application of pressure, since it is not crosslinked or has been created without a crosslinker or is undercrosslinked and is therefore thermoplastic deformable and remains.
  • the PU foam of the layer material has a specific weight of 0.8 to 1.05 kg / dm 3 .
  • the layer of PU foam has a thickness of 0.030 to 0.450 mm, preferably 0.075 to 0.450 mm.
  • Polyurethanes are used for the layer, advantageously aliphatic or aromatic polyurethanes based on polyether or polyester or polycarbonate.
  • the layer of PU foam can contain pigments and / or crosslinking agents and / or polyacrylates and, if necessary, the intended hollow microspheres instead of a struck gas.
  • the layer of solidified, dried PU foam advantageously has a Shore A hardness of 28 to 68. A structuring is formed or embossed on the surface of the layer and the further layer applied to the layer.
  • the structured layer even if it contains crosslinking agents, ie is undercrosslinked, is and remains thermoplastic.
  • the layer of PU foam has a thickness which is only 2 to 18%, preferably 3 to 9%, thicker than a layer which is formed from an equal weight amount of non-foamed PU dispersion or non-foamed PU dispersion mixture of the same composition after this amount has been spread over an area of the same size as the PU foam.
  • the Shore A hardness is measured in such a way that a large number of the layers to be examined are made and stacked from the respective material, preferably from solidified or dried or structured PU foam, and thus a test specimen with a thickness of 5 mm based on to the DIN ISO 7619-1 standard, which is then measured.
  • the usability and processability of the layer material is optimized or surface protection of the structured PU foam is achieved if, in the case of a carrier layer formed by a textile material, a thin layer of foamed soft PVC or of a cross-linked PU material is formed between the surface of the textile material and the layer.
  • Dispersion or a crosslinked PU dispersion mixture preferably made of aliphatic polyurethane based on polyester or polyether or polycarbonate or of a polyacrylate dispersion, which layer has a thickness of 0.25 to 0.40 mm and a connecting layer for the to be applied Layer made of PU foam, the two layers optionally forming a total thickness of 0.35 to 0.60 mm.
  • the further layer advantageously has a greater Shore A hardness than the layer made of PU foam or has a hardness of more than 70 Shore A and optionally contains 1 to 4% by weight of polysiloxanes.
  • the further layer preferably consists of more than 45% by weight of polyether-polyurethane based on polycarbonate, such as the product Aquaderm Finish HW2 from Lanxess AG.
  • polyether-polyurethane based on polycarbonate
  • the grain leather is a full-grain cowhide, preferably cowhide split leather, calf leather, goat leather, pig leather, sheep leather, water buffalo leather or kangaroo leather, in which leather the grain layer is advantageously at least 5% up to 60% mechanically removed.
  • a leather fiber material can contain shredded punching waste from upper leather and / or synthetic fibers.
  • a microfiber fleece is provided as the carrier layer, it is advantageous if the fibers of the microfiber fleece consist of polyester or polyamide, the cavities between the fibers being impregnated or filled with a plastic, preferably based on polyurethane, which has a foam structure or a coagulated microcell structure having.
  • the PU foam can advantageously have an open-line structure and / or be permeable to air and / or a water vapor permeability of more than 0.050 mg / cm 2 / h, preferably of more than 0.12 mg / cm 2 / h, according to DIN EN ISO 14268 have, with which advantages are achieved especially in stamped parts for shoes.
  • the layer material is particularly advantageous for the production of objects such as, for example, cuts, stamped parts, shoe parts, sports and work shoes, shoe insoles, bags, leather goods, steering wheel covers, upholstery covers, interior wall linings and seat covers for motor vehicles and partially coating for the protection area of textiles uniforms, work clothes, safety clothing.
  • the objects created according to the invention have a surface of any shape by means of a die, in which grain leather structures, textile structures, geometric structures, names, logos and surface areas of different structure and / or different roughness can be formed. All that is required is to design the structure-giving surface of the die made of silicone rubber or silicone resin accordingly.
  • the surfaces of the die can be designed by molding, for example a textile, mechanically or by laser ablation or in a 3D printing process. For this purpose, it is not absolutely necessary for the die used for the structuring in the production from layer material to have been surface-processed, but the die used can also be a negative die of an originally created positive die.
  • the invention makes it possible to save material on the polyurethane to be used, since the PU dispersions are foamed or contain gas and the amount of polyurethane required is therefore reduced by the gas bubbles contained in the PU foam. This also results in a lower weight for the layer made of PU foam. Only water-based PU dispersions are used, which means that the production process is environmentally friendly and harmful or environmentally harmful process residues are avoided. After all, when stamping stamped parts, it is possible to change different dies quickly, making it easy to individually manufacture objects with different surface designs. It is particularly advantageous if the carrier layer of blanks has been coated with PU foam using the screen printing method.
  • the structuring of format parts and stamped parts is easy to handle, in contrast to entire leather skins or sheet goods.
  • the format or stamped parts can be used, for example in a shoe factory, by means of a computer-controlled tool of a color printing machine and / or fed to an embossing device and removed again.
  • small matrices can be structured easily and inexpensively using digital control. Energy can be saved because the matrix is or remains hot during the structuring process.
  • the structuring process takes only a few seconds.
  • the production of the die with a silicone or textile surface is extremely cost-effective and, in contrast to stamping tools made of metal or stamping rollers, can be carried out within a day.
  • the layer material according to the invention is created in such a way that a layer 2 of a PU foam is attached or applied to the surface of a carrier layer 1.
  • the backing layer 1 is a textile material
  • this textile material can be used as a base layer for precoating on the surface with a layer 5 made of a soft PVC or a PU foam, created from a PU dispersion or PU dispersion mixture or from one Polyacrylate dispersion can be provided in order to be able to combine the layer 2 of PU foam with the rough textile material.
  • the layer 2 is embossed with the die 4, the layer 2 is deformed, but does not penetrate into the carrier layer 1.
  • a further layer 3 of a non-foamed PU dispersion or a non-foamed PU dispersion mixture is applied to the layer 2 made of PU foam before it is structured.
  • a die 4 shown schematically in FIG. 1 the indicated surface structure 7 can be given to the layer 2 or the further layer 3 present thereon.
  • the carrier layer 1 and the die 4 are pressed together.
  • the die 4 can be heated to the required temperature for the embossing process in order to bring the PU foam to the desired softening temperature bring to.
  • the layer 2 can be heated before it comes into contact with the die 4, for example with an infrared radiator.
  • the surface of layer 2 or further layer 3 is smooth and flat.
  • the use of a PU impact foam or PU foam with hollow microspheres offers the advantage over non-foamed or non-gas-containing coatings that the surface-structured PU foam is compressible and deformable when it is embossed under temperature and pressure. Air and moisture that are present when placed on the layer 2 on the die 6 can escape, so that there is no blowholes and bubbles.
  • the layer material can be punched into blanks before further processing, and the blanks are then independently subjected to embossing or surface structuring under pressure and temperature.
  • the further layer 3 can either be applied directly to the PU foam layer 2 or it is applied to the die 4 and dried on the die in an anhydrous or almost water-free manner and, if necessary, pre-crosslinked or undercrosslinked such that it can be stripped off immediately and hot and can be inseparably connected to the layer 2 during embossing; the embossed layer material no longer shows how layer 3 was applied.
  • PU dispersions are hot-dried, hairline cracks and cavities can occur, which, however, are healed during structuring according to the invention by plasticizing the layer, in particular on the basis of the selected prints, and no longer interfere.
  • the procedure according to the invention advantageously uses only non-toxic materials that can be processed economically and safely even by unskilled workers.
  • embossing of an already dried PU foam is gentle on the die, since the crosslinker contained in the PU foam is no longer wet and does not come into contact with the die to the extent that it is the case with conventional coatings, because crosslinkers act aggressively on silicone dies and on them corrode.
  • the specific weight of the PU foam When calculating the specific weight of the PU foam, it should be taken into account that it can contain pigments or additives which have different specific weights depending on the application. For example, titanium dioxide as a white additive for coloring is very heavy, whereas pigments of a different color can have a significantly lower specific weight. If the open-line PU Micro hollow spheres filled with gas, which are known to represent closed cells, must be taken into account when calculating the density by deduction.
  • the foamed and thermoplastic layer 2 made of PU foam is compressed by means of heat and pressure to adopt the negative structure of the die 4.
  • microfoam is compressed in such a way that some of the microcells are lost and the PU foam still has an open-line microfoam structure, but then only has a weight of 0.80 to 1.05 kg / dm 3 .
  • a non-foamed, compact layer produced with the same formulation has a density of 1,050 to 1,120 kg / dm 3 . According to the invention, this results in an advantage in terms of weight and material saved. Due to the controllable compression of the PU foam during embossing, in contrast to non-foamed coatings, deeper structures can be displayed even at low pressure and it is surprising that the softness is retained.
  • the layer 2 is permeable to water vapor and air, expanding gas or any residual water vapor which arises during hot pressing is discharged through the layer 2 into the carrier layer 1 and there are no voids, bubbles and cracks.
  • the air or residual gases that expand under heat and cannot escape in or through the die through the open-line PU foam or through the carrier layer 1 can be dissipated. If the layer did not have an open-line microstructure, defects would appear in the grain valleys of the matrices, which would present themselves as undesirable pores and gloss spots.
  • the thin, harder, non-foamed layer 3 is also air-permeable under pressure, so that the air that is in the grain valleys of the die 4 can also escape.
  • Structured surfaces by hot pressing are mainly used for shoes, steering wheels, bags, leather goods, etc.
  • format parts for example in the dimensions from 0.35 to 0.9 m 2, can be produced simply by punching out sets of format parts from the carrier layer 1 used with little punching waste.
  • a format part can be made so large that it covers the shaft parts for a pair of shoes, for example.
  • the complete PU dispersion mixture advantageously contains up to 4.2% by weight of crosslinking agent, based on the total weight of the PU dispersion mixture, before foaming.
  • the dried PU dispersion mixture is accordingly undercrosslinked and is or remains thermoplastic.
  • 8 to 25% by weight of a 40 to 50% acrylic dispersion, which can advantageously be crosslinked with isocyanate, can be added to the 5 respective PU dispersion mixtures to improve the hydrolysis resistance.
  • a 50% PU dispersion i.e. 50 parts of solid and 50 parts of water
  • this film shrinks or collapses when dried by heat by about 50% due to water loss.
  • the film becomes cracked when dried (e.g. in a heat drying duct) at 120 ° C because a skin forms on the surface, which makes it difficult to remove water from the film under the skin. Drying must therefore take place slowly and at a low temperature below 80 ° C over a longer period of time, which is uneconomical.
  • the advantage of the invention is that the PU foam is not applied directly to the final carrier layer as in the reversal process. Part of the water is absorbed by the carrier and can escape at temperatures of 100 to 120 ° C in less than two minutes without creating cracks and voids that are not curable when structuring.
  • the respective PU dispersion mixture (s) contain foaming agents for foaming and for stabilizing the whipped foam, in the simplest case an foaming agent containing ammonia in an amount of 0.5 to 2% by weight 25 (based on the total weight) of the respective PU dispersion mixture with additives.
  • foaming agent containing ammonia in an amount of 0.5 to 2% by weight 25 (based on the total weight) of the respective PU dispersion mixture with additives.
  • Thickeners for example based on acrylics (Wesopret A2), can be added to the respective PU dispersion or the PU dispersion mixture in an amount of 1 to 4% by weight (based on the total weight of the respective PU Dispersion with supplements.
  • the PU foam is formed by stirring in gas or air using stirrers known per se, similar to a stirrer for producing whipped cream or egg whites.
  • the PU dispersions used are aqueous PU dispersions.
  • the softening point is measured and checked on the Kofler Bank.
  • the PU dispersion mixture comprises 18 to 52% by weight of a PU dispersion in the form of a heat-activated contact adhesive or a mixture of such PU dispersions, the PU dispersions or the mixture having a PU solids content of 40 to 50% and being heat-activatable and already pasty and sticky at a temperature of 45 ° C.
  • Such PU dispersions are heat-activated PU dispersion contact adhesives based on polyurethane, such as the product Luphen from BASF or KECK-DIS 779 from Keck Chemie GmbH or Köracoll 3350 from Kömmerling Chemische Fabrik GmbH.
  • polyurethane such as the product Luphen from BASF or KECK-DIS 779 from Keck Chemie GmbH or Köracoll 3350 from Kömmerling Chemische Fabrik GmbH.
  • a crosslinker such as Aquaderm XL 80 from Lanxess AG in Cologne
  • the PU dispersion mixture which contains the heat-activatable contact adhesive, does not lose its thermoplastic properties, even if the dried, water-free layer 2 made of PU foam when the surface is shaped by means of heat and pressure to a temperature of above 110 ° C., preferably above 145 ° C, has been brought.
  • the PU foam either contains no crosslinker or is undercrosslinked in such a way that its thermoplastic properties or its thermoplastic deformability are retained.
  • This PU dispersion with melt or contact adhesive properties is mixed with a PU dispersion or several PU dispersions to the extent of 39 to 73% by weight, based on the total weight of the PU dispersion mixture, whose softening point is higher than 125 ° C lies, but these PU dispersions or the mixture of such PU dispersions themselves have no hot melt or contact adhesive properties.
  • the invention also eliminates the known disadvantage that coatings on hydrophobic substrates produced with PU dispersions only achieve insufficient adhesion or bonding.
  • a hydrophobic carrier prevents the penetration of PU dispersion, which usually contain more than 40% water, into the surface of the carrier.
  • This disadvantage of PU dispersions for coating which is known in the leather industry, is improved according to the invention because, after drying, the PU foam used according to the invention, when structured, behaves like a heat-activated hot-melt adhesive which can penetrate into the finest depressions of a carrier under pressure.
  • the PU foam anchors in the backing like a hot melt adhesive and improves adhesion.
  • thermoplasticity a layer with a thickness of 1.0 mm is formed from a dried, not yet crosslinked PU foam, ie a layer made from PU foam and / or PU bubbles containing gas bubbles, and the one 0.02 mm has non-thermoplastic non-foamed layer and this is assessed in the heating oven or on the Kofler bench at a temperature, in particular from 90 ° C. to 165 ° C., preferably from 110 to 150 ° C., with regard to the properties mentioned.
  • this layer of PU foam is pressed in a press with a silicone rubber matrix with the desired surface structure, which has a Shore A hardness of 75, at temperatures from 1 10 ° C to 165 ° C and press times from 2 to 18 s and a pressure of 4 to 48 kg / cm 2 .
  • the PU foam film has to be highly viscous sticky, but must not be too viscous, must optimally map the matrix and must be easily removable from the matrix without deformation, without changing the structure that is formed.
  • the commercial PU dispersions mentioned meet this requirement.
  • Silicone rubber impression compounds or silicone resins are used, the matrices having a Shore A hardness of 25 to 98.
  • the density of the matrices is more than 1, 150 g / cm 3 and they are cross-linked by condensation or addition.
  • the matrices created can be engraved by laser or mechanically or can be produced in a 3D printing process.
  • a matrix for structuring a format part cut out of the layer material can, if this matrix was produced in the 3D printing process, also consist of a material other than a silicone polymer.
  • the melting point of this material must be above 185 ° C and still have the same hardness at this temperature and only a maximum of 5% different than at 20 ° C.
  • epoxy and polyester resins or low melting metal alloys It is also possible to form webs and extensions or spikes in the case of such matrices or materials in order to form capillaries in the layers 2, 3 with simultaneous structuring. The invention is explained in more detail below with the aid of examples.
  • the three-dimensional structure of a braiding material consisting of 5 mm wide leather straps with depressions between the leather straps of 0.6 to 0.9 mm, was transferred to a die by molding with a silicone rubber compound.
  • the die has a thickness of 2.2 mm and a hardness of 86 Shore A and shows exactly the structure in the negative.
  • a mixture for a layer 2 was prepared, consisting of:
  • the wet dispersion surface looked homogeneous.
  • Drying was carried out in a heating oven with air at 105 ° C. in 2.5 minutes to a water content of 0.8%. The thickness of the dried foam layer was then 0.27 mm.
  • This mixture had a viscosity of 25 seconds in a Ford cup with a diameter of 4 mm.
  • 70 g were applied wet and dried to freedom from water at a temperature of 110 ° C. in 1 minute. The fine hairline cracks were visible.
  • the dry layer was 0.025 mm thick.
  • shoe and bag parts were cut out of the layer material with a flat surface and structured in three dimensions.
  • the silicone rubber matrix with its negative structure had a temperature of 145 ° C.
  • the pressure on the part to be structured was 9 kg / cm 2 . He was held up for 10 seconds. The part was then removed from the hot die 4 without effort and pulled off the die without errors.
  • the hairline cracks in the foam layer were closed or removed during plasticization under pressure.
  • the three-dimensional surface had the same appearance and structure as the braided material made of leather straps.
  • Cross sections of the coating showed no hairline cracks or voids in the foam layer at a 50x magnification.
  • the finished part was still as soft after structuring and was only 0.02% thinner than before structuring.
  • EXAMPLE 2 A format blank for a pocket 22 x 28 cm was cut out of the same coated sheet material as in Example 1 and embossed three-dimensionally with a textile structure, namely at a temperature of 140 ° C. and a pressure of 8 kg / cm 2 and one Dwell time of 7 seconds.
  • the textile material was a self-patterned grid-like polyester fabric with a thickness of 0.6 mm and was connected to a 1.0 mm thin aluminum plate.
  • the three-dimensionally structured part showed the textile structure exactly negative. The pulling off of the textile matrix was easy and without Gluing possible because the thin, non-foamed layer 3 adapts to the layer 2 and the structuring textile surface without becoming sticky.
  • the grain side of a cow grain leather was sanded down with 0.05 mm sandpaper grain 180.
  • a PU foam with a thickness of 0.220 mm was applied to the ground side by means of an opposing roller.
  • the water content was reduced to 1.3% by weight in the course of 2.5 minutes.
  • the PU foam only decreased in thickness during the drying process by 0.06 mm.
  • the foam was created from 420 g PU dispersion called KECK-DIS 779 from Keck Chemie GmbH with heat-activated contact adhesive properties with a solids content of approx. 40% and 480 g polyurethane dispersion with a high softening point of over 140 ° C and without adhesive properties an amorphous structure based on polyester and a solids content of approx. 40% with the designation DLV-N from Lanxess AG as well as 20 g meliofoam paste, 30 g thickener, 50 g pigment.
  • the PU dispersion mixture had a softening point or range which allowed excellent embossing at a temperature of 125 ° C.
  • This mixture had a volume of 1.07 l and was whipped up or expanded to a volume of 1.35 l by blowing in air with a commercially available foam beater.
  • the foam which had a whipped cream-like consistency, was applied to the sanded side of the grain leather with a thickness of 0.220 mm and dried.
  • the embossing took place after 48 hours, the water content of the PU foam being less than 1% by weight.
  • the embossing was carried out with a die temperature of 125 ° C and a pressure of 8 kg / cm 2 . The pressure was maintained for 11 seconds.
  • the structure of the backing or leather was not visible through the foam or layer 2.
  • the connection or the layer formation was free of voids and bubbles; no idea occurred.
  • a further layer 3 was formed on the layer 2 made of PU foam, which, as previously stated, was created, the water vapor permeability was 0.8 mg / cm 2 / h.
  • a layer of PU dispersion mixture which was not foamed, was formed in a thickness of 0.020 mm after drying on the die 4 used for structuring. Based on their total weight, this PU dispersion mixture was created with 60 g PU dispersion based on polycarbonate ether with the name Aquaderm Finish HW2 from Lanxess AG with a solids content of approx.
  • polyester-based PU dispersion with a solids content of 40% by weight and the designation DLV-N from Lanxess AG were mixed in.
  • This PU dispersion mixture also contained 1.8 g of XL 80 from Lanxess AG as a crosslinking agent, 5 g of pigment paste black, 3 g of polysiloxane, 1 g of matting agent TS 100 and 20 g of water.
  • a dried layer of such a PU dispersion has a Shore A hardness of more than 75.
  • This PU dispersion mixture with the specified additives was applied to the die 4 without foaming 10 minutes before the structuring process. It was dried to less than 1% water content.
  • the connection of this further layer 3 to the layer 2 made of PU foam located on the carrier 1 was carried out in the course of contacting the layer 2 with the die 4 at the above-mentioned stamping temperature and stamping pressure.
  • This further layer 3 was inseparably connected to the layer 2 made of PU foam.
  • This layer 3 has a hardness of 75 Shore-A.
  • the resultant high adhesion of PU dispersion-based layers to hydrophobic supports, in particular to hydrophobized leathers in combination with the water vapor permeability, is a prerequisite in particular for safety shoes of classes S1 and S2 and, with the layer material according to the invention, is dependent on the thickness of layer 2 without Further fulfilled.
  • PU dispersions are used as PU dispersions for creating the PU foam for layers 2 and 5. These commercially available PU dispersions are based on aliphatic or aromatic polyester or polyether or polycarbonate polyurethanes. Such PU dispersions have a solids content of 35 to 52. The pH of such PU dispersions is between 6.5 and 9.5. After this
  • the film that forms has an elongation at break of 500 to 1100%.
  • These PU dispersions are crosslinkable, e.g. with XL 80.
  • the hardness of a dried and crosslinked, non-foamed film or layer 3 of PU dispersion mixtures which can be used is 45 to 95 Shore-A, preferably 70 to 80 Shore-A.
  • the layers formed are odorless and free of inadmissible chemicals.
  • the thin layer 3 made of non-thermoplastic, non-foamed polyether based on polyether improves the wear behavior or the abrasion behavior and the bending strength of the layer 2.
  • a crosslinker was not added to the layer 2 PU foam in the present example.
  • a PU dispersion mixture was created with:
  • a layer of 0.25 mm was applied to a microfiber fleece with an oppositely driven application roller and dried within 2 minutes in a circulating air dryer at a temperature of 115 ° C. to 1.0% by weight water content. After 3 hours, the layer 3, as in Example 3, was applied directly to this layer 2, in an amount such that the dry layer 3 has a thickness of 0.02 mm and at a temperature of 135 ° C and a pressure of 8 kg / cm 2 for 15 seconds with a surface-structured silicone matrix and structured.
  • stamped parts show the positive exactly the structure of the negative matrix, which had the appearance of kangaroo leather.
  • Layer 2 had a thickness of 0.100 mm and the adhesion between the support and layer 2 was 38 N / cm.
  • a PU foam according to Example 2 was applied to a kangaroo leather with ground scars using a roller in a thickness of 0.24 mm and dried at a temperature of 95 ° C. to 1% by weight of water. Then shoe uppers were punched out for soccer shoes and, as shown in Example 4, structured.
  • Layer 3, as created in Example 3, was created in Screen printing process applied to the layer 2 in such a way that the layer 3 has a dry thickness of 0.018 mm.
  • the thickness of layer 2 was 0.1-10 mm and the adhesion between support 1 and layer 2 was 22 N / cm.
  • the dried layer 2 has a thickness of 0.10 mm.
  • shoe uppers are punched out.
  • the solids content of this PU dispersion mixture was 35% by weight.
  • this PU dispersion contained 5% by weight of red pigment paste.
  • a carrier made of textile material was precoated with a soft PVC foam and another carrier made of textile material was coated with PU foam as a sheet material with a thickness of 0.30 mm and a composition corresponding to Example 4, as used to form a layer 2 was used, but contains 5 wt .-% crosslinker.
  • a heat-structurable layer 2 made of PU foam by means of a doctor blade and having a thickness of 0.15 to 0.45 mm was applied to each of these precoated supports and dried to a water content of less than 1% by weight.
  • An unfoamed layer 3 of a PU dispersion mixture with a thickness of 0.035 mm was applied to this layer 2.
  • This PU dispersion mixture had a solids content of 35% by weight and a crosslinker content of 3% by weight.
  • the blank or layers 2 and 3 were structured at a temperature of 155 ° C. and firmly connected to one another and to layer 5.
  • the invention is particularly advantageous for the production of format and blank parts, for example for shoes or steering wheels. The result is an all-over good connection between the respective carrier material 1 and the layer 2.
  • This PU dispersion contains polycarbonate-based polyurethanes, e.g. Aquaderm Finish HW2 from Lanxess 15 AG, and / or aliphatic polyester and / or polyether and has a hardness after crosslinking of more than 75 Shore-A.
  • polycarbonate-based polyurethanes e.g. Aquaderm Finish HW2 from Lanxess 15 AG, and / or aliphatic polyester and / or polyether and has a hardness after crosslinking of more than 75 Shore-A.
  • PU dispersion mixtures of this type contain a solids content of 25 to 35% by weight and, as an additive, 2 to 3% by weight of crosslinking agent, up to 6% by weight of pigments, 1 to 3% by weight of polysiloxane and matting agents.
  • This layer 3 is applied to the dried PU layer 2 in the manner already described 20.
  • a pre-coating is carried out with a layer 5 made of foamed soft PVC or a crosslinkable PU foam or a crosslinkable polyacrylate dispersion. It is advantageous here to apply the foam layer 2 to the layer 5 by means of a doctor blade. After this layer has dried, layer 3 is applied to this layer 2, preferably with a pressure roller. The applied PU layers 2 and 3 are dried on the web-shaped carrier 1 with the layer 5 in the continuous dryer. The three-dimensional structuring is carried out in such a way that format parts and blanks having the layers 5 and 2 or 3 on the carrier layer 1 are punched out of the sheet material.
  • the layer 2 made of PU foam and the non-foamed layer 3 or the format parts are brought to a temperature, in particular from 145 to 165 ° C., by means of the heated die 4 or infrared emitters.
  • the temperature and / or the embossing speed and / or the pressure such that the PVC layer is at least slightly co-structured.
  • the PU foam should not be thin, but pasty and easy to shape under pressure in order to be able to reproduce the fine structures of the die.
  • An advantageous consistency of the PU foam of layer 2 is when the PU foam has a melt viscosity similar to that of soft PVC at a temperature of 160 to 180 ° C., that is to say it is flowable and deformable under pressure. This also applies if another layer 3 is applied to this layer 2 before the structuring of layer 2.
  • the formation of a corresponding degree of softening or a desired deformation consistency can be controlled via the amount of crosslinking agent used and / or via the mixing ratio of PU dispersions with a low or higher softening point or softening range.
  • Matting agents in particular the TS100 matting agent from Evonik Degussa GmbH used for layers 2 and 3, improve the feel, facilitate drying, lead to a dry grip and improve water vapor permeability.
  • Layer 2 is dried under heat in a dryer or continuous dryer.
  • the water content in the dried PU dispersion or PU dispersion mixture when exposed to heat it can also be determined how large the residual water content is after certain different dwell times in the drying oven. It is therefore easily possible to achieve a desired residual water content or to set the required temperature and residence time for it. Free of water can also occur can be achieved in this way, or the necessary parameters can be specified for production.
  • the water is advantageously removed completely or almost completely.
  • layer 2 is particularly suitable for sanded grain leather and backing 1 made of microfiber fleece and for leather fiber materials, from which shaped or stamped parts for shoes and leather goods are created that are to be structured on the surface.
  • layer 2 is compressed, the resilience, abrasion resistance and the bending behavior of the layer 2 are improved.
  • the structuring or the design of the surface by means of heat and pressure and a silicone rubber matrix or a matrix made of textile material can also be carried out in a vacuum process, that is to say in the case of suppression.
  • a vacuum process that is to say in the case of suppression.
  • matrices with textile surfaces can be used for this, or the space between the press plates 15 is evacuated.
  • Such pressing processes using vacuum or vacuum are known.
  • reinforcement and / or molded parts for the 20 layer material on the die 4 and / or on the layer 2. In the pressing process taking place under pressure and at elevated temperature, these parts are firmly connected to layer 2 and layer 3.
  • These reinforcement or molded parts can be designed as desired and have the form of strips, circles, stars, geometric or other figures, etc.
  • the main materials that can be used are plastic films that connect to layer 3, especially those made of thermoplastic PUR.
  • the Köracoll 3350 contact adhesive from Kömmerling Chemische Fabrik GmbH, Germany, and the DIS type 779 30 adhesive from Jakob KECK Chemie GmbH, Germany, can also be used as a PU dispersion with heat-activated hot melt adhesive properties to create the PU dispersion mixture.
  • embossing of the layer material, in particular stamped parts can also take place after prolonged storage, e.g. of 6 months, without loss of quality.
  • the matrix made of silicone rubber material or silicone resin has a Shore-A hardness of 25 to 98.
  • the die is thus designed to be pressure-elastic and can compensate for unevenness, such as can occur in the backing layer 1 if it is a natural material such as leather.
  • the silicone rubber matrices and the matrices with textile surfaces can be supported with a heatable metal base 20 and heated to the temperature provided for the structuring process.
  • a pressure-elastomeric support part 10 is used between the carrier layer 1 of the stamped part 30 and the press plate 12, ie a metal plate of the press used for the structuring process, which has a thickness of about 1 to 8 mm, preferably 2 to 6 mm, has a foamed structure and a Shore-A hardness that is comparable to the Shore-A hardness of the silicone rubber matrix 4. Thickness fluctuations in the carrier layer 1 can thus be fully compensated for, so that the embossed area of the stamped part or the stamped part has the same stamping structure everywhere. Furthermore, any partial hardening of the carrier layer 1 is completely ruled out, although the carrier layer 1 can have thickness fluctuations of 5 to 10%.
  • Such support parts 10 on the pressure-elastic material can also be arranged between the die 4 and the metal plate 20 or in place of the metal plate 20. It is also possible to use Astacin Finish PS from BASF for the PU coating dispersions used in layer 2, which still have no stickiness or adhesive properties at 125 ° C.
  • the product Aquaderm Finish HW2 from Lanxess AG has proven to be very advantageous for thin layer 3.
  • the layer 2 Even if the layer 2 is not cross-linked or under-cross-linked and the layer 3 is completely cross-linked or under-cross-linked, a firm, inseparable connection occurs between the layers 2, 3.
  • the layer 2 remains thermoplastic and the further layer 3, which is thinner and harder than the layer 2 and possibly not thermoplastic, cannot be embossed separately after a three-dimensional structuring, but can be embossed several times or structured with other embossings.
  • the blank 30 comprises a carrier layer 1 and any layer 5 that may be present, which is advantageously formed on a structured fabric.
  • the layer 2 is applied to the carrier layer 1 and the further layer 3 is applied to this layer 2.
  • a finish layer 6 applied to the layer 3 can be a colored layer or a colored or colored pattern film which has approximately the same thickness as the layer 3.
  • the finish layer 6 can, for example, also be a printed or sprayed-on leather paint.
  • a stamped part or the blank 30 is applied to the die 4 with its surface structure 7.
  • the die 4 rests on a heatable or temperature-controllable base or metal plate 8 which can be heated with a heating unit (not shown).
  • the insert part 10 or the support part 10 made of elastomeric material, which is carried by the press stamp 12, is located between the press stamp 12 and the carrier layer 1. This elastomeric material serves to compensate for unevenness in the carrier layer 1, which is a natural product.
  • the coloring or finish layer 6 is always applied to the further layer 3 before structuring and assumes the same structure as the layer 3.
  • the color and / or the degree of gloss and / or the embossing for individual blanks can thus be regulated individually in the desired areas. This enables individual production that only requires a few meters of layer material. For custom-made products, it is currently necessary to manufacture or accept a few hundred meters of layer material. It is therefore possible to make high savings or to minimize wasted resources.
  • 4 symbols and / or brands and / or marks can be formed in the silicone rubber matrix, which are transferred to the stamped part or blank when structuring.
  • Protection against copying can also be achieved if the further layer 3 and / or any color print applied to this layer 3 deviate in color from the color of layer 2.
  • the further layer 3 and / or the color print can be removed by means of a laser, in particular pixel by pixel, so that the color of the layer 2 becomes visible.
  • continuous capillaries can also be formed in the layers 2, 3, with which the water vapor permeability of the layer material or a region of the object produced, which was created with the stamped part, can be set to a desired value.
  • the backing layer 1 is not visible through the PU foam of the layer 2, and different backing layers can thus be given the same appearance by structuring the surface of the layers 2, 3 in the same way.
  • the PU dispersions are all aqueous dispersions.
  • one or more PU dispersions with hot melt or contact adhesive properties and one or more PU dispersions without such properties can be used or mixed.
  • the heat-activatable PU dispersions are made of aliphatic polyurethane based on polyether or polyester and can also contain adhesive resins.
  • the PU dispersions have a pH of 6 to 9 and are miscible with each other.
  • the PU dispersion mixture has a pH value of 6 to 9 in the uncrosslinked state and an elongation at break of 550 to 1 100% in dried or solidified form.
  • the hardness is between 28 and 75 Shore-A.
  • the non-thermoplastic PU dispersions are made of aliphatic polyester, polyether, polyurethane or polycarbonate polyurethanes. They are also fully miscible with one another. However, they do not have any adhesive properties between 95 and 125 ° C. Like the heat-activatable PU dispersions, they generally have a solids content of 35 to 52% by weight.
  • a mixture approach for layer 2 for a PU dispersion mixture preferably contains one to three PU dispersions with heat-activated adhesive properties and one to four PU dispersions with different hardness without adhesive properties.
  • the properties of layer 2 such as hardness, density, thermal embossability, adhesive properties, softness, permanent bending behavior,
  • Resistance to hydrolysis and the connection of the layers to one another can be optimally adapted to the respective application.
  • Layer 2 which is advantageously thermoplastic and can therefore be shaped independently of time, offers considerable production-related, technical advantages. According to the invention and important is the combination of layers 2 and 3. Layer 2 is thermoplastic and therefore only insufficiently resistant to abrasion when exposed to heat and also has an insufficient resistance to MEK or isopropanol. This disadvantage is made up for by layer 3, which is composed of polyether, polyester 5, preferably polycarbonate polyurethane, such as product HW2, and which both contain 2 to 5% by weight of crosslinking agent and can also be fully crosslinked. In the event that the limit of 4.2% by weight crosslinker is exceeded, layer 3 is no longer thermoplastic.
  • a cross-linked layer 3 is not an obstacle to embossing, although it is not thermoplastic, since, due to its small thickness 10, it is completely adapted when structuring the surface shape given to the thicker layer 2 and completely adopts the structures of the die 4.
  • the thermal abrasion resistance shows no damage at an ambient temperature of 50 ° C based on DIN EN ISO 17076-1 H18 1000g 500x.
  • Layer 3 is 0.015 to 0.060 mm thick and is always thinner and harder than layer 2.
  • Layer 3 consists of a PU dispersion mixture, which is preferably composed of more than 45% by weight of polycarbonate polyurethane.
  • the layer 3 is subordinate to the structuring of the thermoplastic layer 2 regardless of its degree of crosslinking and its hardness, it is important that it is always significantly thinner than the layer 2 and does not become sticky even at temperatures of 125 to 165 ° C.
  • the specified thicknesses for layers 2, 3 apply to dry layers. When applying, enough PU dispersion must be applied that after drying a layer 2 thickness of 0.075 to 0.45 mm is created. Layer 3 has a thickness of 0.015 to 0.060 mm; this strength is always to be understood dry. Important critical points were examined, namely the adhesion between the backing layer and the layer 2 as well as the wear resistance or abrasion and the fatigue behavior, or it was examined how the material at elevated temperatures, for example 50 ° C., in use at normal temperatures, for example 22 ° C, behaves and what happens when solvents such as MEK or isopropanol get onto the surface.
  • the adhesion of the coating was tested based on DIN EN ISO 1 1644. No changes were found between normal temperature and an ambient temperature of 50 ° C. The layer material tested at 50 ° C had about 6% higher values than the layer material tested at normal temperature. Ground kangaroo leather served as the backing layer 1. All results were above the setpoint of 12 N.
  • thermoplastic, foamed or gas bubbles-containing, crosslinker-free or low-crosslinker layer 2 absorbs like a sponge due to its foam structure MEK, swells and becomes sticky. In combination with the further layer 3, especially if it has a high proportion of
  • Polycarbonate based on polyether such as the product Aquaderm Finish HW2 from Lanxess AG, prevents the thin additional layer 3, even though it also only 2 to 4 % Contains crosslinker, but swelling and dissolving of layer 2. If, for example, 1 g MEK is applied to an area of 100 x 100 mm, the surface does not swell or does not interfere. After evaporation, the embossing shows the previous grain structure again. Only a slight shine remains. Acetone behaves similarly. Isopropanol does not dissolve, swell or shine the surface.
  • layer 2 is to have a softness of less than 55 Shore-A, it is possible within the scope of the invention to add 5 to 20% by weight of the total mixture of a soft PU dispersion with the name Epotal FLX 3621 from the company to the total PU dispersion mixture To add BASF. After solidification, this Epotal FLX 3621 PU dispersion has a hardness of less than 28 Shore-A. The amount added is subtracted from the non-thermoplastic PU dispersions.
  • the structured silicone rubber layer of the die 4 can advantageously be connected to a metal plate 20, preferably an aluminum plate.
  • a textile material based on polyester with a basis weight of 30 to 150 g / m 2 is embedded in the silicone rubber material on the back of the silicone rubber or the matrix in order to prevent the thermal expansion of the silicone rubber.
  • the silicone rubber with the embedded textile material advantageously has a thickness of 0.6 to 2.5 mm.
  • the connection of the matrix 4 to the metal plate 20 favors the heat transfer from the heating plate 8 via the metal plate 20 to the silicone rubber of the die 4.
  • This aluminum plate, if any, is 0.8 to 10.0 mm thick. It can have thorn-like webs 19 to approximately 2.8 mm in length.
  • the space or the distances between the webs or thorns 19 can be filled with silicone rubber, which bears the embossing pattern, in such a way that during the embossing the tips protruding from the silicone rubber penetrate the layer 3 and the layer 2 and become visible when peeling off Leave indentations in the layer material.
  • these spikes or webs 19 penetrate through the layers 2 and 3 and advantageously penetrate up to a maximum of 0.4 mm into the carrier layer 1.
  • the breathability of the layer material can thus be improved without significantly weakening the carrier layer 1.
  • the webs or thorns can have a round cross-section but also any other shape.
  • the distances between the individual webs are 4 to 12 mm.
  • the metal plates with the thorns or webs 19 can be prefabricated.
  • the thickness of the silicone rubber matrix or the textile matrix can be used to specify how deep the webs penetrate the layers 2, 3 or penetrate into the carrier layer 1.
  • Fig. 3 such a die 4, which is penetrated by webs or projections and tips 19, is shown schematically.
  • the stamped part to be embossed is to be provided with a textile structure
  • the spaces between the thorn-like webs 19 can also be covered or filled with any surface structure with a textile material specifying the embossing pattern.
  • textile material takes the place of the structured silicone rubber material.
  • the plate 20 carries a temperature-resistant structure or a temperature-resistant textile material, from which the surface is molded.
  • the use of other materials is also possible.
  • the invention relates not only to a method for producing a surface-structured layer material, but also to a method for structuring format parts created, cut or punched out from the layer material according to the invention.
  • the layer material is in the form of stamped or format parts.
  • a particular advantage of the invention results if it is not the layer material itself, but rather shaped and stamped parts which are produced from it.
  • the format and stamped parts are structured during structuring by means of a pressure elastic on or on the layer 1 or the back of the support part 10 resting on or resting on it, which is at least as large as the part to be structured, is loaded and embossed. This not only results in pressure equalization in the case of fluctuations in thickness in layer 1. It also ensures that the PU foam is pressed and structured over the full area of the cut to be structured into the up to 1.1 mm deep recesses in the structure-giving matrix can be.
  • the pressure-elastic material 10 is advantageously fastened to the pressure stamp 12 in the form of a pressure plate.
  • the pressure-elastic material must be compressible by more than 4% at a pressure of 10 kg / cm 2 and should have a thickness of 1.5 to 12 mm. It should also withstand temperatures of at least 125 ° C and reset itself in less than 4 seconds after relieving pressure.
  • the pressure-elastic material 10 can be applied in one or more layers. For example, it can be formed from an elastomeric foam, for example from chloroprene or silicone rubber.
  • the pressure-elastic material 10 can also consist of a non-woven material with a thickness of 0.5 to 1.5 mm, which is coated with a very soft layer of silicone rubber with a Shore A hardness between 20 and 55.
  • Nonwovens impregnated with elastomers for example made of polyester fibers or felt, can also be used, which are impregnated with silicone rubber and then have a density between 0.32 and 0.89 g / cm 3 . Impregnated materials of this type have proven themselves because, during the structuring, moisture or gases present can penetrate into these materials and be removed. Furthermore, because of their silicone finish, such materials do not stick to the carrier layer 1 during the structuring process.
  • the use of a pressure-elastic support part 10 has a considerable positive influence on the quality of the embossing.
  • a material made of cellulose fibers can also be used as a textile material that can be used for the carrier layer 1, e.g. one called TEXON, which is used with a thickness between 0.8 and 2.8 mm.
  • TEXON is a cellulose fiber material which is manufactured by the company Texon Mockmühl GmbH in Mockmühl, Germany.
  • a split foam made of EVA (ethylene-vinyl acetate copolymer) with a thickness of 1.0 to 6 mm and a density of 0.15 to 0.65 g / cm 3 can also be used for the carrier layer 1.
  • EVA ethylene-vinyl acetate copolymer
  • These two materials mentioned can advantageously be used as a carrier or carrier layer 1.
  • a material that is produced from coated leather fiber punch waste can be used as the carrier layer 1.
  • Such a recycling product is under other manufactured by the company Ledertech Deutschland GmbH in Bopfingen, Germany.
  • Such layers 1 also support the embossability or the embossing behavior of the PU whipped foam.
  • the stamp plate can also be heated, in particular heated in a controlled manner.
  • the back of the carrier layer 1 can advantageously be e.g. a lining material or a layer or layer forming a lining material made of a 0.1 to 0.3 mm thick film of PUR can be connected to layer 1 over its entire surface or only in places as reinforcement.
  • the metal plate 20 carrying the die 4 can advantageously have a higher temperature than the die 4 itself. This facilitates the adjustment of the carrier temperature.
  • the structuring die 4 consists of silicone rubber.
  • silicone rubber matrices 4 made of silicone rubber, it can be advantageous for the embossing process if silicone rubber matrices are used which contain hollow microspheres or which are made from a silicone rubber foam.
  • the density of the silicone rubber matrices containing the hollow microspheres can be 12 to 25% lower than the density of matrices which are made of silicone rubber without hollow microspheres.
  • the silicone rubber adhesive with which the silicone rubber matrices are connected to the metal plate 20 of the press die can also contain 10 to 25% by weight of hollow thermoplastic microspheres. This improves the elasticity of pressure, particularly in the case of dies 4 with a textile surface.
  • the gases formed during the structuring can escape via the matrix 4 having a textile surface, in particular air and moisture can be removed laterally from the matrices.
  • the stamp carries a pressure-elastic support part 10.
  • gas in particular air or nitrogen
  • Hollow microspheres also contain a gas in their hollow core, for example isobutane. Stirring in gas and / or adding hollow microspheres always results in a foam containing gas bubbles that have completely comparable properties.
  • a PU whipped foam is equivalent to a foam made with hollow microspheres.
  • foams with hollow microspheres can be used which have the same values with regard to density, viscosity etc. or the same embossing parameters as the whipped foams.
  • it is also easily possible to produce or use a PU foam by adding hollow microspheres to the PU dispersion mixture and also blowing in gas.
  • Layer 2 thus has a foam structure which is obtained by stirring in air and / or by adding hollow microspheres.
  • the essential other parameters for the structure of the layer material do not change.
  • microencapsulated gas ie gas-containing hollow microspheres
  • the hollow microspheres forming closed cells. Since closed gas cells are also formed when the gas is stirred into the PU foam, the foam structure is comparable.
  • the gas bubbles that are produced using hollow microspheres have a diameter of about 20 to 50 m. Its cover is made of thermoplastic. Before they are added, they are moist and have a bulk density of 32 to 39 kg / m 3 .
  • Example 3 50 g of a dispersion mixture, as indicated for layer 3 in Example 3, were then applied by application with a synchronizing roller and dried to a water content of less than 1% by weight.
  • Insoles for sandals were punched out of the TEXON material coated in this way and structured with a textile matrix from which needles with a length of 0.4 mm protrude or protrude to form perforations.
  • the blanks were structured between a pressure-elastic support part 10 resting on or resting on the textile backing layer 1 of the blank 30 at a pressing time of 10 seconds and a temperature of 130 ° C. and a pressure of 13 kg / cm 2 . There was a structuring exactly depicting the matrix 4 with visible capillaries.
  • the stamped part which was impermeable to water vapor before structuring, had a water vapor permeability of 1.1 mg / cm 2 / h after structuring and perforation with the needles.
  • a shoe upper was cut out of the coated microfiber fleece and structured and structured with visible capillaries using a silicone rubber matrix 4 with a negative nappa leather structure and a Shore A hardness of 85, from which 0.45 mm long needles 19 protruded.
  • the pressure-elastic layer 10 consisted of a foamed silicone rubber with a density of 75 g / cm 3 .
  • the pressing pressure was 17 kg / cm 2 and the pressing time was 9 seconds at a temperature of 140 ° C. After structuring and formation of the capillaries, the water vapor permeability was 0.9 mg / cm 2 / h.
  • the support part 10 was inserted between the punch 12 and the stamped part 30 and the die 4 and the heating plate 8 or the support plate 20.
  • the pressure-elastic layer or the support part 10 can also be connected, for example glued, to the press die 12.
  • the hollow microspheres used to create the PU foam containing gas cells are known under the name Expancel. This company sells the 551 WE40 and 551 WE20. The manufacturer is Akso-Nobel in Sweden.
  • the pressure-elastic support part 10 made of foamed silicone rubber is compressed to a greater extent on the grain crests, and the support part 10 is less compressed in the grain valleys.
  • An inserted pressure-elastic support part e.g. silicone rubber foam is therefore compressible and presses the blank or stamped part into the recesses of the die. Any moisture and air that may be present and which expands when exposed to heat cannot escape or be removed through the die, but through the lateral edges of the stamped part.
  • the die is made of silicone rubber with a hardness of 85 Shore-A.
  • cellulose fiber material such as the TEXON product with a thickness of 0.8 to 2.5 mm as the carrier layer.
  • EVA split foams with a density of 0.2 to 0.55 g / cm 3 and a thickness of 1.2 to 4.5 mm can also be used.
  • the backing layer 1 can have a plastic coating with a thickness of between 0.10 and 0.5 mm serving as a lining.
  • the PU foam of layer 2 is compressed or the PU foam is pushed away in the direction of depressions or grain valleys.
  • a compact PU material cannot easily be embossed at the low temperatures according to the invention, since the material is compressed during the embossing and must be able to flow.
  • the PU foam containing gas bubbles which is easily deformable at the pressures used and, after softening at the temperatures specified according to the invention, offers considerable advantages.
  • the die 4 can advantageously be at the bottom and the layer material with the layer 2 of PU foam is placed or arranged on it with the layer 2 facing downward. However, the die 4 can also be placed on the stamped part 30 from above.
  • Layer 2 behaves thermoplastic at the time of the surface design and becomes so plastic under pressure and heat that it also forms or forms the finest microstructures of the die surface in layer 3, provided that it is not thermoplastic anyway. Nevertheless, the support layer 1 with the structured layers 2, 3 can be removed from the die 4 immediately after the embossing, that is to say when the layers 2, 3 are still hot. It can also be advantageous if the layer 2 and the further layer 3 are applied to shaped blanks or stamped parts. Depending on the application, it may be advantageous to have carrier layers already coated with PU foam 2 and layer 3 1, which are available either as flat parts of a given shape or dimension or as coated skins or leather, to be structured at a given point in time and then punched or brought into the desired shape. The shaping for the carrier layer 1 can thus take place before or after the structuring.
  • the press pressure required for the structuring can be applied with a press stamp 12. Part of the required pressing pressure can also be applied by deep drawing or evacuating the space between blank 30 and die 4.
  • a pressure membrane can be arranged over the blank 30 and the die 4 and the space between the membrane and a support for the die 4 or the space below the membrane is evacuated.
  • pressure pads 39 which can be pressurized with gas or liquids, can be arranged or formed below and / or above the die 4 or the blank 30 and / or below the press die 12.
  • a paper of this type is interesting if points between the thorns 19 are to be structured.
  • the paper has a thin coating of silicone resin which has the embossed pattern and is placed on the further layer 3.
  • the mandrels 19 carried by a press plate or press stamp placed on the die 4 made of paper penetrate through the die paper through the layers 2 and 3 max. 0.65 mm deep in the backing layer 1 or the leather. In this way, a controlled, controllable water vapor permeability can be achieved through the holes formed by the thorns 19.
  • Air-permeable matrices 4 are particularly advantageous for larger format parts, in particular made of leather, for example half cowhide or goat skins, or for plate formats up to 3.5 m 2 .
  • the air can escape laterally from the matrices 4 when structuring if the surface of the die 4 consists, for example, of textile fibers or of monofilaments made of plastic or metal.
  • the surface is compacted, so that a previously existing water vapor permeability is at least partially, but usually completely, lost.
  • the structure embossing according to the invention in which not only the structure but also continuous capillaries are formed in the layers 2 and 3, which present themselves as partial perforation because they do not penetrate or not appreciably penetrate the carrier layer 1, surprisingly becomes an exactly predeterminable water vapor permeability enables.
  • FIG. 4 schematically shows the structuring process with the removal of gases generated during the structuring.
  • FIG. 4 shows a press structure which can be advantageously used in practice for structuring layer materials according to the invention with a comparable function, as is shown in FIG. 2. These layer materials are in lumpy, not too large form.
  • lumpy blanks 30 of limited size are to be structured or processed.
  • Such parts can be coated or uncoated, pre-punched, or are structured and, after the structuring process, brought to the desired size or processed into stamped parts.
  • the press comprises a press ram 12 which can be moved up and down in the direction of the blank 30.
  • the press die 12 is adjustable relative to a support or a lower press plate 32 of a press table.
  • the inside of the press table has a heating device 8 in particular.
  • the piece to be structured or a blank 30 is placed on the die 4.
  • the press area is surrounded on all sides by seals 36, which seal the space between the underside of the press punch 12 and the surface of the support or the press plate 32 when the press punch 12 is moved, so that in the direction of the arrow via a recess 37 which is formed in the press plate 32 34 air 5 can be sucked off. In this way, the gases emerging from the piece 30 to be processed during the structuring process can also be removed.
  • the blank 30 is loaded with a predetermined force.
  • This force can be the atmospheric pressure, for example, when, as in a deep-drawing process, the air 10 present between the punch 12 and the press plate 32 is extracted.
  • the plunger 12 is moved to its lowest position and locked, additional or alternatively, by introducing a pressure medium according to arrow 33 through a recess 38 in the plunger 12 into a space 39 between the plunger or the pressing part 12 and a membrane 40, further pressure can be exerted on the to be machined blank 30 to be applied 15. For this purpose, it is necessary to fix the position of the press die 12 in relation to the press plate 32 in advance.
  • the pressing die 12 itself can apply the required pressing force.
  • Any pressure fluids can be used as pressure media for the application of the membrane 40.
  • the advantage of such a press is that the membrane 40 evenly distributes the pressure over the surface of the die 4 or the piece or blank 30 to be machined, and thus also in the event of unevenness in the surface of the piece 30 opposite the die 4 , can be compensated.
  • Another advantage of this arrangement lies in the fact that emerging gases emerge laterally from the die 4 and / or the piece 30 to be structured and can be discharged through the opening 37.
  • the pressure-elastic support part 10 on the press ram 12 is optionally provided.
  • Forming capillaries in a polymer coating in order to achieve a desired water vapor permeability is known to be difficult
  • Water vapor permeability is not controllable.
  • Whipped foams and coagulated foams, depending on their density and the final finish applied, are highly fluctuating to impermeable with regard to water vapor permeability, especially when the leather has been embossed with a pressure of more than 60 kg / cm 2 .
  • the perforations are made with a plate or die, from which up to 2.8 mm long pointed needles or spikes 19 protrude.
  • the tips or thorns 19 have a shaft diameter between 0.6 to 2.6 mm. They are arranged in a number of 2 to 10 pieces per cm 2 .
  • the thorns protrude from the structuring material of the die 4, for example textile material, silicone rubber or structured coated paper, and penetrate into the die 4 when the die 4 comes into contact with it.
  • the spikes 19 protrude from the die or the structuring material of the die advantageously a maximum of 1.6 mm and advantageously penetrate a maximum of 0.25 mm into the carrier layer 1.
  • the structuring and simultaneous perforation or the structuring and possibly subsequent perforation with such a die or needle-bearing plate is carried out at temperatures between 110 to 160 ° C.
  • the pressing or the application of the pressing pressure is advantageously carried out with a metal roller which moves over the plate from one side to the other and which is coated with a pressure-elastic material corresponding to a support part 10.
  • the contact pressure is 4 to 48 kg / cm 2 ; the pressing time exerted by the roller is between 8 and 20 seconds.
  • These conditions correspond to the conditions that are met when structuring with a press stamp.
  • the layer material Before structuring the blanks 30 with a plate and a metal roller stressing them, the layer material had a water vapor permeability of 0.3 mg / cm 2 / h in an examination. After four perforations per cm 2 had been formed , the water vapor permeability was 1.25 mg / cm 2 / h.
  • the needles had a shaft diameter of 1.5 mm and protruded 0.
  • the pressure roller covered with pressure-elastic material had a diameter of 28 cm.
  • the material to be structured was preheated to 60 ° C with infrared rays.
  • two rollers can be provided, between which the carrier layer 1 contacted with the matrice 4 is sent.
  • one of the rollers preferably the upper roller, has a pressure-elastic covering, which presses the layer material with the predetermined pressure onto the metal die 4 with its structuring surface made of silicone rubber or textile material. This is the easiest way if layer material is structured with plate-shaped matrices 4 and a warm underlay.
  • Structuring used. This is done regardless of whether it is punched parts, small format blanks or large parts such as half of the cattle hides.
  • Corrected grain leather which means grain leather that has an embossed polymer finish at least 0.04 mm thick, has no noteworthy
  • the lead time is usually a few weeks.
  • the already structured layer material is e.g. a quartered cowhide skin with the side coated and structured with layers 2 and 3 placed on the needle matrix.
  • the needle matrix and the needles or pins have a temperature between 90 and 150 ° C.
  • the structured layer material is then pressed onto the needle matrix.
  • the invention proposes a very light, inherently, in particular elastic, between the webs or needles 19 to arrange compressible material with low thermal conductivity as a so-called auxiliary material and in such a way that not only the distances between the needles 19 are filled, but the material also covers the needles 19.
  • the auxiliary material compresses in the desired manner, to the extent that the needles released penetrate layers 2 and 3.
  • Soft, cotton-like nonwovens and peeling foams made of polyurethane or a soft elastomeric material with a density between 40 and 170 kg / m 2 are suitable as such a care aid material.
  • This auxiliary material can be used several times.
  • the heating device 8 inside the die 4, in particular if the die is made of silicone rubber.
  • This embodiment simplifies the stamping or the construction of the press unit required for the stamping.
  • the embossing temperature for the PU Foam of layers 2 and 3 is regulated very precisely and thus the surface structure of the layer material is optimized.

Abstract

L'invention concerne un procédé de production d'un matériau stratifié présentant une structure de surface et comprenant une couche de support (1) à laquelle est liée une couche (2) composée de polyuréthane. Un cuir, de préférence un cuir poncé, un cuir refendu de bovin, un matériau textile, de préférence un tissu ou un tricot, une matière à base de fibres de cellulose, une mousse refendue, une matière à base de fibres de cuir ou un non-tissé de microfibres est utilisé en tant que couche de support (1), en particulier sous forme de morceaux, et est lié à la couche (2). Sur la couche de support (1) est appliquée en tant que couche (2) au moins une, de préférence une seule, couche composée d'une mousse PU contenant en particulier des bulles de gaz, de préférence d'une mousse battue PU contenant éventuellement des microbilles creuses et/ou d'une mousse PU contenant des microbilles creuses. Selon l'invention, - la mousse PU contenant en particulier des bulles de gaz est produite au moyen d'un mélange de dispersions PU, les différentes dispersions PU utilisées pour la production du mélange de dispersions présentant à l'état sec des points de ramollissement différents, - pour la production du mélange de dispersions PU sont mélangées une ou plusieurs dispersions PU présentant des caractéristiques d'adhérence par fusion ou collage et un point de ramollissement à l'état sec supérieur à 40 °C, de préférence supérieur à 45 °C, dans une quantité de 18 à 52 % en poids du mélange de dispersions PU produit, et une ou plusieurs dispersions PU dépourvues de caractéristiques d'adhérence par fusion ou collage et présentant un point de ramollissement supérieur à 95 °C, de préférence supérieur à 125 °C, dans une quantité de 39 à 73 % en poids du mélange de dispersions PU produit, - le mélange de dispersions PU de la couche (2) est appliqué sur la couche de support (1) dans une épaisseur telle qu'il présente à l'état sec une épaisseur de 0, 075 à 0,450 mm, de préférence de 0,150 à 0,280 mm, - avant ou en même temps qu'une structuration de la mousse PU, une autre couche (3) composée d'une dispersion PU non expansée constituant un mélange de plusieurs dispersions PU est appliquée sur la couche (2), - avant ou après l'application de la mousse PU, en particulier après son séchage, la couche de support (1) est éventuellement fragmentée ou coupée en découpes ou pièces formatées et les découpes ou pièces formatées revêtues sont soumises à un gaufrage ou à une structuration sous pression ou à chaud, et - la couche de support (1), l'autre couche (3) et la couche (2) sont comprimées et liées les unes aux autres par l'application d'une pression de contact de 4 à 48 kg/cm2, de préférence de 4 à 48 kg/cm2, en particulier de 18 à 25 kg/cm2, et structurées au moyen d'une matrice (4).
PCT/EP2019/069529 2018-12-13 2019-07-19 Matériau stratifié et procédé de production d'un matériau stratifié WO2020119961A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA3122879A CA3122879A1 (fr) 2018-12-13 2019-07-19 Materiau stratifie et procede de production d'un materiau stratifie
EP19742584.6A EP3894624B1 (fr) 2018-12-13 2019-07-19 Matériau multicouches et son procédé de production
US17/312,338 US20220040946A1 (en) 2018-12-13 2019-07-19 Layered material and method for producing a layered material
CN201980091647.0A CN113423886A (zh) 2018-12-13 2019-07-19 层状材料和生产层状材料的方法

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DE102019110290.1 2019-04-18
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EP1300474A1 (fr) * 2001-10-04 2003-04-09 Philipp Schaefer Nappa bovin pleine fleur et son procédé de préparation
EP1644539A1 (fr) 2003-11-15 2006-04-12 Philipp Schaefer Substrat pourvu d'un appret
EP1887128A1 (fr) * 2006-08-09 2008-02-13 Konrad Hornschuch AG Procede de fabrication d'un cuir artificiel lamine permeable a l'air
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EP3248833A1 (fr) * 2015-01-22 2017-11-29 LG Hausys, Ltd. Housse de siège pour automobile et son procédé de fabrication
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DE4230997A1 (de) 1992-09-16 1994-03-24 Sandoz Ag Spritzbeständiger wässriger Schaum, dessen Herstellung und Verwendung
EP1300474A1 (fr) * 2001-10-04 2003-04-09 Philipp Schaefer Nappa bovin pleine fleur et son procédé de préparation
EP1644539A1 (fr) 2003-11-15 2006-04-12 Philipp Schaefer Substrat pourvu d'un appret
EP1887128A1 (fr) * 2006-08-09 2008-02-13 Konrad Hornschuch AG Procede de fabrication d'un cuir artificiel lamine permeable a l'air
WO2009049728A2 (fr) * 2007-10-12 2009-04-23 Philipp Schaefer Cuir revêtu
EP3248833A1 (fr) * 2015-01-22 2017-11-29 LG Hausys, Ltd. Housse de siège pour automobile et son procédé de fabrication
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CN115056550B (zh) * 2022-05-27 2023-12-01 青岛天智达高科产业发展有限公司 一种辐射交联聚乙烯热缩式卡套的制备方法

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