HOT-MELT LAMINATED DECORATIVE LAMINATE

Abstract

The invention relates to a decorative laminate and methods of manufacturing thereof, in particular a structured decorative laminate, including at least the following immediately consecutive and mutually bonded layers A-B-C-D: A: on the visible side, a functional layer comprising one or more ionomers and optionally one or more filler materials and/or functional additives dispersed in the layer; B: an intermediate polymer layer comprising a mixture consisting of 5 to 95% by weight of extrudable ionomer, extrudable ionomer mixture or extrudable ionomer blend and 95 to 5% by weight of a polyolefin; C: a tie layer comprising one or more modified plastics for the tie; D: on the substrate side, a decorative layer;
characterised in that the layered composite consisting of the layers A, B and C is coextruded and hot-melt laminated with the substrate-side decorative layer at a temperature above the fusion temperature of the layered composite.

Claims

1. A decorative laminate, comprising at least the following immediately consecutive and mutually bonded layers A-B-C-D: A: on the visible side, a functional layer comprising one or more ionomers and optionally one or more filler materials and/or functional additives dispersed in the layer; B: an intermediate polymer layer comprising a mixture consisting of 5 to 95% by weight of extrudable ionomer, extrudable ionomer mixture or extrudable ionomer blend and 95 to 5% by weight of a polyolefin; C: a tie layer comprising one or more modified plastics for the tie; D: on the substrate side, a decorative layer; characterised in that the layered composite consisting of the layers A, B and C is coextruded and hot-melt laminated with the substrate-side decorative layer at a temperature above the fusion temperature of the layered composite.

2. The decorative laminate according to claim 1, characterised in that one or more patterns are plastically embossed on the visible side of the decorative laminate simultaneously in the same step, during hot-melt laminating.

3. The decorative laminate according to claim 1, characterised in that it contains no PVC and/or melamine resin.

4. The decorative laminate according to claim 1, characterised in that the functional layer layer A and the intermediate layer B comprise the same ionomer or ionomer mixture.

5. The decorative laminate according to claim 1, characterised in that the polyolefin of the intermediate polymer layer B is selected from polyethylene and polypropylene and mixtures of the same.

6. The decorative laminate according to claim 1, characterised in that the modified plastic(s) for the tie comprise(s) one or more polymer(s) modified with maleic anhydride, alkylated maleic anhydride and/or carboxylic acid, in particular one or more copolymer(s) or grafted (co)polymers of monomers which support carboxylic acid functionality, in particular maleic anhydride and/or alkylated maleic anhydride with polypropylene, polyethylene, ethyl-vinyl acetate (EVA), ethylene-butyl acrylate (EBA), ethylene-acrylic acid (EAA), ethylene-methacrylic acid (EMAA), maleic acid acetate (MAH) and/or polyacrylate rubber (ACM).

7. The decorative laminate according to claim 1, characterised in that the decorative layer D contains an extrudable thermoplastic polymer selected from the group consisting of polyethylenes, polypropylenes and polybutylenes, polystyrene, polyamide, polyester and mixtures of the same.

8. The decorative laminate according to claim 1, characterised in that it comprises at least the consecutive and mutually bonded layers F-A-B-C-D, wherein the layer F denotes one or more mutually bonded layers which contains 60 to 100% by weight of thermoplastic extrudable ionomer, as well as filler materials as applicable, and wherein the functional layer A contains 5 to 40% by weight of one or more non-migratory anti-static agents.

9. The decorative laminate according to claim 1, characterised in that the functional layer A exhibits a thickness in the range of 1 to 200 ?m, preferably 5 to 100 ?m; and/or the intermediate polymer layer B exhibits a thickness in the range of 10 to 500 ?m, the tie layer C exhibits a thickness in the range of 1 to 100 ?m, the substrate-side decorative layer D exhibits a thickness of 10 to 500 ?m; and/or the additional layer F exhibits a thickness of 1 to 200 ?m

10. A method of covering a floor or manufacturing a floor covering wall panels, roof panels or furniture film, said method comprising a step of covering a floor or manufacturing a floor covering, wall panels, roof panels or a furniture film, with a decorative laminate in accordance with claim 1.

11. A layered body comprising a decorative laminate in accordance with claim 1, as a floor covering, furniture film or 3D film.

12. The floor covering according to claim 11, characterised in that it comprises at least one other layer E which is a substrate layer which adjoins the layer D and is connected to the layer D directly, via a bonding layer or adhesive layer, by lamination or by mechanical connecting elements.

13. A method for manufacturing a decorative laminate according to claim 1, characterised in that the layered composite consisting of at least the layers A, B and C, or F, A, B and C, is coextruded in a first step and hot-melt laminated with the decorative layer D at a temperature above the fusion temperature of the layered composite in the second step.

14. The method according to claim 13, characterised in that one or more patterns are plastically embossed on the visible side of the decorative laminate simultaneously in the same step, during hot-melt laminating, wherein the temperature of the layered composite does not drop below the fusion temperature of the layered composite A-B-C or F-A-B-C, respectively, between the first and second method steps.

15. The method according to claim 14, characterised in that the second method step is performed at a temperature of 150 to 300? C.

16. The decorative laminate according to claim 9, wherein the functional layer A exhibits a thickness in the range of 5 to 100 ?m.

17. The decorative laminate according to claim 9, wherein the intermediate polymer layer B exhibits a thickness in the range of 40 to 300 ?m.

18. The decorative laminate according to claim 9, wherein the tie layer C exhibits a thickness in the range of 5 to 30 ?m.

19. The decorative laminate according to claim 9, wherein the substrate-side decorative layer D exhibits a thickness of 50 to 150 ?m.

20. The decorative laminate according to claim 9, wherein the additional layer F exhibits a thickness of 10 to 100 ?m.

21. The method of claim 10, wherein the manufacturing step is manufacture of plywood board or chipboard, a 3D film, or a printed film.

22. The floor covering according to claim 12, wherein the substrate layer E comprises one of the following layers: a layer which prevents slipping, a heat-insulating layer, a sound-absorbing layer, a heat-conducting layer, an adhesive layer, a plywood or chipboard layer, a wood-plastic composite layer and a fibre-reinforced concrete layer.

Description

[0066] FIG. 1 shows a cross-section of an embodiment of the decorative laminate of the invention which exhibits the layered structure A-B-C-D. In this example, the layers are composed of:

[0067] Layer A (50 ?m) 93% by weight of Surlyn ionomer and 7% by weight of silica as a filler material;

[0068] Layer B (230 ?m) 80% by weight of Surlyn ionomer and 20% by weight of metallocene polyethylene (metallocene PE);

[0069] Layer C (20 ?m) maleic-anhydride-modified polyethylene as a modified plastic for the tie;

[0070] Layer D (300 ?m) paper or plastic film which is printed on using casein ink and coated (10 ?m) with primer.

[0071] FIG. 2 shows a cross-section of another embodiment of the decorative laminate, for example as a floor covering which exhibits the layered structure A-B-C-D-E. In this example, the layers are composed of:

[0072] Layer A (50 ?m) 94% by weight of Surlyn ionomer and 6% by weight of silica as a filler material;

[0073] Layer B (230 ?m) 87% by weight of Surlyn ionomer and 13% by weight of metallocene polyethylene;

[0074] Layer C (20 ?m) maleic-anhydride-modified polyethylene as a modified plastic for the tie;

[0075] Layer D (300 ?m) paper or plastic film which is printed on using casein ink and coated (10 ?m) with primer; Layer E (2000 ?m) WPC.

[0076] FIG. 3 shows a cross-section of another embodiment of the decorative laminate, for example as a furniture film which exhibits the layered structure F-A-B-C-D. In this example, the layers are composed of:

[0077] Layer F (50 ?m) varnish;

[0078] Layer A (80 ?m) 100% by weight of extrudable ionomer;

[0079] Layer B (150 ?m) 91% by weight of the same ionomer as in layer A and 9% by weight of metallocene polyethylene;

[0080] Layer C (5 ?m) maleic-anhydride-modified polyethylene as a modified plastic for the tie;

[0081] Layer D (100 ?m) PET which is printed on using casein ink and coated (10 ?m) with primer.

[0082] In one modification, BOPP (biaxially orientated polypropylene) was used instead of PET in layer D.

[0083] FIG. 4 shows a cross-section of another embodiment of the decorative laminate in accordance with the invention, for example as a furniture film which exhibits the layered structure A-B-C-D-E. In this example, the layers are composed of:

[0084] Layer A (80 ?m) 100% by weight of Surlyn ionomer;

[0085] Layer B (120 ?m) 95% by weight of the same Surlyn ionomer as in layer A and 5% by weight of metallocene polyethylene;

[0086] Layer C (10 ?m) maleic-anhydride-modified polyethylene as a modified plastic for the tie;

[0087] Layer D (90 ?m) paper which is printed on using casein ink and coated (10 ?m) with primer;

[0088] Layer E (1500 ?m) plywood layer, wood.

[0089] FIG. 5 shows a schematic and typical structure of the method in accordance with the invention, wherein a composite made of: a layer A, which consists for example of ionomer containing filler materials; a intermediate polymer layer B containing ionomer and polyethylene; and a (substrate-side) tie layer C as a molten mass 2; is coextruded in the nozzle 1 at a temperature of 200 to 280? C. and then immediately connected on the substrate side, at the same temperature, to a layer of paper D/3 which is printed on and which is fed via a roller 4, for example a rubber roller. The layer D and the layered composite A-B-C are hot-melt laminated and simultaneously embossed on the visible side in this embodiment between the embossing roller 5 and the roller 4 at temperatures in the range of for example 150 to 300? C. at the same time as they are converged or immediately after they have been converged.

EXAMPLES

Example 1

[0090] A structured decorative laminate exhibiting the following sequence of layers was manufactured according to the method in accordance with the invention, wherein the layers A, B and C were coextruded at 250? C. and then immediately hot-melt laminated with the polypropylene layer D (having a wood grain pattern printed on it in casein ink and provided with primer) while still at 230? C. and at a linear load of 14.5 kN/m (145 N/cm), wherein a plastic wood texture pattern (the surface roughness R.sub.Z of the die engraving of the embossing roller was 120 ?m) was embossed on the visible side, and a structured decorative laminate in accordance with the invention was thus obtained.

[0091] Layer A (50 ?m) 95% by weight of ionomer (Surlyn? 1706 by Dupont), 5% by weight of silica having a particle size of 2 to 50 ?m (95%);

[0092] Layer B (230 ?m) 85% by weight of ionomer (Surlyn? 1706 by Dupont) and 15% by weight of metallocene polyethylene;

[0093] Layer C (20 ?m) maleic-anhydride-modified polyethylene as a modified plastic for the tie;

[0094] Layer D (120 ?m, including a maximum of 10 ?m of primer) polypropylene film which is printed on using casein ink and coated with primer.

[0095] Table 1 lists some parameters for characterising the multi-layered composite film of Example 1 and Comparative Example 2.

[0096] In the examples, the thickness of the layers and/or of the decorative laminate or layered composite were set and monitored as an arithmetical mean via the throughput of the extruders in a way which is usual in the art.

Comparative Example 2

[0097] A structured decorative laminate exhibiting the following sequence of layers was manufactured along the lines of Example 1. Unlike Example 1, the intermediate layer B did not contain polyolefin:

[0098] Layer A (50 ?m) 95% by weight of ionomer (Surlyn? 1706 by Dupont), 5% by weight of silica having a particle size of 2 to 50 ?m (95%);

[0099] Layer B (230 ?m) 100% by weight of ionomer (Surlyn? 1706 by Dupont);

[0100] Layer C (20 ?m) maleic-anhydride-modified polyethylene as a modified plastic for the tie;

[0101] Layer D (120 ?m, including a maximum of 10 ?m of primer) polypropylene film which is printed on using casein ink and coated with primer.

[0102] The layered composite films of Example 1 and Comparative Example 2 were laminated with chipboard/hot-melt adhesion and tested for scratch resistance (DIN 438-2), abrasion resistance, wear resistance (DIN EN 13329) and resistance to staining (DIN 438-2).

[0103] The wear value according to DIN 13329:2013-12 was measured using SH4, alternating after each 200 revolutions.

[0104] Table 1 compares Example 1 and Comparative Example 2

TABLE-US-00001 TABLE 1 Comparative Example 1 Example 2 Overall thickness A-B-C-D 420 ?m 420 ?m Embossing depth index I.sub.P 16.62 Density 0.985 g/cm.sup.3 Grammage 3.913 g/100 cm.sup.2 Young's modulus, longitudinal 360 MPa 472 MPa Maximum elongation, longitudinal 251% 244% Elongation at rupture, longitudinal 251% 244% wear at a thickness of 420 ?m 3840 2400 (DIN EN ISO 527-3/1B/200) The average surface roughness R.sub.Z was determined using the MAHR perthometer.

Example 3

[0105] In Example 3, the same sequences of layers ABC as in Example 1 was coextruded at 250? C. and then immediately hot-melt laminated with the same polypropylene layer D (having a wood texture pattern printed on it in casein ink and provided with primer) while still at 230? C. and at a linear load of 14.5 kN/m (145 N/cm), using a smooth roller. The decorative laminate obtained was cooled to room temperature and reheated to 125? C. in a subsequent step, and a plastic wood grain pattern was embossed on it at this temperature using the same embossing roller as in Example 1 and at the same linear load, in order to obtain a structured decorative laminate.

[0106] The embossing depth index I.sub.P was determined after cooling. To this end, the respective roughness of Example 1 which is hot-melt embossed in accordance with the invention and of Example 3 which is subsequently embossed is measured at five respectively matching points in the embossment. Even before it is held at an elevated temperature, significant differences in roughness and embossing depth index I.sub.P were measurable (Table 2).

[0107] The structured decorative laminates were then placed in the furnace for 30 minutes at 135? C. and then assessed optically, and the embossing depth index was determined again. While the structure embossed on the hot-melt embossed sample (Example 1) was still visible, the embossment on the subsequently embossed sample was already no longer identifiable.

[0108] The roughness was again measured at five respectively matching points in the embossment in order to determine the embossing depth index I.sub.P (Table 2).

[0109] The layered composite films were laminated with chipboard/hot-melt adhesion and tested. The layered composites in accordance with the invention exhibited good to very good results throughout, including in terms of scratch resistance (DIN 438-2), abrasion resistance and resistance to staining (DIN 438-2).

TABLE-US-00002 TABLE 2 Without being held at an elevated temperature After 30 minutes being held at an elevated temperature of 135? C. visible side substrate side embossing visible side substrate side embossing R.sub.Z [?m] R.sub.Z [?m] depth index I.sub.P Appearance R.sub.Z [?m] R.sub.Z [?m] depth index I.sub.P Appearance Example 1 96.93 13.88 16.62 embossment 47.52 8.35 13.55 embossment clear, clear, faintly matt, matt gloss, natural natural appearance appearance Example 3 80.96 29.88 6.45 embossment 5.88 6.83 2.05 embossment poor, no longer faint spots of visible, gloss gloss

Example 4

[0110] The surface roughness R.sub.Z of decorative films which exhibit the layered structure of Examples 1 and 3, which were on the one hand hot-melt embossed in accordance with the invention along the lines of Example 1 or subsequently embossed using the same embossing rollers along the lines of Example 3, were correlated with the surface roughness R.sub.Z of the embossing rollers used which exhibit a wood texture pattern (wood) or leather texture pattern (leather), respectively. Table 3 shows the impression ratios obtained. The value achieved for subsequent embossing was always less than 75%, while values of over 80% were achieved for hot-melt embossing.

TABLE-US-00003 TABLE 3 hot-melt embossed subsequently embossed wood leather wood leather R.sub.Z roller [?m] 120 110 120 110 R.sub.Z Film [?m] 96.93 106.66 80.96 80.18 impression ratio 81% 97% 67% 73%