EP2646214A1

EP2646214A1 - Method for producing multi-layer composite bodies

Info

Publication number: EP2646214A1
Application number: EP11788867.7A
Authority: EP
Inventors: Paul Andrew Simpson; Jürgen Herrmann; Lothar Wefers
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-12-03
Filing date: 2011-12-01
Publication date: 2013-10-09
Also published as: TWI545010B; WO2012072740A1; TW201302461A; CN103237640A; KR20130124519A; JP2014500166A

Abstract

The invention relates to a method for producing multi-layer composite bodies, characterized in that the following steps are carried out consecutively: (a) providing a negative or positive mold by means of power-modulated laser engraving with a surface structure in the form of an image or a pattern which comprises at least one element (D) that is different from geometric elements, numbers and letters, wherein the screen angles, hole depths or tapers within the surface structure are different; (b) optionally casting a negative mold from the positive mold; (c) spraying the negative mold with a plastic formulation, wherein the negative mold has a temperature between 50 and 200ºC; (d) allowing the plastic formulation to solidify to form a film; (e) joining the film with a substrate (A); and (f) separating the mold, wherein steps (e) and (f) can be carried out in any arbitrary order.

Description

Process for producing multilayer composites

The present invention relates to a process for the production of multilayer composites, characterized in that one carries out the following steps in succession:

(a) provide a negative or positive die by power modulated laser engraving having a surface structure in the form of an image or pattern having at least one element (D) other than geometric elements, numbers and letters, with screen angles, hole depths or tapers are different within the surface texture,

(b) optionally forming a negative template from the positive template,

(c) spraying the negative template with a plastic formulation, the negative template having a temperature in the range of 50 to 200 ° C,

(d) solidifying the plastic formulation into a film,

(e) connecting the film to a substrate (A),

(f) and one separates the matrix,

where you can perform the steps (e) and (f) in any order.

Furthermore, the present invention relates to multilayer composite bodies comprising (A) a substrate,

(B) optionally at least one tie layer and

(C) a plastic layer having a surface structure of its visible side,

wherein plastic layer (C) has on its visible side at least one image or pattern which has at least one element (D) different from geometric elements, numbers and letters

and wherein screen angles, hole depths or tapers are different within the surface texture.

Furthermore, the present invention relates to matrices.

Numerous substrates are provided with a coating to achieve a particularly beautiful appearance and a particularly pleasant feel (feel). Coatings with polymeric films have proven to be particularly versatile. Polymeric films can usually be made versatile and, depending on the material, can also be printed to achieve an interesting design.

WO 2005/47549 discloses a process by which leather can be coated. This gives matrices which have been patterned and onto which a plastic dispersion is applied when the matrix is warm. For example, imitation leather or leather with a comfortable grip can be obtained. A coated leather having complicated images is not disclosed in WO 2005/47549. EP 2006/092440 discloses a process by which coated leathers can be produced whose coating has hairs. Such leathers have a velvety surface with a comfortable grip. However, complex images can not be applied in sufficient quality in many cases according to the disclosed method.

WO 2007/033968 and WO 2008/017690 disclose methods by which, for example, numbers, letters or logos are engraved on a die with the aid of a laser and then, with the aid of the die, a film is produced which is applied to a substrate , However, complex images can not be applied in sufficient quality in many cases according to the disclosed method.

WO 2009/106503 discloses a method of providing textile surfaces with a coating which corresponds, for example, to grain leather or the texture of wood. This is done by applying a polyurethane layer, which was previously produced on a matrix. The polyurethane layer has hairs that have, for example, a circular diameter and a conical shape.

It was the object to provide a process for the production of composite bodies, by which even complicated images with sufficient quality can be transferred to coated substrates, without having to compromise on the handle and appearance of the surface.

Accordingly, the method defined above was found.

Multilayer composites are understood in the following to mean those materials which

(A) have at least one substrate and

(C) at least one plastic layer,

which are interconnected.

Numerous materials are suitable as substrate (A), for example metal foils, paper, cardboard, cardboard, wood, thermoplastic molded parts, preferably leather, textile, non-wovens (nonwovens), artificial leather, paper and wood.

The connection between substrate (A) and plastic layer (C) can be in various configurations, for example in the form of a coherent film or selectively, in the form of strips, as a grid, for example as a square or honey-shaped or diamond-shaped grid. Multilayer composite bodies produced by the process according to the invention contain at least one substrate (A) and at least one plastic layer (C) which has a complicated image on its visible side. In the context of the present invention, complicated or complex images are taken to mean those images which have at least one element (D) different from geometric elements, numbers and letters which is present once or several times on the visible side of the substrate coated according to the invention. Examples of such elements (D) may include, for example, animals, plants, humans including human beings' portraits, non-geometrically designed buildings such as cathedrals, automobiles, landscapes, country shapes, cartoon characters, and especially sports or art celebrity imagery. In the context of the present invention, complicated patterns are understood to mean those patterns which have at least one element (D) different from geometrical elements which occurs once or several times, for example animals, plants, humans including human beings, non-geometrically designed buildings such as, for example Cathedrals, cars, landscapes, country shapes, cartoon characters, and celebrity imagery from sports or art.

A scar pattern of a leather and the patterning of wood as such are neither considered as a complicated picture nor as a complicated pattern in the sense of the present application.

Geometric elements are, for example, circles, ellipses, in whole or in part, squares, rectangles, parallelograms, trapezoids, triangles, regular pentagons, regular hexagons, regular octagons, straight lines or stretches.

In one embodiment of the present invention, complicated images include at least one element (D) and at least one geometric element.

In another embodiment of the present invention, complicated images include at least one element (D) but not a geometric element.

In a preferred embodiment of the present invention, the complicated image does not have regular repeat units. By this is meant to be understood that - unlike patterns as in a wallpaper - the motives are not repeated constantly. In another embodiment of the present invention, complicated patterns have certain repeating units, which preferably comprise element (D).

In an embodiment of the present invention, the image or pattern, in addition to element (D), may comprise at least one further element selected from geometric elements, numbers and letters.

In one embodiment of the present invention, the image or pattern may represent a combination of two different patterns that merge into one another. For example, the image or pattern may represent a scar pattern of a leather associated with a pattern of a fabric or knit, for example, by an imitated seam or seamless.

In one embodiment of the present invention, the pattern or preferably the image is produced by elevations or depressions having a height or depth in the range from 1 to 3000 μm, which are formed by different screens, by different geometries (shapes) or by different heights or Depths give a different visual impression. In one embodiment of the present invention, the elevations or depressions differ individually or preferably in groups in that they have different geometries, different heights or depths or different grids. The method according to the invention comprises a number of steps, which are described below.

In a first step, also referred to below as step (a), one provides a negative or positive die by power-modulated laser engraving with a surface structure in the form of an image or pattern comprising at least one of geometric elements, numbers and letters having different element (D), wherein screen angle, hole depth or tapers are different within the surface structure. Positive matrices can also be called patricks.

Positive or negative matrices can be chosen from numerous materials, so you can choose, for example, metal matrices, as metals, for example, nickel, chromium or aluminum are suitable. Furthermore, plastic matrices are suitable, for example, polyurethane, polyamide or polyvinyl alcohol (PVA). Preference is given to matrices which contain at least one polymeric material as binder, silicone matrices are very particularly preferred. In one embodiment of the present invention, one selects positive matrices of plastic matrices, for example, polyurethane, polyamide or polyvinyl alcohol. In one embodiment of the present invention, negative matrices are selected from silicone matrices.

In one embodiment of the present invention, positive matrices are selected from pre-exposed plastic matrices, for example polyurethane, polyamide or polyvinyl alcohol.

By "of polyurethane", "of polyvinyl alcohol" or "of polyamide" is to be understood that the relevant template consists of more than half of polyurethane, polyvinyl alcohol or polyamide, but may also contain other substances, such as fillers, preservatives, Antioxidants and / or coatings.

In one embodiment of the present invention, one selects matrices, preferably negative matrices, in sheet form. In another embodiment of the present invention, one selects dies which are mounted on a cylinder or those dies which themselves have a cylindrical shape. Dies having cylindrical shape are preferably seamless. Matrices having cylindrical shape are particularly well suited for a continuous variant of the method according to the invention.

In one embodiment of the present invention, a die comprising an elastomeric layer or a layer composite comprising an elastomeric layer on a support, wherein the elastomeric layer comprises a binder and optionally further additives and auxiliaries, is selected. The preparation of such a template may then include the following steps:

1) application of a liquid binder, optionally containing additives and / or auxiliaries, to a surface provided with an image or a pattern, for example a positive matrix,

Curing the liquid binder, for example by thermal curing, radiation curing or by aging,

3) separating the thus obtainable template and optionally applying to a carrier, for example a metal plate or a metal cylinder. In one embodiment of the present invention, the procedure is to apply a liquid silicone to an imaged or patterned surface, age and cure the silicone, and then peel it off. The silicone film thus obtained is then glued on an aluminum support.

In a preferred embodiment of the present invention, a die is provided which has a laser-engravable layer or a layer composite comprising a laser-engravable layer on a support, wherein the laser-engravable layer comprises a binder and optionally further additives and auxiliaries. The laser-engravable layer is also preferably elastomeric.

In a preferred embodiment, the production of a die comprises the following steps: 1) providing a laser-engravable layer or a layer composite comprising a laser-engravable layer on a support, the laser-engravable layer comprising a binder and preferably additives and auxiliaries,

2) thermochemical, photochemical or actinic amplification of the laser-engravable layer,

3) Provide the laser-engravable layer with a surface texture

Power-modulated laser engraving. The laser-engravable layer, which is preferably elastomeric, or the layer composite can be present on a support, preferably they are present on a support. Examples of suitable backings include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene, polypropylene, polyamide or polycarbonate fabrics and films, preferably PET or PEN films. Also suitable as a carrier papers and knitted fabrics, such as cellulose. Conical or cylindrical tubes made of the said materials, so-called sleeves, can also be used as the carrier. Also suitable for sleeves are glass fiber fabrics or composite materials made of glass fibers and polymeric materials. Further suitable carrier materials are metallic carriers such as solid or tissue-shaped, flat or cylindrical carrier made of aluminum, nickel, steel, magnetizable spring steel or other iron alloys.

In one embodiment of the present invention, the support may be coated with an adhesive layer for better adhesion of the laser-engravable layer. In another embodiment of the present invention, no adhesive layer is required. The laser-engravable layer comprises at least one binder, which may be a prepolymer, which reacts to a polymer in the course of a thermochemical reinforcement. Suitable binders can be selected depending on the desired properties of the laser-engravable layer or the matrix, for example with regard to hardness, elasticity or flexibility. Suitable binders can be subdivided essentially into 3 groups, without the binders being intended to be limited thereto.

The first group includes such binders having ethylenically unsaturated groups. The ethylenically unsaturated groups can be crosslinked photochemically, thermochemically, by means of electron beams or with any combination of these processes. In addition, a mechanical reinforcement can be made by means of fillers. Such binders are, for example, those which comprise copolymerized 1,3-diene monomers, such as isoprene or 1,3-butadiene. The ethylenically unsaturated group can function once as a chain building block of the polymer (1, 4 incorporation), or it can be bound to the polymer chain as a side group (1, 2 incorporation). Examples include natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile-butadiene rubber, acrylonitrile-butadiene-styrene (ABS) copolymer, butyl rubber, styrene-isoprene rubber, polychloroprene, polynorbornene rubber, ethylene Propylene-diene rubber (EPDM) or polyurethane elastomers having ethylenically unsaturated groups.

Other examples include thermoplastic elastomeric block copolymers of alkenyl aromatics and 1,3-dienes. The block copolymers may be either linear block copolymers or radial block copolymers. Typically, they are triblock copolymers of the A-B-A type, but they may also be A-B type diblock polymers or those having multiple alternating elastomeric and thermoplastic blocks, e.g. A-B-A-B-A. It is also possible to use mixtures of two or more different block copolymers. Commercially available triblock copolymers often contain certain proportions

Two-block copolymers. Diene units can be 1, 2, or 1, 4 linked. Both block copolymers of styrene-butadiene and of styrene-isoprene type can be used. They are available, for example under the name Kraton ^® commercially. Furthermore, also usable thermoplastic elastomeric block copolymers having terminal blocks of styrene and a random styrene-butadiene-M are ittelblock which are available under the name Styroflex ^®.

Other examples of ethylenically unsaturated binder include modified binders in which crosslinkable groups are introduced into the polymeric molecule by grafting reactions.

The second group includes such binders having functional groups. The functional groups are thermochemical, by means of electron beams, photo- chemically or by any combination of these processes crosslinkable. In addition, a mechanical reinforcement can be made by means of fillers. Examples of suitable functional groups include -Si (HR ¹ ) 0-, -Si (R ¹ R ² ) O-, -OH, -NH ₂ , -NHR ¹ , -COOH, -COOR ¹ , -COH N ₂ , -O -C (0) NHR ¹ , -S0 ₃ H or -CO-. Examples of binders include silicone elastomers, acrylate rubbers, ethylene-acrylate rubbers, ethylene-acrylic acid rubbers or ethylene-vinyl acetate rubbers and their partially hydrolyzed derivatives, thermoplastic elastomeric polyurethanes, sulfonated polyethylenes or thermoplastic elastomeric polyesters. R ¹ and, if present, R ^{2 are} different or preferably identical and selected from organic groups and in particular C 1 -C 6 -alkyl.

In one embodiment of the present invention, it is possible to use binders which have both ethylenically unsaturated groups and functional groups. Examples include addition-crosslinking silicone elastomers having functional and ethylenically unsaturated groups, copolymers of butadiene with (meth) acrylates, (meth) acrylic acid or acrylonitrile, and also copolymers or block copolymers of butadiene or isoprene with functionalized styrene derivatives, for example block copolymers of butadiene and hydroxystyrene. The third group of binders includes those which have neither ethylenically unsaturated groups nor functional groups. These include, for example, polyolefins or ethylene / propylene elastomers or products obtained by hydrogenation of diene units, such as, for example, SEBS rubbers. Polymer layers which contain binders without ethylenically unsaturated or functional groups generally have to be reinforced mechanically, with the aid of high-energy radiation or a combination thereof, in order to enable optimum sharp-edged structuring by means of laser. It is also possible to use mixtures of two or more binders, which may be both binders from in each case only one of the groups described, or mixtures of binders from two or all three groups. The possible combinations are limited only insofar as the suitability of the polymer layer for the laser structuring process and the molding process must not be adversely affected. For example, a mixture of at least one elastomeric binder which has no functional groups can advantageously be used with at least one further binder which has functional groups or ethylenically unsaturated groups. In one embodiment of the present invention, the proportion of binder (s) in the elastomeric layer (s) is from 30% to 99% by weight relative to the sum of all of the components of the subject elastomeric layer or the relevant laser-engravable layer, preferably 40 to 95 wt .-%, and most preferably 50 to 90 wt .-%.

Optionally, the elastomeric layer or laser-engravable layer may comprise reactive low molecular weight or oligomeric compounds. Oligomeric compounds generally have a molecular weight of not more than 20,000 g / mol. Reactive low molecular weight and oligomeric compounds will hereinafter be referred to as monomers for the sake of simplicity. On the one hand, monomers can be added in order to increase the rate of photochemical or thermochemical crosslinking or crosslinking by means of high-energy radiation, if desired. When using binders from the first and second group, the addition of monomers for acceleration is generally not mandatory. In the case of binders from the third group, the addition of monomers is generally recommended, without this necessarily being necessary in every case.

Regardless of the crosslink speed issue, monomers can also be used to control the crosslink density. Depending on the nature and amount of the low molecular weight compounds added, further or narrower networks are obtained. As monomers on the one hand known ethylenically unsaturated monomers can be used. The monomers should be substantially compatible with the binders and have at least one photochemically or thermochemically reactive group. They should not be volatile. The boiling point of suitable monomers is preferably at least 150 ° C. Particularly suitable are amides of acrylic acid or methacrylic acid with mono- or polyfunctional alcohols, amines, amino alcohols or hydroxy ethers and esters, styrene or substituted styrenes, esters of fumaric or maleic acid or allyl compounds. Examples include n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, dipropylene glycol diacrylate, tripropyric acid. glycol diacrylate, dioctyl fumarate, N-dodecyl maleimide and triallyl isocyanurate.

Particularly suitable for the thermochemical reinforcement monomers include reactive low molecular weight silicones such as cyclic siloxanes, Si-H-functional siloxanes, siloxanes with alkoxy or ester groups, sulfur-containing siloxanes and silanes, dialcohols such as 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, diamines such as 1, 6-hexanediamine, 1, 8-octanediamine, amino alcohols such as ethanolamine, diethanolamine, butylethanolamine, dicarboxylic acids such as 1, 6-hexanedicarboxylic acid, terephthalic acid , Maleic acid or fumaric acid. It is also possible to use monomers which have both ethylenically unsaturated groups and functional groups. As examples of its ω-hydroxyalkyl (meth) acrylates, such as ethylene glycol mono (meth) acrylate, 1, 4-butanediol mono (meth) acrylate or 1, 6-hexanediol mono (meth) acrylate.

Of course, mixtures of different monomers can be used, provided that the properties of the elastomeric layer are not adversely affected by the mixture. In general, the amount of added monomers 0 to 40 wt .-% with respect to the amount of all components of the elastomeric layer or the laser-engravable layer concerned, preferably 1 to 20 wt .-%.

In one embodiment, one or more monomers may be employed with one or more catalysts. It is thus possible to accelerate silicone matrices by adding one or more acids or by organotin compounds to the step 2) of providing the template. Suitable organotin compounds can be: di-n-butyltin dilaureate, di-n-butyltin diactanoate, di-n-butyltin di-2-ethylhexanoate, di-n-octyltin di-2-ethylhexanoate and di-n-butylbis (1-oxoneodecyloxy) stannane , The elastomeric layer or the laser-engravable layer may further comprise additives and auxiliaries, for example IR absorbers, dyes, dispersing aids, antistatic agents, plasticizers or abrasive particles. The amount of such additives and auxiliaries should as a rule not exceed 30% by weight with respect to the amount of all components of the elastomeric layer or the relevant laser-engravable layer.

The elastomeric layer or the laser-engravable layer can be constructed from a plurality of individual layers. These individual layers can be of the same, approximately the same or different material composition. The thickness of the laser-engravable layer or of all individual layers together is generally between 0.1 and 10 mm, preferably 0.5 to 3 mm. The thickness can be suitably selected depending on the application technology and machine process parameters of the laser engraving process and the molding process. The elastomeric layer or the laser-engravable layer may optionally further comprise an upper layer having a thickness of not more than 300 μm. The composition of such a topsheet can be selected for optimal engravability and mechanical stability while selecting the composition of the underlying layer for optimum hardness or elasticity.

In one embodiment of the present invention, the top layer itself is laser engravable or in the course of laser engraving together with the underlying Removable layer. The topsheet comprises at least one binder. It may further comprise an absorber for laser radiation or even monomers or auxiliaries. Preferred matrices are silicone matrices. Silicone matrices are to be understood below as meaning those matrices for whose preparation at least one binder is used which has at least one, preferably at least three 0-Si (R ¹ R ² ) -O- groups per molecule. Here, R ¹ and R ^{2 are} different or preferably the same as defined above.

In another embodiment of the present invention, a nickel template is used as the template. Suitable nickel matrices consist essentially of a homogeneous nickel layer. Nickel layers can have a thickness in the range of 100 mm to 10 mm.

As a laser for laser engraving in step (a), for example, one can select an optical laser. Also suitable are CC lasers, Nd-Y AG lasers, fiber lasers and UV lasers. In the case of laser engraving in step (a), holes are engraved or engraved in the laser-engravable layer in a grid-like manner, wherein the grid can have, for example, square grid points or rectangular grid points or individual grid areas arranged in honeycomb patterns, for example. The delimitation of different areas can then be achieved, for example, by having a different screen angle in different areas.

Holes in the context of the present invention are not only those holes that pass through the laser-engravable layer, but also trough-like depressions.

The laser engraving in step (a) is power modulated laser engraving. By this is meant that during laser engraving the power of the laser is not left constant, but modulated according to the desired hole depth. In this case, screen angle, hole depth or tapers within the surface structure, so the engraved surface structure, different. By this is meant that individual engraved holes or groups of different holes each have different screen angles, hole depths or tapering holes, all holes may be different or the holes may be different in groups, or a few individual holes may be different. In one embodiment of the present invention, one selects beam sources with a laser power, ie maximum output power, in the range of 5 to 5000 W, preferably in the range of 10 to 2000 W, particularly preferably in the range of 50 to 500 W.

In one embodiment of the present invention, one modulates the power of the beam source in the range of zero to 100% of the laser power. Such a modulation can be done in the MHz range. In one embodiment of the present invention, one engraves in the range of 100 to 10,000 holes per cm ² , preferably in the range of 4,000 to 5,000 holes per cm ² .

In one embodiment of the present invention, the engraved holes have an average depth in the range of one to 3,000 μιη, preferably 50 to 500 μιη.

In one embodiment of the present invention, some holes within the surface structure may be made as conical holes and other holes cylindrical, conical, wedge-shaped or bulbous.

In one embodiment of the present invention, some holes within the surface structure may be made as cylindrical holes and other holes may be bulbous or conical.

In one embodiment of the present invention, some holes within the surface structure may be made as hemispherical cups and others cylindrical, conical, conical, wedge-shaped or bulbous. In one embodiment of the present invention, the holes differ in geometry. This is preferably to be understood as meaning the geometry of the cross-sectional area. For example, holes can have a round, elliptical or angular cross section, for example square, triangular, rhombic, a cross section in the form of a regular pentagon or regular hexagon (honeycomb) or regular octagon. Semicircles, stars and compound geometric elements are also possible.

In one embodiment of the present invention, groups of holes within the surface structure differ by the screen angle. For example, it is possible to have two areas of the same or different Power-modulated laser engraving provides the surface texture with an image or pattern containing at least one element (D).

Overall, a template according to the invention is obtained by carrying out step (a). Depending on whether those locations in the die which are formed as holes in a composite body should also be a hole or a - preferably formed like a hare - elevation, it is in the matrix according to the invention to a negative or a positive die. Optionally, after the actual laser engraving process, in step (a), the laser-engravable layer is washed to remove gravitational residues, for example with a round washer or a continuous washer with a cleaning agent.

In the manner described, the die can be produced as a negative die or as a positive die.

In one embodiment of the present invention, a step (b) is carried out for carrying out the method according to the invention: the molding of one or more negative matrices from the positive template produced in step (a). For example, you can do the following for casting:

1) applying a liquid binder, optionally containing additives and / or adjuvants, to an imaged or patterned surface on the positive template,

2) curing the liquid binder, for example by thermal curing, radiation curing or by aging,

3) separating the thus obtainable negative template and optionally applying to a support, for example a metal plate or a metal cylinder.

In another embodiment of the present invention, step (b) is omitted. To carry out the process according to the invention, step (c) is carried out, namely spraying the negative template with a plastic formulation, wherein the negative template has a temperature in the range of 50 to 200 ° C, preferably 75 to 150 ° C, more preferably at least 90 ° C. In this case, the temperature measured is that which is measured at the surface of the die, which comes into contact with plastic formulation, at the beginning of the spraying.

The spraying can be done simply or repeatedly. As a plastic formulation, it is possible to choose, for example, solutions of polymers, for example in organic solvent, and preferably aqueous formulations, in particular aqueous dispersions, for example aqueous suspensions or aqueous emulsions.

By aqueous, in connection with the plastic formulation, it is understood that it contains water, but less than 5% by weight, based on the dispersion, preferably less than 1% by weight of organic solvent. Most preferably, no volatile organic solvent can be detected. For the purposes of the present invention, volatile organic solvents are understood as meaning those organic solvents which have a boiling point of up to 200 ° C. under normal pressure. Suitable plastics in plastic formulations are, for example: polystyrene, polyacrylates and in particular polyurethanes. Suitable polyacrylates are, for example, copolymers of (meth) acrylic acid with one or more (meth) acrylic acid C 1 -C 10 -alkyl esters, in particular with methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.

Suitable polyurethanes are obtainable by reaction of

(i) isocyanates, preferably diisocyanates, with

(ii) isocyanate-reactive compounds, usually having a molecular weight (Mw) of 500 to 10,000 g / mol, preferably 500 to 5,000 g / mol, more preferably 800 to 3,000 g / mol, and

(iii) chain extenders having a molecular weight of from 50 to 499 g / mol,

optionally in the presence of catalysts and / or conventional additives. In the following, by way of example, the starting components and processes for the preparation of the preferred polyurethanes (PU) are set forth. The components (i), (ii), (iii) customarily used in the preparation of the polyurethanes (PU) and, if appropriate, catalysts and / or additives are described below by way of example:

As isocyanates (i) it is possible to use generally known aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene diisocyanate 1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-isocyanato-3,3,5-trimethyl-5-isocyanato methylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or 2,6-cyclohexane-di- isocyanate and / or 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1 , 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate. Preferably, 4,4'-MDI is used. Also preferred are aliphatic diisocyanates, especially hexamethylene diisocyanate (HDI).

As isocyanate-reactive compounds (ii) it is possible to use the generally known isocyanate-reactive compounds, for example polyesterols, polyetherols and / or polycarbonatediols, which are usually also grouped under the term "polyols", with molecular weights (M _w ) in the region of 500 and 8,000 g / mol, preferably 600 to 6,000 g / mol, in particular 800 to 3,000 g / mol, and preferably an average functionality to isocyanates of 1, 8 to 2.3, preferably 1, 9 to 2.2, in particular 2. Polyether polyols are preferably used, for example those based on generally known starter substances and customary alkylene oxides, for example ethylene oxide, 1,2-propylene oxide and / or 1,2-butylene oxide, preferably polyetherols based on polyoxytetramethylene (polyTHF), 1 , 2-propylene oxide and ethylene oxide.Polyetherols have the advantage that they have a higher hydrolytic stability than polyesterols, and are preferably as component (ii), in particular for the production of soft polyurethanes, polyurethane (PU 1).

Particularly suitable polycarbonate diols are aliphatic polycarbonate diols, for example 1,4-butanediol polycarbonate and 1,6-hexanediol polycarbonate.

As the polyester diols are those mentioned by polycondensation of at least one primary diol, preferably at least one primary aliphatic diol, for example ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol or more preferably 1, 4-dihydroxymethylcyclohexane (as Mixture of isomers) or mixtures of at least two of the abovementioned diols on the one hand and at least one, preferably at least two, dicarboxylic acids or their anhydrides on the other hand. Preferred dicarboxylic acids are aliphatic dicarboxylic acids such as adipic acid, glutaric acid, succinic acid and aromatic dicarboxylic acids such as phthalic acid and in particular isophthalic acid.

Polyetherols are preferred by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, to diols such as ethylene glycol, 1, 2-propylene glycol, 1, 2-butylene glycol, 1, 4-butanediol, 1, 3-propanediol, or to triols such For example, glycerol, produced in the presence of highly active catalysts. Such highly active catalysts include cesium hydroxide and dimetal cyanide catalysts, also referred to as D MC catalysts. A frequently used D MC catalyst is the zinc hexacyanocobaltate. The D MC catalyst can after the reaction are left in the polyetherol, it is preferably removed, for example by sedimentation or filtration.

Instead of a polyol, it is also possible to use mixtures of different polyols.

To improve the dispersibility can be used as isocyanate-reactive compounds (ii) proportionately one or more diols or diamines having a carboxylic acid group or sulfonic acid group (ϋ '), in particular alkali metal or ammonium salts of 1, 1 -dimethylolbutansäure, 1, 1 -dimethylolpropionsäure or

Suitable chain extenders (iii) are known aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499 g / mol and at least two functional groups, preferably compounds having exactly two functional groups per molecule, for example Diamines and / or alkanediols having 2 to 10 C atoms in the alkylene radical, in particular 1, 3-propanediol, butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, hexa- , Hepta-, octa, nona and / or Dekaalkylenglykole having 3 to 8 carbon atoms per molecule, preferably corresponding oligo- and / or polypropylene glycols, whereby mixtures of chain extenders (iii) can be used.

More preferably, components (i) to (iii) are difunctional compounds, i. Diisocyanates (i), difunctional polyols, preferably polyetherols (ii) and difunctional chain extenders, preferably diols.

Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (i) and the hydroxyl groups of components (ii) and (iii) are tertiary amines known per se, such as, for example, triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo- (2,2,2) octane ("DABCO") and similar tertiary amines, and in particular organic metal compounds such as titanic acid esters, iron compounds such as iron - (III) - acetylacetonate, tin compounds, eg, tin diacetate, tin dioctoate, tin dilaurate, or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, etc. The catalysts are usually used in amounts of from 0.0001 to 0.1 parts by weight per 100 Parts by weight of component (ii) used. In addition to catalyst, one or more auxiliaries and / or additives may also be added to components (i) to (iii). Examples which may be mentioned are blowing agents, antiblocking agents, surface-active substances, fillers, for example fillers based on nanoparticles, in particular fillers based on CaC0 ₃ , furthermore nucleating agents, lubricants, dyes and pigments, antioxidants, for example against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers, metal deactivators. In a preferred embodiment, the additives also include hydrolysis protectants such as, for example, polymeric and low molecular weight carbodiimides. Preferably, the soft polyurethane contains triazole and / or triazole derivative and antioxidants in an amount of 0.1 to 5 wt .-% based on the total weight of the relevant soft polyurethane. As antioxidants are generally suitable substances which inhibit or prevent unwanted oxidative processes in the plastic to be protected. In general, antioxidants are commercially available. Examples of antioxidants are sterically hindered phenols, aromatic amines, thiosynergists, trivalent phosphorus organophosphorus compounds, and hindered amine light stabilizers. Examples of sterically hindered phenols can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001 ([1]), pp. 98-107 and pp. 16-161. Examples of aromatic amines can be found in [1] pp. 107-108. Examples of thiosynergists are given in [1], p.104-105 and p.1 12-1 13. Examples of phosphites can be found in [1], p.109-1 12. Examples of hindered amine light are stabilizers given in [1], p.123-136. For use in the antioxidant mixture are preferably phenolic antioxidants. In a preferred embodiment, the antioxidants, in particular the phenolic antioxidants, have a molecular weight of greater than 350 g / mol, more preferably greater than 700 g / mol and a maximum molecular weight (M _w ) of at most 10,000 g / mol, preferably up to a maximum of 3,000 g / mol on. Furthermore, they preferably have a melting point of at most 180 ° C. Furthermore, antioxidants are preferably used which are amorphous or liquid. Also, as additive (s), mixtures of two or more antioxidants can be used.

In addition to the stated components (i), (ii) and (iii) and optionally catalyst and additives, it is also possible to use chain regulators (chain terminators), usually having a molecular weight of 31 to 3000 g / mol. Such chain regulators are compounds which have only one isocyanate-reactive functional group, for example monofunctional alcohols, monofunctional amines and / or monofunctional polyols. By means of such chain regulators, a flow behavior, in particular in the case of soft polyurethanes, can be adjusted in a targeted manner. Chain regulators can generally be used in an amount of 0 to 5, preferably 0.1 to 1, parts by weight, based on 100 parts by weight of component (ii), and fall by definition under component (iii). In addition to the stated components (i), (ii) and (iii) and optionally catalyst and additives, it is also possible to use one or more crosslinking agents having two or more isocyanate-reactive groups towards the end of the synthesis reaction, for example hydrazine hydrate.

To adjust the hardness of polyurethane (PU), components (ii) and (iii) can be selected in relatively broad molar ratios. Suitable examples are molar ratios of component (ii) to total chain extenders (iii) of 10: 1 to 1:10, in particular from 1: 1 to 1: 4, wherein the hardness of the soft polyurethanes with increasing content of (iii ) increases. The reaction for the preparation of polyurethane (PU) may be at a ratio of 0.8 to 1, 4: 1, preferably at a ratio of 0.9 to 1, 2: 1, more preferably at a ratio of 1, 05 to 1 , 2: 1. The index is defined by the ratio of the total isocyanate groups of component (i) used in the reaction to the isocyanate-reactive groups, i. the active hydrogens, the components (ii) and optionally (iii) and optionally monofunctional isocyanate-reactive components as chain terminators such as e.g. Mono alcohols. In addition to plastic, plastic dispersion used in step (c) may contain further components, for example one or more surfactants and / or one or more hardeners. Suitable hardeners are compounds which can crosslink a plurality of plastic molecules, preferably several polyurethane molecules, with one another, for example during thermal activation. Particularly suitable are hardeners based on trimeric diisocyanates, in particular based on aliphatic diisocyanates such as hexamethylene diisocyanate. Examples of particularly suitable hardeners are compounds described as compound (V) in WO 2009/106503.

In addition to plastic and optionally hardener, plastic dispersion used in step (c) may contain further compounds, for example one or more silicone compounds, which may have no or preferably one or more reactive groups per molecule. Suitable reactive groups are, for example, carboxylic acid derivative groups such as, for example, carboxylic acid methyl esters or carboxylic anhydrides, in particular succinic anhydride groups, and particularly preferably carboxylic acid groups.

Examples of reactive groups are further primary and secondary amino groups, for example NH (iso-C3H ₇₎ groups, NH (n-C3H ₇₎ groups, NH (cyclo-C6Hn) - groups, and NH (n-C4Hg) groups, particularly NH (C2H ₅₎ groups, and NH (CH ₃₎ - groups, and most preferably NH ₂ groups.

Furthermore, aminoalkylamino groups are preferred, for example -NH-CH ₂ -CH ₂ -NH ₂ groups, -NH-CH2-CH ₂ -CH 2 N H ₂ groups,

-NH-CH ₂ -CH ₂ -NH (C ₂ H ₅ ) groups, -NH-CH ₂ -CH ₂ -CH ₂ -NH (C ₂ H ₅ ) groups,

-NH-CH ₂ -CH ₂ -NH (CH ₃ ) groups, -NH-CH ₂ -CH ₂ -CH ₂ -NH (CH ₃ ) groups. Further suitable additives are selected from pigments, matting agents, light stabilizers, antistatic agents, antisoil, anticancer resin, thickeners, in particular polyurethane-based thickeners, and hollow microspheres.

In one embodiment of the present invention, in step (c), a plastic formulation having a solids content in the range from 1 to 50%, preferably 25 to 35%, is sprayed.

The spraying of - preferably aqueous - plastic formulation on the negative template can be carried out by methods known per se, in particular by spraying with a spray gun or with one or more spray nozzles, which can be fixed or movable incorporated into an apparatus.

For spraying - preferably aqueous - plastic formulation on the negative die one can make use of various devices. In particular, airless and air spray systems are suitable.

Preferably sprayed - preferably aqueous - plastic formulation having a temperature in the range of 15 to 30 ° C, particularly preferably 20 to 25 ° C. In one embodiment of the present invention, the - preferably aqueous - plastic formulation used for spraying has a dynamic viscosity at room temperature up to a maximum of 500 mPa · s, preferably of at most 200 mPa · s. In one embodiment of the present invention, the preferably aqueous plastic formulation used for spraying has a pH in the range from 4 to 10, preferably in the range from 6 to 8.

In step (d), the plastic formulation which has been sprayed onto the negative template in step (b) is allowed to solidify into a film. The solidification can be achieved, for example, by removing, for example by evaporation, organic solvent in which the above-mentioned plastic is formulated, or preferably the water in which the above-mentioned plastic is dispersed, suspended or emulsified.

Step (d) can be carried out at different temperatures. Suitable temperatures are for example 30 to 90 ° C. Step (d) can be carried out at any pressure, preferably atmospheric pressure.

At the end of step (d), a film-shaped plastic is obtained, which in the context of the present invention is also referred to as "film" for short.

The film may, for example, have a thickness in the range from 70 to 300 μm.

In step (e), the film is bonded to a substrate (A). Substrate (A) will be described below in detail. The bonding can be accomplished, for example, by lamination, gluing or welding and strengthened by, for example, pressing or calendering.

Of course, the film obtained in step (d) is bonded to substrate (A) so that the patterned side is the visible side.

For example, in step (e), an organic adhesive is applied by application of an organic adhesive which is applied over the whole area or preferably in the form of a perforated layer, that is to say not the entire surface, preferably an organic adhesive.

In one embodiment of the present invention, in step (e), organic adhesive is provided in a dot-shaped, strip-shaped or latticed fashion, for example in the form of diamonds, rectangles, squares or a honeycomb structure.

Organic adhesive can be selected from adhesives based on polyvinyl acetate, polyacrylate or in particular polyurethane, preferably of polyurethanes having a glass transition temperature below 0 ° C. The curing of the organic adhesive can be carried out, for example, thermally, by actinic radiation or by aging.

In another embodiment of the present invention, an adhesive net is applied in step (e).

In one embodiment of the present invention, organic adhesive has a maximum thickness of 100 μm, preferably 50 μm, more preferably 30 μm, very preferably 15 μm, determined after application and curing. In a step (f) of the process according to the invention, the die is separated off, for example by mechanical stripping. You can perform the steps (e) and (f) in any order. So you can first step (e) perform and then step (f). In another embodiment of the present invention, step (f) is performed first, followed by step (e).

In one embodiment of the present invention, the film of step (d) is porous.

In a preferred embodiment of the present invention, the film of step (d) has pores in the form of capillaries that run the full thickness (cross section) of the film.

In one embodiment of the present invention, the film from step (d) has on average at least 100, preferably at least 250, pores in the form of capillaries per 100 cm ² .

In one embodiment of the present invention, the pores in the form of capillaries have an average diameter in the range of 0.005 to 0.05 mm, preferably 0.009 to 0.03 mm. In one embodiment of the present invention, the pores in the form of capillaries are evenly distributed over the film of step (d). However, in a preferred embodiment of the present invention, the pores in the form of capillaries are unevenly distributed throughout the film of step (d). In one embodiment of the present invention, the pores in the form of capillaries are substantially bent. In another embodiment of the present invention, the pores in the form of capillaries have a substantially straight course. Pores in the form of capillaries can impart air and water vapor permeability to the film of step (d) without the need for perforation. In one embodiment of the present invention, the water vapor transmission rate of the film of step (d) may be above 1.5 mg / cm ² -h, as measured according to DIN 53333. Thus, it is possible for moisture, such as perspiration, to be passed through the film of step (FIG. d) can migrate through.

In one embodiment of the present invention, the film of step (d), in addition to the capillaries, still has pores that do not go the full thickness of the film.

By the method according to the invention can be produced multilayer composites, which have a velvety appearance and a very pleasant feel and on which images or patterns with excellent durability can be. Such patterns or images can be complicated and meet significant design requirements. Such images or patterns may for example have a flip-flop effect, ie, depending on the viewing angle they have a different appearance. When done in black, they have a pleasantly deep black tone. If you do it with a porous film, they are permeable to water vapor and insensitive to sweat stains. Due to their complexities and clever design, such images can serve as copy protection or as an original identifier.

Another object of the present invention are multilayer composite bodies containing

(A) a substrate,

(B) optionally at least one tie layer and

(C) a plastic layer having hairs with a surface structure on its visible side,

wherein plastic layer (C) on its visible side has at least one image or pattern which has at least one of geometric elements, numbers and letters different element (D)

Numerous materials are suitable as substrate (A), for example metal foils, paper, cardboard, cardboard, wood, thermoplastic molded parts, preferably leather, textile, non-wovens (nonwovens), artificial leather, paper and wood. Examples of textile are woven and knitted fabrics.

The connection between substrate (A) and plastic layer (C) can be in various configurations, for example in the form of a coherent film or selectively, in the form of strips, as a grid, for example as a square or honey-shaped or diamond-shaped grid.

Substrate (A) may have any thickness adapted to the material of the substrate.

Plastic layer (C) has hairs.

In one embodiment of the present invention, plastic layer (C) has an average thickness in the range from 15 to 300 μm, preferably from 20 to 150 μm, particularly preferably from 25 to 80 μm, the length of the hairs not being included. The meaning of the terms image, pattern and a description of element (D) can be found above.

In one embodiment of the present invention, in addition to element (D), the image may include one or more geometric elements, numbers or letters.

In one embodiment of the present invention, different parts of the image or pattern are produced by different three-dimensional structuring of the synthetic material layer (C).

In a preferred embodiment of the present invention, the image, which may preferably be complicated, does not have regular repeat units. By this it should be understood that - in contrast to patterns like a taboo - the motifs are not repeated all the time.

In another embodiment of the present invention, patterns have certain repeating units, which preferably comprise element (D). In one embodiment of the present invention, the image or pattern, in addition to element (D), may comprise at least one further element selected from geometric elements, numbers and letters.

In an embodiment of the present invention, the image or pattern may represent a combination of two different patterns that merge into one another. For example, the image or pattern may represent a scar pattern of a leather associated with a pattern of a fabric or knit, for example, by an imitated seam or seamless. This compound then preferably corresponds to the element (D).

In one embodiment of the present invention, the pattern or preferably the image is generated by elevations or depressions having a height or depth in the range from 1 to 3000 μm, which differ by different rasters, by different formations or by different heights or depths convey a visual impression.

In one embodiment of the present invention, the elevations or depressions differ in groups in that they have different three-dimensional geometries, different heights or depths or different screenings. In one embodiment of the present invention, plastic layer (C) may comprise at least two different polyurethanes which are also referred to as (C1) and (C2) in the context of the present invention, polyurethane (C1) having a Shore A hardness of less than 60 and also called "soft polyurethane" and wherein polyurethane (C2) has a Shore A hardness in the range of about 60 to 120 and is also referred to as "hard polyurethane". The Shore A hardness is determined, for example, according to DIN 53505 after 3 s.

In one embodiment of the present invention, polyurethane (C1) has a mean particle diameter in the range of 100 to 300 nm, preferably 120 to 150 nm, determined by laser light scattering.

In one embodiment of the present invention, polyurethane (C2) has an average particle diameter in the range of 100 to 300 nm, preferably 120 to 150 nm, determined by laser light scattering.

In one embodiment of the present invention, the hardness of polyurethane (C1) or polyurethane (C2) is adjusted by different proportions of IPDI as diisocyanate.

In one embodiment of the present invention, plastic layer (C) is impermeable to air. In another embodiment of the present invention, plastic layer (C) is porous, for example in that plastic layer has capillaries which pass through the entire thickness of the plastic layer.

Multilayer composite bodies according to the invention can be produced, for example, by the process according to the invention described above. Inventive multilayer composites have a velvety appearance and a very pleasant feel. On composite bodies according to the invention can be pictures or samples with excellent durability. Such patterns or images can be complicated and meet significant design requirements. Such images or patterns may for example have a flip-flop effect, ie, depending on the viewing angle they have a different appearance. When done in black, they have a pleasantly deep black tone. If you do it with a porous film, they are permeable to water vapor and insensitive to sweat stains. Due to their complexities or clever design, such images can serve as copy protection or as an original identifier. A further subject of the present invention is a negative template which has on one side at least one negative of an image or pattern which comprises at least one element (D) different from geometrical elements, numbers and letters. and which is generated by elevations and depressions that give a different visual impression in different screens or in different heights or depths. In one embodiment of the present invention, the elevations or depressions differ individually or preferably in groups in that they have different geometries, different heights or depths under different screenings or screen angles. Dies according to the invention are very well suited for the production of multilayer composite bodies according to the invention. Another object of the present invention is therefore the use of negative matrices according to the invention for the production of multilayer composite bodies according to the invention. A method for producing matrices of the invention has been described above.

The invention will be explained by working examples. Working Examples:

I. Preparation of Matrices of the Invention A liquid silicone was cast on a flat pad. The mixture was allowed to cure by adding thereto a solution of di-n-butylbis (1-oxoneodecyloxy) stannane as a 25% by weight solution in tetraethoxysilane as an acidic curing agent to obtain an average 2 mm thick silicone rubber layer as the base of a template served. The die was glued to a 1.5 mm thick aluminum support.

With the help of a CO2 laser engraved circular holes, which had the characteristics according to Table 1. The power of the beam source was modulated by an acousto-optic modulator.

These characteristics were different in different regions of the matrix. The arrangement of the regions produced different shades and thereby the image of a kicking football player.

Inventive die 1 was obtained. Table 1: Characteristics for Holes in Die 1 According to the Invention

Distance is the distance between two holes to understand. The distance between the holes is the distance to the nearest hole, from hole center to hole center.

Terms from Table 1 are explained in more detail in Figure 1.

Lt: hole depth,

ZA: cylindrical approach

P: plateau

A die according to the invention was obtained. II. Production of Plastic Dispersions

As plastics, polyurethanes were selected in each case.

11.1 Preparation of an Aqueous Polyurethane Dispersion Disp.1

In a stirred vessel was mixed with stirring:

7 wt .-% of an aqueous dispersion (particle diameter: 125 nm, solids content: 40%) of a soft polyurethane (C1 .1), prepared from hexamethylene diisocyanate and isophorone diisocyanate in a weight ratio of 13:10 as diisocyanates and as diols a polyester diol with a Molecular weight M _w of 800 g / mol, prepared by polycondensation of isophthalic acid, adipic acid and 1, 4-Dihydroxymethylcyclohexan (isomer mixture) in a molar ratio of 1: 1: 2, 5 wt .-% 1, 4-butanediol

(b1.2), and also 3% by weight of monomethylated polyethylene glycol and 3% by weight of H2N-CH 2 CH 2 -NH-CH 2 CH 2 -COOH,% by weight, based in each case on polyesterdiol (b1.1), softening point of soft polyurethane ( C1.1): 62 ° C, softening starts at 55 ° C, Shore hardness A 54,

65% by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (C2.1) obtainable by reacting isophorone diisocyanate, 1,4-butanediol, 1,1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol with a molecular weight M _w of 4200 g / mol, softening point of 195 ° C, Shore hardness A 86,

3.5% by weight of a 70% by weight solution (in propylene carbonate) of compound (1.1),

6 wt .-% of a 65 wt .-% aqueous dispersion of the silicone compound according to Example 2 of EP-A 0 738 747

2% by weight of carbon black,

0.5% by weight of a polyurethane-based thickener,

1 wt .-% hollow microspheres of polyvinylidene chloride, filled with isobutane, diameter 20 μιη, commercially available z. B. as Expancel® the Fa. Akzo Nobel.

This gave aqueous dispersion Disp.1 having a solids content of 35% and a kinematic viscosity of 25 seconds at 23 ° C, determined according to DIN EN ISO 2431, as of May 1996.

II.2 Preparation of an Aqueous Formulation Disp.2 In a stirred vessel, the mixture was mixed while stirring:

7 wt .-% of an aqueous dispersion (particle diameter: 125 nm), solids content: 40%) of a soft polyurethane (C1 .1), prepared from hexamethylene diisocyanate and isophorone diisocyanate in a ratio by weight 13:10 as diisocyanates and as diols a polyester a molecular weight M _w of 800 g / mol, prepared by polycondensation of isophthalic acid, adipic acid and 1, 4-dihydroxymethylcyclohexane (mixture of isomers) in a molar ratio of 1: 1: 2, 5 wt .-% 1, 4-butanediol, 3 wt. % by weight of methylated polyethylene glycol and 3% by weight of H2N-CH 2 CH 2 -NH-CH 2 CH 2 -COOH,% by weight, based in each case on polyester diol, softening point of 62 ° C., softening starts at 55 ° C., Shore hardness A 54,

65 wt .-% of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane, obtainable by reacting isophorone diisocyanate, 1, 4-butanediol (C1 .2), 1, 1 -dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having a molecular weight M _w of 4200 g / mol, polyurethane (C2.2) had a softening point of 195 ° C, Shore hardness A 90,

3.5% by weight of a 70% by weight solution (in propylene carbonate) of compound (1.1), NCO content 12%,

2% by weight of carbon black. This gave a polyurethane dispersion Disp.2 having a solids content of 35% and a kinematic viscosity of 25 sec., Determined after at 23 ° C according to DIN EN ISO 2431, as of May 1996.

III. Production of a plastic film

Inventive die 1 was placed on a heatable pad and heated to 91 ° C. The mixture was then sprayed through a spray nozzle Disp.1, namely 88 g / m ² (wet). The application was carried out without admixing air with a spray nozzle having a diameter of 0.46 mm, at a pressure of 65 bar. It was allowed to solidify at 91 ° C until the surface was no longer sticky.

The spray nozzle was mobile at a height of 20 cm from the continuous base in the direction of movement thereof and moved transversely to the direction of movement of the base. The pad had passed the spray nozzle after about 14 seconds and had a temperature of 59 ° C. After about two minutes exposure to dry, 85 ° C warm air, the crosslinked polyurethane film (C.1) thus prepared was nearly anhydrous.

In an analogous arrangement ² of wet Disp.2 as a bonding layer (B.1) was added immediately after the thus-coated mold according to the invention 50 g / m applied and then allowed to dry. A die coated with plastic film (C.1) and bonding layer (B.1) was obtained.

A dipped coagulated polyester nonwoven (A.1), also called substrate (A.1) for short, with a weight per unit area of 180 g / m ² , was sprayed with Disp.2 at 30 g / m ² (wet). The thus sprayed substrate (A.1) was allowed to dry for several minutes.

IV. Preparation of a multilayer composite body according to the invention Subsequently, sprayed substrate (A.1) with the sprayed side was placed on the still-warm bonding layer (B.1) which is located on the matrix together with plastic film (C.1) and in one Press at 4 bar and 1 10 ° C for 15 seconds. Subsequently, the composite multilayer composite material MSV.1 according to the invention thus obtained was removed from the press and the die was removed.

The multilayer composite material MSV.1 according to the invention thus obtained was characterized by a pleasant feel, an optic identical to the original one. looks like the football player is out, as well as breathability. In addition, the multilayer composite material MSV.1 according to the invention was easily cleaned of soiling such as dust. MSV.1 showed the image of a football player with great precision.

The work steps according to II. To IV. Could be repeated several times with the same die, without the image quality diminishing.

Claims

claims

Process for the production of multilayer composites, characterized in that the following steps are carried out successively:

(b) optionally forming a negative template from the positive template,

(d) solidifying the plastic formulation into a film,

(e) connecting the film to a substrate (A),

(f) and one separates the matrix,

where you can perform the steps (e) and (f) in any order.

A method according to claim 1, characterized in that one selects an optical laser as the laser in step (a).

A method according to claim 1 or 2, characterized in that one selects negative matrices of silicone matrices.

Method according to one of claims 1 to 3, characterized in that one selects positive matrices of plastic matrices of polyurethane, polyamide or polyvinyl alcohol.

Method according to one of claims 1 to 4, characterized in that one selects a laser power in the range of 5 to 5000 W in step (a).

Method according to one of claims 1 to 5, characterized in that is selected as the plastic formulation in step (c) an aqueous polyurethane dispersion containing at least two different polyurethanes, wherein a polyurethane (C1) has a Shore A hardness in the range of 60, and another polyurethane (C2) has a Shore A hardness in the range of about 60 to 100.

7. The method according to any one of claims 1 to 6, characterized in that the image or pattern further comprises at least one element which is selected from geometric elements, numbers and letters. 8. The method according to any one of claims 1 to 7, characterized in that the image has no regular repeat units.

Method according to one of claims 1 to 8, characterized in that the pattern or image is generated by elevations or depressions with a height or depth in the range of 1 to 3000 μιη, which by different rasters, by different formations or by different heights o - give the depths a different visual impression.

Method according to one of claims 1 to 9, characterized in that the elevations or depressions differ in groups in that they have different geometries, different heights or depths or different grids.

Method according to one of claims 1 to 10, characterized in that the film from step (d) is porous.

Multilayer composite containing

(A) a substrate,

(B) optionally at least one tie layer and

(C) a plastic layer having hairs with a surface structure on its visible side,

13. A composite according to claim 12, characterized in that substrate (A) is selected from leather, textile, non-wovens, paper, wood and artificial leather.

14. Composite body according to one of claims 12 or 13, characterized in that the image additionally comprises geometric elements, numbers or letters. 15. A composite according to any one of claims 12 to 14, characterized in that different parts of the image or pattern by different dreidi- dimensional structuring of the visible side of the plastic layer (C) are generated.

16. A composite according to any one of claims 12 to 15, characterized in that the image has no regular repeating units.

17. A composite according to any one of claims 12 to 16, characterized in that the pattern or image has elevations or depressions, which mediate a different visual impression by different screens or by different heights or depths in the range of 1 to 3000 μιη.

Composite body according to one of claims 12 to 17, characterized in that plastic layer (C) contains at least two different polyurethanes, wherein one polyurethane (C1) has a Shore hardness A in the range of less than 60, and another polyurethane (C2) a Shore Hardness A in the range of over 60 to 100 has.

Composite body according to one of claims 12 to 18, characterized in that the elevations or depressions differ in groups in that they have different three-dimensional geometries, different heights or depths or different grids.

20. A composite body according to any one of claims 12 to 19, characterized in that the plastic layer (C) is porous.

21. Composite body according to one of claims 12 to 20, characterized in that the image or pattern represents a combination of two different patterns which merge into each other. A composite according to claim 21, characterized in that the image or pattern represents the grain pattern of a leather associated with a pattern of a fabric or knitwear.

23. Negative matrix having on one side at least one negative of an image or pattern comprising at least one of geometric elements, numbers and

Letters different element (D), and which is generated by elevations or depressions, which give a different visual impression in different rasters o- or at different heights or depths.

24. Negative die according to claim 23, characterized in that the elevations or depressions differ in groups in that they have different geometries, different heights or depths or different screens.

Use of negative matrices according to claim 23 or 24 for the production of composite bodies according to any one of claims 12 to 20.