Multilayered, comprising a main polyolefin-based layer and a textile underlayer

Abstract

The present invention relates to a multilayer comprising at least: a) a main layer based on polyolefin, b) a surface layer of thermoplastic polymer, c) a protective layer of cross-linked polyurethane, and d) a textile underlayer. The invention also relates to the use of this multilayer, particularly in the field of leather goods.

Description

Title of the invention: Multilayer comprising a main layer based on polyolefin and a textile underlayer. Field of the invention

[0001] The present invention relates to a thermoplastic polyolefin-based multilayer, the main layer of which comprises at least one polyolefin. The invention relates to the use of this multilayer in the fields of leather goods, protective clothing, and seat upholstery. Previous art

[0002] Generally speaking, coated textiles used in leather goods are employed as a substitute or replacement for natural materials such as leather. These materials have a particularly delicate appearance and must therefore be of impeccable visual quality. They must also exhibit good resistance to various mechanical stresses, particularly abrasion and repeated bending.

[0003] To date, we know of coated textiles, which consist of a textile structure covered with a multilayer coating, typically based on polyvinyl chloride, polyurethane or acrylic.

[0004] Generally, plastic-coated textiles have a woven textile structure composed, for example, of polyester, cotton, linen, or blended yarns (e.g., cotton and polyester). The coating layer is made from polymers such as polyvinyl chloride (PVC) and provides the desired appearance (grain, color, gloss).

[0005] PVC-based plastic-coated textiles have significant drawbacks, such as the emission of volatile organic compounds (VOCs) that cause unpleasant odors and negative environmental impacts when burned. The components of PVC-based formulations, particularly thermal stabilizers and plasticizers, are subject to regular revisions of health and safety regulations.

[0006] In a context of reducing environmental impacts, polyolefin-based materials offer recycling opportunities compared to PVC, which is more difficult to reprocess.

[0007] Thermoplastic polyolefins are not standard materials in the field of coatings, due to their flexural strength and flexibility, which are generally lower than those of conventional materials. However, new grades of thermoplastic polyolefins recently brought to market and Specially formulated products enhance the desired properties. For certain applications, this coated textile often undergoes a treatment that gives it an irregular surface, visually replicating the grain of leather.

[0008] In the luxury leather goods sector, in particular, the family of plastic-coated textile products based on thermoplastic polyolefins, possibly incorporating recycled plastic materials (RPM) and / or bio-based materials for the coated layer, is not yet used for manufacturing leather goods. Indeed, significant formulation work is required to achieve the performance of current benchmark products based on polyvinyl chloride (PVC). The latter remains a standard material in the field despite its drawbacks in terms of odor, environmental impact, and health effects.

[0009] With a view to reducing product weight, diversifying finishes (grain, color, printing, etc.), reducing solvents in finishing processes, reducing VOCs, and decreasing environmental impact, developing new products with polyolefin materials, whether or not incorporating MPRs and / or bio-based materials, is becoming essential. However, it is crucial not to alter the characteristics of the resulting products. Flexibility, resistance to mechanical abrasion, resistance to bending, and organoleptic properties (such as noise and feel, for example) must remain unchanged, particularly in the field of multilayer materials intended for leather goods or the textile industry (especially protective clothing) or furniture (for example, seat upholstery).

[0010] Furthermore, replacing the PVC-coated cotton / polyester fabric with a fabric coated with olefinic materials provides significant gains on four impact indicators (freshwater eutrophication, incidence of diseases from fine particles, acidification, freshwater ecotoxicity). Description of the invention

[0011] The present invention relates to a multilayer combining different layers of polyolefin and / or polyurethane.

[0012] More specifically, the present invention relates to a multilayer comprising at least: a) a main layer having a lower face FICp and an upper face FSCp, the main layer having a thickness between 0.15 and 2.0 mm and a basis weight between 100 and 700 g / m2, the main layer having a composition, throughout its thickness, comprising at least 50% by mass of polyolefin, b) a surface layer which may be multilayered having a thickness less than or equal to 0.50 mm and a basis weight less than 450 g / m2, the surface layer being a thermoplastic polymer film, preferably selected from: polyolefin; polyurethane and mixtures thereof, the surface layer having a lower face FICs opposite the upper face FSCp of the main layer, and an upper face FSCs, c) a protective layer facing the top face of the surface layer, the protective layer being based on cross-linked polyurethane and having a polyurethane content between 1 and 40 g / m2, d) a textile underlayer facing the lower face FICP of the main layer.

[0013] In a particular embodiment, the thickness of the surface layer is advantageously less than 0.45 mm, and the basis weight is advantageously less than 400 g / m². In another embodiment, the surface layer has a thickness less than or equal to 0.15 mm and a basis weight less than 100 g / m².

[0014] The expression "opposite" means that two elements are facing each other. This also covers the case where two layers are separated by an intermediate layer, for example by a layer of glue or by dots of glue. Undercoat

[0015] The multilayer comprises a sublayer, opposite the lower face FICp of the main layer.

[0016] This underlayer is made of textile material.

[0017] The textile material underlayer and the main layer are advantageously joined together, for example, by gluing or laminating, or during the extrusion of the main layer.

[0018] Thus, the multilayer comprises an underlayer made of textile material (for example, a fabric, a knit (and in particular a jersey), a three-dimensional textile, a non-woven material, etc.) which is bonded to the underside FICP of the main layer. In this case, the textile underlayer advantageously has a thickness of between 0.1 and 6 mm and a basis weight advantageously between 30 and 500 g / m².

[0019] The textile may in particular be composed of natural or synthetic or artificial yarns, for example polyester, polyamide, cotton, linen, or a blend (cotton and polyester for example). It may also be composed of silk or viscose yarns.

[0020] The multilayer may include a polyolefin foam underlayer, which is advantageously extruded or bonded to the outer face (opposite to the main layer) of the textile layer. In this case, the polyolefin foam underlayer advantageously has a thickness of between 1 and 6 mm, preferably 1.5 mm. at 3 mm, and a density advantageously between 67 and 100 kg / m3, preferably between 67 and 71 kg / m3. This embodiment is particularly suited to the field of leather goods. Main layer

[0021] The composition of the main layer comprises, over its entire thickness, by mass at least 50% polyolefin, advantageously 80 to 95%.

[0022] When the multilayer includes a textile underlayer, the main layer advantageously comprises at least 50% by mass of polyolefin.

[0023] Advantageously, the main layer has a density between 0.89 and 0.97, more advantageously between 0.89 and 0.92. The density may be lower when the main layer has a cellular structure.

[0024] The main layer has a basis weight of between 100 and 700 g / m2, more advantageously between 250 and 600 g / m2, and even more advantageously between 400 and 500 g / m2.

[0025] The main layer has a thickness of between 0.15 and 2 mm, advantageously between 0.30 and 0.65 mm, more advantageously between 0.45 and 0.55 mm.

[0026] According to a particular embodiment, the main layer has a basis weight of between 400 and 500 g / m2 and a thickness advantageously between 0.45 and 0.55 mm, for example a basis weight of 400 g / m2 and a thickness of 0.45 mm.

[0027] According to a particular embodiment, the polyolefin of the main layer is a mixture of linear polyolefin and / or crosslinked polyolefin.

[0028] Advantageously, the composition of the main layer comprises polyolefins. Advantageously, the metallocene catalytic technology for manufacturing this polyolefin material makes it possible to limit migration phenomena and eliminate the need for plasticizers to obtain flexibilities corresponding to the requirements of leather goods, protective clothing, and seat coverings.According to a particular embodiment, the composition of the main layer comprises: - a linear polyolefin and / or a crosslinked polyolefin, - at least one additive selected from: stabilizers (in particular thermal stabilizers), antioxidants, flame retardants, anti-UV agents, lubricants, fillers (for example silica), expanding agents, hot melt adhesives (advantageously polyolefin or polyurethane based), mineral fillers, vegetable fillers, crosslinking agents, colorants, pigments and mixtures thereof, the linear polyolefin being selected from the group comprising polyethylenes, polypropylenes, polybutenes, polypentenes, poly(4-methylpentene), olefin copolymers, elastomeric polyolefins and mixtures thereof, the. crosslinked polyolefin being selected from the group comprising polyethylenes, polypropylenes, polybutenes, olefin copolymers, plastomers, styrenic resins, elastomers and mixtures thereof.

[0029] In general, the composition of the main layer may include compounds of plant origin, for example starch.

[0030] Linear polyolefin is advantageously chosen from the group comprising polyethylenes, polypropylenes, polybutenes, polypentenes, poly(4-methylpentene), olefin copolymers (for example ethylene-propene (EP) copolymers, ethylene-propene-diene (EPDM) copolymers...), plastomers (for example octene-ethylene copolymers), elastomeric polyolefins and their mixtures.

[0031] The thermoplastic grades are chosen for their hardness between 30 and 70 shore A, more advantageously between 35 and 50 shore A.

[0032] The present invention therefore makes it possible to produce materials whose properties generally require PVC and / or PU.

[0033] However, according to a particular embodiment, the main layer is free of PVC and / or PU, while exhibiting flexibility properties comparable to those of PVC and / or PU-based products. Surface layer

[0034] As already indicated, the multilayer comprises a surface layer having a lower face FICs opposite the upper face FSCp of the main layer, and an upper face FSCs-

[0035] The surface layer has a thickness less than or equal to 0.50 mm, advantageously between 0.070 mm and 0.35 mm and more advantageously between 0.20 mm and 0.30 mm. It can therefore have a thickness between 0.20 and 0.50 mm.

[0036] The surface layer has a basis weight of less than 450 g / m2, advantageously less than 400 g / m2, more advantageously less than 300 g / m2. It advantageously has a basis weight of at least 60 g / m2.

[0037] The surface layer has a weight advantageously between 80 and 250 g / m2, more advantageously between 80 and 150 g / m2.

[0038] When the basis weight of the surface layer is less than 110 g / m2 (advantageously at least 60 g / m2), its thickness is advantageously less than or equal to 0.12 mm, and more advantageously between 0.07 mm and 0.12 mm.

[0039] The surface layer is advantageously a thermoplastic polymer film, preferably selected from: polyolefin; and their mixtures.

[0040] According to a particular embodiment, the surface layer may be a thermoplastic polymer multilayer, for example, a polyolefin multilayer or a multilayer having at least one polyolefin layer. The multilayer may also include at least one layer made of a polyolefin blend. Protective layer

[0041] As already indicated, the multilayer includes a protective layer facing the top face of the surface layer.

[0042] The protective layer is based on cross-linked polyurethane and has a polyurethane basis weight of between 1 and 40 g / m², advantageously between 15 and 25 g / m². A person skilled in the art will adjust the basis weight of the protective layer to ensure a sufficient level of abrasion resistance.

[0043] According to a variant of the invention, a primary layer of the same nature as the protective layer can be deposited between the surface layer and the protective layer.

[0044] According to another embodiment of the invention, a primer layer can be deposited on the surface layer, then a pattern can be printed on this primer layer, and then the protective layer is deposited on top of this printed pattern.

[0045] The primary layer has a surface mass advantageously between 1 and 10 g / m2, for example 5 g / m2.

[0046] The surface layer can be treated, for example by a treatment (plasma, corona, etc.), before the deposition of the primary layer. This treatment improves the alignment of the primary layer.

[0047] Furthermore, the primer layer improves the bond between the surface layer and the protective layer by acting as a binder. Multilayer and its use

[0048] According to a particular embodiment, the multilayer comprises (is advantageously constituted) the following layers: - protective layer with a weight between 1 and 40 g / m2, - surface layer with a basis weight of less than 450 g / m2, for example less than 300 g / m2, - main layer with a weight of less than 700 g / m2, - glue layer, - textile underlayer.

[0049] According to another particular embodiment, the multilayer comprises (is advantageously constituted) the following layers: - protective layer with a weight between 1 and 40 g / m2, - surface layer with a basis weight of less than 400 g / m2, for example less than 300 g / m2 - main layer having a basis weight of less than 700 g / m2.

[0050] The multilayer may have a structure comprising at least the following layers: protective layer / primary layer / surface layer / main layer / optionally glue layer / textile underlayer, the primary layer or the surface layer being advantageously printed.

[0051] The multilayer may also have a structure comprising at least the following layers: protective layer / primary layer / surface layer / main layer / optionally glue layer / textile underlayer / optionally glue layer / foam underlayer, the primary layer or the surface layer being advantageously printed.

[0052] According to another particular embodiment, the multilayer comprises (is advantageously made up of the following layers: - protective layer with a weight between 1 and 40 g / m2, - surface layer with a basis weight of less than 450 g / m2, for example less than 300 g / m2, - main layer with a weight of less than 700 g / m2, - textile underlayer.

[0053] According to another particular embodiment, the multilayer comprises (is advantageously made up of the following layers: - protective layer with a weight between 1 and 40 g / m2, - surface layer with a basis weight of less than 450 g / m2, for example less than 300 g / m2, - main layer with a weight of less than 700 g / m2, - a textile underlayer, - layer of glue, - foam underlay.

[0054] The multilayer may include one or more intermediate layers, for example made of polyolefin.

[0055] The multilayer can be grained and / or printed.

[0056] The multilayer material according to the invention can be used in particular in one of the following fields: leather goods, protective clothing, seat coverings, etc. Method for preparing the multilayer material

[0057] The present invention also relates to a method for manufacturing the multilayer. This method comprises the preparation of a laminate including a main layer, a surface layer and a protective layer, the main layer having a lower face FICP and an upper face FSCp, the surface layer having a lower face FICs opposite the upper face FSCp of the main layer, and an upper face FSCs, the protective layer being deposited on the upper face FSCs of the surface layer.

[0058] Optionally, the multilayer can be grained, advantageously in line in a calender.

[0059] During the extrusion assembly process, the graining cylinder can press the material to give it its final shape.

[0060] According to a particular embodiment, the main layer is extruded onto the surface layer, the surface layer being, prior to extrusion, a thermoplastic polymer film (advantageously polyolefin) associated with the protective layer.

[0061] According to another particular embodiment, the main layer is extruded between the surface layer and a sub-layer, the surface layer being, prior to extrusion, a thermoplastic polymer film associated with the protective layer, the sub-layer being made of textile.

[0062] The textile underlayer is advantageously combined with the main layer by calendering.

[0063] The textile underlayer can also be associated with the main layer by gluing, for example by means of a layer of glue or dots of glue.

[0064] According to another particular embodiment, the main layer is associated with the textile underlayer by direct calendering (without glue) or indirect calendering (with glue).

[0065] According to another particular embodiment, the main layer is advantageously prepared by extrusion of thermoplastic granules.

[0066] As already indicated, the invention also relates to the use of this multilayer in the field of leather goods. Example

[0067] According to one example, the multilayer was prepared as follows: - Extrusion of the main layer (220°C, 350 g / m2, 700 µm, density: 0.5) (monolayer in expanded polyolefin + dye and UV stabilizer) onto the surface of the fabric underlayer (composed of 100% polypropylene, 200 g / m2), - Bonding (by extrusion) of the surface layer (220°C, 300 g / m2, 0.330 mm, density: 0.9) (polyolefin formulation) onto the upper face of the main layer, - Corona treatment, - Application of a primer layer (5g / m2 of cross-linked polyurethane) to the upper surface of the surface layer, - Printing on the primary layer (1 g / m2 of colored polyurethane), - Application of a protective layer (4x5g / m2 of cross-linked polyurethane) on the printing layer, - Consolidation and post-graining of the multilayer by passing through a calender (rubber / steel).

[0068] The main layer comprises (by mass) 100% polyolefin (of which 4.5% is cross-linked polyolefin).

Claims

Demands

1. Multilayer comprising at least: a) a main layer having a FICP bottom face and an FSCp top face, the main layer having a thickness of between 0.15 and 2.0 mm and a basis weight of between 100 and 700 g / m2, the main layer having a composition, throughout its thickness, comprising at least 50% by mass of polyolefin, and b) a surface layer having a thickness less than or equal to 0.50 mm and a basis weight of less than 450 g / m2, the surface layer being a thermoplastic polymer film, preferably selected from: polyolefin;polyurethane and their mixtures, the surface layer having a lower face FICs opposite the upper face FSCp of the main layer, and an upper face FScs, c) a protective layer opposite the upper face FSCs of the surface layer, the protective layer being based on cross-linked polyurethane and having a polyurethane weight between 1 and 40 g / m2, d) a textile underlayer opposite the lower face FICp of the main layer.;

2. Multilayer according to claim 1, characterized in that the surface layer has a thickness less than or equal to 0.15 mm and a basis weight less than 100 g / m2.

3. Multilayer according to claim 1 or 2, characterized in that the multilayer has a structure comprising at least the following layers: protective layer / primary layer / surface layer / main layer / optionally adhesive layer / textile underlayer, the primary layer or the surface layer being advantageously printed.

4. Multilayer according to any one of claims 1 to 3, characterized in that the multilayer has a structure comprising at least the following layers: protective layer / primary layer / surface layer / main layer / optionally adhesive layer / textile underlayer / optionally adhesive layer / under- foam layer, the primary layer or surface layer being advantageously printed.

5. Multilayer according to any one of claims 1 to 4, characterized in that the composition of the main layer is a mixture of linear polyolefin and / or crosslinked polyolefin.

6. Multilayer according to any one of claims 1 to 5, characterized in that the composition of the main layer comprises: - a linear polyolefin and / or a cross-linked polyolefin, - at least one additive selected from: stabilizers, antioxidants, flame retardants, UV inhibitors, lubricants, fillers, blowing agents, hot melt adhesives, mineral fillers, vegetable fillers, cross-linking agents, colorants, pigments and mixtures thereof, the linear polyolefin being selected from the group comprising polyethylenes, polypropylenes, polybutenes, polypentenes, poly(4-methylpentene), olefin copolymers, elastomeric polyolefins and mixtures thereof, the cross-linked polyolefin being selected from the group comprising polyethylenes, polypropylenes, polybutenes, olefin copolymers, plastomers, styrenic resins, elastomers and their mixtures.

7. Multilayer according to any one of claims 1 to 6, characterized in that the surface layer is a polyolefin film having a thickness between 0.070 mm and 0.50 mm.

8. Multilayer according to any one of claims 1 to 7, characterized in that the composition of the main layer comprises compounds of vegetable origin, advantageously starch.

9. A method for manufacturing the multilayer according to any one of claims 1 to 8, comprising the preparation of a laminate comprising a main layer, a surface layer and a protective layer, the main layer having a lower face FICP and a top face FSCp, the surface layer having a lower face FICs opposite the top face FSCp of the main layer, and a top face FScs, the protective layer being deposited on the upper face FSCs of the surface layer, the main layer being extruded between the surface layer and a textile underlayer, the surface layer being, prior to extrusion, a thermoplastic polymer film associated with the protective layer, the underlayer being textile.

10. A method for manufacturing the multilayer according to any one of claims 1 to 8, comprising the preparation of a laminate comprising a main layer, a surface layer and a protective layer, the main layer having a lower face FICp and a top face FSCp, the surface layer having a lower face FICs opposite the top face FSCp of the main layer, and a top face FScs, the protective layer being deposited on the top face FScs of the surface layer, the main layer being associated with a textile underlayer by direct calendering without glue or by indirect calendering with glue.

11. A method according to claim 9 or 10, characterized in that the main layer is extruded onto the surface layer, the surface layer being, prior to extrusion, a thermoplastic polymer film associated with the protective layer.

12. Use of the multilayer according to any one of claims 1 to 8, in the field of leather goods.