JP2014500166A - Multilayer composite manufacturing method - Google Patents

Abstract

  A method for producing a multilayer composite comprising: (a) a surface structure in the form of an image or pattern having at least one element (D) different from geometric elements, numbers and letters; Preparing a female or male mold by power-modulated laser engraving, with varying raster angles, pore depths or tapering shapes within the surface structure, (b) optionally from male to female mold (C) spraying the plastic compound onto the female mold, wherein the female mold has a temperature in the range of 50-200 ° C. and (d) solidifying the plastic compound. (E) The step of bonding the coating to the substrate (A), (f) The step of removing the mold are sequentially performed, and the working steps (e) and (f) are optional. It can be carried out in the order of The process of the layer composite.

Description

The present invention includes the following work steps:
(A) Prepare a female or male mold by power-modulated laser engraving with a surface structure in the form of an image or pattern having at least one element (D), which is different from geometric elements, numbers and letters The process, the screen angle in the surface structure, the depth of the pores or the tapered shape varies,
(B) optionally forming a female mold from a male mold;
(C) spraying the plastic compound on the female mold, wherein the female mold has a temperature in the range of 50-200 ° C;
(D) solidifying the plastic compound into a film;
(E) a step of bonding the coating to the substrate (A);
(F) sequentially performing the steps of removing the mold;
In this case, the working steps (e) and (f) relate to a method for producing a multilayer composite, characterized in that they can be carried out in any order.

Furthermore, the present invention provides
(A) substrate,
A multilayer composite comprising (B) optionally at least one bonding layer and (C) a plastic layer having one surface structure on its visible side,
In this case, the plastic layer (C) has at least one image or at least one element (D) on the visible side of the plastic layer (C), which is different from geometric elements, numbers and letters, or Has a pattern,
And it is related with the said multilayer composite in which the screen angle, the depth of a pore, or a taper shape differs in the surface structure in that case.

  Furthermore, the present invention relates to a mold.

  Many substrates are provided with a coating in order to achieve a particularly beautiful appearance and a particularly pleasant touch (tactile sensation). In so doing, coatings with polymer coatings have proven to be particularly multi-faceted. Polymer coatings can often be formed in multiple ways and, depending on the material, can also be printed to achieve interesting shapes.

  WO 2005/47549 discloses a method by which leather can be coated. A mold with a pattern is manufactured, and when the mold is hot, a plastic dispersion is applied over the mold. For example, an artificial leather or leather having a pleasant hand feeling can be obtained. Coated leather with complex images is not disclosed in WO 2005/47549.

  From the description of EP 2006/092440, it is known how a coated leather can be produced in which the coating has fine hairs. This type of leather has a velvety surface with a pleasant feel. However, complex images cannot often provide sufficient quality by the disclosed methods.

  WO 2007/033968 and WO 2008/017690 describe a method in which a laser is used to engrave, for example, numbers, letters or logos into a mold, which is then used to produce a coating and to bring this coating onto a substrate. It is disclosed. However, complex images cannot often provide sufficient quality by the disclosed method.

  WO 2009/106503 discloses a method of how a fiber surface can be provided with a coating corresponding to, for example, a silver crust or wood pattern. For this purpose, a polyurethane layer previously produced on the mold is applied. The polyurethane layer has fine hairs having, for example, a circular diameter and a conical shape.

  There was a problem of providing a method of manufacturing a composite that does not need to be deleted during the surface feel and appearance of the surface and that can transfer a complex image of sufficient quality to a coated substrate.

  Accordingly, the method defined at the beginning was found.

Multi-layer composites, as described below,
Connected to each other,
It is interpreted as a material having (A) at least one substrate and (C) at least one plastic layer.

  As the substrate (A), many materials such as metal foil, paper, cardboard, cardboard, wood and thermoplastic molded products are suitable, and leather, woven fabric, non-woven fabric (fleece material), artificial leather, paper are preferable. And wood.

  The bonding of the substrate (A) and the plastic layer (C) can be in various ways, for example in the form of a continuous coating, or in the form of dots, in the form of strips, as a grid, for example a square grid or It may be configured as a honeycomb-like grid or a diamond-shaped grid.

  The multilayer composite produced by the method according to the invention comprises at least one substrate (A) and at least one plastic layer (C) having a complex image on its visible side.

  In so doing, complex images differ within the scope of the invention from geometric elements, numbers and letters which are present once or several times on the visible side of a substrate coated according to the invention, It is interpreted as an image having at least one element (D). Examples of this type of element (D) are humans, including animals, plants, human portraits, non-geometrically drafted buildings, such as cathedrals, cars, landscapes, country shapes, animations and especially It may be a celebrity photo from sports or art.

  Complex patterns are within the scope of the present invention at least one element (D), which is different from geometric elements, present once or several times, for example humans, including animal, plant, human portraits, It is interpreted as a pattern with non-geometrically drafted buildings, such as cathedrals, plus photographs of celebrities from cars, landscapes, country shapes, animations and sports or arts.

  The leather silver pattern and the wood itself pattern are not considered as complex images or as complex patterns for the purposes of the present invention.

  Geometric elements can be, for example, circles, ellipses, all or part of each, squares, rectangles, parallelograms, trapezoids, triangles, regular pentagons, regular hexagons, regular octagons, lines or lines It is.

  In an embodiment of the invention, the complex image comprises at least one element (D) and at least one geometric element.

  In another embodiment of the invention, the complex image contains at least one element (D) but no geometric elements.

  In a preferred embodiment of the invention, the complex image does not have regular repeating units. On the other hand, if the pattern is different from that of wallpaper, the motif should be interpreted as not constantly repeating.

  In another embodiment of the invention, the complex pattern has a certain repeating unit, especially comprising element (D).

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

  In an embodiment according to the present invention, the image or pattern can be a combination of two different patterns that migrate to each other. For example, the image or pattern can be a silver pattern on the leather that is associated with the pattern of the woven or knitted product, for example with or without a simulated seam.

  In an embodiment according to the invention, the pattern or in particular the image is in the range of 1 to 3000 μm, which conveys different visual impressions by different screens, different geometric shapes (shapes) or different heights or depths. Generated by a ridge or recess having a height or depth.

  In an embodiment of the invention, the ridges or recesses are individually distinguished by the ridges or recesses having different geometric shapes, different heights or depths or different screens. Or specifically differentiated by group.

  The method according to the invention comprises a plurality of steps as described below.

  In a first step, hereinafter also referred to as step (a), having a surface structure in the form of an image or pattern having at least one element (D) different from geometric elements, numbers and letters, Female or male molds are prepared by power-modulated laser engraving, with different screen angles, pore depths or tapered shapes in the surface structure.

  The male mold is also called the father mold.

  The male or female mold may be selected from a number of materials, i.e. a metal mold, for example, can be selected, and for example nickel, chromium or aluminum are suitable as the metal. Furthermore, plastic molds, for example from polyurethane, polyamide or polyvinyl alcohol (PVA) are suitable. A mold comprising at least one polymer material as a binder is preferred, and a silicone mold is particularly preferred.

  In an embodiment of the invention, a plastic mold, for example a male mold from polyurethane, polyamide or polyvinyl alcohol, is selected.

  In an embodiment of the invention, a female mold from the silicone mold is selected.

  In an embodiment of the invention, a pre-exposed plastic mold is selected, for example a male mold from polyurethane, polyamide or polyvinyl alcohol.

  In this context, “from polyurethane”, “from polyvinyl alcohol” or “from polyamide” means that more than half of the mold consists of polyurethane, polyvinyl alcohol or polyamide, but other substances, for example It should be construed that it may contain fillers, preservatives, antioxidants and / or coatings.

  In an embodiment of the invention, a plate-shaped mold, in particular a female mold, is selected. In another embodiment of the present invention, a mold mounted on a cylinder is selected, or a mold that itself has the shape of a cylinder. The mold having the shape of a cylindrical body is particularly configured without a seam. A mold having the shape of a cylinder is particularly well suited for the continuous variant of the process according to the invention.

In an embodiment of the invention, a mold having an elastomeric layer or layer composite comprising an elastomeric layer on a carrier is selected, wherein the elastomeric layer comprises a bonding agent and any further additives and auxiliaries. The manufacture of such a mold further includes the following steps:
1) applying a liquid bonding agent optionally containing additives and / or auxiliaries onto a surface provided with an image or pattern, for example a male mold,
2) A step of curing the liquid bonding agent by, for example, thermal curing, radiation curing or aging,
3) Separating the mold thus obtained and optionally bringing it onto a support such as a metal plate or metal cylinder.

  In an embodiment of the present invention, liquid silicone is provided on a surface with an image or pattern, the silicone is aged, and thus cured, and then pulled away. The silicone film thus obtained is further bonded onto an aluminum carrier.

  In a preferred embodiment of the invention, a mold is provided having a laser-engraveable layer or layer composite comprising a laser-engraveable layer on a carrier, wherein the laser-engraveable layer comprises a bonding agent as well as an optional Further additives and auxiliaries. Furthermore, the laser engraveable layer is in particular an elastomer.

In a preferred embodiment, the mold manufacture comprises the following steps:
1) preparing a laser-engraveable layer or layer composite comprising a laser-engraveable layer on a carrier, the laser-engraveable layer comprising a bonding agent and in particular additives and auxiliaries;
2) The step of strengthening the laser-engravable layer thermochemically, photochemically or by actinic radiation,
3) including the step of providing a surface structure on the laser engraveable layer by power modulated laser engraving.

  A laser-engravable layer or layer composite, in particular an elastomer, can be present on the carrier, in particular the layer is present on the carrier. Examples of suitable carriers include woven fabrics and films from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene, polypropylene, polyamide or polycarbonate, preferably PET or PEN films. Similarly, knits made of paper and eg cellulose are suitable as carriers. Conical or cylindrical tubes from the aforementioned materials, so-called sleeves, can also be used as carriers. Also suitable for the sleeve are glass fiber fabrics or composite materials from glass fibers and polymeric materials. Further suitable carrier materials are metal carriers such as bulk or woven planar or cylindrical carriers from aluminum, nickel, steel, magnetizable spring steel or another iron alloy.

  In an embodiment of the invention, the carrier may be coated with an adhesion layer for better adhesion of the laser engraveable layer. In another embodiment of the invention, no adhesion layer is required.

  The laser engraveable layer includes at least one bonding agent, which may be a prepolymer that reacts to the polymer during the course of thermochemical strengthening. A suitable bonding agent can be selected depending on the desired properties of the laser-engravable layer or the desired properties of the mold, for example in relation to hardness, elastic modulus or flexibility. Suitable bonding agents can be mainly divided into three groups, but the bonding agents are not limited thereto.

  The first group includes binders having ethylenically unsaturated groups. The ethylenically unsaturated group can be cross-linked photochemically, thermochemically, by electron beam, or any combination of the above processes. Furthermore, mechanical strengthening can be performed with fillers. This type of bonding agent is, for example, a bonding agent containing a 1,3-diene monomer such as isoprene or 1,3-butadiene after polymerization. In this case, the ethylenically unsaturated group can once function as a chain constituent unit of the polymer (incorporation into 1,4-), or the ethylenically unsaturated group can be used as a side group (1,2- Can be attached to the polymer chain. 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- Examples include diene rubber (EPDM) or a polyurethane elastomer having an ethylenically unsaturated group.

  Further examples include thermoplastic elastomer block copolymers from alkenyl aromatic compounds and 1,3-dienes. The block copolymer can be a linear block copolymer or can be a radial block copolymer. It is typically an ABA type ternary block copolymer, but may also be an AB type binary block copolymer, or a plurality of alternating elastomeric blocks and thermoplastic blocks ABA. It may be a block copolymer having -B-A. Mixtures of two or more various block copolymers may be used. Commercially available ternary block copolymers often contain a proportion of the diblock copolymer. The diene units may be bonded at the 1,2-position or 1,4-position. Styrene-butadiene type block copolymers as well as styrene-isoprene type block copolymers may be used. The block copolymer is commercially available, for example under the name Kraton®. Furthermore, thermoplastic elastomer block copolymers with end blocks from styrene and random styrene-butadiene intermediate blocks can also be used and are available under the name Styroflex®.

  Further examples of binders having ethylenically unsaturated groups include modified binders in which crosslinkable groups are introduced into the polymer molecule by a graft reaction.

The second group includes a bonding agent having a functional group. The functional groups can be cross-linked thermochemically, by electron beam, photochemically, or any combination of these processes. Furthermore, mechanical strengthening can be performed with fillers. Examples of suitable functional ^{groups, -Si (HR 1) O -} , - Si (R 1 R 2) O -, - OH -, - NH 2, -NHR 1, -COOH, -COOR 1, -COHN _{2, -O-C (O)} NHR 1, including -SO ₃ H or -CO-. Examples of binders are silicone elastomers, acrylate rubbers, ethylene-acrylate rubbers, ethylene-acrylic acid rubbers or ethylene-vinyl acetate rubbers and their partially hydrolyzed derivatives, thermoplastic elastomer polyurethanes, sulfonated polyethylenes Or a thermoplastic elastomer polyester. In this case, R ¹ and, when present, R ² are different or in particular identical and are selected from organic groups, in particular C ₁ -C ₆ alkyl.

  In embodiments of the present invention, a binder having an ethylenically unsaturated group as well as a functional group can be used. Examples include addition crosslinkable silicone elastomers having functional groups and ethylenically unsaturated groups, copolymers of butadiene and (meth) acrylates, (meth) acrylic acid or acrylonitrile, and also having functional groups with butadiene or isoprene. Copolymers or block copolymers with styrene derivatives, such as block copolymers of butadiene and 4-hydroxystyrene.

  A third group of bonding agents are bonding agents that have no ethylenically unsaturated groups and no functional groups. Mention may be made here of, for example, polyolefins or ethylene / propylene elastomers or products obtained by hydrogenation of diene units, for example SEBS rubber.

  Polymer layers containing binders that are free of ethylenically unsaturated groups or functional groups are often mechanically energetic radiation or from it to allow the possibility of optimum sharp-angle structuring by the laser. Must be strengthened by combination.

  A mixture of two or more binders may be used, where each may be a binder from only one of the groups described, or two groups or all three It may be a mixture of binders from the group. Combination possibilities are limited only when the suitability of the polymer layer should not adversely affect the laser structuring process and the molding process. Preferably, a mixture of at least one elastomeric binder, for example without functional groups, and at least one further binder with functional groups or ethylenically unsaturated groups can be used.

  In an embodiment of the present invention, the proportion of the bonding agent or binders in the elastomer layer or the laser-engraveable layer is 30 masses with respect to the sum of all components of the elastomer layer or the laser-engraveable layer. % To 99% by weight, preferably 40 to 95% by weight, particularly preferably 50 to 90% by weight.

  Optionally, the elastomeric layer or laser-engraveable layer can comprise a reactive low molecular weight compound or oligomeric compound. The oligomeric compound generally has a molecular weight of 20000 g / mol or less. Reactive low molecular weight compounds and oligomeric compounds are hereinafter referred to as monomers for simplicity.

  Monomers, on the one hand, may be added to increase the rate of photochemical or thermochemical crosslinking or crosslinking with energy-rich radiation, as long as this is desired. When using bonding agents from the first group and the second group, it is generally not necessary to force the addition of monomers for acceleration. In the case of a bonding agent from the third group, it is usually advisable to add a monomer, although this is not always necessary anyway.

  Regardless of the problem of cross-linking rate, the monomer may be used for control of cross-linking density. Depending on the type and amount of low molecular weight compound added, a wider or narrower network is obtained. On the other hand, known ethylenically unsaturated monomers may be used as monomers. The monomer should be primarily compatible with the binder and have at least one photochemically or thermochemically reactive group. This monomer must not be readily volatile. Preferably, the boiling point of suitable monomers is at least 150 ° C. Amides, amines, aminoalcohols or hydroxyethers and hydroxyesters of acrylic acid or methacrylic acid with monofunctional or polyfunctional alcohols, styrene or substituted styrene, fumaric acid or maleic acid esters or allyl compounds are particularly suitable. Yes. Examples are n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonane. Diol diacrylate, trimethylol propane trimethacrylate, trimethylol propane triacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, dioctyl fumarate, N-dodecyl maleimide and triallyl isocyanurate.

  In particular, monomers suitable for thermochemical reinforcement are 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, For example, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, diamine, such as 1,6-hexanediamine, 1,8-octanediamine, amino alcohol, such as Ethanolamine, diethanolamine, butylethanolamine, dicarboxylic acids such as 1,6-hexanedicarboxylic acid, terephthalic acid, maleic acid or fumaric acid.

  Monomers having an ethylenically unsaturated group, for example a functional group, may be used. Examples include ω-hydroxy-alkyl (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 various monomers may be used provided that the properties of the elastomer layer are not adversely affected by the mixture. As a rule, the amount of monomer added is 0 to 40% by weight, preferably 1 to 20% by weight, based on the amount of all components of the elastomer layer or the laser-engravable layer.

  In one embodiment, one or more monomers can be used with one or more catalysts. That is, a silicone mold can accelerate step 2) of preparing the mold by the addition of one or more acids or by an organotin compound. Suitable organotin compounds may be: di-n-butyltin dilaurate, di-n-butyltin diactanoate, di-n-butyltin di-2-ethylhexanoate, di-n- Octyltin di-2-ethylhexanoate and di-n-butylbis (1-oxoneodecyloxy) stannane.

  In addition, the elastic layer or laser-engravable layer can contain additives and auxiliaries, such as IR absorbers, dyes, dispersion aids, antistatic agents, plasticizers or abrasive particles. The amount of additives and auxiliaries of this kind should generally not exceed 30% by weight, based on the amount of all components of the elastic layer or the laser engraveable layer.

  The elastic layer or the laser engraveable layer may be composed of a plurality of individual layers. The individual layers may have the same material composition, approximately the same material composition, or different material compositions. The thickness of the laser-engraveable layer or all the individual layers together is typically 0.1 to 10 mm, preferably 0.5 to 3 mm. The above-mentioned thickness can be appropriately selected as a parameter for the laser engraving process and a parameter for the molding process depending on the technical process used and the mechanical process.

  Furthermore, the elastic layer or the laser engraveable layer can optionally have a surface layer having a thickness of 300 μm or less. The composition of such a surface layer can be selected in relation to optimal engraving and mechanical stability, while the composition of the underlying layer is related to optimal hardness or modulus. Selected.

  In an embodiment of the present invention, the surface layer itself can be laser engraved or removed together with the layers underlying the surface layer during laser engraving. The surface layer includes at least one bonding agent. Furthermore, the surface layer can contain an absorber for the laser beam or can contain monomers or auxiliaries.

A preferred mold is a silicone mold. Hereinafter, the silicone mold means at least one bonding agent having at least one, preferably at least three O—Si (R ¹ R ² ) —O— groups per molecule for the production of the silicone mold. Is interpreted as the type used. R ¹ and R ² are then defined differently or advantageously as defined above.

  In another embodiment of the invention, a nickel mold is used as the mold. A suitable nickel mold consists mainly of a uniform nickel layer. The nickel layer can have a thickness in the range of 100 mm to 10 mm.

  As the laser for laser engraving in the step (a), for example, an optical laser can be selected. Furthermore, CO2 laser, Nd-YAG laser, fiber laser and UV laser are suitable.

  In the case of laser engraving in step (a), the pores are engraved or baked into a laser-engraveable layer in a screen fashion, the screen being arranged in individual areas, for example in a square It can have a plurality of screen dots or a plurality of screen dots arranged in a rectangle or a plurality of screen dots arranged in eg a honeycomb pattern. The definition of the various ranges can be achieved, for example, by having different screen angles in the various ranges.

  In this case, the pores are not only pores generated by the layer capable of laser engraving within the scope of the present invention, but also depressions in the form of depressions.

  The laser engraving in step (a) is power-modulated laser engraving. It is understood therein that the laser power does not remain constant during engraving but modulates in proportion to the desired pore depth. In so doing, the screen angle, the pore depth or the tapered shape varies within the surface structure, ie within the sculpted surface structure. Among them, individual sculpted pores or individually sculpted groups of various pores have different screen angles, pore depths or tapered shapes of said pores, respectively, and practically all It is understood that the pores may vary, or the pores may vary from group to group, or only a few of the individual pores may vary.

  In an embodiment of the invention, a beam source with a laser 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, ie a maximum starting power, is selected.

  In an embodiment of the invention, the output of the beam source is modulated within a range of 0-100% of the laser output. This type of modulation can be performed in the MHz range.

In an embodiment of the present invention, the range of 1 cm ² per 100 to 10000 pieces of pores is advantageously engraved within the 1 cm ² per 4000-5000 amino pores.

  In an embodiment of the invention, the engraved pores have an average depth in the range of 1 to 3000 μm, preferably 50 to 500 μm.

  In embodiments of the invention, some of the pores in the surface structure can be formed as conical pores, and another pore is formed in a cylindrical, conical, wedge or drum shape. be able to.

  In embodiments of the invention, some pores in the surface structure can be formed as cylindrical pores, and another pore can be formed in a drum shape or a cone shape.

  In an embodiment of the present invention, some pores in the surface structure can be formed in the shape of a hemispherical bowl, and another pore is cylindrical, conical, right cone, wedge shaped or drum shaped. Can be formed.

  In an embodiment of the invention, the pores are distinguished by a geometric shape. Among them, it should be understood that the cross-sectional geometry is advantageous. For example, the pores may be round, oval or angular, eg crossing in the shape of a square, triangle, rhombus, regular pentagon or regular hexagon (honeycomb) or regular octagon. Can have a surface. Semicircular, star and assembled geometric elements are also possible.

  In an embodiment of the invention, the groups of pores in the surface structure are distinguished by screen angle. Thus, for example, two ranges that are the same or different are possible.

  By means of power-modulated laser engraving, the surface structure obtains an image pattern comprising at least one element (D).

  By performing step (a) as a whole, the mold according to the invention is obtained. Depending on whether the position in the mold, which is configured as a pore, should be similar to the pore in the composite or in particular a ridge configured in the form of a fine hair, Is female or male.

  Optionally, after the intrinsic laser engraving step in step (a), the laser engraveable layer is washed with a detergent, for example using a circular washer or a continuous washer, for the removal of engraving residues.

  In the manner described, the mold can be manufactured as a female mold or as a male mold.

In an embodiment of the invention, step (b) is carried out in order to carry out the method according to the invention: molding of one or more female dies from the male mold produced in step (a). For molding, for example, it can be carried out as follows:
1) Applying a liquid bonding agent, optionally containing additives and / or auxiliaries, onto the male surface with an image or pattern;
2) Curing the liquid bonding agent by, for example, heat curing, radiation curing or aging,
3) The female mold thus obtained is separated and optionally brought on a carrier, for example a metal plate or a metal cylinder.

  In another embodiment of the invention, step (b) is discontinued.

  In order to carry out the process according to the invention, step (c) is carried out, i.e. the female mold is sprayed with a plastic formulation, the female mold being in the range of 50-200C, preferably 75-150C. Particularly preferably, it has a temperature of at least 90 ° C. In doing so, the temperature measured at the start of spraying on the surface of the mold, which is in contact with the plastic compound, is measured.

  The spraying can be performed once or several times.

  As plastic formulations, it is possible to select, for example, solutions of polymers in organic solvents, in particular aqueous formulations, in particular aqueous dispersions, such as aqueous suspensions or emulsions.

  Aqueous is understood in relation to plastic formulations to include that the plastic formulation contains water but contains less than 5% by weight, preferably less than 1% by weight of organic solvent, based on the dispersion. Is done. It is particularly advantageous that no volatile organic solvent can be detected. A volatile organic solvent is understood within the scope of the present invention to be an organic solvent having a boiling point of up to 200 ° C. at normal pressure.

Suitable plastics in the plastic formulation are, for example, the following: polystyrene, polyacrylates and in particular polyurethanes. Suitable polyacrylates are, for example, (meth) acrylic acid and one or more (meth) acrylate -C ₁ -C ₁₀ alkyl esters, especially methyl acrylate, methyl methacrylate, ethyl acrylate, n- butyl (meth) acrylate and It is a copolymer with 2-ethylhexyl (meth) acrylate.

Suitable polyurethane is
(I) an isocyanate, preferably a diisocyanate,
(Ii) compounds reactive with isocyanates, usually having a molecular weight (Mw) of 500-10000 g / mol, preferably 500-5000 g / mol, particularly preferably 800-3000 g / mol, and (iii) 50- A chain extender having a molecular weight of 499 g / mol;
It is obtained by reacting optionally in the presence of a catalyst and / or conventional additives.

In the following, by way of example, the starting components and the advantageous process for producing polyurethane (PU) are described. Ingredients (i), (ii), (iii) and optionally catalysts and / or additives usually used in the production of polyurethane (PU) will now be described by way of example:
Isocyanates (i) generally known aliphatic isocyanates, cycloaliphatic isocyanates, araliphatic isocyanates and / or aromatic isocyanates such as trioctamethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate And / or octamethylene diisocyanate, 2-methyl-pentamethylene-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-methyl-cyclohexane (isophorone diisocyanate, IPDI), 1, -Bis (isocyanatomethyl) cyclohexane and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 1,4-cyclohexane-diisocyanate, 1-methyl-2,4-cyclohexane-diisocyanate and / or 1- Methyl-2,6-cyclohexane-diisocyanate and / or 4,4′-dicyclohexylmethane-diisocyanate, 2,4′-dicyclohexylmethane-diisocyanate and 2,2′-dicyclohexylmethane-diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and / or 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4-toluylene diene Isocyanate and / or 2,6-toluylene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl - diphenyl - diisocyanate, 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate may be used. Preferably, 4,4′-MDI is used. Moreover, aliphatic diisocyanates, in particular hexamethylene diisocyanate (HDI), are preferred.

As a compound (ii) reactive to isocyanate, a molecular weight usually in the range of 500 to 8000 g / mol, preferably 600 to 6000 g / mol, in particular 800 to 3000 g / mol, included in the concept of “polyol”. Generally known isocyanate-reactive compounds having an average functionality for isocyanates of ( _Mw ) and preferably 1.8 to 2.3, preferably 1.9 to 2.2, in particular 2, For example, polyesterol, polyetherol and / or polycarbonate diol may be used. Preferably, polyether polyols such as polyether polyols based on generally known initiator materials and conventional alkylene oxides such as ethylene oxide, 1,2-propylene oxide and / or 1,2-butylene oxide, preferably poly Polyetherols based on oxytetramethylene (polyTHF), 1,2-propylene oxide and ethylene oxide are used. Polyetherol has the advantage that the polyetherol has higher hydrolytic stability than polyesterol, and polyurethane (PU1) is preferred as component (ii), in particular for producing soft polyurethanes.

  As polycarbonate diols, mention may in particular be made of aliphatic polycarbonate diols, such as 1,4-butanediol-polycarbonate.

  As polyester diol, in one aspect, at least one primary diol, in particular at least one primary aliphatic diol, such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or particularly advantageous 1,4-dihydroxymethylcyclohexane (as a mixture of isomers) or at least two mixtures of said diols can be prepared by polycondensation, on the other hand, at least one dicarboxylic acid, preferably at least two dicarboxylic acids Or the polyester diol which can be manufactured by polycondensing these anhydrides can be mentioned. Preferred dicarboxylic acids are aliphatic dicarboxylic acids such as adipic acid, glutaric acid, succinic acid and aromatic dicarboxylic acids such as phthalic acid and especially isophthalic acid.

  The polyetherol is preferably an alkylene oxide, in particular ethylene oxide, propylene oxide and mixtures thereof, and diols such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,4-butanediol, It is prepared by adding 1,3-propanediol, or triol, such as glycerin, in the presence of a highly active catalyst. Such highly active catalysts are, for example, cesium hydroxide and double metal cyanide catalysts, also called DMC catalysts. A frequently used DMC catalyst is zinc hexacyanocobaltate. The DMC catalyst can be left in the polyetherol after the reaction, in particular the DMC catalyst is removed, for example, by precipitation or filtration.

  Instead of a polyol, a mixture of various polyols may be used.

のアルカリ金属塩またはアンモニウム塩が使用されてもよい。 In order to improve dispersibility, the proportion of one or more diols or diamines having a carboxylic acid group or a sulfonic acid group, in particular 1,1-dimethylolbutane, as the compound (ii) reactive to isocyanate Acid, 1,1-dimethylolpropionic acid or

Alkali metal salts or ammonium salts may be used.

  As chain extenders (iii), known aliphatic compounds, araliphatic compounds, aromatic compounds and / or alicyclic compounds having a molecular weight of 50 to 499 g / mol and at least two functional groups, advantageously Compounds having exactly two functional groups per molecule, for example diamines and / or alkanediols having 2 to 10 C atoms in the alkylene group, in particular 1,3-propanediol, butanediol- 1,4, hexanediol-1,6 and / or dialkylene glycol, trialkylene glycol, tetraalkylene glycol, pentaalkylene glycol, hexaalkylene glycol, heptaalkylene glycol having 3 to 8 carbon atoms per molecule, Octaalkylene glycol, nonaalkylene glycol Le and / or deca alkylene glycol, preferably oligo- propylene glycol and / or polypropylene glycol corresponding is used, a mixture of chain extenders (iii) may be used at that time.

  Particularly preferably, components (i) to (iii) are difunctional compounds, i.e. diisocyanates (i), difunctional polyols, preferably polyetherol (ii) and difunctional chain extenders, preferably diols. It is.

  Particularly suitable catalysts for promoting the reaction of the NCO groups of diisocyanate (i) with the hydroxyl groups of components (ii) and (iii) are tertiary amines known per se, such as triethylamine, dimethyl-cyclohexylamine. , N-methylmorpholine, N, N′-dimethylpiperazine, 2- (dimethylaminoethoxy) -ethanol, diazabicyclo- (2,2,2) -octane (“DABCO”) and similar tertiary amines, and especially Organometallic compounds such as titanic acid esters, iron compounds such as iron (III) acetylacetonate, tin compounds such as tin diacetate, tin dioctanoate, tin dilaurate or tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin Acetate, dibutyltin dilaurate or the like. The catalyst is usually used in an amount of 0.0001 to 0.1 parts by mass per 100 parts by mass of component (ii).

In addition to the catalyst, one or more auxiliaries and / or additives may be used for components (i) to (iii). For example, foaming agents, antiblocking agents, surfactants, fillers, for example fillers based on nanoparticles, in particular fillers based on CaCO ₃ , nucleating agents, slip aids, dyes and pigments, Antioxidants such as substances that resist hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers, metal deactivators are mentioned. In preferred embodiments, the additives are hydrolysis protectants such as high molecular weight carbodiimides and low molecular weight carbodiimides. Preferably, the flexible polyurethane contains triazole and / or a triazole derivative and an antioxidant in an amount of 0.1 to 5% by mass relative to the total mass of the flexible polyurethane. Suitable antioxidants are generally substances that inhibit or prevent undesired oxidation processes in the plastic to be protected. In general, antioxidants are commercially available. Examples of antioxidants are sterically hindered phenols, aromatic amines, thiosynergists, organophosphorus compounds of trivalent phosphorus, and hindered amine light stabilizers. Examples of sterically hindered phenols are found in Plastics Additive Handbook, 5th edition, H.C. Zweifel, Hanser Publishers, Muenchen, 2001 ([1]), pages 98-107 and pages 116-121. Examples of aromatic amines are [1]. Can be found in pages 107-108. Examples of thiosynergists are described in [1], pages 104-105 and pages 112-113. Examples of phosphites can be found in [1], pages 109-112. Examples of hindered amine light stabilizers are described in [1], pages 123-136. For use in the antioxidant mixture, phenolic antioxidants are preferably suitable. In a preferred embodiment, the antioxidant, in particular the phenolic antioxidant, has a molar mass of more than 350 g / mol, particularly preferably more than 700 g / mol and up to 10000 g / mol, preferably up to 3000 g / mol. Having a molar mass (M _w ). Furthermore, the antioxidant preferably has a melting point of up to 180 ° C. Furthermore, an antioxidant which is amorphous or liquid is preferably used. Similarly, a mixture of two or more antioxidants may be used as the additive or additives.

  In addition to the components (i), (ii) and (iii) described, and optionally catalysts and additives, chain length regulators (chain terminators) having a molecular weight of 31 to 3000 g / mol are usually used. May be. Such chain length regulators are simply one compound having a functional group reactive with isocyanate, such as a monofunctional alcohol, a monofunctional amine and / or a monofunctional polyol. With such a chain length regulator, the flow behavior, in particular in the case of flexible polyurethanes, can be intentionally adjusted. The chain length regulator can generally be used in an amount of 0 to 5 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of component (ii), and as specified by component (iii). included.

  In addition to the described components (i), (ii) and (iii), and optionally catalysts and additives, one or more crosslinkers having two or more groups reactive towards isocyanates, for example Hydrazine hydrate may be used around the end of the constitutive reaction.

  In order to adjust the hardness of the polyurethane (PU), components (ii) and (iii) can be selected in a relatively wide range of molar ratios. For example, a molar ratio of component (ii) of 10: 1 to 1:10, in particular 1: 1 to 1: 4, to all chain extenders to be used is suitable, in which the content of (iii) is As it increases, the hardness of the flexible polyurethane increases. The reaction for producing polyurethane (PU) has an index of 0.8 to 1.4: 1, preferably an index of 0.9 to 1.2: 1, particularly preferably 1.05 to 1.2: 1. Can be done at the index of Said index is the total isocyanate group of component (i) used in the reaction, the component (ii) is reactive to isocyanate, ie active hydrogen and optionally (iii) and optionally linked. It is defined by the ratio of monofunctional components reactive with isocyanate, such as monoalcohols, as terminators.

  In addition to the plastic, the plastic dispersion used in step (c) can contain further components, for example one or more surfactants and / or one or more curing agents. A compound capable of cross-linking a plurality of plastic molecules, preferably a plurality of polyurethane molecules, is suitable as a curing agent during thermal activation. Curing agents based on trimer diisocyanates, in particular based on aliphatic diisocyanates, for example hexamethylene diisocyanate, are particularly suitable. Examples of particularly suitable curing agents are the compounds described in WO 2009/106503 as compound (V).

  The plastic dispersion used in step (c), in addition to the plastic and optionally the curing agent, has no further compounds such as reactive groups or one or more reactive groups per molecule. One or more silicone compounds may be included. Examples of reactive groups include the following: carboxylic acid derivatives, such as carboxylic acid methyl esters or carboxylic anhydrides, in particular succinic anhydride groups, and particularly preferably carboxylic acid groups.

Furthermore, examples of reactive groups include primary and secondary amino groups such as NH (isoC ₃ H ₇ ) group, NH (n-C ₃ H ₇ ) group, NH (cycloC ₆ H _11). ) And NH (n-C ₄ H ₉ ), in particular NH (C ₂ H ₅ ) and NH (CH ₃ ), particularly preferably NH ₂ .

Furthermore, an aminoalkylamino group, for example, —NH—CH ₂ —CH ₂ —NH ₂ group, —NH—CH ₂ —CH ₂ —CH ₂ —NH ₂ group,
_{-NH-CH 2 -CH 2 -NH (} C 2 H 5) _{group, -NH-CH 2 -CH 2 -CH} 2 -NH (C 2 H 5) group,
An —NH—CH ₂ —CH ₂ —NH (CH ₃ ) group and an NH—CH ₂ —CH ₂ —CH ₂ —NH (CH ₃ ) group are preferred.

  Further suitable additives are pigments, matting agents, light stabilizers, antistatic agents, antifouling agents, Antiknarz, thickeners, in particular thickeners based on polyurethane, and micro hollow spheres Is selected from.

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

  Spraying female molds, especially aqueous plastic compounds, can be carried out in a manner known per se, in particular using a spray gun, or can be incorporated into the device in a fixed or mobile manner. This can be done by spraying with a spray nozzle.

  Various devices can be handled, especially for spraying female plastics with aqueous plastic formulations. In particular, airless spray systems and air spray systems are suitable.

  Preference is given to spraying a particularly aqueous plastic formulation having a temperature in the range 15-30 ° C., particularly preferably 20-25 ° C.

  In an embodiment of the invention, the particularly aqueous plastic formulation used for spraying has a dynamic viscosity at room temperature of up to 500 mPa · s, in particular up to 200 mPa · s.

  In an embodiment of the invention, the particularly aqueous plastic formulation used for spraying has a pH value in the range of 4-10, in particular in the range of 6-8.

  In step (d), the plastic compound sprayed on the female mold in step (b) can be solidified into a coating. Solidification can be achieved, for example, by removing the organic solvent in which the plastic is blended, or in particular water in which the plastic is dispersed, suspended or emulsified, for example by evaporation.

  Step (d) can be carried out at various temperatures. A suitable temperature is, for example, 30 to 90 ° C.

  Step (d) can be carried out at any pressure, and normal pressure is preferred.

  At the end of step (d), a film-like plastic is obtained, which is called a “film” for short in the scope of the present invention.

  The coating can have a thickness in the range of 70 to 300 μm, for example.

  In the step (e), the coating film is bonded to the substrate (A). The substrate (A) is described in detail below. This joining can be achieved, for example, by laminating, pasting or gluing or welding and can be reinforced, for example, by pressing or calendering.

  Of course, the coating obtained in step (d) is joined to the substrate (A) so that the side with the pattern or image is the visible side.

  For example, in step (e) by applying an organic adhesive, in particular in the form of a layer which is applied over the entire surface or in particular in the form of a layer with a small hole pattern, ie not necessarily covering the entire surface Be joined.

  In an embodiment of the invention, in step (e) the organic adhesive is applied in the form of dots, strips or grids, for example in the form of diamonds, rectangles, squares or honeycomb structures.

  The organic adhesive can be selected from adhesives based on polyvinyl acetate, polyacrylates or in particular polyurethanes, in particular polyurethanes having a glass temperature below 0 ° C.

  Organic adhesives can be cured, for example, thermally, by actinic radiation, or by aging.

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

  In an embodiment of the invention, the organic adhesive has a maximum thickness of 100 μm, preferably 50 μm, particularly preferably 30 μm, particularly preferably 15 μm, measured after application and curing.

  In step (f) of the method according to the invention, the molds are separated, for example by mechanical drawing.

  In doing so, the working steps (e) and (f) can be carried out in any order. That is, step (e) can be performed first, and then step (f) can be performed. In another embodiment of the present invention, step (f) is performed first, followed by step (e).

  In an embodiment of the invention, the coating from step (d) is porous.

  In a preferred embodiment of the invention, the coating from step (d) has pores in the form of capillaries that span the entire thickness (cross-section) of the coating.

In an embodiment of the invention, the coating from step (d) has an average of at least 100, preferably at least 250 pores per 100 cm ^{2 in} the form of capillaries.

  In an embodiment of the invention, the pores have an average diameter in the range of 0.005 to 0.05 mm, preferably 0.009 to 0.03 mm, in the form of a capillary.

  In an embodiment of the invention, the pores are uniformly distributed in the form of capillaries over the coating or coatings from step (d). However, in a preferred embodiment of the invention, the pores are distributed unevenly in the form of capillaries over the coating from step (d).

  In an embodiment of the invention, the pores are mainly curved in the form of capillaries. In another embodiment of the invention, the pores have a primarily straight extension in the form of a capillary.

Capillary shaped pores can impart air and water vapor permeability to the coating or coatings from step (d) without the need for perforations. In an embodiment of the present invention, the water vapor permeability of the coating or coatings from step (d) can exceed 1.5 mg / cm ² * h as measured by DIN 53333. That is, it is possible to transfer moisture, such as sweat, through the coating from step (d).

  In an embodiment of the invention, the coating from step (d) has pores that do not reach the full thickness of the coating in addition to the capillaries.

  The method according to the invention makes it possible to produce multilayer composites that can be images or patterns that have a velvety appearance and a very pleasant hand and have excellent durability. This type of pattern or image can be complex and can be sufficient for a great number of design requirements. This type of image or pattern can have, for example, a Philip flop effect, i.e. the image or pattern has different appearance images depending on the viewing angle. If the image or pattern is implemented in black, the image or pattern has a pleasant deep black tone. When the image or pattern is implemented with a porous coating, the image or pattern is water vapor permeable and insensitive to sweat spots. This type of image can be used as copy protection or as an original characteristic mark, depending on the complexity of the image and the skilled design.

A further subject of the present invention is
(A) substrate,
A multilayer composite comprising (B) a plastic layer with fine hair, optionally having at least one bonding layer and (C) one surface structure on its visible side,
In this case, the plastic layer (C) has at least one image or at least one element (D) on the visible side of the plastic layer (C), which is different from geometric elements, numbers and letters, or Has a pattern,
In this case, the multi-layer composite described above has different screen angles, pore depths or tapered shapes in the surface structure.

  As the substrate (A), many materials such as metal foil, paper, cardboard, cardboard, wood and thermoplastic molded products are suitable, and leather, woven fabric, non-woven fabric (fleece material), artificial leather, paper are preferable. And wood. Examples of fibers are woven and knitted fabrics.

  The bonding of the substrate (A) and the plastic layer (C) can be in various ways, for example in the form of a continuous coating, or in the form of dots, in the form of strips, as a grid, for example a square grid or It may be configured as a honeycomb-like grid or a diamond-shaped grid.

  The substrate (A) can have any thickness that is compatible with the material of the substrate.

  The plastic layer (C) has fine hairs.

  In an embodiment of the invention, the plastic (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 fine hair being included in the calculation It has not been.

  The meaning of the concept of image and pattern and the explanation of the element (D) have been described above.

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

  In an embodiment of the invention, different parts of the image or pattern are created by different three-dimensional structuring of the plastic layer (C).

  In a preferred embodiment of the invention, images that may be particularly complicated do not have regular repeating units. This should be construed that the motifs are not constantly repeated, unlike patterning as in wallpaper.

  In another embodiment of the invention, the pattern has certain repeating units, particularly comprising element (D).

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

  In an embodiment of the present invention, the image or pattern can be a combination of two different patterns that migrate to each other. For example, the image or pattern may be a leather silver pattern that is associated with a pattern of a woven or knitted product, for example with or without a simulated seam. Furthermore, these joints correspond in particular to element (D).

  In an embodiment of the invention, the pattern or in particular the image has a height or depth in the range of 1 to 3000 μm that conveys different visual impressions by different screens, different shapes or different heights or depths. Generated by a ridge or recess having.

  In an embodiment of the invention, the ridges or recesses are distinguished from group to group by the ridges or recesses having different solid geometric shapes, different heights or depths or different screenings. The

  In an embodiment of the invention, the plastic layer (C) can comprise at least two different polyurethanes, also referred to as (C1) and (C2), within the scope of the invention, in which case the polyurethane (C1 ) Has a Shore A hardness in the range of less than 60, and is also referred to as “soft polyurethane”, and the polyurethane (C2) has a Shore A hardness in the range of greater than 60 to 120; Also called “rigid polyurethane”. In so doing, the Shore A hardness is measured after 3 seconds, for example according to DIN 53505.

  In an embodiment of the invention, the polyurethane (C1) has an average particle size, measured by laser light scattering, in the range of 100 to 300 nm, preferably 120 to 150 nm.

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

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

  In an embodiment of the invention, the plastic layer (C) is air impermeable. In another embodiment of the invention, the plastic layer (C) is porous and is characterized, for example, by having a capillary through which the plastic layer passes through the entire thickness of the plastic layer.

  The multilayer composite according to the invention can be produced, for example, by the method according to the invention described at the beginning. The multilayer composite according to the invention has a velvety appearance and a very pleasant feel. On the composite according to the invention, there may be an image or pattern with excellent durability. This type of pattern or image can be complex and can be sufficient for a great number of design requirements. This type of image or pattern can have, for example, a Philip flop effect, i.e. the image or pattern has different appearance images depending on the viewing angle. If the image or pattern is implemented in black, the image or pattern has a pleasant deep black tone. When the image or pattern is implemented with a porous coating, the image or pattern is water vapor permeable and insensitive to sweat spots. This type of image can be used as copy protection or as an original characteristic mark, depending on the complexity of the image and the skilled design.

  A further subject of the present invention has at least one element (D), which is different from geometric elements, numbers and letters, and has various visual characteristics in various screenings or at various heights or depths. A female mold having at least one female mold of an image or pattern on one side, created by ridges or recesses that convey the impression.

  In an embodiment of the present invention, the ridges or recesses are individually defined by the ridges or recesses having different geometric shapes, different heights or depths at different screening or screen angles. Differentiated, or specifically grouped.

  The mold according to the invention is very well suited for producing the multilayer composite according to the invention. A further subject of the present invention is therefore the use of the female mold according to the invention for producing a multilayer composite according to the invention.

  The method for producing the mold according to the invention has been described above.

Schematic diagram illustrating the concept from Table 1 in detail.

  The invention is illustrated by working examples.

Working example:
I. Mold Production According to the Invention Liquid silicone was cast on a flat substrate. A solution of di-n-butylbis (1-oxoneodecyloxy) stannane as a 25% by weight solution in tetraethoxysilane is added as an acidic curing agent and used as a mold substrate, with an average thickness of 2 mm A silicone rubber layer was obtained and cured. This mold was bonded onto a 1.5 mm thick aluminum carrier.

Circular pores having the characteristic values listed in Table 1 were engraved using a CO ₂ laser. At that time, the output of the beam source was modulated by an acousto-optic modulator.

  This characteristic value is expressed in various areas of the mold. Various shadows were produced by the arrangement of the areas, thereby producing an image of a soccer ball player kicking.

  A mold 1 according to the invention was obtained.

  The distance can be interpreted as a distance between two pores. As the distance between the pores, the distance to each subsequently placed pore, in fact, the center of the pore from the center of the pore is measured.

  A mold according to the invention was obtained.

II. Production of plastic dispersion Polyurethane was selected as the plastic.

の７０質量％の溶液（プロピレンカーボネート中）３．５質量％、
欧州特許出願公開第０７３８７４７号明細書の実施例２によるシリコーン化合物の６５質量％の水性分散液６質量％、
カーボンブラック２質量％、
ポリウレタンをベースとする増粘剤０．５質量％、
例えば、Ａｋｚｏ Ｎｏｂｅｌ社のＥｘｐａｎｃｅｌ（登録商標）として商業的に入手可能な、イソブタンで充填された、ポリ塩化ビニリデンからなるマイクロ中空球１質量％、直径２０μｍ。 II. 1 Aqueous polyurethane dispersion Disp. Production of 1 The following were mixed with stirring in a stirring vessel:
Hexamethylene diisocyanate and isophorone diisocyanate in a 13:10 mass ratio of hexamethylene diisocyanate to isophorone diisocyanate as diisocyanate, and 1: 1 of isophthalic acid to adipic acid to 1,4-dihydroxymethylcyclohexane (isomer mixture) as diol : 2 molar ratio of isophthalic acid, adipic acid and 1,4-dihydroxymethylcyclohexane (mixture of isomers), 5% by weight of 1,4-butanediol (b1.2), and one methylated polyethylene glycol 3 was prepared by mass%, as well as _{H 2 N-CH 2 CH 2} -NH-CH 2 CH 2 -COOH3 mass% polycondensation, prepared from a polyester diol having a molecular weight M _w of the 800 g / mol, soft poly Aqueous dispersion of letan (C1.1) 7 mass% (particle size: 125 nm, solid content: 40%), mass% based on polyester diol (b1.1), softening point of soft polyurethane (C1.1): 62 Softening at 55 ° C, Shore hardness A54,
Isophorone diisocyanate, 1,4-butanediol, 1,1-dimethylol propionic acid, obtained by reacting a polypropylene glycol having a molecular weight M _w of hydrazine hydrate and 4200 g / mol, rigid polyurethane (C2.1) An aqueous dispersion of 65% by mass (particle size: 150 nm), softening point of 195 ° C., Shore hardness A86,
Compound (I.1)

70% by weight solution (in propylene carbonate) 3.5% by weight,
6% by weight of a 65% by weight aqueous dispersion of a silicone compound according to Example 2 of EP-A-0738747,
2% carbon black,
0.5% by weight of a thickener based on polyurethane,
For example, 1% by weight of micro hollow spheres made of polyvinylidene chloride, filled with isobutane, commercially available as Expando® from Akzo Nobel, diameter 20 μm.

  An aqueous dispersion Disp, 1 was obtained having a solid content of 35% and a dynamic viscosity of 25 seconds at 23 ° C., measured according to DIN EN ISO 2431, May 1996 standard.

II. 2 Aqueous formulation Disp. Preparation of 2 The following were mixed with stirring in a stirring vessel:
Hexamethylene diisocyanate and isophorone diisocyanate in a 13:10 mass ratio of hexamethylene diisocyanate to isophorone diisocyanate as diisocyanate, and 1: 1 of isophthalic acid to adipic acid to 1,4-dihydroxymethylcyclohexane (isomer mixture) as diol : 2 molar ratio of isophthalic acid, adipic acid and 1,4-dihydroxymethylcyclohexane (isomer mixture), 1,4-butanediol 5% by mass (b1.2), 1 methylated polyethylene glycol 3% % and was prepared by _{H 2 N-CH 2 CH 2} -NH-CH 2 CH 2 -COOH3 mass% polycondensation, prepared from a polyester diol having a molecular weight M _w of the 800 g / mol, flexible polyurethane Aqueous dispersions 7 wt% of the C1.1) (particle size: 125 nm, solids content: 40%), by weight% for the polyester diol, respectively, a softening point of 62 ° C., the softening starting at 55 ° C., Shore hardness A54,
Isophorone diisocyanate, 1,4-butanediol (C1.2), 1,1-dimethylol propionic acid, obtained by reacting a polypropylene glycol having a molecular weight M _w of hydrazine hydrate and 4200 g / mol, rigid polyurethane An aqueous dispersion of 65% by mass (particle size: 150 nm), polyurethane (C2.2) had a softening point of 195 ° C., Shore hardness A90,
70% by mass solution of compound (1.1) (in propylene carbonate) 3.5% by mass, NCO content 12%,
2% by mass of carbon black.

  An aqueous dispersion Disp, 2 was obtained having a solids content of 35% and a dynamic viscosity of 25 seconds at 23 ° C., measured according to DIN EN ISO 2431, May 1996 standard.

III. Production of a plastic coating A mold 1 according to the invention was placed on a heatable substrate and heated to 91 ° C. Subsequently, Disp. 1 was actually sprayed at 88 g / m ² (wet). This application was performed at a pressure of 65 bar using a spray nozzle having a diameter of 0.46 mm, without air entrainment. Solidified at 91 ° C. until the surface was no longer sticky.

  The spray nozzle was movably arranged in the same base movement direction at a height of 20 cm from the continuous base, and moved laterally with respect to the base movement direction. The substrate passed through the spray nozzle after about 14 seconds and had a temperature of 59 ° C. After being bombarded with dry hot air at 85 ° C. for about 2 minutes, the crosslinked polyurethane coating (C.1) thus produced was almost anhydrous.

In the same device, immediately after the thus coated mold according to the invention, Disp. 2 50 g / m ² was applied by a wet method and subsequently dried.

  A mold coated with a plastic coating (C.1) and a bonding layer (B.1) was obtained.

A soaked and agglomerated polyester fleece (A.1), also referred to as substrate (A.1) for short, having a mass per unit area of 180 g / m ² , Disp. 2 was sprayed at 30 g / m ² (wet). The substrate (A.1) sprayed in this way was dried for several minutes.

IV. Production of the multilayer composite according to the invention The sprayed side of the sprayed substrate (A.1) is subsequently placed on the mold together with the plastic coating (C.1), the still hot bonding layer (B.1). ) And compressed in a press at 4 bar and 110 ° C. for 15 seconds. Subsequently, the multilayer composite material MSV. 1 was removed from the press and the mold was removed.

  The multilayer composite material MSV. Reference numeral 1 indicates a pleasant tactile sensation (hand touch), and the same appearance and breathability as the original photograph of a soccer ball player. Furthermore, the multilayer composite material MSV. 1 can easily purify contaminants such as dust.

  MSV. 1 showed a soccer ball player image with high accuracy.

  II. ~ IV. The work process by can be repeated several times with the same mold without degrading the image quality.

  Lt depth of pore, ZA cylindrical protrusion, P flat area, α solid angle

Claims (25)

A method for producing a multilayer composite comprising the following work steps:
(A) Prepare a female or male mold by power-modulated laser engraving with a surface structure in the form of an image or pattern having at least one element (D), which is different from geometric elements, numbers and letters The process, the screen angle in the surface structure, the depth of the pores or the tapered shape varies,
(B) optionally forming a female mold from a male mold;
(C) spraying the plastic compound on the female mold, wherein the female mold has a temperature in the range of 50-200 ° C;
(D) solidifying the plastic compound into a film;
(E) a step of bonding the coating to the substrate (A);
(F) sequentially performing the steps of removing the mold;
In this case, the steps (e) and (f) can be carried out in any order, and a method for producing a multilayer composite.   2. The method according to claim 1, wherein an optical laser is selected as the laser in the operation step (a).   3. Method according to claim 1 or 2, characterized in that a female mold from the silicone mold is selected.   4. The method according to claim 1, wherein a male mold consisting of a plastic mold from polyurethane, polyamide or polyvinyl alcohol is selected.   5. The method according to claim 1, wherein a laser power in the range of 5 to 5000 W is selected in the working step (a).   An aqueous polyurethane dispersion comprising at least two different polyurethanes is selected as the plastic formulation in process step (c), in which polyurethane (C1) has a Shore hardness A in the range of less than 60 and a further polyurethane The method according to any one of claims 1 to 5, characterized in that (C2) has a Shore hardness A in the range of greater than 60 to 100.   7. A method according to any one of the preceding claims, characterized in that the image or pattern further comprises at least one element selected from geometric elements, numbers and letters.   8. A method according to any one of claims 1 to 7, characterized in that the image has no regular repeating units.   The pattern or image is raised or recessed with a height or depth in the range of 1-3000 μm that conveys different visual impressions by different screenings, by different shapes, or by different heights or depths The method according to claim 1, wherein the method is created by:   The ridges or recesses are distinguished from group to group by the ridges or recesses having different geometric shapes, different heights or depths or different screenings. Item 10. The method according to any one of Items 1 to 9.   11. A method according to any one of claims 1 to 10, characterized in that the coating from step (d) is porous. (A) substrate,
A multilayer composite comprising (B) a plastic layer with fine hair, optionally having at least one bonding layer and (C) one surface structure on its visible side,
In this case, the plastic layer (C) has at least one image or at least one element (D) on the visible side of the plastic layer (C), which is different from geometric elements, numbers and letters, or Has a pattern,
And the said multilayer composite in which the screen angle, the depth of a pore, or a tapering shape is various in the surface structure in that case.   13. Composite according to claim 12, characterized in that the substrate (A) is selected from leather, woven fabric, non-woven fabric, paper, wood and artificial leather.   14. Composite according to claim 12 or 13, characterized in that the image further comprises geometric elements, numbers and letters.   15. Composite according to any one of claims 12 to 14, characterized in that different parts of the image or pattern are produced by different three-dimensional structuring on the visible side of the plastic layer (C). body.   16. A composite according to any one of claims 12 to 15, characterized in that the image does not have regular repeating units.   The pattern or image has ridges or recesses that convey different visual impressions by different screenings or by different heights or depths in the range of 1-3000 μm. The complex according to any one of the above.   The plastic layer (C) comprises at least two different polyurethanes, wherein the polyurethane (C1) has a Shore hardness A in the range of less than 60 and the further polyurethane (C2) is in the range of greater than 60 to 100 A composite according to any one of claims 12 to 17, characterized in that it has a Shore hardness A of   Said ridges or recesses are distinguished from group to group by said ridges or recesses having different three-dimensional geometries, different heights or depths or different screenings The complex according to any one of claims 12 to 18.   20. Composite according to any one of claims 12 to 19, characterized in that the plastic layer (C) is porous.   21. A composite according to any one of claims 12 to 20, characterized in that the image or pattern is a combination of two different patterns that migrate to each other.   22. Composite according to claim 21, characterized in that the image or pattern is a leather silver pattern associated with a pattern of woven or knitted products.   Ridges or depressions that have at least one element (D), different from geometric elements, numbers and letters, and convey various visual impressions in various screenings or at various heights or depths A female mold having at least one female mold of an image or pattern on one side, created by   The ridges or recesses are distinguished from group to group by the ridges or recesses having different geometric shapes, different heights or depths or different screenings. Item 24. A female mold according to Item 23.   25. Use of a female mold according to claim 23 or 24 for producing the composite according to any one of claims 12 to 20.

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