BIO-BASED ARTIFICIAL LEATHER

Abstract

The present invention relates to a layered material and a method of producing the same.

The layered material has one or more layers, including at least one foamed layer, said foamed layer comprising a first polymer and a second polymer, said foamed layer having a high BBC.

Claims

1. Layered material with four or more layers with the following order: textile support layer; foamed layer A; non-foamed top layer; and varnish layer; wherein layer A comprises: 0-20 weight percent polyethylene as the first polymer, 30-80 weight percent ethylene propylene diene monomer (EPDM) as the second polymer; 10-40 weight percent filler, wherein the organic component of layer A has a bio-based carbon content (BBC) of at least 50% as determined by ASTM D6866-16 Method B (AMS); and wherein the layered material has a thickness of up to 4 cm.

2. The layered material according to claim 1, wherein the foamed layer A has been extruded or calendered using a blowing agent.

3. The layered material according to claim 1, wherein the non-foamed top layer has a thickness less than layer A.

4. The layered material according to claim 1, wherein the layer A is radiation crosslinked with electron beams.

5. The layered material according to claim 1, wherein layer A has a hot set at 200° C. of less than 100%, preferably less than 50%, measured according to DIN EN 60811-507.

6. The layered material according to claim 2, wherein an expandable lightweight filler is used as blowing agent in the foamed layer A.

7. The layered material according to claim 1, in the form of an artificial leather.

8. The layered material according to claim 1, wherein the non-foamed top layer comprises: 1-20 weight percent polyethylene as the first polymer, 30-80 weight percent ethylene propylene diene monomer (EPDM) as the second polymer; 10-40 weight percent filler, 0-3 weight percent silicone additive, and 0.5-3 weight percent antioxidant and/or UV absorber wherein the organic component of the top layer has a bio-based carbon (BBC) content of at least 50%, as determined by ASTM D6866-16 Method B (AMS); and wherein the layered material has a thickness of up to 4 cm; preferably, the material of layer A and the top layer is identical, with the difference that the top layer is not foamed and, in particular, has no blowing agents.

9. The layered material according to claim 2, wherein the foamed layer comprises: 1-15 weight percent of polyethylene, 50-80 weight percent ethylene propylene diene monomer (EPDM), as the second polymer, 10-40 weight percent filler(s), 1-3 weight percent expanded hollow microspheres, 0-3 weight percent silicone additive, and 0.5-3 weight percent antioxidant and/or UV absorber.

10. The layered material according to claim 1, wherein the varnish layer comprises or consists of acrylic resin, polyurethane and/or polytetrafluoroethylene (Teflon).

11. Method for producing the layered material according to claim 1, comprising: a) providing the textile support layer, the composition for layer A, and the composition for the non-foamed top layer, b) extruding or calendering the components of step (a) into a layered material, and c) applying the varnish layer to the layered material from step b).

12. The method of claim 11, further comprising: d) radiation crosslinking of the layered material with electron beams, with continuous passage of the layered material through a device for irradiation.

13. Layered material having four or more layers, at least one of which is a foamed layer A, which has been prepared using an extrusion process or a calendering process, wherein the following composition is extruded or calendered: 1-15 weight percent of polyethylene as the first polymer, 50-80 weight percent of a second polymer selected from the group consisting of ethylene propylene diene monomer (EPDM), ethylene vinyl acetate copolymer (EVA), polyethylene octene (POE), ethylene butyl acrylate copolymer (EBA), and ethylene methacrylate copolymer; 10-40 weight percent filler, wherein the organic component of the foamed layer has a bio-based carbon (BBC) content of at least 50%, as determined by ASTM D6866-16 Method B (AMS), and wherein the layered material has a thickness of up to 4 cm.

Description

[0210] The present disclosure will be further explained with reference to figures:

[0211] FIG. 1a/b shows the layered material VKL068 with 1% Expancel 950MB80, extruded at 200° C. (without mixing elements) at different magnifications. Before the picture was taken, the test sample (or tape) was split. The purpose of splitting the sample is to be able to observe the core of the material and in particular the way in which the dye is dispersed, as well as the distribution and size of the microbubbles after the microspheres have expanded during extrusion. Here, “ . . . extruded . . . without mixing elements . . . ” means that the screw in the extruder is constructed with conveying only. In principle, for a screw of an extruder there are the conveying elements (these serve in particular to convey the mass), and the mixing (these serve in particular to improve mixing/integration of the various components). Therefore, it can be observed that the distribution of the components is better/more homogeneous with the mixing elements. [0212] Image acquisition method: The specimen to be photographed as a thin film is placed on the specimen holder of a LEICA MS5 microscope. The desired magnification is selected and a photo is taken using a JENOPTIK Model ProgRes Speed XT Core 5 camera.

[0213] FIG. 2a/b shows the layered material VKL070 with 1% Expancel 950MB80 extruded at 180° C. (without mixing elements) at different magnifications. Before the picture was taken, the test sample was split.

[0214] FIG. 3a/b shows the layered material VKL070 with 1.5% Expancel 950MB120 extruded at 200° C. (with mixing elements) at different magnifications. Before the image was taken, the test sample was split. It was observed that the dispersion of the color masterbatch and the distribution of microbubbles become more homogeneous when mixing elements are used during extrusion. Here, “ . . . extruded . . . with mixing elements . . . ” means that the screw in the extruder is constructed with conveying and mixing elements.

[0215] FIG. 4a/b shows the layer material VKL070 with 1.5% Expancel 950MB120 extruded at 200° C. (with mixing elements) at different magnifications. The images were taken from the tape surface.

[0216] FIG. 5 shows the structure of a device for radiation crosslinking, where the reference signs are as follows: 1: Radiation crosslinking apparatus; 2: Accelerator; 3: High voltage generator pressure tank with SF.sub.6 gas; 4: Accelerator tubes; 5: Deflection magnet; 6: Layered material.

EXAMPLES

[0217] The production of layered materials according to the invention can be carried out as described below.

[0218] The first step is about homogeneously mixing the various components of the compound, which is then used for extrusion or calendering of the layered material. A bus kneader can be used advantageously for this purpose. First, the entire compounding system must be cleaned and assembled. The various raw materials, except the blowing agent, for example Expancel microspheres, and the color masterbatch, are metered/incorporated into the bus kneader according to the desired composition for the compound.

[0219] The temperature profile is selected according to the raw materials so that sufficient shear allows good distribution of the various components. The compound mass is granulated and the corresponding granules are then cooled down to room temperature.

[0220] A second step is about extruding or calendering a film with the granules as produced above. For example, an extruder with a wide slot die, the width of which is selected depending on the width of the artificial leather coil or layered material to be produced, can be used advantageously for this purpose. First, the entire extrusion system must be cleaned and assembled. The granules, this time with the blowing agent for the foamed layer, for example the Expancel microspheres, and the color masterbatch, are metered and/or incorporated in the extruder according to the desired composition for the compound. Preferably, a screw with conveying and mixing is used so that the microspheres and the color masterbatch can be distributed well and homogeneously.

[0221] The temperature profile is chosen depending on the starting materials (compound in granular form) and in particular according to the types of microspheres to allow optimal expansion of the microspheres.

[0222] No blowing agent is used for the top layer, which is coextruded with the foamed layer. The compound for the top layer can be the same compound as for the foamed layer. However, the compound may be slightly different, but in any case it is also bio-based. However, it does not contain a blowing agent. Both compounds are then coextruded on a textile carrier material (cotton, cotton/polyester . . . ).

[0223] In a third step, the varnish is then applied to the top layer surface and dried. Before applying the varnish layer, it may be necessary to use a pretreatment, such as surface activation by a cold plasma corona treatment, to activate the surface of the top layer and enable good adhesion of the varnish.

[0224] In a fourth step, it is then possible, if desired, to perform radiation crosslinking of the previously obtained vegan bio-based artificial leather film or layered material. The radiation dose and thus the corresponding crosslinking density are selected according to the intended application. For a film thickness of about 1 mm, and with a 1.05 MeV voltage, a radiation dose of 25 to 300 KGy, preferably 50 to 100 KGy, can advantageously be selected.

[0225] Using the method described above and the starting materials described below, the layered material samples VKLO68, VKL070, VKL074, VKL075 (see Table 1), and VKL062, VKL063, VKL064, VKL065, VKL066, VKL067, and VKL069 (see Table 2) were prepared.

[0226] SLL318 is a bio-based LLDPE (Linear Low Density Polyethylene) from the company BRASKEM/Brazil (represented in Europe by the company FKuR (Germany)). The Bio-based content is at least 87%.

[0227] Hydrocarb 95T-OG is natural chalk from the company OMYA.

[0228] DC 50-320 is a silicone additive (50% silicone on EVA polymer as carrier) from Dow Corning.

[0229] Keltan ECO 5470 is a bio-based EPDM from ARLANXEO/Netherlands.

[0230] Kelton 5508 ECO is a bio-based EPDM from ARLANXEO/Netherlands.

[0231] Expancel 950MB80 are microspheres from the company AKZO NOBEL (Sweden), which can expand very much with heat (from a given temperature, from about 120 to about 200° C. depending on the type).

[0232] Songnox 1010 is a phenolic antioxidant.

TABLE-US-00001 TABLE 1 VKL068 VKL074 VKL070 VKL075 SLL318 (LLDPE) 33.50 33.50 25.00 25.00 Hydrocarb 95T-OG (chalk) 29.50 28.00 29.50 27.50 DC 50-320 (EVA base, silicone  2.00  2.00  2.00  2.00 additive) Keltan ECO 5470 (EPDM) 33.70 42.20 Keltan 5508 ECO = Keltan ECO 35.20 44.20 5470 powdered with chalk (EPDM) Expancel  1.00  1.00  1.00  1.00 950 MB 80 (microspheres) Songnox 1010 (antioxidant)  0.30  0.30  0.30  0.30 Total 100.00  100.00  100.00  100.00  Colors Masterbatch (optional) 2% Black MB 2% Black MB 2% Black MB 2% Black MB Mechanics 1 mm plate 21.4.sup.1) 20.3.sup.1) 16.2.sup.1) 20.5.sup.1) σ (strength) in MPa 18.3.sup.2) 18.0.sup.2) 17.7.sup.3) 16.1.sup.3) Mechanics 1 mm plate >800.sup.1)    942.sup.1)   >700.sup.1)    917.sup.1)   ε (Elongation at break) in % >600.sup.2)    >600.sup.2)    522.sup.3)   515.sup.3)   Mechanics 1 mm plate  4.5.sup.1)  4.0.sup.1)  3.3.sup.1)  2.8.sup.1) σ.sub.10 (strength at 10%  4.4.sup.2)  3.5.sup.2) elongation) in MPa  4.8.sup.3)  3.2.sup.3) Hot set (200° C.) 50/10.sup.2) — 35/10.sup.2) — 25/5.sup.3)  15/5.sup.3)  BBC (Bio-based Content),   74.80%   74.80%   72.75%   72.75% calculated BBC (Bio-based Content)   74.80%   75.01%   72.75%   72.78% measured by BetaAnalytic according to ASTM D6866-16 Method B (AMS) .sup.1)not crosslinked .sup.2)cross-linked with 50 kGy .sup.3)cross-linked with 100 kGy

TABLE-US-00002 TABLE 2 VKL062 VKL063 VKL064 VKL065 VKL066 VKL067 VKL069 SLL318 38.00 37.00 37.00 37.00 36.70 36.70 30.00 (LLDPE) Hydrocarb 29.70 29.70 29.70 29.70 29.50 29.50 29.50 95T-OG DC 50-  2.00  3.00  2.00  2.00  2.00  2.00  2.00 320 (EVA base) Keltan 30.00 30.00 30.00 30.00 29.50 29.50 37.20 ECO 5470 Expancel  1.00  2.00  1.00 950 MB 80 Expancel  1.00  2.00 980 MB 120 Songnox  0.30  0.30  0.30  0.30  0.30  0.30  0.30 1010 Total 100.00  100.00  100.00  100.00  100.00  100.00  100.00  Colors 2% Black 2% Black 2% Black 2% Black 2% Black 2% Black 2% Black Masterbatch MB MB MB MB MB MB MB Mechanics 1 mm 20.7.sup.1) 21.4.sup.1) 18.9.sup.1) 19.2.sup.1) 19.0.sup.1) 18.2.sup.1) 19.0.sup.1) plate σ 16.8.sup.4) 17.0.sup.4) 16.9.sup.3) 16.8.sup.3) 18.2.sup.2) (strength) 14.7.sup.5) 16.5.sup.5) 16.7.sup.4) 16.1.sup.4) 16.5.sup.3) in MPa Mechanics 1 mm 796.sup.1)   832.sup.1)   808.sup.1)   793.sup.1)   838.sup.1)   796.sup.1)   1101.sup.1)    plate ε 553.sup.4)   441.sup.4)   527.sup.3)   525.sup.3)   >600.sup.2)    (Elongation 392.sup.5)   410.sup.5)   471.sup.4)   453.sup.4)   527.sup.3)   at break) in % Mechanics 1 mm  4.7.sup.1)  4.7.sup.1)  5.3.sup.1)  5.1.sup.1)  4.0.sup.1) plate σ.sub.10  5.2.sup.3)  5.1.sup.3)  4.0.sup.2) (strength  5.1.sup.4)  5.4.sup.4)  4.0.sup.3) at 10% elongation) in MPa Hot set 30/5.sup.2) 30/10.sup.2) 30/10.sup.2) 30/10.sup.2) 40/10.sup.2) (200° C.) 15/5.sup.3) 15/5.sup.3)  30/5.sup.3)  25/5.sup.3)  20/5.sup.3)  BBC (Bio-   76.90%   75.66%   75.66%   75.66%   74.58%   74.58%   73.96% based Content) .sup.1)not crosslinked .sup.2)cross-linked with 50 kGy .sup.3)cross-linked with 100 kGy .sup.4)cross-linked with 150 kGy .sup.5)cross-linked with 200 kGy

[0233] The mechanical properties of VKL070 seem to be particularly good compared to PVC or PUR artificial leathers. Elongation at break >500% and strength >16 MPa when crosslinked at 50 or 100 KGy. The hot set values are desirably low. This means that the material is very well crosslinked after radiation crosslinking, with the Bio-based Content (BBC) of organic component being above 72%. For a standard artificial leather made of PVC or PUR, the BBC is only 0%.

TABLE-US-00003 TABLE 3 LKL086 SLL318 (LLDPE)  7.50 Hydrocarb 95T-OG (chalk) 27.70 DC 50-320 (EVA base, silicone  2.00 additive) Keltan ECO 5470 (EPDM) Keltan 5508 ECO = Keltan ECO 62.50 5470 powdered with chalk (EPDM) Expancel 950 MB 80 (microspheres) Songnox 1010 (antioxidant)  0.30 Total 100.00  Colors Masterbatch (optional) 2% Black MB Mechanics 1 mm plate 16.1.sup.1) σ (strength) in MPa Mechanics 1 mm plate 918.sup.1)   ε (Elongation at break) in % Mechanics 1 mm plate  1.2.sup.1) σ.sub.10 (strength at 10% elongation) in MPa Hot set (200° C.) BBC (Bio-based Content) 67% .sup.1)not crosslinked

[0234] The use of higher amounts of EPDM and lower amounts of LLDPE results in significantly reduced σ10 values. This is particularly advantageous for the use of artificial leather, so that the properties do not become too stiff or paper-like, but instead acquire a leather-like flexibility.

[0235] The invention also relates to the following embodiments, wherein the term “claim” means “embodiment”.

[0236] 1. Layered material having one or more layers, including at least one layer A, said layer A comprising: [0237] 10-50 weight percent polyethylene as the first polymer, [0238] 10-50 weight percent of a second polymer selected from the group consisting of ethylene propylene diene monomer (EPDM), ethylene vinyl acetate copolymer (EVA), polyethylene octene (POE), ethylene butyl acrylate copolymer (EBA), and ethylene methacrylate copolymer (EMA); [0239] 10-40 weight percent filler, [0240] wherein the organic component of layer A has a bio-based carbon content (BBC) of at least 50% as determined by ASTM D6866-16 Method B (AMS); [0241] and wheren [0242] the layered material has a thickness of up to 4 cm.

[0243] 2. The layered material according to claim 1, wherein layer A is a foamed layer.

[0244] 3. The layered material according to claim 2, wherein the foamed layer A has been extruded using a blowing agent.

[0245] 4. The layered material according to any one of claims 1 to 3, wherein the layer A is radiation crosslinked with electron beams.

[0246] 5. The layered material according to any one of claims 1 to 4, wherein layer A has a hot set at 200° C. of less than 100%, preferably less than 50%, measured according to DIN EN 60811-507.

[0247] 6. The layered material according to any one of claims 2 to 5, wherein an expandable lightweight filler is used as blowing agent in the foamed layer A.

[0248] 7 The layered material according to any one of claims 1 to 6, in the form of a artificial leather.

[0249] 8. The layered material of any one of claims 1 to 7, wherein the second polymer in layer A is ethylene-propylene-diene monomer (EPDM), or ethylene-vinyl acetate copolymer (EVA).

[0250] 9. The layered material according to any one of claims 2 to 8, wherein the foamed layer comprises: [0251] 20-35 weight percent polyethylene, [0252] 30-50 weight percent ethylene propylene diene monomer (EPDM), as the second polymer, [0253] 20-35 weight percent filler(s), [0254] 1-3 weight percent expanded hollow microspheres, [0255] 0-3 weight percent silicone additive, and [0256] IIch—0.5-3% weight percent antioxidant and, or UV absorber.

[0257] 10. The layered material according to any one of claims 1 to 9, wherein layer A is applied to a support layer.

[0258] 11. A method of producing the layered material according to any one of claims 1 to 10, comprising: [0259] a) providing the composition for layer A, [0260] b) extruding the composition from step (a) into a layered material.

[0261] 12. The method of claim 11, further comprising: [0262] c) radiation crosslinking of layer A with electron beams, with continuous passage of layer A or the entire layered material through a device for irradiation.

[0263] 13. Layered material having one or more layers, at least one of which is foamed layer A, which has been prepared using an extrusion process, wherein the following composition is extruded: [0264] 10-50, weight percent polyethylene as the first polymer, [0265] 10-50 weight percent of a second polymer selected from the group consisting of ethylene propylene diene monomer (EPDM), ethylene vinyl acetate copolymer (EVA), polyethylene octene (POE), ethylene butyl acrylate copolymer (EBA), and ethylene methacrylate copolymer; [0266] 10-40 weight percent filler,

[0267] wherein the organic component of the foamed layer has a bio-based carbon (BBC) content of at least 50%, as determined by ASTM D6866-16 Method B (AMS), and wherein the layered material has a thickness of up to 4 cm.

Cited Publications

[0268] US 2013/0022771 A1 [0269] US 2011/0183099 A1 [0270] EP2342262 (B1)