TWI545010B - Multilayer composite structures and process for producing the same - Google Patents

Description

Multi-layer composite structure and manufacturing method thereof

The present invention relates to a method of making a multilayer composite structure comprising continuously performing the following operations: (a) using a power modulated laser engraving to provide a surface structure in the form of an image or a pattern to a master or a male mold, wherein Having at least one element (D) that is not a geometric element, is not a number, and is not a letter, and wherein there is a difference in screen angle, depth of dent, or sharpness value within the surface structure, (b) as appropriate From the male mold molding master mold, (c) spraying the plastic preparation on the master mold, wherein the temperature of the master mold is in the range of 50 ° C to 200 ° C, (d) solidifying the plastic preparation to obtain the film, and (e) bonding the film To the substrate (A), (f) and the removal of the mold, wherein operations (e) and (f) can be performed in any desired order.

The invention further relates to a multilayer composite structure comprising (A) a substrate, (B) at least one bonding layer as appropriate, and (C) a plastic layer having a surface structure on its visible side, wherein the plastic layer (C) is Having at least one image or pattern on the visible side, wherein this has at least one element (D) that is not a geometric element, is not a number, and is not a letter, and wherein within the surface structure, at a screen angle, a depth of depression Or pointed There is a difference in the value of the cut.

The invention further relates to a mold.

Many substrates are coated to achieve a particularly attractive appearance and a particularly comfortable hand (tactile quality). Polymeric films have been used in coatings which are particularly versatile here. The polymeric film is generally versatile and, if the material is suitable, can be printed to achieve the desired effect.

WO 2005/47549 discloses a method of coating leather. A mold is made and it has a pattern, and when the mold is warm, a plastic dispersion is applied to the mold. For example, it is possible to obtain natural or synthetic leather with a comfortable hand. WO 2005/47549 does not disclose any coated leather with complex images.

WO 2006/092440 discloses a method of making coated leather having a coating having less hair-like characteristics. These leathers have a soft surface with a comfortable feel. However, in many cases, the disclosed methods are not capable of coating complex images of superior quality.

WO 2007/033968 and WO 2008/017690 disclose the use of laser engraving, for example, numbers, letters or logos into a mold and subsequent use of a mold to make a mold applied to the substrate. However, in many cases, the disclosed methods are not capable of coating complex images of superior quality.

WO 2009/106503 discloses a method of providing a coating on a fabric surface corresponding to, for example, a grain or wood grain. To this end, a layer of polyurethane previously made on the mold is applied. The polyurethane layer has a smaller hair-like character, which has, for example, a circular cross section and a conical shape

One goal is to provide a method that can produce a composite structure and can also transfer complex images of sufficient quality to the coated substrate without sacrificing the feel and appearance of the surface.

Therefore, the method defined in the preamble has been found.

The expression "multilayer composite structure" hereinafter means a material having (A) at least one substrate and (C) having at least one plastic layer, wherein the substrate and the plastic layer have been bonded to each other.

A wide variety of materials are suitable for use as the substrate (A), examples being metal foil, paper, cardboard, cardboard, wood, thermoplastic molds, and preferably natural leather, fabric, non-woven, synthetic leather, paper, and wood.

The bond between the substrate (A) and the plastic layer (C) can take various forms, such as an adhesive film or a dot, strip or grid (e.g., square or honeycomb or diamond shaped grid).

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

For the purposes of the present invention, the expression "complex or complex image" as used herein means an image having at least one element (D) that appears once or repeatedly on the visible side of the substrate coated in the present invention. And the element is not a geometric element, not a number and not a letter element. Possible examples of elements of this type (D) are animals, plants, humans (including human portraits), non-geometrically designed buildings (such as cathedrals), cars, landscapes, and states. Drawings of cartoons, cartoon characters, and (specifically) sports or artistic celebrities.

For the purposes of the present invention, the expression "complex pattern" means having at least one pattern that appears once or repeatedly and is not a geometric element (D), examples being animals, plants, humans (including human portraits), Non-geometrically designed buildings (such as cathedrals), cars, landscapes, country shapes, cartoon characters, and drawings of sports or artistic celebrities.

For the purposes of this application, the texture pattern of the leather and the wood grain itself are neither complex images nor complex patterns.

Examples of geometric elements are circles, ellipses (in whole or in part in each case), squares, rectangles, parallelograms, irregularograms, triangles, regular pentagons, regular hexagons, regular octagons, and straight or non-linear .

In one 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 a regular repeating unit. This means that (unlike in patterns such as the pattern of the wallpaper) the pattern is not constantly repeated.

In another embodiment of the invention, the complex pattern has certain repeating units that preferably comprise element (D).

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

In one embodiment of the invention, the image or pattern may represent two adjacent A combination of different patterns. For example, the image or pattern may represent a textured pattern of leather associated with the pattern of the knit or knit, for example by means of stitching or without any stitching.

In one embodiment of the invention, the pattern or preferred image is produced by making protrusions and depressions having heights and depths in the range of 1 μm to 3000 μm, respectively, wherein the patterns or images are via a screen Variations, changes in geometry (shape) or changes in height or depth produce different appearances.

In one embodiment of the invention, the protrusions and depressions are individually different or preferably different in groups having different geometries, different heights, and different depths or different screens.

The method of the present invention includes a plurality of steps, and such steps are described below.

In a first step (hereinafter also referred to as step (a)), a power modulated laser engraving is used to provide a surface structure in the form of an image or a pattern to a master or a male mold, wherein this has at least one element (D) ), the element is not a geometric element, is not a number, and is not a letter, and wherein there are differences in screen angle, depth of dent, or sharpness value within the surface structure.

The male and female molds can be selected from a number of materials.

For example, it is therefore possible to select a metal mold, examples of which are suitable for metals such as nickel, chromium and aluminum. Plastic molds are also suitable, for example made of polyurethane, polyamide or polyvinyl alcohol (PVA). It is preferably a mold comprising at least one polymeric material as a binder, and is preferably a polyoxymethane mold.

In one embodiment of the invention, the male mold is selected from a plastic mold, such as polyurethane, polyamide or polyvinyl alcohol.

In one embodiment of the invention, the master mold is selected from the group consisting of polyoxyxene molds.

In one embodiment of the invention, the male mold is selected from pre-exposed plastic molds, such as polyurethane, polyamide or polyvinyl alcohol.

The expression "made of polyurethane", "made of polyvinyl alcohol" or "made of polyamine" means that most of the relevant molds are made of polyurethane. Made of polyvinyl alcohol or polyamide, but the mold may also contain other substances such as fillers, preservatives, antioxidants and/or coatings.

In one embodiment of the invention, a mold in the form of a plate, preferably a master mold, is selected. In another embodiment of the invention, a mold that has been attached to the cylinder or a mold that has a cylindrical shape itself is selected. The mold having a cylindrical shape is preferably seamless. Molds having a cylindrical shape have particularly good applicability to successive variants of the method of the invention.

In one embodiment of the invention, a mold having an elastomer layer or a layer composite comprising an elastomer layer on a support is selected, wherein the elastomer layer comprises a binder and optionally other additives and auxiliaries. The production of a mold of this type may then comprise the steps of: 1) coating a liquid adhesive comprising an additive and/or an additive, as appropriate, onto an image or patterned surface, for example onto a male mold, 2) for example via Thermal hardening or radiation curing or hardening of the liquid adhesive via aging, 3) separating the resulting mold and optionally applying it to a carrier such as a metal plate or metal cylinder.

In one embodiment of the invention, the process applies a liquid polyfluorene oxide to an image having an image or a pattern to age the polyfluorene oxide and thus hard And then peel it off. The resulting polyoxygen oxide foil was then bonded to an aluminum support.

In a preferred embodiment of the invention, there is provided a mold having a laser-engravable layer or a layer composite comprising a laser-engravable layer on a carrier, wherein the laser-engravable layer comprises a binder and optionally other Additives and additives. The laser-engravable layer is further preferably an elastomer.

In a preferred embodiment, the fabrication of the mold comprises the steps of: 1) providing a laser-engravable layer or a layer composite comprising a laser-engravable layer on a carrier, wherein the laser-engravable layer comprises a binder and preferably It also contains additives and additives. 2) Thermochemical, photochemical or actinic hardened laser engraved layers, 3) Laser engraving using power modulation to provide a surface structure to the laser-engravable layer.

A laser-engravable layer or layer composite, preferably an elastomer, may be present on the support, and is preferably present on the support. Examples of suitable carriers include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene, polypropylene, polyamine Or a woven fabric and foil made of polycarbonate, preferably a PET foil or a PEN foil.

For example, paper and knitted fabrics made of cellulose are also suitable as carriers. The carrier used may also comprise a conical or cylindrical tube made of such materials, referred to as a sleeve. Other materials suitable for the casing are glass fiber woven fabrics or composite materials made of glass fibers and polymeric materials. A metal carrier, such as a solid carrier made of aluminum, nickel, magnetizable spring steel or other type of steel or other iron alloy and in the form of a woven material, sheet or cylinder, is also suitable for carrying Body material.

In one embodiment of the invention, the carrier may be coated with an adhesive layer to improve the adhesion of the laser-engravable layer. In another embodiment of the invention, an adhesive layer is not required.

The laser-engravable layer comprises at least one binder which may be a prepolymer which is reacted to obtain a polymer during thermochemical hardening. Suitable binders can be selected, for example, for hardness, elasticity or flexibility depending on the desired properties of the laser-engravable layer or mold. Suitable binders can be divided into three groups in nature without any intention to limit the binder.

The first group comprises a binder having an ethylenically unsaturated group. The ethylenically unsaturated groups can be crosslinked by photochemical, thermochemical means, by means of electron beams or by any desired combination of such methods. It is also possible to use mechanical hardening by means of a filler. An example of this type of binder is a binder comprising a 1,3-diene monomer such as isoprene or 1,3-butadiene. The ethylenically unsaturated group herein may serve on the one hand as a chain unit of the polymer (1,4-incorporated) or it may be pendant to the polymer chain (1,2-incorporated). Examples which may be mentioned are 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) and polyurethane elastomer with ethylenically unsaturated groups body.

Other examples include thermoplastic elastomer block copolymers made from alkenyl aromatics and 1,3-dienes. The block copolymer may relate to a linear block copolymer or a radial block copolymer. It usually involves a type A-B-A triblock copolymer, but It may also be a type A-B diblock polymer or a block polymer having a plurality of alternating elastomers and thermoplastic blocks, such as A-B-A-B-A. It is also possible to use mixtures of two or more different block copolymers. Commercially available triblock copolymers typically comprise a specific proportion of diblock copolymer. The diene unit can be a 1,2- or 1,4-linkage. It is possible to use not only a styrene-butadiene type block copolymer but also a styrene-isoprene type block copolymer. For example, it is available from Kraton®. It is also possible to use thermoplastic elastomer block copolymers having end blocks made of styrene and having a random styrene-butadiene center block, which block copolymers are commercially available from Styroflex®.

Other examples of the binder having an ethylenically unsaturated group include a modified binder in which a crosslinkable group is introduced into a polymerized molecule via a graft reaction.

The second group contains a binder having a functional group. The functional groups can be crosslinked in a thermochemical manner, by means of electron beam, photochemical means or by any desired combination of such methods. It is also possible to use mechanical hardening by means of a filler. Examples of suitable functional groups include -Si(HR ¹ )O-, -Si(R ¹ R ² )O-, -OH, -NH ₂ , -NHR ¹ , -COOH, -COOR ¹ , -COHN ₂ , -OC (O) NHR ¹ , -SO ₃ H or -CO-. Examples of the binder include a polyoxyxene elastomer, an acrylate rubber, an ethylene-acrylate rubber, an ethylene-acrylic rubber, and an ethylene-vinyl acetate rubber, and a partially hydrolyzed derivative of the binder, a thermoplastic elastomer polyamine group. Acid esters, sulfonated polyethylenes and thermoplastic elastomer polyesters. R ¹ and, when present, R ^{2 are} different or preferably identical and are selected from the group consisting of organic groups, and in particular C ₁ -C ₆ alkyl groups.

In one embodiment of the invention, it is possible to use not only an olefinic system A saturated group and a binder having a functional group. Examples include an addition-crosslinking polyoxyxene elastomer having a functional group and an ethylenically unsaturated group, and a copolymer of butadiene with (meth) acrylate, (meth) acrylate or (meth) acrylonitrile, and Also included are (block) copolymers of butadiene or isoprene with a styrene derivative having a functional group, such as a block copolymer made of butadiene and 4-hydroxystyrene.

The third group of binders includes those binders which have neither an ethylenically unsaturated group nor a functional group. Examples which may be mentioned herein are polyolefins and ethylene/propylene elastomers and products obtained via hydrogenated diene units, an example being SEBS rubber.

Polymeric layers comprising binders having no ethylenically unsaturated groups or functional groups must generally be hardened by mechanical means or by means of high energy radiation or by using a combination of such methods to allow the use of lasers to achieve a desired sharp edge. Structured.

It is also possible to use a mixture of two or more binders, and such binders may involve a mixture of adhesives from only one of the groups or binders from two or all three groups, respectively. The only limitation on the possible combinations is that there is no adverse effect on the suitability of the polymer layer for the laser structuring process and for the molding process. For example, it may be preferred to use a mixture of at least one elastomeric binder having no functional groups and at least one other binder having a functional group or an ethylenically unsaturated group.

In one embodiment of the invention, the proportion of binder in the elastomer layer or associated laser-engraveable layer is from 30% to 99% by weight based on the total of all components of the associated elastomer layer or associated laser-engraveable layer, 40 weights is preferred % to 95% by weight, and excellently 50% by weight to 90% by weight.

The elastomeric layer or laser-engraveable layer may optionally comprise a reactive low molecular weight or oligomeric compound. The molar mass of the oligomeric compound typically does not exceed 20,000 g/mol. For the sake of simplicity, reactive low molecular weight and oligomeric compounds will hereinafter be referred to as monomers.

Monomers may be added on the one hand to increase the rate of photochemical or thermochemical crosslinking or crosslinking by means of high energy radiation to the desired extent. When using binders from the first and second groups, it is generally not necessary to add monomers for acceleration. In the case of adhesives from the third group, it is generally preferred to add the monomers, but this is not an essential requirement in all cases.

Regardless of the problem of cross-linking rate, it is also possible to use monomers to control the crosslink density. The resulting network structure has a small or large density as a function of the nature and amount of the added low molecular weight compound. The monomers which can be used are, on the one hand, known ethylenically unsaturated monomers. The monomers are essentially intended to be compatible with the binder and have at least one photochemical or thermochemically reactive group. It should not have significant volatility. The boiling point of the suitable monomer is preferably at least 150 °C. Particularly suitable materials are acrylic acid or methacrylic acid and monohydric or polyhydric alcohols, amines, amino alcohols or hydroxy ethers and hydroxy esters of decylamine, and other particularly suitable materials are styrene and substituted styrene, anti-butene Diacid or maleic acid esters and allyl compounds. Examples include n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl 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, tripropylene glycol C Oleate, dioctyl fumarate, N-dodecyl maleimide and triallyl isocyanurate.

Particularly suitable for thermochemically hardening monomers comprising reactive low molecular weight polyoxyxides, such as cyclodecane, Si-H functional oxiranes, alkoxy or alkoxy groups having alkoxy or ester groups, sulfur-containing oxanes and a diol; for example, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol; a diamine such as 1,6-hexanediamine, 1,8-octanediamine; an amino alcohol such as ethanolamine, diethanolamine, butylethanolamine; a dicarboxylic acid such as 1,6-hexanedicarboxylic acid, terephthalic acid, maleic acid and antibutene acid.

It is also possible to use a monomer having not only an ethylenically unsaturated group but also a functional group. Examples which may be mentioned are ω-hydroxyalkyl (meth)acrylates, such as ethylene glycol mono(meth)acrylate, 1,4-butanediol mono(meth)acrylate and 1,6-hexyl Glycol mono (meth) acrylate.

It is of course also possible to use mixtures of the various monomers as long as the properties of the elastomer layer are not adversely affected by the mixture. The amount of monomer added is usually from 0 to 40% by weight, preferably from 1% to 20% by weight, based on the total of the elastomer layer or the related laser-engraveable layer.

In one embodiment, it is possible to use one or more monomers with one or more catalysts. It is therefore possible to accelerate the step of providing the mould via step 2) via the addition of one or more acids or via an organotin compound. Suitable organotin compounds can be: di-n-butyltin dilaurate, di-n-butyltin dioctoate, di-n-butyltin di-2-ethylhexanoate, di-n-octyltin di-2-ethylhexanoate and Di-n-butylbis(1-oxoinodecyloxy)stannane.

The elastomer layer or the laser-engravable layer may further comprise additives and auxiliaries, for example Such as IR absorbers, dyes, dispersants, antistatic agents, plasticizers or abrasive particles. The amount of such additives and auxiliaries should generally be no more than 30% by weight, based on the total of the elastomer layer or the associated laser-engraveable layer.

The elastomer layer or the laser-engravable layer may be composed of a plurality of individual layers. The individual layers may be constructed of the same, approximately the same or different materials. The laser-engravable layer or all individual layers together typically have a thickness of from 0.1 mm to 10 mm, preferably from 0.5 mm to 3 mm. The thickness can be appropriately selected according to the laser engraving program associated with the technical application and the technical machine and the process parameters of the molding program.

The elastomer layer or the laser-engravable layer may also optionally have a coating thickness not exceeding 300 μm. The composition of the overlying layer can be selected for ideal engravability and mechanical stability, and the composition of the layer below it can be selected for the desired hardness or elasticity.

In one embodiment of the invention, the overlying layer itself is laser-engravable during the laser engraving process or is removable with the layer beneath it. The overlying layer comprises at least one binder. It may additionally comprise an absorber or monomer or adjuvant for laser radiation.

The preferred mold is a polyoxynitride mold. The expression "polyoxymethane mold" hereinafter means a mold made by using at least one binder having at least one, preferably at least three O-Si(R ¹ R ² )-O- groups per molecule. Here, R ¹ and R ^{2 are} as defined above or are preferably the same.

In another embodiment of the invention, the mold used comprises a nickel mold. Suitable nickel molds consist essentially of a homogeneous nickel layer. The thickness of the nickel layer can range from 100 mm to 10 mm.

For example, an optical laser can be selected as the laser for the laser engraving process in step (a). CO ₂ lasers, Nd-YAG lasers, fiber lasers, and ultraviolet lasers are also suitable.

In the laser engraving process of step (a), the depressions are engraved or branded into a laser-engravable layer in the form of a screen, wherein individual regions of the screen may, for example, have screen dots arranged in a square form or in a rectangular form Arranged screen dots or screen dots arranged, for example, in a honeycomb pattern. The boundaries of the various regions can then be achieved, for example, by differences in the screen angles of the various regions.

For the purposes of the present invention, the depressions herein are not only depressions of the perforated laser-engravable layer but also depressions in the form of notches.

The laser engraving process in step (a) involves power modulated laser engraving. This means that during the engraving process, the laser power is not kept constant and is actually modulated according to the desired depth of the recess. Here, there is a difference in the screen angle, the depth of the depression or the value of the sharpness in the surface structure (that is, the engraved surface structure). This means that individual engraving depressions or different depression groups have different screen angles, depression depths or sharpness values for the depressions, and in particular it is possible that all the depressions are different or the depressions are different or the individual depressions are different.

In one embodiment of the invention, the laser power rating (ie, maximum output power) of the selected radiation source is in the range of 5 W to 5,000 W, preferably in the range of 10 W to 2,000 W, and particularly preferably 50. W to 500 W range.

In one embodiment of the invention, the power of the radiation source is modulated over a range of 0 to 100% laser power rating. This type of modulation can be done in the MHz region.

In one embodiment of the invention, the number of recesses per cm ^{2 of} engraving is in the range of 100 to 10,000 depressions/cm ² , preferably in the range of 4,000 to 5,000 depressions/cm ² .

In one embodiment of the invention, the engraved depressions have an average depth in the range of from 1 μm to 3,000 μm, preferably from 50 μm to 500 μm.

In one embodiment of the invention, certain depressions within the surface structure may be conical depressions, and other depressions may be cylindrical, conical, wedge or convex.

In one embodiment of the invention, certain depressions within the surface structure may be cylindrical depressions, and other depressions may be convex or conical.

In one embodiment of the invention, certain depressions within the surface structure may have the shape of a small hemispherical bowl, and other depressions may be cylindrical, conical, wedge or convex.

In one embodiment of the invention, there is a difference in the geometry of the depressions. This preferably means the geometry of the cross-sectional area. For example, the depressions may have a circular, elliptical or multi-faceted cross-section, such as a square, a triangle or a diamond, or have a cross-section in the form of a regular pentagon or a regular hexagon (honeycomb) or a regular octagon. Other possibilities are combinations of semicircles, stars and geometric elements.

In one embodiment of the invention, there is a difference in screen angle between the sets of depressions within the surface structure. It is therefore possible, for example, that the two regions are the same or different.

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

The overall result of performing step (a) is to obtain a mold of the present invention. The mold of the present invention is a master mold or a male mold, which is designed as a recess according to the mold. Whether the point is intended to be a depression in the composite structure or is intended to be a protrusion (preferably similar to a small hair-like structure).

After the actual laser engraving procedure in step (a), the laser engraved layer is washed with a circular or linear washer, as appropriate, using a cleaning composition to remove engraving residue.

The method can be used to make a mold in the form of a master or in the form of a male mold.

In one embodiment of the invention, the method of the invention involves step (b): molding one or more master molds from the male mold produced in step (a). The molding procedure can be, for example, as follows: 1) coating a liquid adhesive comprising additives and/or auxiliaries as appropriate onto an image or patterned surface, for example onto a male mold, 2) for example via thermal hardening or radiation Curing or hardening the liquid adhesive via aging, 3) separating the resulting master and optionally applying it to a carrier such as a metal plate or metal cylinder.

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

The method of the present invention involves the step (c) of spraying a plastic formulation onto the master mold, wherein the temperature of the master mold is in the range of 50 ° C to 200 ° C, preferably 75 ° C to 150 ° C, and particularly preferably at least 90 ° C. The temperature measured herein is the temperature measured at the surface of the mold that is in contact with the plastic formulation at the beginning of the spray process.

The spraying process can be carried out once or repeatedly.

Examples of optional plastic formulations are solutions of the polymer, for example in an organic solvent, and are preferably aqueous formulations, in particular aqueous dispersions, for example Such as aqueous suspensions or aqueous emulsions.

In the case of a plastic formulation, the term "aqueous" means that it comprises water and less than 5% by weight, preferably less than 1% by weight, of organic solvent based on the dispersion. It is especially preferred that no detectable volatile organic solvent is present. For the purposes of the present invention, the expression "volatile organic solvent" means an organic solvent having a boiling point of up to 200 ° C at atmospheric pressure.

Examples of suitable plastics in plastic formulations are: polystyrene, polyacrylates and, in particular, polyurethanes. Examples of suitable polyacrylates are (meth)acrylic acid with one or more C ₁ -C ₁₀ alkyl (meth)acrylates, in particular with methyl acrylate, methyl methacrylate, ethyl acrylate, Copolymer of n-butyl methacrylate and 2-ethylhexyl (meth) acrylate.

Suitable polyurethanes can be obtained by the following reaction: (i) isocyanates, preferably diisocyanates, and (ii) are reactive toward isocyanates and usually have from 500 g/mol to 10,000 g/mol, preferably 500 g/ a compound having a molar mass (M _w ) of mol to 5,000 g/mol, particularly preferably from 800 g/mol to 3,000 g/mol, and (iii) having an increase in the mass of moor from 50 g/mol to 499 g/mol Chain extenders, as appropriate in the presence of catalysts and/or customary additives.

The starting components and manufacturing methods of the preferred polyurethanes (PU) will be described below by way of example. The components (i), (ii) and (iii) which are usually used for the manufacture of polyurethanes (PU) and optionally catalysts and/or additives will be described by way of example: Isocyanates which can be used (i ) are known as aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, such as propylene diisocyanate, diacetyl diisocyanate Ester, pentane diisocyanate, hexamethylene diisocyanate, heptane diisocyanate and/or octyl diisocyanate, 2-methylglutaryl 1,5-diisocyanate , 2-ethyl butane diisocyanate, pentane dicarboxylate, 1,4-diisocyanate, 1-isocyanato-3, 3,5-trimethyl-5-isocyanate methylcyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatomethyl)cyclohexane and/or 1,3 - bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane 2,4-diisocyanate and/or 1-methylcyclohexane 2,6-diisocyanate and/or dicyclohexylmethane 4,4'-diisocyanate, dicyclohexylmethane 2,4'-diisocyanate and dicyclohexylmethane 2,2'-diisocyanate, diphenylmethane 2, 2'-diisocyanate, diphenylmethane 2,4'-diisocyanate and / or diphenylmethane 4,4'-diisocyanate (MDI), 1,5-diisocyanate, naphthyl ester (NDI), 2 , 4-diisocyanate toluene diester and / or 2,6-diisocyanate toluene diester (TDI), diphenylmethane diisocyanate, 3,3'-diisocyanate dimethyl diphenyl ester, Diphenylethane 1,2-diisocyanate and/or diisocyanate Acid phenyl diester. It is preferred to use 4,4'-MDI. Also preferred are aliphatic diisocyanates, in particular hexamethylene diisocyanate (HDI).

The isocyanate-reactive compound (ii) may comprise well-known compounds which are reactive toward isocyanates, such as polyesterols, polyether alcohols and/or polycarbonate diols, to cover the other of these compounds. A term "polyol" having a molar mass in the range of from 500 g/mol to 8,000 g/mol, preferably from 600 g/mol to 6,000 g/mol, in particular from 800 g/mol to 3,000 g/mol (M _w ) and preferably the isocyanate has an average functionality of from 1.8 to 2.3, preferably from 1.9 to 2.2, in particular 2. Preference is given to using polyether polyols, for example polyether polyols based on well-known starting materials and customary alkylene oxides, such as ethylene oxide, 1,2-propylene oxide and/or 1,2-butylene oxide. Preferably, it is a polyether alcohol based on polytetrahydrofuran (polyTHF), 1,2-propylene oxide and ethylene oxide. The advantage of polyether alcohols is that they have higher hydrolysis resistance than polyesterols, and polyether alcohols are preferred as component (ii), in particular for the manufacture of soft polyurethanes (PU1).

Specific polycarbonate diols which may be mentioned are aliphatic polycarbonate diols, examples being 1,4-butanediol polycarbonate and 1,6-hexanediol polycarbonate.

Polyester diols which may be mentioned are at least one primary diol, preferably at least one primary aliphatic diol (for example ethylene glycol, 1,4-butanediol, 1,6-hexanediol) via polycondensation. , neopentyl glycol or particularly preferably 1,4-dihydroxymethylcyclohexane (in the form of a mixture of isomers) or a mixture of at least two of the above diols) and at least one, preferably at least two, on the other hand A polyester diol produced by a dicarboxylic acid or an anhydride of such dicarboxylic acids. Preferred dicarboxylic acids are aliphatic dicarboxylic acids such as adipic acid, glutaric acid and succinic acid; and aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.

It is preferred to form an alkylene oxide (specifically ethylene oxide, propylene oxide or a mixture thereof) and a diol (for example, ethylene glycol, 1,2-propanediol, 1,2-butane) in the presence of a highly active catalyst. Polyether alcohols are produced by adducts of alcohols, 1,4-butanediol or 1,3-propanediol or with triols such as glycerol. Examples of such highly active catalysts are cesium hydroxide and a metal cerium cyanide catalyst, also known as DMC catalysts. The usual DMC catalyst used is zinc hexacyanocobaltate (III). After the reaction, the DMC catalyst can be retained in the polyether alcohol, but is preferably removed, for example, via deposition or filtration.

It is also possible to use a mixture of various polyols in place of a polyol.

In order to improve the dispersibility, the isocyanate-reactive compound (ii) may also contain a certain proportion of one or more diols or diamines having a carboxylic acid group or a sulfonic acid group (ii'), in particular, 1,1 - dimethylol butyrate, 1,1-dimethylolpropionic acid or An alkali metal or ammonium salt.

The chain extender (iii) used comprises aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds known per se having a molar mass of from 50 g/mol to 499 g/mol and having at least two functional groups. Preference is given to compounds having exactly two functional groups per molecule, examples being diamines and/or alkanediols having from 2 to 10 carbon atoms in the alkylene moiety, in particular 1,3-propanediol, 1,4 - butanediol, 1,6-hexanediol and/or dialkyl glycol, trialkyl glycol, tetraalkylene glycol, pentacyclodiol, hexadecanediol having 3 to 8 carbon atoms per molecule, Heptadecanediol, octanediol, nonanediol and/or decadecanediol and preferably corresponding oligopropylene glycol and/or polypropylene glycol, and it is also possible to use a mixture of chain extenders (iii) herein.

Particularly (i) to (iii) particularly preferably relate to difunctional compounds, i.e. diisocyanates (i), dihydroxy polyols (preferably polyether alcohols (ii)) and difunctional chain extenders (preferably diols) ).

Suitable catalysts which, in particular, accelerate the reaction between the NCO groups of the diisocyanate (i) and the hydroxyl groups of the components (ii) and (iii) are the tertiary amines known per se, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane ("DABCO") and similar tertiary Amines, and in particular organometallic compounds such as tetravalent titanium esters, iron compounds (such as iron(III) acetylacetonate), tin compounds (eg For example, tin diacetate, tin dioctoate, tin dilaurate or a dialkyltin salt of an aliphatic carboxylic acid (dibutyltin diacetate, dibutyltin dilaurate) or the like. The catalyst is usually used in an amount of from 0.0001 part by weight to 0.1 part by weight per 100 parts by weight of the component (ii).

It is also possible to add one or more auxiliaries and/or additives to the components (i) to (iii) together with the catalyst. The following examples may be mentioned: blowing agents, anti-sticking agents, interfacial active substances, fillers (such as nanoparticle-based fillers, in particular CaCO ₃ based fillers), and nucleating agents, slip agents, dyes And pigments, antioxidants (for example for hydrolysis, light, heat or discoloration), inorganic and/or organic fillers, reinforcing agents and plasticizers and metal deactivators. In a preferred embodiment, a hydrolysis stabilizer such as a polymeric and low molecular weight carbodiimide is included in the additive. The soft polyurethane preferably comprises a triazole and/or triazole derivative and an antioxidant in an amount of from 0.1% by weight to 5% by weight based on the total weight of the related soft polyurethane. Suitable antioxidants are generally substances which inhibit or prevent undesired oxidation processes in the plastic to be protected. Antioxidants are generally commercially available. Examples of antioxidants are hindered phenols, aromatic amines, thiosynergists, organophosphorus compounds of trivalent phosphorus, and hindered amine light stabilizers. Examples of hindered phenols are found in Plastics Additive Handbook, Fifth Edition, edited by H. Zweifel, Hanser Publishers, Munich, 2001 ([1]), pages 98 to 107 and pages 116 to 121. Examples of aromatic amines are found in [1], pages 107 to 108. Examples of thio synergists are given in [1], pages 104 to 105 and pages 112 to 113. Examples of phosphites are found in [1], pages 109 to 112. Examples of hindered amine light stabilizers are given in [1], pages 123 to 136. Phenolic antioxidants are preferably suitable for use in the antioxidant mixture. In a preferred embodiment, the molar mass of the antioxidant, in particular the phenolic antioxidant, is greater than 350 g/mol, particularly preferably greater than 700 g/mol, and the maximum molar mass ( _Mw ) is up to 10,000. g/mol, preferably up to 3,000 g/mol. Further, the melting point thereof is preferably at most 180 °C. Further, it is preferred to use an antioxidant in an amorphous or liquid form. It is also possible to use a mixture of two or more antioxidants as an additive.

It is also possible to use, with the components (i), (ii) and (iii) and optionally catalysts and additives, chain regulators which generally have a molar mass of 31 g/mol to 3,000 g/mol (chain termination) Agent). These chain regulators are compounds having only one isocyanate-reactive functional group, examples being monohydric, monoamine and/or monohydric polyols. These chain regulators are useful for the controlled adjustment of flow characteristics, particularly in soft polyurethanes. The chain regulator may be used in an amount of usually from 0 part by weight to 5 parts by weight, preferably from 0.1 part by weight to 1 part by weight, based on 100 parts by weight of component (ii), and is defined as part of component (iii) .

Near the end of the reaction with increased molecular weight, it is also possible to use one or more of the components (i), (ii) and (iii) and optionally catalysts and additives to have two or more pairs of isocyanates. Crosslinker of a sexual group (such as hydrazine hydrate).

Components (ii) and (iii) can be selected in a relatively broad range of molar ratios to adjust the hardness of the polyurethane (PU). Examples of suitable molar ratios of component (ii) to the chain extender (iii) used are 10:1 to 1:10, specifically 1:1 to 1:4, wherein soft polyurethanes The hardness increases as the content of (iii) increases. The index for the reaction to produce the polyurethane (PU) may range from 0.8:1 to 1.4:1. It is preferably 0.9:1 to 1.2:1, particularly preferably 1.05:1 to 1.2:1. By the total number of isocyanate groups used in component (i) during the reaction, and the monofunctional component (for example, one element) which acts as a chain terminator and is reactive toward isocyanate in component (ii) and, where appropriate, (iii) and, where appropriate, The ratio of the number of groups reactive with isocyanate (i.e., the number of active hydrogen atoms) in the alcohol) defines an index.

In addition to plastic, the plastic dispersion used in step (c) may also contain other components, such as one or more surfactants and/or one or more hardeners. Suitable hardeners are compounds which, for example, are thermally activated to crosslink a plurality of plastic molecules, preferably a plurality of polyurethane molecules. Particularly suitable hardeners are hardeners based on trimeric diisocyanates and in particular based on aliphatic diisocyanates such as hexamethylene diisocyanate. An example of a hardener having excellent applicability is a compound described as compound (V) in WO 2009/106503.

The plastic dispersion used in step (c) may contain, in addition to plastics and optionally a hardener, other compounds, such as one or more polyoxyxides, wherein the compounds may or may not have one or more per molecule. Multiple reactive groups. Examples of reactive groups which may be mentioned are: carboxylic acid derivative groups (examples are methyl carboxylates) or carboxylic anhydrides (specifically succinic anhydride groups), and particularly preferably carboxylic acid groups.

Other examples of reactive groups are primary and secondary amine groups, such as NH (iso C ₃ H ₇ ) groups, NH (positive C ₃ H ₇ ) groups, NH (cyclo C ₆ H ₁₁ ) groups, and NH (positive C) ₄ H ₉ ) group, specifically NH(C ₂ H ₅ ) group and NH(CH ₃ ) group, and excellent NH ₂ group.

Further preferred is an aminoalkylamino group such as -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, -NH-CH ₂ -CH ₂ -NH(CH ₃ ) group, -NH-CH _2- CH ₂ -CH ₂ -NH(CH ₃ ) group.

Other suitable additives are additives selected from the group consisting of pigments, matting agents, light stabilizers, antistatic agents, antifouling agents, anti-vibration agents, thickeners (specifically, polyurethane-based thickeners) And hollow microbeads.

In one embodiment of the invention, the solids content of the plastic formulation applied by spraying in step (c) is in the range of from 1% to 50%, preferably from 25% to 35%.

Spraying of a (preferably aqueous) plastic formulation onto a master mold may be achieved by methods known per se, in particular by using a spray gun or by spraying with one or more nozzles, wherein the spray guns or nozzles may be fixed or Mobilely incorporated into the device.

A variety of equipment can be used to spray (preferably water) plastic formulations onto the master. Airless spray systems and air spray systems are especially suitable.

Preferably, the sprayed plastic formulation is preferably aqueous, in the range of from 15 ° C to 30 ° C, especially from 20 ° C to 25 ° C.

In one embodiment of the invention, the (preferably aqueous) plastic formulation for the spray process has a dynamic viscosity of at most 500 mPa at room temperature. s, preferably up to 200 mPa. s.

In one embodiment of the invention, the (preferably aqueous) plastic formulation for the spray process has a pH in the range of 4 to 10, preferably in the range of 6 to 8.

In the step (d), the plastic formulation which has been applied to the master by spraying in the step (b) is solidified to obtain a film. For example, by removing (for example, by evaporating) the organic solvent in which the plastic is formulated or preferably the plastic component The water is dispersed, suspended or emulsified to achieve solidification.

Step (d) can be carried out at various temperatures. Examples of suitable temperatures are from 30 ° C to 90 ° C.

Step (d) can be carried out at any desired pressure, preferably atmospheric pressure.

Step (d) gives a plastic in the form of a film, and for the purposes of the present invention, the abbreviated term "film" is also used for this material.

The thickness of the film may be, for example, 70 μm to 300 μm.

In step (e), the film is bonded to the substrate (A). The substrate (A) is described in detail below. Bonding can be achieved, for example, via lamination, bonding or welding, and for example by application of calendering pressure.

Of course, the film obtained in the step (d) is bonded to the substrate (A) in the step (d) such that the side having the pattern or image is the visible side.

For example, in step (e), bonding is achieved by applying an organic binder applied to the entire surface or preferably in the form of a discontinuous layer (ie, a layer that does not cover the entire surface). It is preferably an organic binder.

In one embodiment of the invention, the organic binder is applied in the form of dots, strips or grids in step (e), such as diamonds, rectangles or squares or having a honeycomb structure.

The organic binder may be selected from the group consisting of polyvinyl acetate, polyacrylate or, in particular, polyurethane, preferably a polyurethane having a glass transition temperature of less than 0 ° C. .

The organic binder can be cured, for example, thermally, via actinic radiation, or via aging.

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

In another embodiment of the invention, the maximum thickness of the organic binder measured after coating and hardening is 100 μm, preferably 50 μm, particularly preferably 30 μm, and excellent 15 μm.

In step (f) of the method of the invention, the mold is separated, for example, via mechanical stripping.

Operations (e) and (f) can be performed in any desired order herein. For example, step (e) can be performed first and then step (f) can be performed. In another embodiment of the invention, step (f) may be performed first and then step (e) may be performed.

In one embodiment of the invention, the membrane from step (d) is porous.

In a preferred embodiment of the invention, the membrane from step (d) has pores in the form of capillaries throughout the thickness (cross section) of the membrane.

In one embodiment of the invention, the average number of pores in capillary form per 100 cm ² in the film from step (d) is at least 100, preferably at least 250.

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

In one embodiment of the invention, the pores in the form of a capillary have a uniform distribution in the film from step (d). However, in a preferred embodiment of the invention, the pores in the form of capillaries have an uneven distribution in the film from step (d).

In one embodiment of the invention, the pores in the form of a capillary are generally Bent on. In another embodiment of the invention, the pores in the form of a capillary are substantially straight.

The pores in the form of a capillary allow the membrane from step (d) to be permeable to air and to water vapor without the need for perforations. In one embodiment of the invention, the membrane from step (d) may have a water vapor permeability greater than 1.5 mg/cm ² . h, measured according to DIN 53333. Thus moisture (such as sweat) can migrate through the membrane from step (d).

In one embodiment of the invention, the film from step (d) has not only a capillary but also an aperture that does not penetrate the entire thickness of the film.

The method of the present invention produces a multilayer composite structure having a velvety appearance and a very comfortable hand and having an image or pattern having excellent durability thereon. Such patterns or images can be complex and can meet complex design requirements. Such images or patterns may, for example, exhibit a positive and negative effect, wherein their appearance varies with the angle of observation. If it is black, it exhibits a very dark black color. If it uses a porous membrane, it allows water vapor to permeate and is less susceptible to sweat staining. This type of image can be protected from copying or act as an initial identification by virtue of its complexity and clever design.

The present invention further provides a multilayer composite structure comprising (A) a substrate, (B) at least one bonding layer optionally selected, and (C) a plastic layer having a small hair-like characteristic and having a surface structure on a visible side thereof, wherein The plastic layer (C) has at least one image or pattern on its visible side, wherein this has at least one that is not a geometric element, is not a number, and is not a letter The element (D), and wherein there is a difference in the screen angle, the depth of the depression or the value of the sharpness within the surface structure.

Many materials are suitable for use as the substrate (A), examples being metal foil, paper, cardboard, cardboard, wood and thermoplastic molds, preferably natural leather, fabric, non-woven, synthetic leather, paper and wood. Examples of fabrics are woven and knitted fabrics.

The bond between the substrate (A) and the plastic layer (C) can take various forms, such as in the form of an adhesive film or in the form of dots, strips or grids (e.g., square or honeycomb or diamond shaped grids).

The thickness of the substrate (A) can be any desired thickness suitable for the substrate material.

The plastic layer (C) has a small hairy character.

In one embodiment of the invention, the plastic layer (C) has an average thickness in the range of 15 μm to 300 μm, preferably 20 μm to 150 μm, particularly preferably 25 μm to 80 μm, excluding small hair-like features. length.

The meaning of the terms image and pattern and the description of element (D) are given above.

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

In one embodiment of the invention, various portions of the image or pattern are produced by varying the three dimensional structure of the plastic layer (C).

In a preferred embodiment of the invention, the image that preferably exhibits complexity does not have a regular repeating unit. This means that (unlike in patterns such as the pattern of the wallpaper) the pattern is not constantly repeated.

In another embodiment of the invention, the pattern has certain preferred inclusion elements Repeat unit of (D).

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

In one embodiment of the invention, an image or pattern may represent a combination of two different patterns that are contiguous. For example, the image or pattern may represent a textured pattern of leather that has been combined, for example, by stitching or seamlessly combining the pattern of the knit or knit. This combination then preferably corresponds to element (D).

In one embodiment of the invention, the pattern or preferred image is produced by making protrusions or depressions having a height or depth in the range of 1 μm to 3,000 μm, respectively, wherein the patterns or images are via a screen Variations, changes in shape, or changes in height or depth produce different appearances.

In one embodiment of the invention, the protrusions or depressions are respectively different in a group having different three-dimensional geometric shapes, different heights, and different depths or different screens.

In one embodiment of the invention, the plastic layer (C) may comprise at least two different polyurethanes, also referred to as (C1) and (C2) for the purposes of the present invention, wherein the polyamine group The Shore hardness of the acid ester (C1) is in the range of less than 60 and is also referred to as "soft polyurethane", and the Shore of the polyurethane (C2) Hardness A is in the range of above 60 to 120 and this is also referred to as "hard polyurethane". The Shore A hardness is determined herein after 3 seconds, for example according to DIN 53505.

In one embodiment of the invention, the average particle size of the polyurethane (C1) is from 100 nm to 300 nm, preferably 120 nm, as determined by laser light scattering. Up to 150 nm.

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

In one embodiment of the invention, the hardness of the polyurethane (C1) and/or the polyurethane (C2) is adjusted via the difference in the ratio of IPDI as the diisocyanate.

In one embodiment of the invention, the plastic layer (C) is air impermeable. In another embodiment of the invention, the plastic layer (C) is porous, for example because the plastic layer has a capillary that extends through the entire thickness of the plastic layer.

The multilayer composite structure of the present invention can be produced, for example, by the method of the present invention as described in the introduction. The multilayer composite structure of the present invention has a soft surface with a very comfortable hand. There may be an image or pattern with excellent durability on the composite structure of the present invention. Such patterns or images can be complex and can meet complex design requirements. Such images or patterns may, for example, exhibit a positive and negative effect, wherein their appearance varies with the angle of observation. If it is black, it exhibits a very dark black color. If it uses a porous membrane, it allows water vapor to permeate and is less susceptible to sweat staining. This type of image can be protected from copying or act as an initial identification by virtue of its complexity and clever design.

The invention further provides a master mold having an image or pattern of at least one female mold on one side, wherein this has at least one element (D) that is not a geometric element, is not a number, and is not a letter, and wherein the Variations in the screen or changes in height or depth result in protrusions or depressions of different appearances.

In one embodiment of the invention, the protrusions and depressions are different The geometric shapes or different heights or depths are individually different or preferably different from the different screens or screen angles.

The mold of the present invention has excellent applicability for making the multilayer composite structure of the present invention. The invention therefore further provides for the use of the master mold of the invention to make the multilayer composite structure of the invention.

The method of making the mold of the present invention has been described above.

The examples are intended to illustrate the invention.

Example: I. Making the mold of the present invention

The liquid polyoxygen is poured onto the flat mat. Hardening by adding 25% by weight of a solution of di-n-butyl bis(1-oxo neodecyloxy)stannane as an acidic hardener to tetraethoxy decane to the material, and A layer of polyxylene oxide having an average thickness of 2 mm serving as a susceptor for the mold. The mold material was bonded to an aluminum carrier having a thickness of 1.5 mm.

A circular depression was engraved with a CO ₂ laser having the characteristics given in Table 1. In this paper, an acousto-optic modulator is used to modulate the power of the radiation source.

These features are different in various areas of the mold. The arrangement of the regions produces various shadow effects, thus producing an image of the footballer kicking the ball.

The product is the mold 1 of the present invention.

Spacing means the distance between two depressions. The distance between the depressions is always the distance measured to the nearest neighboring depression, and in particular the distance from the center of the depression to the center of the depression.

Figure 1 provides a more detailed description of the terms in Table 1.

Dd: Depth of depression

Cp: cylindrical protrusion

P: platform

The product is the mold of the invention.

II. Making plastic dispersion

The selected plastic is always a polyurethane.

II.1 Preparation of aqueous polyurethane dispersion Disp.1

The following mixing was carried out in a mixer: 7 wt% of an aqueous dispersion of soft polyurethane (C1.1) (particle size: 125 nm, solid content: 40%), the soft polyurethane Produced from the following: a weight ratio of diisocyanate of 13:10 to hexamethylene diisocyanate and isophorone diisocyanate, and a polyester diol having a molar mass M _w of 800 g/mol as a diol ( By polycondensation molar ratio of 1% by weight: 1% by weight: 2.5% by weight between phthalic acid, adipic acid and 1,4-dihydroxymethylcyclohexane (isomer mixture), 1,4-butyl a diol (b1.2) and 3% by weight of monomethylated polyethylene glycol and 3% by weight of H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH), wherein each weight % value is based on Polyester diol (b1.1), and soft polyurethane (C1.1) has a softening point of 62 ° C and softening starts at 55 ° C, Shore A hardness of 54,

An aqueous dispersion of 65 wt% of hard polyurethane (C2.1) (particle size: 150 nm), the hard polyurethane can be passed through isophorone diisocyanate, 1,4-butyl The reaction of diol, 1,1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having a molar mass M _w of 4,200 g/mol, a softening point of 195 ° C and a Shore A hardness of 86.

3.5% by weight of a 70% by weight solution of the compound (I.1) (in propylene carbonate),

6 wt% of a 65% by weight aqueous dispersion of the polyoxonium compound of Example 2 of EP-A 0 738 747, 2% by weight of carbon black, 0.5% by weight of a polyurethane-based thickener, 1 9% by weight of hollow microspheres made of polydivinylidene chloride, filled with isobutane, having a diameter of 20 μm, are commercially available, for example, from Akzo Nobel as Expancel®.

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

II.2 Making aqueous formulation Disp.2

The following mixing was carried out in a mixer: 7 wt% of an aqueous dispersion of soft polyurethane (C1.1) (particle size: 125 nm, solid content: 40%), the soft polyurethane The ester is produced from the following: a weight ratio of diisocyanate of 13:10 to dihexyl isocyanate and isophorone diisocyanate, and a polyester having a molar mass M _w of 800 g/mol as a diol. Alcohol (1% by weight through polycondensation molar ratio: 1% by weight: 2.5% by weight of phthalic acid, adipic acid and 1,4-dihydroxymethylcyclohexane (isomer mixture), 1,4 -butanediol, 3% by weight of monomethylated polyethylene glycol and 3% by weight of H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH), wherein each weight % value is based on polyester two Alcohol, and softening point is 62 ° C and softening starts at 55 ° C, Shore A hardness is 54,65 wt% of an aqueous dispersion of hard polyurethane (particle size: 150 nm), the hard polyamine The carbamate can be passed through isophorone diisocyanate, 1,4-butanediol (C1.2), 1,1-dimethylolpropionic acid, hydrazine hydrate and molar mass M _w of 4,200 g/mol The reaction of polypropylene glycol is obtained, wherein the softening point of the polyurethane (C2.2) is 195 ° C, Shore A hardness of 90, 3.5% by weight of a compound (I.1) (in propylene carbonate) 70% by weight solution, NCO content of 12%, 2% by weight of carbon black.

This gave the polyurethane dispersion Disp. 2 having a solids content of 35% and a dynamic viscosity of 23 seconds at 23 ° C as determined by DIN EN ISO 2431, issued May 1996.

III. Making plastic film

The mold 1 of the present invention was placed on a heatable mat and heated to 91 °C. Disp.1 was then spray coated by spraying through a nozzle, and specifically at 88 g/m ² (wet). The material was coated at a pressure of 65 bar using a nozzle having a diameter of 0.46 mm in the absence of mixed air. The material was allowed to set at 91 ° C until the surface was no longer viscous.

The nozzle is configured to be movable 20 cm from the moving cushion in the direction of movement of the mat, and the nozzle is moved laterally relative to the direction of movement of the mat. The mat temperature was 59 ° C and it took about 14 seconds to pass through the nozzle. After contact with dry air heated to 85 ° C for about two minutes, the resulting crosslinked polyurethane film (C.1) was almost anhydrous.

In a similar configuration, the mold of the present invention coated in this manner was subsequently subjected to a 50 g/m ² wet Disp. ² coating as a bonding layer (B.1), and then allowed to dry.

The product is a mold coated with a plastic film (C.1) and a bonding layer (B.1).

Specifically, Disp. 2 is sprayed onto a dip-coagulated polyester nonwoven (A.1) having a weight per unit area of 180 g/m ² at 30 g/m ² (wet), for which a short term substrate is also used. (A.1). The resulting sprayed substrate (A.1) was dried for several minutes.

IV. Fabricating the multilayer composite structure of the present invention

Then, the sprayed substrate (A.1) is placed on the spray side at the still hot junction layer. (B.1) (the bonding layer (B.1) is placed on the mold together with the plastic film (C.1)), and pressed in a press at 4 bar and 110 ° C for 15 seconds. The resulting multilayer composite MLC.1 of the present invention was then removed from the press and the mold removed.

The resulting multilayer composite material MLC.1 of the present invention is characterized by a comfortable hand, the same appearance as the original figure of the soccer player, and breathability. In addition, the multilayer composite MLC.1 of the present invention can be easily cleaned to remove dirt, such as dust.

MLC.1 presents an image of a football player with high precision.

The operations II. to IV. can be repeatedly performed with the same mold without deteriorating the image.

FIG. 1 is a view of a depression in the mold 1.

Claims (25)

A method of fabricating a multilayer composite structure, comprising: sequentially using a power modulated laser engraving to provide a surface structure in the form of an image or a pattern to a master or a male mold, wherein the surface structure has an element, the element is not Geometric elements, not numbers and not letters, and wherein different areas of the master or male mold are different in the screen angle in the surface structure; the master mold is molded from the male mold as the case may be; On the master mold, wherein the temperature of the master mold is in the range of 50 ° C to 200 ° C; solidifying the plastic formulation to obtain a film; bonding the film to the substrate; and removing the master mold, the restriction condition is any The combination and removal steps are performed in the desired order. The method of claim 1, wherein the laser of the engraving step is an optical laser. The method of claim 1, wherein the master mold is selected from the group consisting of a polyoxymethane mold. The method of claim 1, wherein the male mold is selected from the group consisting of a plastic mold made of polyurethane, polyamide or polyvinyl alcohol. The method of claim 1, wherein the laser power in the engraving step is in the range of 5W to 5,000W. The method of claim 1, wherein the plastic formulation in the spraying step is an aqueous polyurethane dispersion and comprises at least two different polyamine groups The formate, wherein the poly-carbamate has a Shore hardness A of less than 60 and the other polyurethane has a Shore A hardness in the range of from 60 to 100. The method of claim 1, wherein the image or pattern also has at least one other element selected from the group consisting of geometric elements, numbers, and letters. The method of claim 1, wherein the image or pattern does not have a regular repeating unit. The method of claim 1, wherein the pattern or image is produced via protrusions or depressions having a height or depth in the range of 1 μm to 3,000 μm, respectively, wherein the patterns or images are changed via a screen, via a shape change, or Different appearances are produced via changes in height or depth. The method of claim 9, wherein the protrusions or depressions are respectively different in a group having different geometries, different heights, different depths, or different screens. The method of claim 1, wherein the membrane from the coagulation step is porous. A multilayer composite structure comprising a substrate, optionally a bonding layer, and a plastic layer having a small hair-like feature having a surface structure on a visible side thereof, wherein the plastic layer has an image or pattern on its visible side, The image or pattern has elements that are not geometric elements, are not numbers, and are not letters, and within the surface structure, different regions of the surface are stored at a screen angle The difference is that the plastic layer is disposed on the substrate, and the bonding layer (if present) is disposed between the substrate and the plastic layer. The composite structure of claim 12, wherein the substrate is selected from the group consisting of natural leather, fabric, non-woven, paper, wood, and synthetic leather. A composite structure of claim 12, wherein the image or pattern also has geometric elements, numbers or letters. A composite structure of claim 12, wherein the various portions of the image or pattern are produced by varying the three-dimensional structure of the visible side of the plastic layer. A composite structure of claim 12, wherein the image or pattern does not have a regular repeating unit. A composite structure of claim 12, wherein the pattern or image has protrusions or depressions that produce a different appearance via a change in the screen or via a change in height or depth in the range of 1 μm to 3,000 μm. The composite structure of claim 12, wherein the plastic layer comprises at least two different polyurethanes, wherein the polycarbamate has a Shore A hardness of less than 60 and another polyurethane Shore hardness A is in the range of more than 60 to 100. The composite structure of claim 17, wherein the protrusions or depressions are respectively different in a group having different three-dimensional geometric shapes, different heights, different depths, or different screens. The composite structure of claim 12, wherein the plastic layer is porous. A composite structure of claim 12, wherein the image or pattern represents adjacency A combination of two different patterns. A composite structure according to claim 21, wherein the image or pattern is a textured pattern of leather that has been combined with a pattern of woven or knitted fabric. A master mold having an image or pattern of a female mold on one side, wherein the image or pattern has elements that are not geometric elements, are not numbers, and are not letters, and wherein the image or pattern is via Variations in the screen or changes in height or depth result in protrusions or depressions of different appearances, wherein different regions of the master mold differ in screen angle. The master model of claim 23, wherein the protrusions or depressions are respectively different in a group having different geometries, different heights, different depths, or different screens. A use of the master model of claim 23 or 24 for making a composite structure as claimed in any one of claims 12 to 20.