WO2022248558A1

WO2022248558A1 - Multilayered composite material comprising foamed granules

Info

Publication number: WO2022248558A1
Application number: PCT/EP2022/064215
Authority: WO
Inventors: Yoke Khim Raymond Toh; Yun Shen LO; Timm KROEGER
Original assignee: Basf Se; Basf Coatings Gmbh
Priority date: 2021-05-27
Filing date: 2022-05-25
Publication date: 2022-12-01
Also published as: TW202306775A

Abstract

The present invention relates to a multilayered composite material comprising foamed granules and a film, a process for manufacturing a multilayered composite material, the use of a multilayered composite material for shoes, furniture, seating, automotive interior, medical equipment, industrial applications, fashion bags, fashion accessories, gloves, consumer electronics, wearable devices, headphones, speakers, cushioning, toys, animal toys, saddles, balls and sports equipment, for example sports mats, sport gloves, or as floor covering and wall paneling.

Description

Multilayered composite material comprising foamed granules FIELD OF THE INVENTION

BACKGROUND OF THE INVENTION

Composite materials comprising a film layer and a polyurethane layer are known for applications, where acceptable mechanical properties, appearance and feel are a demand, like for wrapping material. Such composite materials are for example described in W02009/106500.

WO 2019/038129 discloses a process for the preparation of multilayered composite materials, and also multilayered composite materials which can be obtained according to this process, to exhibit a better adhesion of the layers.

In WO 2005/047549 a substrate having a velvet-like, fine-grained surface is described, on which a dressing is applied and wherein the dressing is joined to the substrate by a thin connection layer made of a solidified plastic dispersion. The thin connection may have a foam structure.

US2017/0246848 relates to a process for the coating of roll products such as substrates or textile webs, for the production of velvet surfaces or, respectively, velvet-like surfaces in combination with provision of individual design, and also to a production plant suitable for this purpose.

From US 2017/0051121 coated shaped articles are known, which comprise at least one shaped article comprising foamed beads comprising at least one polyurethane and at least one coating comprising at least one polyurethane.

There is a need to further improve composite materials regarding properties like damping, compression set, durability, breathability, comfort, easy to shape, hydrolysis resistance, flexibility, elasticity, and adherence of layers. In addition, some existing composite materials may comprise different materials, which makes recycling and separating the individual materials difficult, because they are joined closely together.

It was therefore an object of the present invention to provide a multi-layered composite material, which overcomes the existing disadvantages and combines the benefits of improved mechanical properties, appearance, better feel, adhesion of the layers, light weight, and breathability.

SUMMARY OF THE INVENTION

The problem is solved by the features of the independent claims. Preferred embodiments of the present invention are provided by the dependent claims.

The invention therefore relates to a multi-layered composite material which comprises components

(A) comprising at least one polymeric layer comprising foamed granules,

(B) optionally comprising at least one polymeric layer comprising an adhesive material, and

(C) comprising at least one polymeric layer comprising a film, wherein component A is a thermoplastic elastomer and wherein component C is the top-layer.

In a preferred embodiment the thermoplastic elastomer of the foamed granules (component A) is selected from the group consisting of thermoplastic polyurethanes (TPU), thermoplastic polyamides (TPA) and thermoplastic polyetheresters (TPC), thermoplastic polyesteresters (TPC), thermoplastic vulcanizates (TPV), thermoplastic polyolefins (TPO), thermoplastic styrenic elastomers (TPS) and mixtures thereof.

In a preferred embodiment the foamed granules of layer A (or layer of component (A)) are fused together.

In a preferred embodiment the layers of component (A) and component (C) are laminated together without a layer of component (B)

In a preferred embodiment the adhesive material (component B) is present and is based on polyurethanes, polyamides, polyesters, polyolefins or acrylic copolymers.

In a preferred embodiment the adhesive material (component B) has a melting range of 60°C to 125°C.

In a preferred embodiment the material of component C is selected from the group consisting of polyurethane, thermoplastic polyurethane, polyvinylchloride, thermoplastic polyolefins.

In a preferred embodiment the layer A has a thickness of 0.1 to 5 mm and wherein the layer C has a thickness of 1 to 500 pm.

In a preferred embodiment layer C comprises a patterned or a non-patterned surface.

A further aspect of the invention relates to a process for the manufacturing of a multi-layered composite material comprising the steps a) providing an optionally structured mold, b) heating the mold to a temperature at a temperature above 80°C, c) forming a polymeric film layer (C) as top-layer by using the mold of a), d) providing a polymeric foam layer (A) comprising foamed granules of a thermoplastic elastomer, e) optionally slicing the polymeric foam layer (A) from step d), f) optionally applying an adhesive material (component (B)) to the polymeric film layer (C) of step c) and/or to the polymeric foam layer (A) of step d), g) combining the polymeric film layer (C) and polymeric foam layer (A) under a pressure in the range of 1 to 8 bar, preferably 2 to 6 bar, in particular 4 bar.

In a preferred embodiment the mold is a silicone mold structured using laser engraving.

In a preferred embodiment wells are incorporated in the mold, which wells exhibit an average depth in the range from 50 to 250 pm and a center-to-center separation in the range from 50 to 250 pm.

A further aspect of the invention relates to a multi-layered composite material obtained or obtainable by a process according to the present invention.

A further aspect of the invention relates to a use of a multi-layered composite material according to the present invention for shoes, in furniture, seating, automotive interior, medical equipment, industrial applications, fashion bags, fashion accessories, gloves, consumer electronics, wearable devices, headphones, speakers, packaging, protection equipment, as cushioning, toys, animal toys, saddles, balls and sports equipment, for example sports mats, sport gloves, or as floor covering and wall paneling.

A further aspect of the invention relates to an article comprising the multi-layered composite material according to the present invention for shoes, furniture, seating, automotive interior, medical equipment, industrial applications, fashion bags, fashion accessories, gloves, consumer electronics, wearable devices, headphones, speakers, cushioning, toys, animal toys, saddles, balls and sports equipment, for example sports mats, sport gloves, or as floor covering and wall paneling.

DETAILED DESCRIPTION OF THE INVENTION

With regards to the invention, the following can be stated specifically:

According to the present invention, the object is solved by a multi-layered composite material which comprises components

(A) comprising at least one polymeric layer comprising foamed granules,

(B) optionally comprising at least one polymeric layer comprising an adhesive material, and (C) comprising at least one polymeric layer comprising a film, wherein component A is a thermoplastic elastomer and wherein component C is the top-layer.

Surprisingly, it was found that the multi-layered composite materials according to the invention exhibit various advantages. They have agreeable visual and haptical properties and show surprisingly good mechanical properties, such as rubbing fastnesses or buckling strengths. In addition, they exhibit good functional properties and can be satisfactorily cleaned, for example by mechanical cleaning or chemical cleaning, for example using supercritical carbon dioxide or organic solvents, such as hydrocarbons or halogenated hydrocarbons. In particular, they exhibit superior storage and aging properties, in particular hot light aging properties, and hydrolysis properties. In addition, composite materials which have been prepared according to the process according to the invention exhibit a very constant quality, since the aqueous polymer dispersions used have a long shelf life. Additionally, it has been shown that composite materials which have been prepared according to the process according to the invention were, after the preparation, immediately adhesive-free and could, after the preparation, be stacked, wound up or otherwise stored with optional post-curing for up to 48 hours. Unexpected was also that the multi-layered composite materials according to the invention shows improved properties regarding damping, compression set, durability, breathability, comfort, easy to shape, hydrolysis resistance, flexibility, elasticity, adherence of layers and were still light-weight. The multi-layered composite materials according to the invention show also benefits regarding recycling, because a separation of the individual layers before recycling and further processing is not necessary for the multi-layered composite materials of the invention.

In particular, advantages of the multi-layered composite materials are:

Breathability: the top layer of component (C) (polymeric film layer) and the thermoplastic elastomer layer of component (A) (also named substrate layer, base layer, polymeric foam layer) are air permeable. Breathability is in particular enabled due to expanded thermoplastic elastomer beads, which are fused together to form the layer (A) and optionally cut / sliced, allowing a gas and humidity transition.

Recycling: enabled due to for example expanded thermoplastic polyurethane (E-TPU) as foam layer (component A) with polyurethane (PU) and/or thermoplastic polyurethane (TPU) as skin / top-layer / top coat (polymeric film layer of component C). With that only one class of polymers e.g. polyurethanes can be used for the multi-layered composite material. The invention provides a sustainable and recyclable synthetic leather consisting of TPU (100%) or consisting to 100 % of the combination PU and TPU.

Light weight: The inventive material shows low density properties, in particular in a material combination of E-TPU particle foam layer (component A) with a thin film of polyurethane (PU) and/or thermoplastic polyurethane (TPU) as skin / top-layer / top coat (polymeric film layer of component C).

Coloration: coloration of E-TPU slices is possible, either by coloration of E-TPU beads (component A) or due to coating with a colored component C. Coating with component C enables hiding of E-TPU typical surface. Alternatively, a translucent coating with component C keeps bead structure of component A slightly visible through coating surface.

Coloration in combination with surface texturing: Texture creation coming from process to prepare layer (C) combined with its haptic influence (e.g. soft touch surface) and coloration. Surface functionalization: via pigmentation e.g. coloration, effects (metallic, pearls) and function providing additives (e.g. cooling pigments, color changing pigments due to temperatures, other indicators) coming from process to prepare layer (C).

Protection of the E-TPU material via coatings application deriving from layer (C).

In comparison to the state of the art (conventionally coated E-TPU), due to the present invention slices for component A are available, which show homogenously cut surface of E- TPU product which enables a coating and combination with layer C, deriving from the process to prepare layer (C).The component A shows enough breathability, in particular, if E-TPU slices are used. The layer A can be provided in different thicknesses to customize the layer A for different application, for adjusting the weight and for adjusting the slice of component A in order to enable coating with different methods. The number of voids on the sheet surfaces of layer A can be avoided by using roller / rotary press equipment. Furthermore, in comparison to the state of the art (conventionally synthetic leather) the process to prepare layer (C) and to enable a combination with layer (A) maintains breathability / air permeability of the carrier material of layer (A). In case of a E-TPU particle foam as layer (A) very low densities and low weight of the multi-layered composite material can be created and with that the beneficial properties of layer (A) maintain after a combination with layer (C).

- The process to prepare layer (C) preferably is a spray-process application, which allows fine design structures on E-TPU slices surface (particle foam layer of component A).

Further performance advantages are good damping, low compression set, durable, comfort, easy to shape, hydrolysis resistance.

Preferred process options can be summarized as follows:

Processes to manufacture E-TPU sheets (layer of component A) are for example continuous processes (rotary process), which are known from WO 2015/0124587. Component A preferably has a thickness in the range of 1 mm to 5 mm, in particular 1 mm, 2 mm, 3 mm, 4 mm, or 5 mm.

Processes to manufacture component C (Topcoat layer) are known by a person skilled in the art from e.g. W02005047569A1 , wherein component C is selected from the group consisting of a polymer dispersions, polymer dispersion components with high softening point, polymer dispersion components with low softening point.

The component (C) and/or the optional layer (B) is for example a coating material, which is manufactured for direct (without pre-drying (“wet-in-wet”)) lamination with the component (A). Alternatively, the component (C) and/or the optional layer (B) is pre-dried before lamination with the component (A). Additionally, solvent processes or hot melt processes are considerable for lamination purpose. The thickness of component (A) and/or (B) is for example in the range of 0,3 mm to 0,7 mm.

For example, component (C) is a polyurethane (PU) skin, which preferably is applied in a solvent process on E-TPU (component A). The polyurethane skin for example has a thickness in the range of 0.3 mm to 0.7 mm. Alternatively, component (C) is a thermoplastic polyurethane (TPU) skin, which is preferably applied by a hotmelt process on E-TPU (component A). The thermoplastic polyurethane skin for example has a thickness in the range of 0.05 to 0.08 mm. Combinations of PU and TPU are possible as component (C). It is also possible that several layers of component C are applied onto component A.

Coating options (to provide a coat onto component A) comprise in particular - water based polyurethane (PU) coatings formulations solvent based polyurethane (PU), thermoplastic polyurethane, polyvinylchloride coatings formulations coating via reverse coatings process o Spraying of PU1 coating in a structured mold, o Spraying of PU2 coating onto the mold and onto the E-TPU slice or alternatively, spraying PU2 coating onto mold side or onto the E-TPU slice side only, o Pre-drying or not pre-drying of mold and/or E-TPU slice sides, o Laminating of mold side and E-TPU slice in a hot press (applying elevated temperature and pressure), o Delamination of combined build-up from the mold.

Another preferred lamination processing (combining component A and C) comprises in particular

1. Provision of layer C by producing the layer C (for example a TPU film),

2. Provision of E-TPU slice / sheet as layer A (substrate, base material),

3. Provision of a binder (adhesive, glue) to enable sufficient bonding between layer C and layer A, wherein the binder could be for example a liquid adhesive or PUR,

4. Provision of a lamination machine in roller design, which is typically used for synthetic leather manufacturing processes,

5. In step 1, layer A is placed in the lamination machine,

6. In step 2, an adhesive is put on the top of the layer A,

7. In step 3, layer C is laminated with the lamination machine onto the layer A.

Further preferred process options are Heat - Press Method

To obtain the composite material a compression step at the following conditions can be applied:

- Temperature range: 100 - 140 °C,

Pressure for example 0.5 - 10 bar,

- Time: 3 to 5 minutes. Method with pre-drying

Cut slices are integrated in the process,

Glue layer is spray applied to component A and C (two layers), not mandatory,

- A coated E-TPU sample is obtained by a production process with pre-drying of PU2 on E-TPU slice,

PU2 is applied with pre-drying of PU2 on the mold side (mold coating before lamination).

Method without pre-drying (wet-in-wet)

Benefit: less energy consumption,

No drying of the glue,

- A coated E-TPU sample is obtained by a production process without pre-drying of PU2 on E-TPU slice,

PU2 is applied without pre-drying of PU2 on mold side (mold coating before lamination). Solvent Method

Materials: PU layer on the top, and hotmelt layer on the bottom.

Method of Lamination: Heat press lamination. Temp :130°C, Time: 25s ~ 35s.

Hotmelt (HM) Method

Materials: Poly ether or poly ester based thermoplastic polyurethane (TPU) layer / skin and E-TPU sheet / carrier.

Method of Lamination: Coating the TPU layer on the E-TPU sheet with PUR as the binder to laminate TPU and E-TPU sheet.

Preferred options for the optional layer B are adhesives (known by a person skilled in the art from W02005047569A1 ) comprising cross-linked polymer dispersions, polyester-polyurethane dispersions, partially crystalline or semi-crystalline or amorphous components, soft resin and polymer components, especially acrylate based, and the adhesives are applied for example as hotmelt film (known by a person skilled in the art from WO 2019/038129) as liquid, for example in a spraying process, as a heat activatable glue.

A further preferred adhesive provision and lamination is for example conducted by an adhesive grid, adhesive web or adhesive film, which is cut out to the size of the component A and put on the component A by hand. Afterwards, the polyurethane layer (component C) is stripped from the mold and combined with the film on which the adhesive lies, so that the adhesive is between polyurethane layer and component A. For component A and/or C several color and effect options are possible, for example via addition of pigments, dyes, flakes, colored substances and effects additives. Preferred color coating options for component C comprise pigment pastes of pigment row Luconyl NG to colour PU1 and PU2 layers and to achieve the colour appearance of for example Translucent blue, Blue, Black. Polyurethane (PU) waterborne dispersion-based formulations in appropriate coloration.

For component C several design options are considerable which are known for a person skilled in the art. Preferred design options are for example based on laser engraving techniques resulting in technical/artificial and/or natural structures on the surface of the multi-layered composite material, which may be for example an artificial leather (showing leather type surface structures), a mold containing the negative design structure that is achieved on the surface of the final product (multi-layered composite material),

- different designs, which have different names and which are known by a person skilled in the art for example under the trade name “valure” (e.g. Basket, Carbon, Deep Velvet, Brescia Multimold, Domino) and publicly available at https://textile-leather- footwear.basf.com/global/en/functional_coatings_haptic/Virtually_unlimited_design_flexib ility_with_valure.html.

Component (A)

Multi-layered composite material according to the invention generally use a flat substrate as layer (A). Flat substrates are in the context of the present invention those whose expansion in two dimensions is much greater than in the third dimension; for example, width and length of flat substrate, in particular layer (A), can each exceed the thickness by at least a factor of 100 and preferably by at least a factor of 1000. In one embodiment, length and/or width of layer (A) exceed the thickness by a factor of up to 1 000 000. Length and width of layer (A) can in each case be identical or, preferably, different. For example, the length of layer (A) can exceed the width by a factor of 1.1 up to 100.

In one embodiment of the present invention, the length of layer (A) lies in the range from 50 cm to 100 m, preferably up to 50 m, particularly preferably up to 10 m. In one embodiment of the present invention, the width of layer (A) lies in the range from 10 cm to 5 m, preferably up to 2 m.

In one embodiment of the present invention, the thickness of layer (A) lies in the range of from 0.01 mm to 20 mm, preferably from 0.05 mm to 10 mm and in particular from 0.1 mm to 5 mm. Further preferred for layer (A) are ranges from 0.3 mm to 5 mm, preferably from 0.5 mm to 4 mm, more preferably from 0.7 mm to 3 mm and most preferably from 1 mm to 2 mm. The layer (A) can comprise additives. Suitable additives can, for example, be chosen from plasticizers, impact modifiers, stabilizers, colorants, fillers, reinforcing materials, flame retardants, light stabilizers and waxes. For example, polystyrene is a suitable additive.

Thermoplastic elastomers are suitable as polymeric layer comprising foamed granules (component A). The term thermoplastic polymers comprises thermoplastic elastomers in the context of the present invention, in particular the polymeric layer comprising foamed granules, and includes amorphous or semi-crystalline rigid or elastomeric thermoplastics, such as styrene polymers (PS), polyester (PE), polyolefins (PO), polyamides (PA) or thermoplastic polyurethanes (TPU). Preferably polypropylene (PP), polyamide (PA), polyether block amide (PEBA), styrene polymers, polylactic acid (PLA) and biodegradable, aliphatic-aromatic polyesters or mixtures thereof, polyvinyl alcohol (PVOH) or thermoplastic elastomer (TPE) granulates, such as thermoplastic polyurethanes (TPU) or thermoplastic polyester (TPEE) or mixtures of the above-mentioned polymers are used as thermoplastic polymers. Most preferably thermoplastic polyurethanes are used as thermoplastic polymers, in particular thermoplastic elastomers.

Suitable thermoplastic elastomers for producing the particle foam layer, in particular the polymeric layer comprising foamed granules according to the invention, are known per se to the person skilled in the art.

Preferably, the thermoplastic elastomer, in particular directed to the polymeric layer comprising foamed granules, can be thermoplastic polyurethanes (TPU), thermoplastic polyamides, for example polyether copolyamides (TPA), thermoplastic elastomer based on olefin, for example polypropylene or polyethylene (TPO), thermoplastic polyesterelastomers, for example polyetheresters or polyesteresters (TPC), thermoplastic vulcanizate (TPV), thermoplastic styrenic elastomers, for example thermoplastic styrene butadiene block copolymer (TPS), or mixtures thereof.

Preferably, the thermoplastic elastomer has a soft phase with a glass transition temperature Tg in the range of from <10 °C determined by dynamic mechanical thermal analysis determined by loss factor (tan d) according to DIN EN ISO 6721-1-2011-08 at a heating rate of 2 K/min at a frequency of 1 Hz in torsion mode. Deviant from the DIN norm, the temperature was adjusted step wise by 5 K and 35 s per step which corresponds to a continuous heating rate of 2 K/min. The measurements were conducted with a sample with a ratio of width : thickness of 1:6. The sample was prepared by injection molding followed by annealing of the material at 100 °C for 20 h.

Therefore, according to a further embodiment, the present invention is also directed to the process as disclosed below, wherein the thermoplastic elastomer has a soft phase with a glass transition temperature Tg in the range of from < 10 °C more preferable below -10°C, particularly preferred below -30°C determined by dynamic mechanical thermal analysis determined by loss factor (tan d) according to DIN EN ISO 6721-1-2011-08 at a heating rate of 2 K/min at a frequency of 1 Hz in torsion mode. Deviant from the DIN norm, the temperature was adjusted step wise by 5 K and 35 s per step which corresponds to a continuous heating rate of 2 K/min. The measurements were conducted with a sample with a ratio of width : thickness of 1:6. The sample was prepared by injection molding followed by annealing of the material at 100 °C for 20 h.

According to a further embodiment, the present invention is directed to the multi-layered composite material comprising at least one polymeric layer comprising foamed granules as disclosed above, wherein the thermoplastic elastomer has a soft phase with a glass transition temperature Tg in the range of from < 10 °C determined by dynamic mechanical thermal analysis determined by loss factor (tan d) according to DIN EN ISO 6721-1-2011-08 at a heating rate of 2 K/min at a frequency of 1 Hz in torsion mode. Deviant from the DIN norm, the temperature was adjusted step wise by 5 K and 35 s per step which corresponds to a continuous heating rate of 2 K/min. The measurements were conducted with a sample with a ratio of width: thickness of 1:6. The sample was prepared by injection molding followed by annealing of the material at 100 °C for 20 h.

For thermoplastic polyether ester and polyester ester preparation suitable aromatic dicarboxylic acids include e.g. phthalic acid, iso- and terephthalic acid or their esters. Suitable aliphatic dicarboxylic acids include e.g. cyclohexane-1 ,4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids as well as maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated dicarboxylic acids. Suitable diol components are, for example, diols of the general formula HO- (CH2) n-OH, with n = 2 to 20, such as ethylene glycol, propanediol (1,3), butanediol (1,4) or hexanediol (1,6). Polyetherols of the general formula HO- (CH2)n-0- (CH2)m-OH, where n is equal to or different from m and n or m = 2 to 20, unsaturated diols and polyetherols such as butenediol-(1,4); diols and polyetherols containing aromatic units; as well as polyesterols. In addition to the carboxylic acids or their esters mentioned, and the alcohols mentioned, all other common representatives of these classes of compounds can be used to provide the polyether esters and polyester esters used according to the invention for the multi layered composite material comprising at least one polymeric layer comprising foamed granules.

The thermoplastic polyetheramides can be obtained by the reaction of amines and carboxylic acids or their esters by all of the methods known from the literature. Amines and or carboxylic acid also contain ether units of the type R-O-R, where R = organic radical (aliphatic and / or aromatic). In general, monomers of the following classes of compounds are used: HOOC-R'- NH2, where R' can be aromatic and aliphatic, preferably containing ether units of the type R- OR, where R = organic radical (aliphatic and / or aromatic); aromatic dicarboxylic acids, e.g. phthalic acid, isophthalic acid and terephthalic acid or their esters and aromatic dicarboxylic acids containing ether units of the type R-O-R, where R = organic radical (aliphatic and / or aromatic); aliphatic dicarboxylic acids, e.g. cyclohexane-1 ,4-dicarboxylic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid as saturated dicarboxylic acids as well as maleic acid, fumaric acid, aconitic acid, itaconic acid, tetrahydrophthalic acid and tetrahydroterephthalic acid as unsaturated as well as aliphatic dicarboxylic acids R = containing organic units, R being ether units, ether units can be aliphatic and / or aromatic); diamines of the general formula H2N-R " - NH2, where R " is aromatic and aliphatic, preferably containing ether units of the type R-O-R, where R = organic radical (aliphatic and / or aromatic); lactams such as e-caprolactam, pyrrolidone or laurolactam; as well as amino acids.

In addition to the carboxylic acids or their esters mentioned, and the amines, lactams and amino acids mentioned, all other common representatives of these classes of compounds can be used to provide the polyetheramine used according to the invention.

The thermoplastic elastomers with block copolymer structure used according to the invention preferably contain vinylaromatic, butadiene and isoprene as well as polyolefin and vinyl units, for example ethylene, propylene and vinyl acetate units. Styrene-butadiene copolymers are preferred.

The thermoplastic elastomers with block copolymer structure, polyether amides, polyether esters and polyester esters used according to the invention are preferably selected such that their melting points are <300 °C, preferably <250 °C, in particular <220 °C.

The thermoplastic elastomers with block copolymer structure, polyether amides, polyether esters and polyester esters used according to the invention can be partially crystalline or amorphous.

Suitable olefin-based thermoplastic elastomers (TPO) in particular have a hard segment and a soft segment, the hard segment being, for example, a polyolefin such as polypropylene and polyethylene and the soft segment being a rubber component such as ethylene-propylene rubber. Blends of a polyolefin and a rubber component, dynamically cross-linked types and polymerized types are suitable.

For example, structures are suitable in which an ethylene-propylene rubber (EPM) is dispersed in polypropylene; structures in which a cross-linked or partially cross-linked ethylene- propylenediene rubber (EPDM) is dispersed in polypropylene; statistical copolymers of ethylene and an a-olefin, such as propylene and butene; or block copolymers of a polyethylene block and an ethylene / a-olefin copolymer block. Suitable a-olefins are, for example, propylene, 1 -butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-n decene, 3-methyl-1 -butene and 4- methyl-1-pentene or mixtures of these olefins.

Suitable semicrystalline polyolefins are, for example, homopolymers of ethylene or propylene or copolymers containing monomeric ethylene and / or propylene units. Examples are copolymers of ethylene and propylene or an alpha olefin with 4-12 C atoms and copolymers of propylene and an alpha olefin with 4-12 C atoms. The concentration of ethylene or the propylene in the copolymers is preferably so high that the copolymer is semicrystalline. In the case of statistical copolymers, for example, an ethylene content or a propylene content of about 70 mol% or more are suitable.

Suitable polypropylenes are propylene homopolymers or also polypropylene block copolymers, for example statistical copolymers of propylene and up to about 6 mol% of ethylene.

Suitable thermoplastic styrene block copolymers usually have polystyrene blocks and elastomeric blocks. Suitable styrene blocks are selected, for example, from polystyrene, substituted polystyrenes, poly (alpha-methylstyrenes), ring-halogenated styrenes and ring- alkylated styrenes. Suitable elastomeric blocks are, for example, polydiene blocks such as polybutadienes and polyisoprenes, poly (ethylene / butylene) copolymers and poly (ethylene / propylene) copolymers, polyisobutylenes, or also polypropylene sulfides or polydiethylsiloxanes.

Further suitable thermoplastic elastomers are thermoplastic polyurethanes (TPU) Also thermoplastic polyurethanes are well known. They are produced by reaction of isocyanates with isocyanate-reactive compounds for example polyols with number-average molar mass from 500 g/mol to 10000 g/mol and optionally chain extenders with molar mass from 50 g/mol to 499 g/mol, optionally in the presence of catalysts and/or conventional auxiliaries and/or additional substances. For the purposes of the present invention, preference is given to thermoplastic polyurethanes obtainable via reaction of isocyanates with isocyanate-reactive compounds for example polyols with number-average molar mass from 500 g/mol to 10000 g/mol and a chain extender with molar mass from 50 g/mol to 499 g/mol, optionally in the presence of catalysts and/or conventional auxiliaries and/or additional substances.

The isocyanate, isocyanate-reactive compounds for example polyols and, if used, chain extenders are also, individually or together, termed structural components. The structural components together with the catalyst and/or the customary auxiliaries and/or additional substances are also termed starting materials.

The molar ratios of the quantities used of the polyol component can be varied in order to adjust hardness and melt index of the thermoplastic polyurethanes, where hardness and melt viscosity increase with increasing content of chain extender in the polyol component at constant molecular weight of the TPU, whereas melt index decreases.

For production of the thermoplastic polyurethanes, isocyanates and polyol component, where the polyol component in a preferred embodiment also comprises chain extenders, are reacted in the presence of a catalyst and optionally auxiliaries and/or additional substances in amounts such that the equivalence ratio of NCO groups of the diisocyanates to the entirety of the hydroxyl groups of the polyol component is in the range from 1:0.8 to 1:1.3.

Another variable that describes this ratio is the index. The index is defined via the ratio of all of the isocyanate groups used during the reaction to the isocyanate-reactive groups, i.e. in particular the reactive groups of the polyol component and the chain extender. If the index is 1000, there is one active hydrogen atom for each isocyanate group. At indices above 1000, there are more isocyanate groups than isocyanate-reactive groups.

An equivalence ratio of 1:0.8 here corresponds to an index of 1250 (index 1000 = 1:1), and a ratio of 1 :1.3 corresponds to an index of 770.

In a preferred embodiment, the index in the reaction of the abovementioned components is in the range from 965 to 1110, preferably in the range from 970 to 1110, particularly preferably in the range from 980 to 1030, and also very particularly preferably in the range from 985 to 1010.

Preference is given in the invention to the production of thermoplastic polyurethanes where the weight-average molar mass (Mw) of the thermoplastic polyurethane is at least 60 000 g/mol, preferably at least 80000 g/mol and in particular greater than 100000 g/mol. The upper limit of the weight-average molar mass of the thermoplastic polyurethanes is very generally determined by processibility, and also by the desired property profile. The number-average molar mass of the thermoplastic polyurethanes is preferably from 80000 to 300000 g/mol. The average molar masses stated above for the thermoplastic polyurethane, and also for the isocyanates and polyols used, are the weight averages determined by means of gel permeation chromatography (e.g. in accordance with DIN 55672-1, March 2016).

Organic isocyanates that can be used are aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates.

Aliphatic diisocyanates used are customary aliphatic and/or cycloaliphatic diisocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2- methylpentamethylene 1 ,5-diisocyanate, 2-ethyltetramethylene 1 ,4-diisocyanate, hexamethylene 1 ,6-diisocyanate (HDI), pentamethylene 1 ,5-diisocyanate, butylene 1 ,4- diisocyanate, trimethylhexamethylene 1,6-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and/or 1,3- bis(isocyanatomethyl)cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methylcyclohexane

2.4- and/or 2,6-diisocyanate, methylenedicyclohexyl 4,4'-, 2,4'- and/or 2,2'-diisocyanate (H12MDI)

Suitable aromatic diisocyanates are in particular naphthylene 1,5-diisocyanate (NDI), tolylene

2.4- and/or 2,6-diisocyanate (TDI), 3,3’-dimethyl-4,4‘-diisocyanatobiphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethane 4,4‘-diisoyanate (EDI), methylenediphenyl diisocyanate (MDI), where the term MDI means diphenylmethane 2,2’, 2,4’- and/or 4, 4’-diisocyanate, 3,3’- dimethyldiphenyl diisocyanate, 1 ,2-diphenylethane diisocyanate and/or phenylene diisocyanate.

Mixtures can in principle also be used. Examples of mixtures are mixtures comprising at least a further methylenediphenyl diisocyanate alongside methylenediphenyl 4,4’-diisocyanate. The term “methylenediphenyl diisocyanate” here means diphenylmethane 2,2’-, 2,4’- and/or 4,4’- diisocyanate or a mixture of two or three isomers. It is therefore possible to use by way of example the following as further isocyanate: diphenylmethane 2,2’- or 2,4’-diisocyanate or a mixture of two or three isomers. In this embodiment, the polyisocyanate composition can also comprise other abovementioned polyisocyanates.

Other examples of mixtures are polyisocyanate compositions comprising 4,4‘-MDI and 2,4‘- MDI, or4,4‘-MDI and 3,3‘-dimethyl-4,4‘-diisocyanatobiphenyl (TODI) or4,4‘-MDI and H12MDI (4,4'-methylene dicyclohexyl diisocyanate) or4,4‘-MDI and TDI; or4,4‘-MDI and 1,5- naphthylene diisocyanate (NDI).

In accordance with the invention, three or more isocyanates may also be used. The polyisocyanate composition commonly comprises 4,4’-MDI in an amount of from 2 to 50%, based on the entire polyisocyanate composition, and the further isocyanate in an amount of from 3 to 20%, based on the entire polyisocyanate composition.

The polyisocyanate composition may also comprise one or more solvents. Suitable solvents are known to those skilled in the art. Suitable examples are nonreactive solvents such as ethyl acetate, methyl ethyl ketone and hydrocarbons.

As isocyanate-reactive compound it is possible to use a compound which preferably has a reactive group selected from the hydroxyl group, the amino groups, the mercapto group and the carboxylic acid group. Preference is given here to the hydroxyl group and very particular preference is given here to primary hydroxyl groups. It is particularly preferable that the isocyanate-reactive compound is selected from the group of polyesterols, polyetherols and polycarbonatediols, these also being covered by the term “polyols”.

The statistical average number of hydrogen atoms exhibiting Zerewitinoff activity in the isocyanate-reactive compound is at least 1.8 and at most 2.2, preferably 2; this number is also termed the functionality of the isocyanate-reactive compound, and states the quantity of isocyanate-reactive groups in the molecule, calculated theoretically for a single molecule, based on a molar quantity. The isocyanate-reactive compound preferably is substantially linear and is one isocyanate-reactive substance or a mixture of various substances, where the mixture then meets the stated requirement.

Suitable polyols in the invention are homopolymers, for example polyetherols, polyesterols, polycarbonatediols, polycarbonates, polysiloxanediols, polybutadienediols, and also block copolymers, and also hybrid polyols, e.g. poly(ester/amide). Preferred polyetherols in the invention are polyethylene glycols, polypropylene glycols, polytetramethylene glycol (PTHF), polytrimethylene glycol. Preferred polyester polyols are polyadipates, polysuccinic esters and polycaprolactones. In another embodiment, the present invention also provides a thermoplastic polyurethane as described above where the polyol composition comprises a polyol selected from the group consisting of polyetherols, polyesterols, polycaprolactones and polycarbonates.

Examples of suitable block copolymers are those having ether and ester blocks, for example polycaprolactone having polyethylene oxide or polypropylene oxide end blocks, and also polyethers having polycaprolactone end blocks. Preferred polyetherols in the invention are polyethylene glycols, polypropylene glycols, polycaprolactone and polytrimethylene glycol. Preference is further given to polytetramethylene glycol (PTHF).

In a particularly preferred embodiment, the molar mass Mn of the polyol used is in the range from 500 g/mol to 10000 g/mol, preferably in the range from 500 g/mol to 5000 g/mol, in particular from 500 g/mol to 3000 g/mol.

Another embodiment of the present invention accordingly provides a thermoplastic polyurethane as described above where the molar mass Mn of at least one polyol comprised in the polyol composition is in the range from 500 g/mol to 10000 g/mol.

It is also possible in the invention to use mixtures of various polyols.

An embodiment of the present invention uses, for the production of the thermoplastic polyurethane, at least one polyol composition comprising at least polytetrahydrofuran. The polyol composition in the invention can also comprise other polyols alongside polytetrahydrofuran.

Materials suitable by way of example as other polyols in the invention are polyethers, and also polyesters, block copolymers, and also hybrid polyols, e.g poly(ester/amide). Examples of suitable block copolymers are those having ether and ester blocks, for example polycaprolactone having polyethylene oxide or polypropylene oxide end blocks, and also polyethers having polycaprolactone end blocks. Preferred polyetherols in the invention are polyethylene glycols and polypropylene glycols. Preference is further given to polycaprolactone as other polyol.

Examples of suitable polyols are polyetherols such as polytrimethylene oxide and polytetramethylene oxide.

Another embodiment of the present invention accordingly provides a thermoplastic polyurethane as described above where the polyol composition comprises at least one polytetrahydrofuran and at least one other polyol selected from the group consisting of another polytetramethylene oxide (PTHF), polyethylene glycol, polypropylene glycol and polycaprolactone.

In a particularly preferred embodiment, the number-average molar mass Mn of the polytetrahydrofuran is in the range from 500 g/mol to 5000 g/mol, more preferably in the range from 550 to 2500 g/mol, particularly preferably in the range from 650 to 2000 g/mol and very preferably in the range from 650 to 1400 g/mol.

The composition of the polyol composition can vary widely for the purposes of the present invention. By way of example, the content of the first polyol, preferably of polytetrahydrofuran, can be in the range from 15% to 85%, preferably in the range from 20% to 80%, more preferably in the range from 25% to 75%.

The polyol composition in the invention can also comprise a solvent. Suitable solvents are known per se to the person skilled in the art.

Insofar as polytetrahydrofuran is used, the number-average molar mass Mn of the polytetrahydrofuran is by way of example in the range from 500 g/mol to 5000 g/mol, preferably in the range from 550 to 2500 g/mol, particular preferably in the range from 650 to 2000 g/mol. It is further preferable that the number-average nnolar mass Mn of the polytetrahydrofuran is in the range from 650 to 1400 g/mol.

The number-average molar mass Mn here can be determined as mentioned above by way of gel permeation chromatography.

Another embodiment of the present invention also provides a thermoplastic polyurethane as described above where the polyol composition comprises a polyol selected from the group consisting of polytetrahydrofurans with number-average molar mass Mn in the range from 500 g/mol to 5000 g/mol preferably in the range from 550 to 2500 g/mol, particular preferably in the range from 650 to 2000 g/mol. It is further preferable that the number-average molar mass Mn of the polytetrahydrofuran is in the range from 650 to 1400 g/mol.

It is also possible in the invention to use mixtures of various polytetrahydrofurans, i.e. mixtures of polytetrahydrofurans with various molar masses.

Preferably the polyol composition comprises at least one aliphatic polyol, preferably polytetramethylene glycol (polytetrahydrofuran, PTHF).

The number average molecular mass Mn of the polyol composition for example is in the range of from 650 g/mol to 5000 g/mol, preferably in the range of from 2000 g/mol to 3500 g/mol, most preferably in the range of from 2000 g/mol to 3000 g/mol.

Preferably the polyol composition is comprising PTHF and PTHF has a number average molecular mass Mn in the range of from equal or below 1500 g/mol.

Preferably the polyol composition is consisting of PTHF and PTHF has a number average molecular mass Mn in the range of from 1000 g/mol to 1500 g/mol. Preferably the polyol composition is comprising a block copolymer with at least one block of PTHF and preferably the number average molecular mass Mn of the block copolymer is in the range of from 2000 g/mol to 3500 g/mol.

According to a further aspect, the present invention is directed to a preparation for a multi layered composite material comprising at least one polymeric layer comprising foamed granules, wherein the thermoplastic elastomer is a thermoplastic polyisocyanate reaction product obtained or obtainable by reacting the components

(A) a polyisocyanate composition

(B) at least one chain extender

(C) a polyol composition

(D) optionally water

(E) optionally a cross-linker

(F) optionally a plasticizer

(G) optionally additional additives, wherein the preparation contains a polyol composition having a glass transition temperature Tg in the range of from equal or below -50 °C, determined by dynamic mechanical thermal analysis determined by loss factor (tan d) according to DIN EN ISO 6721-2011-08 at a heating rate of 2 K/min at a frequency of 1 Hz.

Chain extenders used are preferably aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds with a molar mass from 50 g/mol to 499 g/mol, preferably having 2 isocyanate- reactive groups, also termed functional groups. Preferred chain extenders are diamines and/or alkanediols, more preferably alkanediols having from 2 to 10 carbon atoms, preferably having from 3 to 8 carbon atoms in the alkylene moiety, these more preferably having exclusively primary hydroxy groups.

Preferred embodiments use chain extenders, these being preferably aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds with molar mass from 50 g/mol to 499 g/mol, preferably having 2 isocyanate-reactive groups, also termed functional groups. It is preferable that the chain extender is at least one chain extender selected from the group consisting of ethylene 1,2-glycol, propane-1 ,2-diol, propane-1 ,3-diol, butane-1 ,4-diol, butane-2, 3-diol, pentane-1 ,5-diol, hexane-1 ,6-diol, diethylene glycol, dipropylene glycol, cyclohexane-1 ,4-diol, cyclohexane-1 ,4-dimethanol, neopentyl glycol and hydroquinone bis(beta-hydroxyethyl) ether (HQEE). Particularly suitable chain extenders are those selected from the group consisting of 1,2-ethanediol, propane-1 ,3-diol, butane-1 ,4-diol and hexane-1 ,6-diol, and also mixtures of the abovementioned chain extenders. Examples of specific chain extenders and mixtures are disclosed inter alia in PCT/EP2017/079049.

The ratio of polyols and chain extender used is varied in a manner that gives the desired hard- segment content, which can be calculated by the formula disclosed in PCT/EP2017/079049. A suitable hard segment content here is below 60%, preferably below 40%, particularly preferably 25%. Crosslinkers can be used as well, moreover, examples being the aforesaid higher-functionality polyisocyanates or polyols or else other higher-functionality molecules having a plurality of isocyanate-reactive functional groups. It is also possible within the context of the present invention for the products to be crosslinked by an excess of the isocyanate groups used, in relation to the hydroxyl groups. Examples of higher-functionality isocyanates are triisocyanates, e.g. triphenylmethane 4,4',4"-triisocyanate, and also isocyan urates, and also the cyanurates of the aforementioned diisocyanates, and the oligomers obtainable by partial reaction of diisocyanates with water, for example the biurets of the aforementioned diisocyanates, and also oligomers obtainable by controlled reaction of semiblocked diisocyanates with polyols having an average of more than two and preferably three or more hydroxyl groups.

The amount of crosslinkers here, i.e. of higher-functionality isocyanates and higher-functionality polyols, ought not to exceed 3% by weight, preferably 1% by weight, based on the overall mixture of components.

Preferably the cross-linker selected from the group consisting of higher-functionality polyisocyanates and higher-functionality polyols increase the stability of the component A. Further preferred is that additional additives selected from the group consisting of filler, lubricants, stabilizer, catalysts, flame retardants or plasticizers are added for adjusting stiffness.

In preferred embodiments, catalysts are used with the structural components. These are in particular catalysts which accelerate the reaction between the NCO groups of the isocyanates and the hydroxyl groups of the isocyanate-reactive compound and, if used, the chain extender.

Examples of catalysts that are further suitable are organometallic compounds selected from the group consisting of organyl compounds of tin, of titanium, of zirconium, of hafnium, of bismuth, of zinc, of aluminum and of iron, examples being organyl compounds of tin, preferably dialkyltin compounds such as dimethyltin or diethyltin, or tin-organyl compounds of aliphatic carboxylic acids, preferably tin diacetate, tin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, bismuth compounds, for example alkylbismuth compounds or the like, or iron compounds, preferably iron(lll) acetylacetonate, or the metal salts of carboxylic acids, e.g. tin(ll) isooctanoate, tin dioctanoate, titanic esters or bismuth(lll) neodecanoate. Particularly preferred catalysts are tin dioctanoate, bismuth decanoate and titanic esters. Quantities preferably used of the catalyst are from 0.0001 to 0.1 part by weight per 100 parts by weight of the isocyanate-reactive compound. Other compounds that can be added, alongside catalysts, to the structural components are conventional auxiliaries. Mention may be made by way of example of surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricating and demolded body aids, dyes and pigments, and optionally stabilizers, preferably with respect to hydrolysis, light, heat or discoloration, inorganic and/or organic fillers, reinforcing agents and/or plasticizers. Stabilizers for the purposes of the present invention are additives which protect a plastic or in particular component A from damaging environmental effects. Examples are primary and secondary antioxidants, sterically hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis stabilizers, quenchers and flame retardants.

According to the present invention, a composition for preparation of the multi-layered composite material comprising at least one polymeric layer comprising foamed granules comprises the thermoplastic elastomer. The composition may comprise further components such as further thermoplastic elastomers or fillers. In the context of the present invention, the term fillers encompasses organic and inorganic fillers such as for example further polymers.

The composition may comprise the thermoplastic elastomer in an amount in the range of from 85 to 100 wt -% based on the weight of the composition.

Unless otherwise noted, the amounts of the components of the composition add up to 100 wt - %.

According to a further embodiment, the present invention is directed to a component A as disclosed above, wherein the composition comprises a filler in an amount in the range of from 0 1 to 20 wt -% based on weight of the composition.

According to a further embodiment, the present invention is directed to the process as disclosed above, wherein the composition comprises a filler in an amount in the range of from 0.1 to 15 wt -% based on the weight of the composition.

The filler may for example be selected from the group consisting of organic fillers such as polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polycarbonates, polyamides, polybutylene terephthalate, polyethylene terephthalates and polylactic acids.

Inorganic fillers such as talcum, chalk, carbon black also can be used in the context of the present invention. Suitable fillers for thermoplastic elastomers are in principle known to the person skilled in the art.

According to a further embodiment, the composition may for example comprise styrene polymers such as atactic, syndiotactic or isotactic polystyrene, more preferably atactic polystyrene.

Atactic polystyrene of the invention, which is amorphous, has a glass transition temperature in the range of 100°C ± 20°C (determined according to DIN EN ISO 11357-1,

February 2017/DIN EN ISO 11357-2, July 2014, Inflection point method). Syndiotactic and isotactic polystyrene of the invention are each semicrystalline and have a melting point in the region respectively of 270°C and 240°C (DIN EN ISO 11357-1, February 2017/DIN EN ISO 11357-3, April 2013, peak melting temperature). The polystyrenes used have a modulus of elasticity in tension of more than 2500 MPa (DIN EN ISO 527-1/2, June 2012).

Commercially available materials can also be used, for example PS 158 K (Ineos), PS 148 H Q (Ineos), STYROLUTION PS 156 F, STYROLUTION PS 158N/L, STYROLUTION PS 168N/L, STYROLUTION PS 153F, SABIC PS 125, SABIC PS 155, SABIC PS 160.

The composition of the component A may also comprise styrene with a modulus of elasticity below 2700 MPa (DIN EN ISO 527-1/2, June 2012), such as styrene polymers selected from the group of the thermoplastic elastomers based on styrene, and of the high-impact polystyrenes (HIPS) which by way of example include SEBS, SBS, SEPS, SEPS-V and acrylonitrile-butadiene-styrene copolymers (ABS), very particular preference being given here to high-impact polystyrene (HIPS).

Commercially available materials can be used here, for example Styron A-TECH 1175, Styron A-TECH 1200, Styron A-TECH 1210, Styrolution PS 495S, Styrolution PS 485N, Styrolution PS 486N, Styrolution PS 542N, Styrolution PS 454N, Styrolution PS 416N, Rochling PS HI, SABIC PS 325, SABIC PS 330.

The use of fillers further reduces the required energy needed for molding to achieve a specified tensile strength, and reduced energy advantageously leads to higher compression strength of the component A obtained.

The materials obtained have a lower melting point compared to the respective materials without filler which is advantageous for the preparation process.

Another preferred embodiment is a component (A) obtained or obtainable by a process for preparing foamed granules for a component (A) comprising the steps of

(i) providing a composition containing a thermoplastic polyurethane, wherein the thermoplastic polyurethane is obtained or obtainable by reacting the components

(A) a polyisocyanate composition

(B) at least one chain extender

(C) a polyol composition with a glass transition temperature Tg in the range of from equal or below -50 °C, determined by dynamic mechanical thermal analysis determined by loss factor (tan d) according to DIN EN ISO 6721- 2011-08 at a heating rate of 2 K/min at a frequency of 1 Hz.,

(D) optionally water

(E) optionally a cross-linker

(F) optionally a plasticizer

(G) optionally additional additives,

(ii) impregnating the composition from step (i) with a blowing agent under pressure,

(iii) expanding the composition from step (i) via pressure drop. Suitable production processes for the thermoplastic elastomers or foams or foamed granules from the thermoplastic elastomers mentioned are likewise known to the person skilled in the art.

Suitable thermoplastic polyether esters and polyester esters can be prepared by all the conventional processes known from the literature by transesterification or esterification of aromatic and aliphatic dicarboxylic acids having 4 to 20 carbon atoms or their esters with suitable aliphatic and aromatic diols and polyols.

According to a further embodiment, the present invention is directed to the process as disclosed above, wherein the thermoplastic polymer is selected from the group consisting of thermoplastic polyurethanes, thermoplastic polyamides and thermoplastic polyetheresters, polyesteresters and mixtures thereof.

According to a further embodiment, the present invention is directed to the process as disclosed above, wherein the thermoplastic elastomer is selected from the group consisting of thermoplastic polyurethanes.

The non-expanded polymer mixture of the composition for a component (A) required for the preparation of the foamed granules is prepared in a known manner from the individual components as well as optionally other components such as processing aids, stabilizers, tolerability agents or pigments. Suitable methods are, for example, common mixing methods with the help of a kneader, continuous or discontinuous, or an extruder such as an identical twin-screw extruder.

The thermoplastic polyurethanes may be produced batchwise or continuously by the known processes, for example using reactive extruders or the belt method by the “one-shot” method or the prepolymer process, preferably by the “one-shot” method. In the “one-shot” method, the components to be reacted, and in preferred embodiments also the chain extender in the polyol component, and also catalyst and/or additives, are mixed with one another consecutively or simultaneously, with immediate onset of the polymerization reaction. The TPU can then be directly pelletized or converted by extrusion to lenticular pellets. In this step, it is possible to achieve concomitant incorporation of other adjuvants or other polymers.

In the extruder process, structural components, and in preferred embodiments also the chain extender, catalyst and/or additives, are introduced into the extruder individually or in the form of mixture and reacted, preferably at temperatures of from 100°C to 280°C, preferably from 140°C to 250°C The resultant polyurethane is extruded, cooled and pelletized, or directly pelletized by way of an underwater pelletizer in the form of lenticular pellets.

It is possible to introduce further additives (components, excipients, fillers) such as impact modifiers, dyes, stabilizers, antioxidants. In this step, some of the above usual excipients (additives, fillers, components) can be added to the mixture. ln a preferred process, a thermoplastic polyurethane is produced from structural components isocyanate, isocyanate-reactive compound including chain extender, and in preferred embodiments the other raw materials in a first step, and the additional substances or auxiliaries are incorporated in a second extrusion step.

It is preferable to use a twin-screw extruder, because twin-screw extruders operate in force- conveying mode and thus permit greater precision of adjustment of temperature and quantitative output in the extruder. Production and expansion of a TPU can moreover be achieved in a reactive extruder in a single step or by way of a tandem extruder by methods known to the person skilled in the art.

Processes for producing foamed pellets from thermoplastic elastomers are known per se to the person skilled in the art. If, according to the invention, a foamed granulate made of the thermoplastic elastomer is used, the bulk density of the foamed granulate is, for example, in the range from 20 g/l to 300 g/l.

The foamed granules according to the invention usually have a bulk density of 50 g/l to 200 g/l, preferably 60 g/l to 180 g/l, more preferably 80 g/l to 150 g/l. The bulk density is measured analogously to DIN ISO 697, wherein in the determination of the above values in contrast to the standard, a vessel with 0.5 I volume is used instead of a vessel with 05 I volume, since especially for the foam particles with low density and large mass a measurement with only 0.5 I volume is too inaccurate.

As stated above, the diameter of the foamed granules is between 0.5 and 30; preferably 1 to 15 and in particular between 3 to 12 mm. For foamed granules that are not spherical, e.g elongated or cylinder-shaped, the longest dimension is meant by diameter.

The production of the foamed granules can be carried out according to the usual methods known in the prior art by

(i) Providing a composition according to the invention;

(ii) Impregnation of the composition with a propellant under pressure;

(iii) Expanding the composition for foamed granules and/or component A by means of pressure drop.

The propellant quantity is preferably 0 1 to 40, in particular 05 to 35 and more preferably 1 to 30 parts by weight, based on 100 parts by weight of the amount of composition used.

In one embodiment the above-mentioned method includes:

(i) Providing a composition according to the invention in the form of a granulate;

(ii) Impregnation of the granulate with a propellant under pressure;

(iii) Expanding the granules by means of pressure drop. Another embodiment of the above-mentioned method includes another step:

(ii) Impregnation of the granulate with a propellant under pressure;

(iii-a) Reducing the pressure to normal pressure without foaming the granules, if necessary by reducing the temperature in advance (iii-b) foaming of the granules by increasing the temperature.

Preferably, the non-expanded granules have an average minimum diameter of 02 - 10 mm (determined via 3D evaluation of the granulate, e.g. via dynamic image analysis with the use of an optical measuring apparatus called Parian 3D by Microtrac).

The individual granules usually have an average mass in the range of 0.1 to 50 mg, preferably in the range of 4 to 40 mg and particularly preferably in the range of 7 to 32 mg. This mean mass of the granules (particle weight) is determined as an arithmetic method by weighing 10 granulate particles each.

In a preferred embodiment the above-mentioned method includes the impregnation of a polymer granulate with a propellant under pressure and subsequent expansion of the granules in step (I) and (II):

(I) Impregnation of the granulate in the presence of a propellant under pressure at elevated temperatures in a suitable closed reaction vessel (e.g autoclaves);

(II) sudden relaxation without cooling.

Herein, the impregnation in step (I) can be carried out in the presence of water as well as optional suspension aids or only in the presence of the propellant and absence of water.

Suitable suspension aids are e.g. water-insoluble inorganic stabilizers, such as tricalcium phosphate, magnesium pyrophosphate, metal carbonates, polyvinyl alcohol and surfactants, such as sodium dodecyl aryl sulfonate. They are usually used in amounts of 0.05 to 10 wt -%, based on the composition of the invention.

The impregnation temperatures are depending on the selected pressure in the range of 100°C- 200°C, wherein the pressure in the reaction vessel is in the range of 2 to 150 bar, preferably in the range of 5 and 100 bar, more preferably in the range of 20 and 60 bar, the impregnation period is generally 0 5 to 10 hours.

The execution of the method in suspension is known to the skilled person and described e.g. in detail in W02007/082838.

When performing the process in the absence of the propellant, care must be taken to avoid the aggregation of the polymer granules. Suitable propellants for carrying out the process in a suitable closed reaction vessel are, for example, organic liquids and gases which are present in a gaseous state under the processing conditions, such as hydrocarbons or inorganic gases or mixtures of organic liquids or gases and inorganic gases, wherein these can also be combined.

Suitable hydrocarbons are, for example, halogenated or non-halogenated, saturated or unsaturated aliphatic hydrocarbons, preferably non-halogenated, saturated or unsaturated aliphatic hydrocarbons.

Preferred organic propellants are saturated, aliphatic hydrocarbons, in particular those with 3 to 8 C atoms such as butane or pentane.

Suitable inorganic gases are nitrogen, air, ammonia or carbon dioxide, preferably nitrogen or carbon dioxide or mixtures of the gases mentioned above.

In a further embodiment, the process comprises impregnation of the granules with a propellant under pressure and subsequent expansion of the granules in step (a) and (b):

(a) Impregnation of the granulate in the presence of a propellant under pressure at elevated temperatures in an extruder;

(b) Granulation of the mass from the extruder under conditions that prevent uncontrolled foaming.

Suitable propellants in this process variant are volatile organic compounds with a boiling point at normal pressure 1013 mbarfrom -25°C to 150°C, in particular -10°C to 125°C Well suited are hydrocarbons (preferably halogen-free), in particular C4-10 alkanes, for example, the isomers of the butane, pentane, hexane, heptane and octane, particularly preferably iso-butane. Other possible propellants are also more sterically demanding compounds such as alcohols, ketones, esters, ethers and organic carbonates.

Herein, the composition in the step (ii) in an extruder is mixed under melting with the propellant under pressure, which is fed to the extruder. The propellant-containing mixture is pressed under pressure, preferably with moderately controlled back pressure (e.g underwater granulation) and granulated. Herein, the melt string foams up, and the foamed granules are obtained by granulation.

The execution of the process via extrusion is known to the skilled person and described in detail, for example, in W02007/082838 and WO2013/153190.

As extruders, all the usual screw machines can be considered, in particular single-screw and twin-screw extruders (e.g type ZSK by Werner & Pfleiderer), co-kneaders, combi-plastic machines, MPC kneaders, FCM mixers, KEX kneader screw extruders and shear roller extruders, as they are disclosed e.g. in Saechtling (ed.), Plastic paperback, 27th edition 3.2.1 and 3.2.4. The extruder is usually operated at a temperature at which the composition (Z1) is present as a melt, for example at 120°C to 250°C, in particular 150°C to 210°C and a pressure after the addition of the propellant of 40 to 200 bar, preferably 60 to 150 bar, particularly preferably 80 to 120 bar to ensure a homogenization of the propellant with the melt.

Herein, the execution can be carried out in an extruder or an arrangement of one or more extruders. For example, in a first extruder, the components can be melted and blended and a propellant can be injected. In the second extruder, the impregnated melt is homogenized and the temperature and pressure is adjusted. If, for example, three extruders are combined with each other, the mixing of the components as well as the injecting of the propellant can be divided into two different process parts. If, as preferably, only one extruder is used, all process steps, melt, mix, injection of the propellant, homogenization and adjustment of the temperature and or pressure are carried out in an extruder.

The foamed granules may also contain dyes. Here, the addition of dyes can be done by different means.

In one embodiment, the manufactured foamed granules can be dyed after manufacture. Here, the corresponding foamed granules are contacted with a carrier liquid contained with a dye, wherein the carrier fluid has a polarity, which is suitable that a sorption of the carrier fluid is carried out in the foamed granules. The implementation may be carried out in analogy with the methods described in the EP 3700969.

Suitable dyes are, for example, inorganic or organic pigments. Suitable natural or synthetic inorganic pigments are, for example, soot, graphite, titanium oxides, iron oxides, zirconia oxides, cobalt oxide compounds, chromium oxide compounds, copper oxide compounds. Suitable organic pigments are, for example, azo-pigments and polycyclic pigments.

In a further embodiment, the ink can be added in the preparation of the foamed granules. For example, the dye can be added to the extruder during the preparation of the foamed granules via extrusion.

Alternatively, already dyed material can be used as a starting material for the preparation of the foamed granules, which is extruded or expanded in the closed vessel according to the above- mentioned methods.

Furthermore, in the process described in WO2014/150122, the supercritical liquid or the heated liquid may contain a dye.

Herein, the tensile and compression properties of the moldings produced from the foamed granules are characterized in that the tensile strength is above 600 kPa (DIN EN ISO 1798,

April 2008), the elongation is above 100% (DIN EN ISO 1798, April 2008) and the compressive voltage above 15 kPa is 10% compression (analogous to DIN EN ISO 844, November 2014; the deviation from the standard is in the height of the sample with 20 mm instead of 50 mm and thus the adjustment of the test speed to 2 mm/min).

The rebound elasticity of the moldings produced from the foamed granules is above 55% (analogous to DIN 53512, April 2000; the deviation from the standard is the test specimen height which should be 12 mm, but in this test is carried out with 20 mm in order to avoid a "smashing" of the sample and measuring the substrate).

The density and compression properties of the manufactured moldings are related. Advantageously, the density of the molded parts is between 75 and 375 kg/m³, preferably between 100 to 300 kg/m³, particularly preferably between 150 to 250 kg/m³ (DIN EN ISO 845, October 2009).

The ratio of the density of the molded to the bulk density of the foamed granules according to the invention is generally between 1.5 and 2 5, preferably at 1.8 to 2.0.

Further object of the present invention is a multi-layered composite material comprising at least one polymeric layer (component A) prepared from the foamed granules according to the invention. Therefore, the foamed pellets are preferably fused.

The preparation of the corresponding moldings can be carried out according to the skilled person known methods

A preferred method for the preparation of a foam molding part includes the following steps:

(A) Inserting the foamed granules according to the invention in a corresponding form,

(B) Fusing of the foamed granules according to the invention from step (A).

The fusion in step (B) is preferably carried out in a closed form, wherein the fusion can be carried out by water vapor, hot air (as e.g. described in EP1979401) or energetic radiation (microwaves or radio waves).

The temperature at the fusion of the foamed granules is preferably below or close to the melting temperature of the polymer from which the particle foam was produced. For the common polymers, therefore, the temperature for fusion of the foamed granules is between 100°C and 180°C, preferably between 120°C and 150°C.

Temperature profiles / residence times can be determined individually, e.g. in analogy to the methods described in the US20150337102 or EP2872309.

Fusing by energetic radiation is generally carried out in the frequency range of microwaves or radio waves, if necessary in the presence of water or other polar liquids, such as polar groups having microwave-absorbing hydrocarbons (such as esters of carboxylic acids and diols or triols or glycols and liquid polyethylene glycol) and can be carried out in analogy to the methods described in EP3053732 or W016146537.

According to the present invention, fusing the foamed pellets is preferably carried out in a mold to shape the component A obtained. In principle, all suitable methods for fusing foamed pellets can be used according to the present invention, for example fusing at elevated temperatures, such as for example steam chest molding, molding at high frequencies, for example using electromagnetic radiation, processes using a double belt press, or variotherm processes.

The thermoplastic polymer foam from which the component A is manufactured can be any open-cell or closed-cell polymer foam that can be produced from a thermoplastic. The thermoplastic polymer foam is particularly preferably a molded foam.

The production of the molding made of the polymer foam can be achieved in any desired manner known to the person skilled in the art: by way of example, webs made of a foamed polymer can be produced, and the moldings can be cut out from the webs. If the polymer foam from which the molding has been produced is a molded foam, the molding can be produced by any process known to the person skilled in the art for the production of moldings made of a molded foam: it is possible by way of example to charge pellets made of an expandable thermoplastic polymer to a mold, to expand the pellets to give foam beads by heating, and then to use pressure to bond the hot foam beads to one another. The pressure is generated here via the foaming of the beads, the volume of which increases while the internal volume of the mold remains the same. Uniform heating can be achieved by way of example by passing steam through the mold. However, it is alternatively also possible to charge pre-expanded beads to the mold. In this case, the procedure begins with complete filling of the mold. In a further step, the volume of the mold is reduced by insertion of a ram at the feed aperture, which has likewise been completely filled with expanded beads, and the pressure in the mold is thus increased.

The expanded beads are thus pressed against one another and can therefore become fused to give the molding. Here again, the fusion of the beads is in particular achieved via passage of steam through the system.

The injection process used to apply the thermoplastic polymer can by way of example be an injection molding process, a transfer-molding process, or an injection compression-molding process. It is possible on the one hand to insert the molding made of thermoplastic polymer into a mold for the injection molding process, transfer-molding process, or injection compression molding process, and then to apply the thermoplastic polymer. Alternatively, it is also possible to utilize, for the over molding process, the mold in which the molding made of the polymer foam is also produced. It is usual to use, for this purpose, molds with displaceable core. If the intention is that the thermoplastic polymer be applied only to one side of the molding made of polymer foam, it is alternatively also possible, after the production of the molding made of polymer foam, to remove one mold half, and to seal the second mold half in which the molding is still present by using another mold half into which the thermoplastic polymer for the functional layer is then injected or forced. For fusing with radiofrequency electromagnetic radiation, the particle foams can preferably be wetted with a polar liquid, which is suitable to absorb the radiation, for example in proportions of 0.1 to 10 wt -%, preferably in proportions of 1 to 6 wt -%, based on the used particle foams. Fusing with radiofrequency electromagnetic radiation of the particle foams can be achieved in the context of the present invention even without the use of a polar liquid. The thermal connection of the foam particles takes place, for example, in a form by means of radiofrequency electromagnetic radiation, in particular by means of microwaves. Electromagnetic radiation with frequencies of at least 20 MFIz, for example of at least 100 MHz, is understood to be high frequency. As a rule, electromagnetic radiation is used in the frequency range between 20 MHz and 300 GHz, for example between 100 MHz and 300 GHz. Microwaves are preferred in the frequency range between 0.5 and 100 GHz, especially preferably 0.8 to 10 GHz and irradiation times between 0.1 and 15 minutes are used. Preferably, the frequency range of the microwave is adjusted to the absorption behavior of the polar liquid or vice versa the polar liquid is selected based on the absorption behavior according to the frequency range of the used microwave device. Suitable methods are described, for example, in WO2016/146537.

Due to the good mechanical properties and the good temperature behavior, the polymer foams according to the invention are particularly suitable for the preparation of moldings. Molded bodies can be prepared from the foamed granules according to the invention, for example by fusing or gluing.

According to a further aspect, the present invention also relates to the use of a foamed granules of the inventions or a foamed granule, obtained or available according to a method of the invention for the preparation of moldings. According to a further embodiment, the present invention also relates to the use of a foamed granules of the inventions or a foamed granulates, obtained or available according to a method of the invention for the preparation of moldings, wherein the preparation of the molding by means of fusing or gluing of the particles is carried out with each other.

The moldings obtained according to the invention are suitable for example for the manufacture of multilayered composite material of the present invention.

According to a further embodiment, the present invention also relates to the use of a foamed granulates or foamed granulates according to the invention obtained or obtainable according to a method of the invention for the preparation of moldings of component A.

The present invention also relates to a further aspect a hybrid material, containing a matrix of a polymer and a foamed granule according to the present invention, in particular of component A. Materials comprise a foamed granulate and a matrix material are referred to in this invention as hybrid materials. The matrix material can be made of a compact material or also of a foam. Polymers suitable as matrix material are known to the skilled person themselves. Suitable in the context of the present invention are, for example, ethylene-vinyl acetate copolymers, binders based on epoxy or also polyurethanes. According to the invention, polyurethane foams or compact polyurethanes such as thermoplastic polyurethanes are suitable.

According to the invention, the polymer is selected in such a way that a sufficient adhesion is given between the foamed granules and the matrix in order to obtain a mechanically stable hybrid material.

The matrix can surround the foamed granules in whole or in part. According to the invention, the hybrid material may contain further components, for example further fillers or also granules. According to the invention, the hybrid material may also contain mixtures of different polymers. The hybrid material may also contain mixtures of foamed granules.

Foamed granules, which can be used in addition to the foamed granules according to the present invention, are known to the skilled person per se. In particular, foamed granules made of thermoplastic polyurethanes are suitable in the context of the present invention.

According to an embodiment, the present invention accordingly also relates to a hybrid material, containing a matrix of a polymer, a foamed granulate according to the present invention and another foamed granule from a thermoplastic polyurethane.

The matrix comprises in the present invention of a polymer suitable in the context of the present invention as matrix material, for example, elastomers or foams, in particular foams based on polyurethanes, for example elastomers such as ethylene vinyl acetate copolymers or also thermoplastic polyurethanes.

Accordingly, the present invention also relates to a hybrid material as previously described, wherein the polymer is an elastomer. Furthermore, the present invention relates to a hybrid material as previously described, wherein the polymer is selected from the group consisting of ethylene vinyl acetate copolymers and thermoplastic polyurethanes.

According to an embodiment, the present invention also relates to a hybrid material containing a matrix of an ethylene-vinyl acetate copolymer and a foamed granule according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material, containing a matrix of an ethylene-vinyl acetate copolymer, a foamed granulate according to the present invention and another foamed granule, for example from a thermoplastic polyurethane.

According to one embodiment, the present invention relates to a hybrid material containing a matrix of a thermoplastic polyurethane and a foamed granulate according to the present invention. According to a further embodiment, the present invention relates to a hybrid material, containing a matrix of a thermoplastic polyurethane, a foamed granule according to the present invention and another foamed granule, for example from a thermoplastic polyurethane.

Preferably, the polymers in the context of the present invention are polyurethanes. Polyurethane in the sense of the invention includes all known elastic polyisocyananate polyaddition products. These include in particular massive polyisocyananate. Polyaddition products, such as viscoelastic gels or thermoplastic polyurethanes, and elastic foams based on polyisocyanate polyaddition products, such as soft foams, semi-hard foams or integral foams. Furthermore, polyurethanes in the sense of the invention elastic polymer blends, containing polyurethane and other polymers, as well as foams from these polymer blends are to be understood. Preferably, the matrix is a hardened, compact polyurethane binder, an elastic polyurethane foam or a viscoelastic gel.

Under a polyurethane binder is understood in the context of the present invention a mixture consisting to at least 50 wt.-%, preferably to at least 80 wt.-% and in particular to at least 95 wt - % of an isocyanate group having prepolymer, hereinafter referred to as isocyanate prepolymer. Here, the viscosity of the inventive polyurethane binder is preferably in a range of 500 to 4000 mPa.s, particularly preferably from 1000 to 3000 mPa.s, measured at 25 °C according to DIN 53 018.

In the context of the invention, polyurethane foams are understood to be foams in accordance with DIN 7726.

The density of the matrix material is preferably in the range of 1,2 to 0.01 g/cm³. Particularly preferred, the matrix material is an elastic foam or an integral foam with a density in the range of 0.8 to 0.1 g / cm³, in particular from 0.6 to 0.3 g / cm³ or compact material, for example a hardened polyurethane binder.

In particular, foams are suitable as matrix material. Hybrid materials containing a matrix material from a polyurethane foam preferably have a good adhesion between matrix material and foamed granules.

According to an embodiment, the present invention also relates to a hybrid material containing a matrix of a polyurethane foam and a foamed granulate according to the present invention.

According to a further embodiment, the present invention relates to a hybrid material, containing a matrix of a polyurethane foam, a foamed granulate according to the present invention and another foamed granule, for example from a thermoplastic polyurethane.

A hybrid material according to the invention, containing a polymer as a matrix and a foamed granulate according to the invention can be prepared, for example, by the components used for the preparation of the polymer and the foamed granules optionally mixed with further components and converted to the hybrid material, wherein the reaction is preferably under conditions under which the foamed granules is substantially stable.

Appropriate methods and reaction conditions for the preparation of the polymer, in particular an ethylene vinyl acetate copolymer or a polyurethane are known to the skilled person per se.

In a preferred embodiment, the hybrid materials of the invention represent integral foams, in particular integral foams based on polyurethane. Suitable methods for the production of integral foams are known to the skilled person per se. The integral foams are preferably manufactured by the one-shot process with the help of low pressure or high-pressure technology in closed, purpose-controlled molds. The molds are usually made of metal, e.g aluminium or steel.

If the hybrid material of the invention comprises an integral foam, the amount of the reaction mixture introduced into the mold is dimensioned in such a way that the obtained molds of integral foams have a density of 0.08 to 0.70 g / cm³, in particular from 0.12 to 0.60 g / cm³. The compaction degrees for the preparation of the moldings with compacted edge zone and cellular core are in the range of 1.1 to 8.5, preferably from 2.1 to 7.0.

Thus, it is possible to produce hybrid materials with a matrix of a polymer and contained therein the foamed granules according to the invention, in which a homogeneous distribution of the foamed particles is present. The foamed granules according to the invention can be easily used in a method for the preparation of a hybrid material, since the individual particles are free- flowing due to their small size and do not place any special requirements on the processing. Techniques for homogeneous distribution of the foamed granules such as slow rotation of the mold can be used.

The reaction mixture for the preparation of the hybrid materials of the invention can optionally also be added aids and / or additives. For example, surface-active substances, foam stabilizers, cell regulators, release agents, fillers, dyes, pigments, hydrolysis protection agents, odour absorbing substances and fungistatic and bacteriostatic substances are mentioned.

In a hybrid material according to the invention, the volume portion of the foamed granules is preferably 20 percent by volume and more, more preferably 50 percent by volume and more preferably 80 percent by volume and more and in particular 90 percent by volume and more, each based on the volume of the hybrid system according to the invention.

The hybrid materials of the invention, in particular hybrid materials with a matrix of cellular polyurethane, are characterized by a very good adhesion of the matrix material with the foamed granules according to the invention. In this process, a hybrid material according to the invention preferably does not rip at the interface of matrix material and foamed granules. This makes it possible to produce hybrid materials that have improved mechanical properties, such as tear resistance and elasticity, compared to conventional polymer materials, especially conventional polyurethane materials at the same density.

The elasticity of hybrid materials according to the invention in the form of integral foams is preferably greater than 40% and particularly preferably greater than 50% according to DIN 53512.

Furthermore, the hybrid materials according to the invention, in particular those based on integral foams show high rebound elasticities at low density. In particular, integral foams based on hybrid materials according to the invention are therefore excellently suited as materials for shoe soles. This preserves light and comfortable soles with good durability properties. Such materials are particularly suitable as midsoles for sports shoes.

The properties of the hybrid materials of the invention can vary depending on the polymer used in wide ranges and can be varied in particular by a variation of the size, shape and texture of the expanded granules, or the addition of further additives, for example also other non-foamed granules such as plastic granules, for example rubber granules, in wide limits.

The hybrid materials of the invention have a high durability and load-bearing capacity, which is particularly noticeable by a high tensile strength and elongation at break. In addition, hybrid materials of the invention have a low density.

The process of the present invention comprises steps (i) and (ii). The process may comprise further steps such as for example temperature treatments or a treatment of the foamed pellets. According to step (i), the foamed pellets are provided, preferably in a suitable mold, and then fused according to step (ii). Preferably, fusing is carried out by thermal fusing of the foamed pellets. According to a further embodiment, the present invention is directed to the process as disclosed above, wherein step (ii) is carried out by thermal fusing.

Component (B)

The polymer layer (C) is bonded to the foam layer (A) optionally via at least one bonding layer (B). Alternatively, a bonding (lamination) between polymer layer (C) and the foam layer (A) is conducted without adhesive bonding layer (B). in case no adhesive layer (B) is applied, the bonding process is conducted preferably by a heat press method at elevated temperature and with pressure.

In case an adhesive polymer (component B) is applied, the adhesive polymer (component B) is in particular selected from the group consisting of liquid adhesive, glue, heat active glue, hot melt glue, adhesive grid, adhesive web, adhesive film, spraying method, water based liquid binder solution or dispersion, or solvent based liquid binder solution or dispersion. Liquid binder solutions or dispersions are for example applied by spraying. A layer combination of polyurethane and thermoplastic polyurethane is in particular laminated by a hot melt glue principle. Bonding layer (B) may comprise an interrupted, i.e., discontinuous, layer, preferably of a cured organic adhesive.

In an embodiment of the present invention, bonding layer (B) comprises a layer applied in point form, stripe form or lattice form, for example in the form of diamonds, rectangles, squares or a honeycomb structure. In that case, polyurethane layer (C) comes into contact with foam layer

(A) in the gaps of the bonding layer (B).

In another embodiment of the present invention, bonding layer (B) comprises a continuous layer.

In an embodiment of the present invention, bonding layer (B) comprises a layer of a cured organic adhesive, for example based on polyvinyl acetate, polyacrylate or in particular polyurethane, preferably based on polyurethanes having a glass transition temperature below 0°C.

The organic adhesive may for example be cured thermally, through actinic radiation or by aging.

In another embodiment of the present invention, bonding layer (B) comprises an adhesive gauze.

In an embodiment of the present invention, the bonding layer (B) has a maximum thickness of 100 pm, preferably 50 pm, more preferably 30 pm, most preferably 15 pm.

In an embodiment of the present invention, bonding layer (B) may comprise microballoons. Microballoons herein are spherical particles having an average diameter in the range from 5 to 20 pm and composed of polymeric material, in particular of halogenated polymer such as for example polyvinyl chloride or polyvinylidene chloride or copolymer of vinyl chloride with vinylidene chloride. Microballoons may be empty or preferably filled with a substance whose boiling point is slightly lower than room temperature, for example with n-butane and in particular with isobutane.

In an embodiment of the present invention, polyurethane layer (C) may be bonded to foam (A) via at least two bonding layers (B) having the same or a different composition. One bonding layer (B) may comprise a pigment with the other bonding layer (B) being pigment free.

In one variant, one bonding layer (B) may comprise microballoons with the other bonding layer

(B) not comprising microballoons.

In another embodiment, the composite material comprises optionally a layer (B) comprising a thermoplastic adhesive polymer with a melting range of 70°C to 130°C. Hence, such a layer is solid at a room temperature of about 21 °C. Such a layer (B), for example called bonding layer (B), can, for example, be a distinct layer which is perforated, which means that the surface is not completely intact, preferably a cured organic adhesive.

In one embodiment, bonding layer (B) exhibits a thickness in the range from one to a maximum of 100 pm, preferably to 50 pm, particularly preferably to 15 pm.

The adhesive polymer is applied in solid form to the layer (A) and/or to layer (C).

The adhesive polymer in stage b) for the most part has a weight per unit area of 0.1 to 1000 g/m², preferably of 1 to 300 g/m² and in particular of 5 to 100 g/m².

The adhesive polymer in stage b) for the most part has a melt volume-flow rate MVR of 1 to 500 cm³/10 min, preferably of 5 to 200 cm³/10 min and in particular of 10 to 100 cm³/10 min. The melt volume-flow rate MVR can be measured at 160°C and 2.16 kg according to ISO 1133-1.

The adhesive polymer preferably has a melting range from 60°C to 125°C and in particular from 85°C to 120°C. The melting range can be determined by means of DSC, e.g. according to ISO 11357.

The adhesive polymer can be applied in stage b) in the form of an adhesive grid, adhesive web or adhesive film.

Adhesive grids can exhibit round or angular (such as square, triangular or hexagonal) openings.

Adhesive webs can comprise fibers which are irregularly assembled.

Adhesive films can form a sheet with a completely intact surface, which usually has no openings.

The adhesive polymers exemplarily comprising a copolyester, copolyimide or aliphatic thermoplastic polyurethane polyester are commercially available in solid form, for example as adhesive grid, adhesive web or adhesive film, such as from AB-Tec GmbH & Co. KG, Iserlohn, Germany; Spunfab Ltd., Cuyahoga Falls, USA; or Protechnic S.A., Cernay, France.

The adhesive polymer can be based on polyurethanes, polyamides, polyesters or polyolefins.

Suitable polyurethanes for the adhesive polymers are such as described subsequently for the polyurethane layer (C), preferably the thermoplastic polyurethanes described subsequently, in particular aliphatic thermoplastic polyurethanes.

Suitable polyamides are copolyamides.

Suitable polyesters are polyethylene terephthalate (PET) and PET copolymers. Suitable polyolefins are polyethylenes (such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), linear medium density polyethylene (LMDPE), linear very-low density polyethylene (VLDPE), linear ultra-low density polyethylene (ULDPE), high density polyethylene (HDPE)) and copolymers of polyethylene. Examples of copolymers of polyethylene are ethylene/vinyl acetate, ethylene/vinyl alcohol, ethylene/octene or ethylene/acrylic acid, such as described, e.g , in W02003064153

In one embodiment, bonding layer (B), as also layer (C), can optionally comprise one or more additives, for example one or more flame retardants, stabilizers, such as antioxidants, light stabilizers and/or water repellants or oil repellants.

Suitable flame retardants are, for example, inorganic flame retardants, halogenated organic compounds, organic phosphorus compounds or halogenated organic phosphorus compounds.

Suitable inorganic flame retardants are, for example, phosphates, such as ammonium phosphates, aluminum hydroxides, alumina trihydrates, zinc borates or antimony oxide.

Suitable halogenated organic compounds are, for example, chloroparaffins, polychlorinated biphenyls, hexabromobenzene, polybrominated diphenyl ethers (PBDE) and other bromine compounds, addition products of hexachlorocyclopentadiene, e.g with cyclooctadiene, tetrabromobisphenol A, tetrabromophthalic anhydride, dibromoneopentyl glycol.

Suitable organic phosphorus compounds are, for example, organic phosphates, phosphites and phosphonates, such as, for example, tricresyl phosphate and te/i-butylphenyl diphenyl phosphate.

Suitable halogenated organic phosphorus compounds are, for example, tris(2,3-dibromopropyl) phosphate, tris(2-bromo-4-methylphenyl) phosphate and tris(2-chloroisopropyl) phosphate.

Preferred flame retardants are, for example, polyvinyl chlorides or polyvinylidene chlorides, as well as copolymers of vinylidene chloride with (meth)acrylic acid esters. Such products are, for example, sold under the trade name Diofan®.

Suitable light stabilizers are, for example, radical traps, such as sterically hindered organic amines (HALS), or peroxide decomposers, such as, for example, benzotriazoles, such as 2-(2- hydroxyphenyl)-2H-benzotriazoles (BTZ) or hydroxybenzophenones (BP). Additional suitable light stabilizers are, for example, (2-hydroxyphenyl)-s-triazines (HPT), oxalanilides or non pigmentary titanium dioxide. Suitable light stabilizers are available, for example, under the trade names Irganox®, Irgastab® or Tinuvin®. Preferred light stabilizers are HALS compounds.

Optional interlayer (D) ln an embodiment of the present invention, multilayered composite material of the present invention can have no further layers. In another embodiment of the present invention, multilayered composite material of the present invention may comprise at least one interlayer (D) disposed between foam (A) and bonding layer (B), between bonding layer (B) and polyurethane layer (C) or between two bonding layers (B), which may be the same or different. Interlayer (D) is selected from textile, paper, batt materials, and batt materials (nonwovens) of synthetic materials such as polypropylene or polyurethane, in particular nonwovens of thermoplastic polyurethane.

In those embodiments where multilayered composite material of the present invention comprises at least one interlayer (D), polyurethane layer (C) will preferably come into direct contact not with foam (A), but with interlayer (D).

In an embodiment of the present invention, interlayer (D) may have an average diameter (thickness) in the range from 0.05 mm to 5 cm, preferably in the range from 0.1 mm to 0.5 cm and more preferably in the range from 0.2 mm to 2 mm.

Preferably, interlayer (D) has a water vapor permeability in the range of greater than 1.5 mg/cm² h, measured according to German standard specification DIN 53333.

Component (C)

Polyurethanes, in particular thermoplastic polyurethanes, are suitable as polymer layer (C). Suitable polyurethanes are all thermoplastic polyurethanes which can be provided in the form preferably of aqueous dispersions. They preferably have a glass transition temperature of less than 0°C, determined, for example, by DSC (Differential Scanning Calorimetry) according to DIN 53765. Preferably, polymer layer (C) is essentially composed of polyurethane.

Polyurethanes (PU) are generally known and commercially available and generally consist of a soft phase of relatively high molecular weight polyhydroxyl compounds, e.g. of polycarbonate, polyester or polyether segments, and of a urethane hard phase formed of low molecular weight chain extenders and di- or polyisocyanates.

Processes for the preparation of polyurethanes (PU) are generally known. Generally, polyurethanes (PU) are prepared by reaction of

(i) isocyanates, preferably diisocyanates, with

(ii) compounds which react with isocyanates, usually with a molecular weight (Mw) of 500 to 10000 g/mol, preferably 500 to 5000 g/mol, particularly preferably 800 to 3000 g/mol, and

(iii) chain extenders with a molecular weight of 50 to 499 g/mol, optionally in the presence of

(iv) catalysts

(v) and/or normal additives. ln the following, the starting components and processes for the preparation of the preferred polyurethanes (PU) are to be explained by way of example. The components (i), (ii), (iii), and also optionally (iv) and/or (v), customarily used in the preparation of the polyurethanes (PU), are to be described below by way of example:

Use may be made, as isocyanates (i), of generally known aliphatic, cycloaliphatic, araliphatic and/or aromatic isocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methyl-1 ,5-pentamethylene diisocyanate, 2-ethyl-1 ,4-butylene diisocyanate, 1 ,5- pentamethylene diisocyanate, 1 ,4-butylene diisocyanate, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl)cyclohexane (isophorone diisocyanate, IPDI), 1 ,4- and/or 1 ,3- bis(isocyanatomethyl)cyclohexane (HXDI), 1 ,4 -cyclohexane diisocyanate, 1 -methyl-2,4- and/or - 2,6-cyclohexane diisocyanate and/or 4,4'-, 2,4'- and/or 2, 2'-dicyclohexylmethane diisocyanate, 2,2'-, 2,4'- and/or 4, 4'-diphenylmethane diisocyanate (MDI), 1 ,5-naphthylene diisocyanate (NDI), 2,4- and/or 2, 6-toluylene diisocyanate (TDI), 3,3'-dimethyldiphenyl diisocyanate, 1 ,2- diphenylethane diisocyanate and/or phenylene diisocyanate. 4,4'-MDI is preferably used. Aliphatic diisocyanates, in particular hexamethylene diisocyanate (HDI), are additionally preferred and aromatic diisocyanates, such as 2,2'-, 2,4'- and/or 4, 4'-diphenylmethane diisocyanate (MDI) and mixtures of the abovementioned isomers are especially preferred.

Use may be made, as compounds which react with isocyanates (ii), of the generally known compounds which react with isocyanates, for example polyesterols, polyetherols and/or polycarbonate diols, which are normally also combined under the term "polyols", with molecular weights (M_w) in the range from 500 to 8000 g/mol, preferably 600 to 6000 g/mol and in particular 800 to 3000 g/mol, and preferably with an average functionality with regard to isocyanates of 1.8 to 2.3, preferably 1.9 to 2.2 and in particular 2. Use is preferably made of polyether polyols, for example those based on generally known starting substances and customary alkylene oxides, for example ethylene oxide, 1 ,2-propylene oxide and/or 1 ,2-butylene oxide, preferably polyetherols based on polyoxytetramethylene (poly-THF), 1 ,2-propylene oxide and ethylene oxide. Polyetherols exhibit the advantage that they have a greater stability to hydrolysis than polyesterols and are preferred as component (ii), in particular for the preparation of soft polyurethanes (PU1).

Mention may be made, as polycarbonate diols, of in particular aliphatic polycarbonate diols, for example 1 ,4-butanediol polycarbonate and 1 ,6-hexanediol polycarbonate.

Mention may be made, as polyester diols, of those which can be prepared by polycondensation of at least one primary diol, preferably at least one primary aliphatic diol, for example ethylene glycol, 1 ,4-butanediol, 1 ,6-hexanediol, neopentyl glycol or particularly preferably 1 ,4- di(hydroxymethyl)cyclohexane (as isomer mixture) or mixtures of at least two of the abovementioned diols, on the one hand, and at least one, preferably at least two, dicarboxylic acids or their anhydrides, on the other hand. Preferred dicarboxylic acids are aliphatic dicarboxylic acids, such as adipic acid, glutaric acid or succinic acid, and aromatic dicarboxylic acids, such as, for example, phthalic acid and in particular isophthalic acid. Polyetherols are preferably prepared by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, to diols, such as, for example, ethylene glycol, 1 ,2- propylene glycol, 1,2-butylene glycol, 1 ,4-butanediol or 1,3-propanediol, or to triols, such as, for example, glycerol, in the presence of highly active catalysts. Such highly active catalysts are, for example, cesium hydroxide and double metal cyanide catalysts, also described as DMC catalysts. A frequently used DMC catalyst is zinc hexacyanocobaltate. The DMC catalyst can be left in the polyetherol after the reaction; preferably, it is removed, for example by sedimentation or filtration.

Mixtures of different polyols can also be used instead of one polyol.

In order to improve the dispersability, use may also be made, as compounds which react with isocyanates (ii), of a proportion of one or more diols or diamines with a carboxylic acid group or sulfonic acid group (b'), in particular alkali metal or ammonium salts of 1 ,1-dimethylolbutanoic acid, 1,1-dimethylolpropionic acid or

Use is made, as chain extenders (iii), of aliphatic, araliphatic, aromatic and/or cycloaliphatic compounds with a molecular weight of 50 to 499 g/mol and at least two functional groups, preferably compounds with exactly two functional groups per molecule, which are known per se, for example diamines and/or alkanediols with from 2 to 10 carbon atoms in the alkylene radical, in particular 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol and/or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and/or decaalkylene glycols with from 3 to 8 carbon atoms per molecule, preferably corresponding oligo- and/or polypropylene glycols, it also being possible to use mixtures of chain extenders (iii).

The components (i) to (iii) are particularly preferably difunctional compounds, i.e. diisocyanates (i), difunctional polyols, preferably polyetherols, (ii) and difunctional chain extenders, preferably diols.

Suitable catalysts (iv), which in particular accelerate the reaction between the NCO groups of the diisocyanates (i) and the hydroxyl groups of the components (ii) and (iii), are tertiary amines, such as, e.g , triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N'- dimethylpiperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.2]octane ("DABCO") and similar tertiary amines, as well as in particular organic metal compounds, such as titanic acid esters, iron compounds, such as, e.g., iron(lll) acetylacetonate, tin compounds, e.g. tin diacetate, tin dioctoate, tin dilaurate or the dialkyltin salts of aliphatic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate or the like, which are known per se. The catalysts are normally used in amounts of 00001 to 0 1 parts by weight per 100 parts by weight of component (ii).

In addition to catalysts (iv), auxiliaries and/or additives (v) can be added to the components (i) to (iii). Mention may be made, for example, of blowing agents, antiblocking agents, surface-active substances, fillers, for example fillers based on nanoparticles, in particular fillers based on CaCC>3, furthermore, nucleating agents, slip agents, dyes and pigments, antioxidants, e.g against hydrolysis, light, heat or discoloration, inorganic and/or organic fillers, reinforcing agents and plasticizers, or metal deactivators. In a preferred embodiment, the component (v) also includes hydrolysis stabilizers, such as, for example, polymeric and low molecular weight carbodiimides. The soft polyurethane preferably comprises triazole and/or triazole derivatives and antioxidants in an amount of 0.1 to 5% by weight, based on the total weight of the relevant soft polyurethane. Suitable as antioxidants are generally substances which hinder or prevent undesirable oxidative processes in the plastic to be protected. Generally, 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 Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), pp 98-107 and p. 116 - p 121 Examples of aromatic amines are found in [1] pp. 107-108. Examples of thiosynergists are given in [1], pp 104-105 and pp. 112-113 Examples of phosphites are found in [1], pp. 109-112. Examples of hindered amine light stabilizers are given in [1], pp 123-136. Phenolic antioxidants are preferably suitable for use in the antioxidant mixture. In a preferred embodiment, the antioxidants, in particular the phenolic antioxidants, exhibit a molar mass of greater than 350 g/mol, particularly preferably of greater than 700 g/mol, and with a maximum molar mass (Mw) up to a maximum of 10000 g/mol, preferably up to a maximum of 3000 g/mol. Moreover, they preferably have a melting point of at most 180°C. Furthermore, use is preferably made of antioxidants which are amorphous or liquid. Likewise, mixtures of two or more antioxidants can also be used as component (v).

In addition to the components (i), (ii) and (iii) and optionally (iv) and (v) mentioned, use may also be made of chain regulators (chain terminators), usually with a molecular weight of 31 to 3000 g/mol. Such chain regulators are compounds which exhibit only one functional group which reacts with isocyanates, such as, e.g , monofunctional alcohols, monofunctional amines and/or monofunctional polyols. Flow behavior, in particular with soft polyurethanes, can be selectively adjusted through such chain regulators. Chain regulators 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 the component (ii), and fall under the definition of the component (iii).

In addition to the components (i), (ii) and (iii) and optionally (iv) and (v) mentioned, crosslinking agents with two or more groups which react with isocyanate can also be used toward the end of the synthesis reaction, for example hydrazine hydrate. The components (ii) and (iii) can be chosen in relatively broad molar ratios in order to adjust the hardness of polyurethane (PU). Molar ratios of component (ii) to total chain extenders (iii) to be used of 10: 1 to 1 : 10, in particular of 1 : 1 to 1 : 4, have proved to be worthwhile, the hardness of the soft polyurethanes increasing with increasing content of (iii). The reaction for the preparation of polyurethane (PU) can be carried out at an index of 0 8 to 1 4: 1 , preferably at an index of 09 to 1 2: 1 , particularly preferably at an index of 1.05 to 1 2: 1 The index is defined by the ratio of the total isocyanate groups of the component (i) used in the reaction to the groups which react with isocyanates, i.e the active hydrogens, of the components (ii) and optionally (iii) and optionally monofunctional components which react with isocyanates as chain terminators, such as, e.g , monoalcohols.

The preparation of polyurethane (PU) can, according to processes known per se, be carried out continuously, for example according to the one-shot or the prepolymer process, or batchwise, according to the prepolymer operation known per se. In these processes, the components (i),

(ii), (iii) and optionally (iv) and/or (v) to be reacted can be mixed with one another successively or simultaneously, the reaction beginning immediately.

Polyurethane (PU) can be dispersed in water according to processes known per se, for example by dissolving polyurethane (PU) in acetone or preparing polyurethane as a solution in acetone, adding water and then removing the acetone, for example by distillation. In an alternative form, polyurethane (PU) is prepared as a solution in N-methylpyrrolidone or N-ethylpyrrolidone, water is added and the N-methylpyrrolidone or N-ethylpyrrolidone is removed.

In one embodiment of the present invention, aqueous dispersions according to the invention comprise two different polyurethanes, polyurethane (PU1) and polyurethane (PU2), of which polyurethane (PU1) is a "soft" polyurethane, which is constructed as described above as polyurethane (PU), and at least one “hard” polyurethane (PU2).

In one embodiment of the present invention, polyurethane (PU1) exhibits a Shore A hardness in the range from over 20 up to at most 90, preferably in the range from 25 to 75, wherein the Shore A hardness has been determined according to DIN 53505 after 3 s.

Hard polyurethane (PU2) can in principle be prepared analogously to soft polyurethane (PU1); however, other compounds (ii) which react with isocyanates or other mixtures of compounds (ii) which react with isocyanates are chosen, also described in the context of the present invention as compounds (ii-2) which react with isocyanates or in short compounds (ii-2).

Examples of compounds (ii-2) are in particular 1 ,4-butanediol, 1 ,6-hexanediol and neopentyl glycol, either in a mixture with one another or in a mixture with polyethylene glycol.

In an alternative form of the present invention, mixtures of diisocyanates, for example mixtures of HDI and IPDI, are each time chosen as diisocyanate (i) for polyurethane (PU2), larger proportions of IPDI being chosen for the preparation of hard polyurethane (PU2) than for the preparation of soft polyurethane (PU1).

In one embodiment of the present invention, polyurethane (PU2) exhibits a Shore A hardness in the range from over 60 up to at most 100, preferably in the range from equal or above 75 or 76 to 98, wherein the Shore A hardness has been determined according to DIN 53505 after 3 s.

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

In one embodiment of the present invention, soft polyurethane (PU1) exhibits an average particle diameter in the range from 100 to 300 nm, preferably 120 to 150 nm, determined by laser light scattering.

In one embodiment of the present invention, polyurethane (PU2) exhibits an average particle diameter in the range from 100 to 300 nm, preferably 120 to 150 nm, determined by laser light scattering.

Polymer layer (C) is preferably a polyurethane layer, a PVC layer, a layer of an epoxy resin, a polyacrylate layer or a polybutadiene layer, particularly preferably a polyurethane layer. Polymer layer (C) is particularly preferably a polyurethane layer.

In one embodiment of the present invention, polymer layer (C) exhibits an average thickness in the range from 15 to 300 pm, preferably from 20 to 150 pm, particularly preferably from 25 to 80 pm.

In one embodiment of the present invention, polymer layer (C) exhibits, on average, at least 100, preferably at least 250 and particularly preferably at least 1000 capillaries per 100 cm².

In one embodiment of the present invention, the capillaries exhibit an average diameter in the range from 0.005 to 0.05 mm, preferably from 0.009 to 0.03 mm.

In one embodiment of the present invention, the capillaries are evenly distributed over polymer layer (C) In a preferred embodiment of the present invention, the capillaries, however, are unevenly distributed over the polymer layer (C)

In one embodiment of the present invention, the capillaries are essentially curved. In another embodiment of the present invention, the capillaries exhibit an essentially linear course.

The capillaries bestow permeability to air and to water vapor on the polymer layer (C), without perforation being necessary. In one embodiment of the present invention, the permeability to water vapor of the polymer layer (C) can be more than 1 5 mg/cm² h, measured according to DIN 53333. It is thus possible, for example, for liquids comprising an active compound to be able to migrate through the polymer layer (C).

In one embodiment of the present invention, polymer layer (C) even exhibits, in addition to the capillaries, pores which do not extend over the total thickness of the polymer layer (C).

In one embodiment, polymer layer (C), in particular polyurethane layer (C), exhibits a pattern. The pattern can be any pattern and, for example, can reproduce the pattern of a leather or of a wood surface. In one embodiment of the present invention, the pattern can reproduce a nubuck leather.

In one embodiment of the present invention, polymer layer (C), in particular polyurethane layer (C), exhibits a velvety appearance.

In one embodiment of the present invention, the pattern can correspond to a velvet surface, for example with small crinite features with an average length of 20 to 500 pm, preferably 30 to 200 pm and particularly preferably 60 to 100 pm. The small crinite features can, for example, exhibit a circular diameter. In a special embodiment of the present invention, the small crinite features have a conical shape.

In one embodiment of the present invention, polymer layer (C), in particular polyurethane layer (C), exhibits small crinite features which are arranged at an average distance of 50 to 350 pm, preferably 100 to 250 pm, from one another.

In case the polymer layer (C), in particular polyurethane layer (C), exhibits small crinite features, the statements refer, with regard to the average thickness, to the polymer layer (C), in particular polyurethane layer (C), without the small crinite features.

In other embodiments, polymer layer (C), in particular polyurethane layer (C), exhibits text, logos or pictures. In one embodiment, polymer layer (C), in particular polyurethane layer (C), exhibits complicated pictures, as are described in WO 2012/072740.

In a preferred embodiment, polymer layer (C), in particular polyurethane layer (C), is formed from an aqueous polymer dispersion, preferably polyurethane dispersion, which comprises at least one crosslinking agent (CA), the at least one crosslinking agent (CA) being at least one polyisocyanate (P) which is blocked with at least one blocking agent (BA).

In a particularly preferred embodiment of the invention, aqueous polymer/polyurethane dispersions for the preparation of bonding layers (B) and/or polymer layer (C), in particular polyurethane layer (C), comprise from 0.1 to 5% by weight of dipropylene glycol dimethyl ether and/or 1 ,2-propanediol diacetate. In a particularly preferred embodiment, suitable crosslinking agents (CA) are added to the aqueous polymer/polyurethane dispersions as a 1 to 80% by weight solution in dipropylene glycol dimethyl ether and/or 1 ,2-propanediol diacetate, preferably as a 30 to 75% by weight solution in dipropylene glycol dimethyl ether and/or 1 ,2-propanediol diacetate.

In another preferred embodiment, aqueous polyurethane dispersions for the preparation of polymer layer (C) comprise 75-100 wt% of a hydrophilic polyfunctional oligomeric isocyanate based on 1 ,6-hexamethylene diisocyanate.

In a preferred embodiment, most part of layer (C) comprises at least one polyisocyanate (P) blocked with blocking agent (BA). Suitable polyisocyanates (P) may be selected from polyisocyanates described further above for component (C). Blocking agents (BA) for polyisocyanates (P) are commonly known to the skilled person in the art and may be selected according to the required deblocking temperature for example. The polyisocyanates (P) blocked with blocking agent (BA) present in the layers (C) can be identical or different.

Process of the invention

The process according to the invention is usually carried out so that a) the polyurethane layer (C) is formed using a mold, b) the adhesive polymer is applied, preferably in solid form, to the foam layer (A) and/or to polyurethane layer (C), and c) the polyurethane layer (C) is combined with the foam layer (A).

Stage (a) can be carried out as follows.

The mold is preferably a silicone mold. Silicone molds are understood to mean, in the context of the present invention, those molds in the preparation of which at least one binder is used which exhibits at least one, preferably at least three, 0-Si(R¹R²)-0- groups per molecule. In this connection, R¹ and - if present - R² are different or, preferably, identical and are chosen from organic groups and preferably Ci-C₆-alkyl, in particular methyl.

In one embodiment of the present invention, the silicone mold is a silicone mold structured using laser engraving.

In another embodiment, the mold is a mold made of ethylene/propylene rubber (EPM) or ethylene/propylene/diene rubber (EPDM).

In one embodiment of the present invention, the mold made of EPM or EPDM is a mold structured using laser engraving.

An aqueous polymer dispersion (thus, for example, the polyurethane (PU1)) is applied to a mold which is preheated to a temperature of at least 80°C, preferably in the range of at least 90°C to 160°C, in particular in the range from 120°C to 140°C, and the water is allowed to evaporate. Preferably, during the inventive process a pressure is applied in the process of joining foam layer (A), optional bonding layer (B) and polyurethane layer (C) in a range of 1 to 8 bar, preferably 2 to 6 bar, in particular 4 bar.

The application of aqueous polymer dispersion to the mold can be carried out according to methods known per se, in particular by spraying, for example with a spray gun.

The mold exhibits a pattern, also known as structuring, which is produced, for example, by laser engraving or by molding.

If it is desired to structure the mold using laser engraving, it is preferable, before the laser engraving, to strengthen the laser-engraveable layer by heating (thermochemically), by irradiating with UV light (photochemically) or by irradiating with high energy radiation (actinically) or any combination thereof.

Subsequently, the laser-engraveable layer or the layer composite is applied to a cylindrical (temporary) backing, for example made of plastic, glass fiber-reinforced plastic, metal or foam, for example using adhesive tape, negative pressure, clamping devices or magnetic force, and engraved as described above. Alternatively, the plane layer or the layer composite can also be engraved as described above. Optionally, during the laser engraving operation, the laser- engraveable layer is washed using a rotary cylindrical washer or a continuous washer with a cleaning agent for removing engraving residues.

In the manner described, the mold can be prepared as a negative mold or as a positive mold.

In a first alternative form, the mold exhibits a negative structure, so that the coating which can be bonded to component (A) can be obtained directly by application of a liquid plastic material to the surface of the mold and subsequent solidification of the polymer.

In a second alternative form, the mold exhibits a positive structure, so that a negative mold is first prepared from the laser-structured positive mold by molding. The coating which can be bonded to a flat backing can subsequently be obtained from this negative mold by application of a liquid plastic material to the surface of the negative mold and subsequent solidification of the plastic material.

Preferably, structure elements having dimensions in the range from 10 to 500 pm are engraved in the mold. The structure elements can be formed as elevations or depressions. The structure elements preferably have a simple geometric shape and are, for example, circles, ellipses, squares, rhombuses, triangles and stars. The structure elements can form a regular or irregular screen. Examples are a classical dot screen or a stochastic screen, for example a frequency- modulated screen. ln one embodiment of the present invention, wells are incorporated in the mold in the structuring of the mold using a laser, which wells exhibit an average depth in the range from 50 to 250 pm and a center-to-center separation in the range from 50 to 250 pm.

For example, the mold can be engraved so that it exhibits "wells" (depressions) which exhibit a diameter in the range from 10 to 500 pm on the surface of the mold. The diameter on the surface of the mold is preferably from 20 to 250 pm and particularly preferably from 30 to 150 pm. The separation of the wells can, for example, be from 10 to 500 pm, preferably from 20 to 200 pm, particularly preferably up to 80 pm.

In one embodiment of the present invention, the mold preferably exhibits, in addition to a coarse surface structure, also a fine surface structure. Both coarse and fine structure can be produced by laser engraving. The fine structure can, for example, be a microroughness with a roughness amplitude in the range from 1 to 30 pm and a roughness frequency of 0.5 to 30 pm. The dimensions of the microroughness are preferably in the range from 1 to 20 pm, particularly preferably from 2 to 15 pm and particularly preferably from 3 to 10 pm.

IR lasers are suitable in particular for laser engraving. However, it is also possible to use lasers with shorter wavelengths, provided that the laser exhibits a satisfactory intensity. For example, a frequency-doubled (532 nm) or frequency-tripled (355 nm) Nd-YAG laser can be used, or also an excimer laser (e.g. 248 nm). A CO2 laser with a wavelength of 10,640 nm can, for example, be used for the laser engraving. Lasers with a wavelength of 600 to 2000 nm are particularly preferably used. For example, Nd-YAG lasers (1064 nm), IR diode lasers or solid-state lasers can be used. Nd/YAG lasers are particularly preferred. The image information to be engraved is transferred directly from the layout computer system to the laser apparatus. The laser can be operated either continuously or in pulsed mode.

As a rule, the mold obtained can be used directly after it has been prepared. If desired, the mold obtained can still be cleaned subsequently. Layer constituents which have been loosened but possibly still not completely removed from the surface are removed by such a cleaning stage.

As a rule, simple treatment with water, water/surfactant, alcohols or inert organic cleaning agents, which are preferably low-swelling, is sufficient.

In an additional stage, an aqueous formulation of a polymer such as PU1 is applied to the mold. Application can preferably be carried out by spraying. The mold should be preheated, if the formulation of polymer is applied, for example to temperatures of at least 80°C, preferably at least 90°C to 160°C, in particular in the range from 120°C to 140°C. The water from the aqueous formulation of polymer evaporates and forms the capillaries in the solidifying polymer layer.

Aqueous is understood to mean, in connection with the polymer dispersion, that it comprises water but less than 5% by weight, based on the dispersion, preferably less than 1% by weight, of organic solvent. Particularly preferably, no volatile organic solvent can be detected. Volatile organic solvents are understood to mean, in the context of the present invention, those organic solvents which, at standard pressure, exhibit a boiling point of up to 200°C.

In one embodiment of the present invention, aqueous polymer dispersion comprises at least one additive chosen from pigments, delustrants, light stabilizers, flame retardants, antioxidants, antistatics, antisoiling agents, antisqueak agents, thickening agents, in particular thickening agents based on polyurethanes, water repellants, oil repellants and hollow microspheres. In one embodiment of the present invention, aqueous polymer dispersion comprises in total up to 20% by weight of additives.

Aqueous polymer dispersion can additionally comprise one or more organic solvents. Suitable organic solvents are, for example, alcohols, such as ethanol or isopropanol and in particular glycols, diglycols, triglycols or tetraglycols and glycols, diglycols, triglycols or tetraglycols dialkoxylated or preferably monoalkoxylated with Ci-C4-alkyl. Examples of suitable organic solvents are ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1 ,2-dimethoxyethane, methyl triethylene glycol ("methyl triglycol") and triethylene glycol n-butyl ether ("butyl triglycol").

In one embodiment of the invention, aqueous polymers, in particular polyurethane dispersions, do not comprise any propylene carbonate.

In a preferred embodiment, polyurethane layer (C) is formed from an aqueous polyurethane dispersion, which optionally comprises at least one crosslinking agent (CA), the at least one crosslinking agent (CA) being at least one polyisocyanate (P) which is optionally blocked with at least one blocking agent (BA), as are defined above.

In one embodiment of the invention, aqueous polyurethane dispersions for the preparation of polymer layer (C) comprise from 0.1 to 5% by weight of dipropylene glycol dimethyl ether and/or 1,2-propanediol diacetate. In a particularly preferred embodiment, suitable crosslinking agents (CA) are added, as 1 to 80% by weight solution in dipropylene glycol dimethyl ether and/or 1,2- propanediol diacetate, preferably as 30 to 75% by weight solution in dipropylene glycol dimethyl ether and/or 1 ,2-propanediol diacetate, to the aqueous polyurethane dispersions for the preparation of the at least one polymer layer (C).

After the curing of the polyurethane layer (C), it is separated from the mold, for example by stripping, and a polymer film is obtained which forms, in the multilayered composite system according to the invention, the polymer layer (C). In a preferred embodiment of the present invention, the mold can also be allowed to act as protective layer and it can be removed only after the preparation of the actual multilayered composite system.

In stage (b), the adhesive polymer is applied, preferably in solid form, to the foam layer (A) and/or to the polyurethane layer (C).

The adhesive polymer in solid form (such as of the adhesive grid, adhesive web or adhesive film) can be applied according to methods known per se, in particular by putting on or pressing on. Application can be carried out continuously or batchwise. The adhesive polymer in solid form can be provided as wound-up product.

In another form, the adhesive polymer is applied in solid form to the polyurethane layer (C).

In another form, the adhesive polymer is applied in solid form to the foam layer (A) and to the polyurethane layer (C).

In a preferred form, the adhesive polymer is applied in solid form to the foam layer (A).

In another preferred embodiment, the adhesive polymer is spray applied to foam layer (A), polyurethane layer (C), or foam layer (A) and polyurethane layer (C).

In stage (c), the polyurethane layer (C) is combined with the foam layer (A).

Usually, the polyurethane layer (C) is combined with the foam layer (A) so that the layer(s) of adhesive polymer come to lie between polyurethane layer (C) and foam layer (A).

The adhesive polymer is for the most part cured, for example thermally, through actinic radiation or through aging, and multilayered composite material according to the invention is obtained. The curing is preferably carried out thermally.

It is also possible to compress the composite system, for example using a calender. Suitable contact pressures can be in the range from 1 to 20 bar, preferably 1.5 to 10 bar and in particular 2 to 5 bar. Suitable contact times can be in the range from 10 seconds to 100 min, preferably 30 seconds to 30 min and in particular 1 to 10 min. Suitable contact temperatures can be in the range from 80°C to 160°C, preferably 90°C to 150°C and in particular 100°C to 140°C.

In another preferred embodiment, the process for manufacturing of the multi-layered composite material according to the present invention comprises the steps a) providing an optionally structured mold, b) heating the mold to a temperature at a temperature above 80°C, c) forming a polymeric film layer (C) as top-layer by using the mold of a), d) providing a polymeric foam layer (A) comprising foamed granules of a thermoplastic elastomer, e) optionally slicing the polymeric foam layer (A) from step d), f) optionally applying an adhesive material (component (B)) to the polymeric film layer (C) of step c) and/or to the polymeric foam layer (A) of step d), g) combining the polymeric film layer (C) and polymeric foam layer (A) under a pressure in the range of 1 to 8 bar, preferably 2 to 6 bar, in particular 4 bar.

For measuring the adhesion of the layers, commonly adhesion tests are known to evaluate the adhesion of a coatings surface to a carrier material (measuring of adhesion breaks).

Multi-layered composite material

According to a further aspect, the present invention is also directed to a multi-layered composite material obtained or obtainable according to a process as disclosed above.

The multi-layered composite material comprising at least one polymeric layer comprising foamed granules according to the present invention can be used for a variety of applications, such as shoes, in furniture, seating, automotive interior, medical equipment, industrial applications, fashion bags, fashion accessories, gloves, consumer electronics, wearable devices, headphones, speakers, packaging, protection equipment, as cushioning, toys, animal toys, saddles, balls and sports equipment, for example sports mats, sport gloves, or as floor covering and wall paneling.

Use of the multi-layered composite material

According to a further aspect, the present invention is thus also directed to the use of the multi layered composite material comprising at least one polymeric layer comprising foamed granules obtained or obtainable according to a process as disclosed above or the multi-layered composite material as disclosed above for shoes, in furniture, seating, automotive interior, medical equipment, industrial applications, fashion bags, fashion accessories, gloves, consumer electronics, wearable devices, headphones, speakers, packaging, protection equipment, as cushioning, toys, animal toys, saddles, balls and sports equipment, for example sports mats, sport gloves, or as floor covering and wall paneling.

The invention is further described by examples. The examples relate to practical and in some cases preferred embodiments of the invention that do not limit the scope of the invention.

EXAMPLES

Materials:

Component A Expanded thermoplastic polyurethane (E-TPU) foam beads as carrier material (substrate) for layer A.

Isocyanate: 4,4‘-methylene diphenyl diisocyanate (MDI)

Chain extender: 1 ,4-butanediol

Polyol: poly tetrahydrofuran (PolyTHF) 1000

Further additives such as catalysts, plasticizers, impact modifiers, fillers, reinforcing materials, flame retardants, stabilizers, light stabilizers, waxes, colorants and/or antioxidants can be added in particular without deviation of the target result. For example, polystyrene is such an additive.

Reference carrier materials for component A o Microfiber, 1.2 mm, solvent borne by Huafon Microfiber o K-leather (kangaroo leather), 0.9 - 1.1 mm, by Packer Leather

Component C valure® PToM: aqueous anionic polyurethane dispersion, 31-38 wt% solids content, pH 6-

8.5, efflux time 10-20 s (DIN53211, 4 mm at 20°C) commercially available from BASF Coatings GmbH.

Pigment: aqueous black pigment preparation, commercially available from BASF SE as Luconyl® NG Black 0066. hardener [curing 75-100 wt% of hydrophilic polyfunctional oligomeric isocyanate agent] HAH01S20: based on 1 ,6-hexamethylene diisocyanate, commercially available from BASF Coatings GmbH.

Production methods:

Manufacturing / Providing of component A

1. Manufacture of thermoplastic polyurethane (TPU)

The production of the following example TPU 1 was carried out in a twin-screw extruder, ZSK58 MC, of the company Coperion with a process length of 48D (12 housings). The discharge of the melt (polymer melt) from the extruder was carried out by means of a gear pump. After the melt filtration, the polymer melt was processed into granules by means of underwater granulation, which were dried continuously in a heating vortex bed, at 40 - 90°C. The polyol, the chain extender and the diisocyanate as well as a catalyst were dosed into the first zone. The addition of further additives, as described above, takes place in Zone 8. The housing temperatures range from 150 to 230 °C. The melting and underwater- granulation are carried out with melting temperatures of 210 - 230°C. The screw speed is between 180 and 240 rpm. The throughput ranges from 180 to 220 kg/h.

2. Manufacture of foamed granules (expanded thermoplastic polyurethane (eTPU)) 2.1 For the production of the expanded particles (foamed granules) from the thermoplastic polyurethane, a twin-screw extruder with a screw diameter of 44 mm and a ratio of length to diameter of 42 was used with subsequent melting pump, a start-up valve with screen changer, a perforated plate and an underwater granulation. The thermoplastic polyurethane was dried before processing at 80 °C for 3 h in order to obtain a residual moisture of less than 0.02 wt.%.

The thermoplastic polyurethane used is dosed via a gravimetric dosing device into the feed of the twin-screw extruder.

After dosing the materials into the feed of the twin-screw extruder, the materials were melted and mixed. Subsequently, the propellants CO2 and N2 were added via one injector each. The remaining extruder length was used for homogeneous incorporation of the propellant into the polymer melt. After the extruder, the polymer/propellant mixture was pressed into a perforated plate (LP) by means of a gear pump (ZRP) via a start-up valve with screen changer (AV) into a perforated plate. Via the perforated plate individual strands are produced. These strands were conveyed to the pressurized cutting chamber of the underwater granulation (UWG) unit, in which the strands are cut into granules and further transported with the water while the granules expanded.

The separation of the expanded particles / granules from the process water is ensured by means of a centrifugal dryer.

The total throughput of the extruder, polymers and propellants was 40 kg/h. The quantities of polymers and propellants used are listed in Table 1. Here, the polymers are always counted as 100 parts while the propellant is additionally counted, so that total compositions above 100 parts are obtained.

Table 1: Proportions of dosed polymers and propellants where the polymers/solids always yield 100 part and the propellants are counted additionally

The temperatures used by the extruder and the subsequent devices as well as the pressure in the cutting chamber of the UWG are listed in Table 2.

Table 2: Temperature data of plant parts

After the separation of the expanded granules from the water by means of a centrifugal dryer, the expanded granules are dried at 60 °C for 3 h to remove the remaining surface water as well as possible moisture in the particle in order to not distort a further analysis of the particles.

2.2 In addition to processing in the extruder, expanded particles were also produced in an autoclave. For this purpose, the pressure vessel was filled with a filling degree of 80% with the solid/liquid phase, wherein the phase ratio was 0.32.

Solid phase is the TPU1 and the liquid phase is a mixture of water with calcium carbonate and a surface-active substance. With pressure onto this solid/liquid phase, the blowing agent / propellant (butane) was pressed into the tight pressure vessel, which was previously rinsed with nitrogen. The quantity is given in Table 3 and calculated in relation to the solid phase (TPU1). The pressure vessel was heated by stirring the solid/liquid phase at a temperature of 50 °C and then nitrogen was pressed into the pressure vessel up to a pressure of 8 bar. Subsequently, further heating was carried out until the desired impregnation temperature (IMT) was reached. When the impregnation temperature and the impregnation pressure were reached, the pressure vessel was relaxed via a valve after a given holding time. The exact manufacturing parameters of the manufacturing of foamed granules in an autoclave (pressure vessel, impregnation vessel) are listed in Table 3.

Table 3: Manufacturing parameters of the impregnated material TPU1

3. Molding / Fusing

3.1 Manufacture of moldings by steam chest molding / water vapour fusing to obtain a mold / particle foam based molded article

The expanded granules were then fused on a molding machine from Kurtz ersa GmbH (Energy Foamer) to square plates with a side length of 200 mm and a thickness of 10 mm or 20 mm by covering with water vapor. With regard to plate thickness, the fusing parameters differ only in terms of cooling. The fusing parameters of the different materials were chosen in such a way that the plate side of the final molded part facing the moving side (Mil) of the tool had as few collapsed eTPU particles as possible. Usually, steaming times in the range of 3 to 50 seconds were used for the respective steps. Through the movable side of the tool, a slit steaming was also carried out if necessary. Irrespective of the experiment, regarding the fixed (Ml) and the movable side of the tool, at the end a cooling time of 120 s was always set at a plate thickness of 20 mm and a cooling time of 100 s was always set with a 10 mm thick plate. The respective molding / steaming conditions are listed! in Table 4 as steam pressures. The plates are stored in the oven for 4 hours at 70 °C.

Table 4: Steaming conditions (steam pressures)

The obtained molded articles (E-TPU molding, component A, particle foam layer) are preferably obtained by steam chest molding process or RF-molding. Alternatively, a double belt press technology process may be applied, which directly results is layers for component A with a thickness of for example 5 mm. Consequently, a subsequent slicing step after molding is not necessary.

4. Slicing

A conventional mechanical cutting process is applied for the molded article from step 3.) in order to obtain slices for the layers of component A with for example a thickness of 1 mm, 2 mm, 3 mm or 5 mm. The cutting of the plates is done on a horizontal splitting machine (of manufacturer Fecken-Kirfel or Baumer). This is a conventional machine used for splitting of foam planks.

Lamination-Process / Combining component A and component C

1. Production of a mold

A silicone mold with a desired pattern was prepared according to the state of the art. Therefore, a polyurethane layer (component C) was formed on the mold by spraying the hot mold with the aqueous polyurethane dispersion comprising valure® PToM, hardener FIAFI01S20 and pigment according to the state of the art. In detail, a liquid silicone was poured onto a surface having the pattern of full grain calf leather. The silicone was cured by adding a solution of di-n-butylbis(l-oxoneodecyloxy)- stannane as 25% by weight solution in tetraethoxysilane as an acidic curative to obtain a silicone rubber layer 2 mm in thickness on average, which served as the mold. The mold was adhered onto a 1.5 mm thick aluminum support. Production of an aqueous polyurethane dispersion Disp.1 The following were mixed in a stirred vessel:

7% by weight of an aqueous dispersion (particle diameter: 125 nm, solids content: 40%) of a soft polyurethane (PU1.1) prepared from hexamethylene diisocyanate (a1.1) and isophorone diisocyanate (a1.2) in a weight ratio of 13:10 as diisocyanates and as diols, a polyester diol (b1.1) having a molecular weight M_w of 800 g/mol, prepared by polycondensation of isophthalic acid, adipic acid and 1 ,4-dihydroxymethylcyclohexane (isomer mixture) in a molar ratio of 1 :1 :2, 5% by weight of 1 ,4-butanediol (b1.2) and also 3% by weight of monomethylated polyethylene glycol (c.1) and also 3% by weight of H2N-CH2CH2-NH-CH2CH2-COOH, % by weight all based on polyester diol (b1.1), softening point of soft polyurethane (PU1.1): 62°C, softening starts at 55°C, Shore A hardness 54,

65% by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (PU2.2), obtainable by reaction of isophorone diisocyanate (a1.2),

1 ,4-butanediol, 1 ,1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having a molecular weight M_w of 4200 g/mol, softening point of 195°C, Shore A hardness 86,

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

6% by weight of a 65% by weight aqueous dispersion of the silicone compound according to Example 2 of EP-A 0 738 747 (f.1)

2% by weight of carbon black,

0.5% by weight of a thickening agent based on polyurethane, 1% by weight of microballoons of polyvinylidene chloride, filled with isobutane, diameter 20 pm, commercially obtainable for example as Expancel® from Akzo Nobel.

This gave an aqueous dispersion Disp.1 having a solids content of 35% and a kinematic viscosity of 25 seconds at 23°C, determined in accordance with DIN EN ISO 2431 , as of May 1996. Production of an aqueous formulation Disp.2 The following were mixed in a stirred vessel:

7% by weight of an aqueous dispersion (particle diameter: 125 nm, solids content: 40%) of a soft polyurethane (PU1.1) prepared from hexamethylene diisocyanate (a1.1) and isophorone diisocyanate (a1.2) in a weight ratio of 13:10 as diisocyanates and as diols, a polyester diol (b1.1) having a molecular weight M_w of 800 g/mol, prepared by polycondensation of isophthalic acid, adipic acid and 1 ,4-dihydroxymethylcyclohexane (isomer mixture) in a molar ratio of 1:1:2. 5% by weight of 1 ,4-butanediol (b1.2), 3% by weight of monomethylated polyethylene glycol (c.1) and also 3% by weight of H2N- CH2CH2-NH-CH2CH2-COOH, % by weight all based on polyester diol (b1.1), softening point of 62°C, softening starts at 55°C, Shore A hardness 54,

65% by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (a2 2), obtainable by reaction of isophorone diisocyanate (a1.2),

1 ,4-butanediol (PU1.2), 1,1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having a molecular weight M_w of 4200 g/mol (b1.3), polyurethane (PU2.2) had a softening point of 195°C, Shore A hardness 90,

3.5% by weight of a 70% by weight solution (in propylene carbonate) of compound (V.1), NCO content 12%,

2% by weight of carbon black.

This gave a polyurethane dispersion Disp.2 having a solids content of 35% and a kinematic viscosity of 25 seconds at 23°C, determined in accordance with DIN EN ISO 2431, as of May 1996. Application of aqueous polyurethane dispersions onto mold from 11.1.

The mold from 11.1. was placed into the process line and via IR oven pre-heated to 120 - 140 °C surface temperature. Disp.1 was then sprayed onto it through a spray nozzle, at 100 g/m² (wet). No air was admixed during application, which was done with a spray nozzle having a diameter of 0.46 mm, at a pressure of 65 bar. This was followed by drying at a surface temperature of 70-100 °C The spray nozzle was located 20 cm above the surface passing underneath it, and could be moved in the transport direction of the surface, and moved transversely to the transport direction of the surface.

In an analogous arrangement, Disp.2 was immediately thereafter applied to the mold thus coated, as bonding layer (B.1) at 50 g/m² wet, and subsequently allowed to dry.

This gave a mold coated with polyurethane film (C.1) and bonding layer (B.1).

Particle foam layer (component A) was sprayed with Disp 2, at 30 g/m² (wet). The particle foam layer can optionally pass a dry hot air oven at 60 °C or pre-dry at ambient conditions e.g. at room temperature of about 21 °C.

Both, mold coated with polyurethane film (C.1) and bonding layer (B.1) as well as particle foam layer (component A) coated with Disp 2 are laminated in a static press at 120 °C set temperature for 20-30 s.

5. Production of an inventive multilayered composite material

Thereafter, particle foam layer (component A) was placed with the sprayed side onto the still hot bonding layer (B.1) which was on the mold together with polyurethane film (C.1), and compressed in a press at 4 bar and 110°C for 15 seconds. The inventive multilayered composite material MSV.1 thus obtained was subsequently removed from the press and the mold was removed from it.

The inventive multilayered composite material MSV.1 thus obtained was notable for pleasant haptics, an appearance which was identical to a leather surface, and also breathability. In addition, the inventive multilayered composite material MSV.1 was easy to clean of soiling such as dust for exannple.

III. Characterization methods

1. Martindale Test:

The Martindale test is a test to evaluate abrasive resistance of surfaces in leather & textile applications.

Equipment: James Heal Martindale machinery Procedure:

^■ Test sample is cut out and positioned in machinery

^■ Abrasive textile and sample are positioned ^■ Weight of 12 kPa is positioned onto sample

^■ Machinery tests 20.000 and 50.000 elliptical cycles and the surface of the samples is optically evaluated (optionally an intermediate evaluation of the surface can be made e.g. after each 1.000 cycles)

^■ References: DIN EN ISO 12947-1 to DIN EN ISO 12947-4 Veslic Test:

The veslic test is a test to evaluate abrasive resistance of surfaces and color fastness of samples

Equipment: VESLIC test equipment Procedure:

^■ Test sample is cut out and positioned in machinery

^■ Wool felt is positioned between stamp and sample surface

^■ Depending on the test (dry wool felt, or wet wool felt) the machinery is set on the cycles to run linear movements on top of the sample surface

• Dry: 2000 cycles

• Wet: 500 cycles

^■ After, the surface of the sample is visually evaluated regarding damages and the wool felt regarding color stain

Bally Flex Test:

The bally flex test is a test to evaluate surface damaging due to folding. Equipment: Bally Flexing Tester Procedure:

^■ Test sample is cut out and positioned in a folded way into the machinery

^■ The machinery is set to the required cycles of folding (usually 100.000 cycles)

^■ After, the surface of the sample is visually evaluated regarding surface damages

^■ Qualitative Rating of mechanical tests (visual inspection):

1 = Sample destroyed

2 = Noticeable to big damage to sample

3 = Slight to noticeable damage to sample

4 = Minor to almost no damage to sample 5 = No or almost no damage / change to sample

4. Air Permeability Test

The air permeability test is a test to evaluate the air permeability of a material. Equipment: I MAC air permeability measurement system

Procedure:

^■ Test sample is cut our and positioned into the machinery between 2 chambers

^■ Both chambers are filled with compressed air

^■ The first chamber is opened to the atmosphere and the second chamber levels out it^'s generated overpressure through the positioned sample

^■ Time is measured between a starting pressure (0,05) and end pressure (0,01 bar) that is reached due to pressure loss in the first chamber

^■ The measurement shows the speed of pressure leveling between the 2 chambers

^■ Time and the volume of the chambers (1,6 I or 10 I) is noted; the smaller the value [time] the better the air permeability.

IV. Results: Table 1

Test samples for mechanical testing

Table 2

Test results for mechanical testing

Table 3

Test samples for air breathability mechanical testing

Table 4

Test results for air breathability mechanical testing

As result, the present invention and with the new combination of materials (multi-layered composite material) shows improved light weight, breathable substrate with smooth / good feeling surface properties. The inventive material shows lighter weight and density as leather in the literature: - Cow leather: 0.4-0.9 g/cm³ (source: https://www.lederzentrum.de/wiki/index.php/Rindsleder)

Kangaroo leather: 0.6-1.0 g/cm³ (source: Prof. Haiko Schuz, FILK Forschungsinstitut fur Leder)

Microfiber: 0.4-0.55 g/cm³

Furthermore, the inventive material is showing comparable performances but reduced weight of E-TPU (lower densities):

E-TPU: 0.2-0.3 g/cm³

The lower densities on E-TPU slices compared to carrier materials like microfiber, kangaroo leather (see above) proves that the inventive material is advantageous and of lighter weight in comparison to the state of the art.

Claims

1. Multi-layered composite material which comprises components

(A) comprising at least one polymeric layer comprising foamed granules,

(C) comprising at least one polymeric layer comprising a film, wherein component A is a thermoplastic elastomer and wherein component C is the top- layer.

2. Multi-layered composite material according to claim 1 , wherein the thermoplastic elastomer of the foamed granules (component A) is selected from the group consisting of thermoplastic polyurethanes (TPU), thermoplastic polyamides (TPA) and thermoplastic polyetheresters (TPC), thermoplastic polyesteresters (TPC), thermoplastic vulcanizates (TPV), thermoplastic polyolefins (TPO), thermoplastic styrenic elastomers (TPS) and mixtures thereof.

3. Multi-layered composite material according to claim 1 or 2, wherein the foamed granules of layer A are fused together.

4. Multi-layered composite material according to any one of claims 1 to 3, wherein the layers of component (A) and component (C) are laminated together without a layer of component (B)

5. Multi-layered composite material according to any one of claims 1 to 4, wherein the adhesive material (component B) is present and is based on polyurethanes, polyamides, polyesters, polyolefins or acrylic copolymers.

6. Multi-layered composite material according to any one of claims 1 to 5, wherein the adhesive material (component B) has a melting range of 60°C to 125°C.

7. Multi-layered composite material according to any one of claims 1 to 6, wherein the material of component C is selected from the group consisting of polyurethane, thermoplastic polyurethane, polyvinylchloride, thermoplastic polyolefins.

8. Multi-layered composite material according to any one of claims 1 to 7, wherein the layer

A has a thickness of 0.1 to 5 mm and wherein the layer C has a thickness of 1 to 500 pm.

9. Multi-layered composite material according to any one of claims 1 to 8, wherein layer C comprises a patterned or a non-patterned surface.

10. Process for the manufacturing of a multi-layered composite material comprising the steps a) providing an optionally structured mold, b) heating the mold to a temperature at a temperature above 80°C, c) forming a polymeric film layer (C) as top-layer by using the mold of a), d) providing a polymeric foam layer (A) comprising foamed granules of a thermoplastic elastomer, e) optionally slicing the polymeric foam layer (A) from step d), f) optionally applying an adhesive material (component (B)) to the polymeric film layer (C) of step c) and/or to the polymeric foam layer (A) of step d), g) combining the polymeric film layer (C) and polymeric foam layer (A) under a pressure in the range of 1 to 8 bar, preferably 2 to 6 bar, in particular 4 bar.

11. Process according to claim 10, wherein the mold is a silicone mold structured using laser engraving.

12. Process according to claim 10 or 11 , wherein wells are incorporated in the mold, which wells exhibit an average depth in the range from 50 to 250 pm and a center-to-center separation in the range from 50 to 250 pm.

13. Multi-layered composite material obtained or obtainable by a process according to any one of claims 10 to 12.

14. Use of the multi-layered composite material according to any one of claims 1 to 9 or 13 for shoes, in furniture, seating, automotive interior, medical equipment, industrial applications, fashion bags, fashion accessories, gloves, consumer electronics, wearable devices, headphones, speakers, packaging, protection equipment, as cushioning, toys, animal toys, saddles, balls and sports equipment, for example sports mats, sport gloves, or as floor covering and wall paneling.

15. Article comprising the multi-layered composite material according to any one of claims 1 to 9 or 13 for shoes, furniture, seating, automotive interior, medical equipment, industrial applications, fashion bags, fashion accessories, gloves, consumer electronics, wearable devices, headphones, speakers, cushioning, toys, animal toys, saddles, balls and sports equipment, for example sports mats, sport gloves, or as floor covering and wall paneling.