Multilayer product comprising a polyolefin-based main layer and a textile sublayer

Abstract

The present invention relates to a multilayer product comprising at least: a) a polyolefin-based main layer, b) a thermoplastic polymer surface layer, c) a protection layer of crosslinked polyurethane, d) a textile sublayer. The invention also relates to the use of this multilayer product, particularly in the field of leatherwork.

Description

[0001] Description

[0002] Title of the invention: Multilayer comprising a main layer based on polyolefin and a textile underlayer

[0003] Scope of the invention

[0004] The present invention relates to a thermoplastic polyolefin-based multilayer material in which the main layer comprises at least one polyolefin. The invention relates to the use of this multilayer material in the fields of leather goods, protective clothing, and seat upholstery.

[0005] Previous art

[0006] Generally, 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.

[0007] 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.

[0008] Generally, plastic-coated textiles have a woven textile structure made, for example, of polyester, cotton, linen, or blended yarns (such as cotton and polyester). The coating layer is made from polymers like polyvinyl chloride (PVC) and provides the desired appearance (texture, color, sheen).

[0009] PVC-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. In a context of reduced environmental impact, polyolefin-based materials offer recycling opportunities compared to PVC, which is more difficult to reprocess.

[0010] 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 introduced to the market and formulated with specific techniques improve the expected properties. For certain applications, this coated textile often undergoes a treatment that gives it an irregular surface, thus visually replicating the grain of leather.

[0011] In the luxury leather goods sector, in particular, the family of plastic-coated textile products based on thermoplastic polyolefins, possibly incorporating recycled plastics (RP) and / or bio-based materials for the coating layer, is not yet used for manufacturing leather goods. Indeed, significant formulation work is required to achieve the performance levels of current benchmark products based on polyvinyl chloride (PVC). PVC remains a standard material in the field despite its drawbacks in terms of odor, environmental impact, and health effects.

[0012] With a view to reducing product weight, diversifying finishes (grain, color, printing, etc.), reducing solvents in finishing processes, lowering VOCs, and minimizing environmental impact, developing new products with polyolefin materials, whether or not they incorporate MPRs and / or are bio-based, is becoming essential. However, it is crucial not to alter the characteristics of the resulting products. Flexibility, resistance to mechanical abrasion, resistance to folding, and organoleptic properties (such as noise and feel) must remain unchanged, particularly in the field of multilayer materials intended for leather goods, the textile industry (especially protective clothing), or furniture (e.g., seat upholstery).

[0013] Furthermore, replacing PVC-coated cotton / polyester fabric with olefin-based coated fabric provides significant gains on four impact indicators (freshwater eutrophication, incidence of diseases from fine particles, acidification, freshwater ecotoxicity).

[0014] Description of the invention

[0015] The present invention relates to a multilayer combining different layers of polyolefin and / or polyurethane.

[0016] More specifically, the present invention relates to a multilayer comprising at least: a) a main layer having a FICP lower face and an FSCP upper 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 2, 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 2 the surface layer being a thermoplastic polymer film, preferably selected from: polyolefin; polyurethane and mixtures thereof, the surface layer having a lower face Fies opposite the upper face FSCP of the main layer, and an upper face F Scs, 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 basis weight of between 1 and 40 g / m² 2 , d) a textile underlayer opposite the FICP underside of the main layer.

[0017] 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. 2 In one embodiment, the surface layer has a thickness less than or equal to 0.15 mm and a basis weight of less than 100 g / m². 2 .

[0018] 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.

[0019] Underlayer The multilayer includes an underlayer, opposite the FICP lower face of the main layer.

[0020] This underlayer is made of textile material.

[0021] The textile underlayer and the main layer are advantageously joined together, for example, by gluing or laminating, or during the extrusion of the main layer.

[0022] Thus, the multilayer comprises a textile underlayer (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 FICP underside of the main layer. In this case, the textile underlayer advantageously has a thickness between 0.1 and 6 mm and a basis weight advantageously between 30 and 500 g / m². 2 .

[0023] Textiles can be made of natural, synthetic, or artificial fibers, such as polyester, polyamide, cotton, linen, or blends (like cotton and polyester). They can also be made of silk or viscose fibers.

[0024] 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 to 3 mm, and a density advantageously between 67 and 100 kg / m³. 3 , preferably between 67 and 71 kg / m 3 This method of implementation is particularly suited to the leather goods sector.

[0025] Main layer

[0026] The composition of the main layer comprises, over its entire thickness, by mass at least 50% polyolefin, advantageously 80 to 95%.

[0027] When the multilayer includes a textile underlayer, the main layer advantageously comprises at least 50% by mass of polyolefin.

[0028] Advantageously, the main layer has a density between 0.89 and 0.97, more advantageously between 0.89 and 0.92. The density can be lower when the main layer has a cellular structure. The main layer has a basis weight between 100 and 700 g / m². 2 , more advantageously between 250 and 600 g / m 2 , and even more advantageously between 400 and 500 g / m 2 .

[0029] 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.

[0030] According to a particular embodiment, the main layer has a basis weight of between 400 and 500 g / m² 2 and a thickness advantageously between 0.45 and 0.55 mm, for example a basis weight of 400 g / m 2 and a thickness of 0.45 mm.

[0031] According to a particular embodiment, the polyolefin of the main layer is a mixture of linear polyolefin and / or cross-linked polyolefin.

[0032] Advantageously, the composition of the main layer comprises polyolefins. Advantageously, the metallocene catalytic technology used to manufacture this polyolefin material limits migration and eliminates the need for plasticizers, thus achieving the necessary flexibility for leather goods, protective clothing, and seat upholstery. In one particular embodiment, the composition of the main layer comprises:

[0033] - a linear polyolefin and / or a cross-linked polyolefin,

[0034] - at least one additive chosen 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, linear polyolefin being chosen from the group including polyethylenes, polypropylenes, polybutenes, polypentenes, poly(4-methylpentene), olefin copolymers, elastomeric polyols and mixtures thereof, crosslinked polyol being chosen from the group including polyethylenes, polypropylenes, polybutenes, olefin copolymers, plastomers, styrenic resins, elastomers and mixtures thereof.

[0035] In general, the composition of the main layer may include compounds of plant origin, for example starch. Linear polyolefin is advantageously chosen from the group including 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), polyolefin elastomers and their mixtures.

[0036] Thermoplastic grades are chosen for their hardness between 30 and 70 shore A, more advantageously between 35 and 50 shore A.

[0037] The present invention therefore makes it possible to produce materials whose properties generally require PVC and / or PU.

[0038] 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.

[0039] Surface layer

[0040] As previously mentioned, the multilayer comprises a surface layer having a lower face Fies opposite the upper face FSCP of the main layer, and an upper face F Scs. The surface layer is in the form of a single-layer or multilayer film.

[0041] 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.

[0042] The surface layer has a basis weight of less than 450 g / m² 2 advantageously less than 400 g / m 2, more advantageously less than 300 g / m 2 It has an advantageous basis weight of at least 60 g / m². 2 .

[0043] The surface layer has a weight advantageously between 80 and 250 g / m² 2 , more advantageously between 80 and 150 g / m 2 .

[0044] When the weight of the surface layer is less than 110 g / m² 2 (advantageously at least 60 g / m 2 ), its thickness is advantageously less than or equal to 0.12 mm, and more advantageously between 0.07 mm and 0.12 mm. The surface layer is advantageously a thermoplastic polymer film, preferably selected from: polyolefin; and their mixtures.

[0045] In film form, the surface layer allows: to limit migration problems between the different layers of the multilayer, and thus create barriers for example to oxygen, moisture, aromas or dyes or pigments (in order to avoid any risk of migration of the color through the multilayer, in particular from the textile underlayer to the surface layer), to increase the mechanical resistance of the surface layer, and therefore of the multilayer, for example to perforation, traction or tearing, abrasion.

[0046] Unlike a foam surface layer, a film surface layer does not require cross-linking. This makes it possible to obtain a surface layer with a thickness greater than approximately 65 µm and a surface mass greater than approximately 60 g / m². 2 .

[0047] Finally, the film configuration, compared to foam, ensures good homogeneity of the surface layer and consistent thickness. Furthermore, the film facilitates surface treatments (e.g., Corona treatment), particularly on the FScs top face of the surface layer. This type of surface treatment improves cohesion with the other layers of the multilayer system in direct contact with the surface layer, especially the adhesion of the protective layer. The improved abrasion resistance results from the better cohesion between the film forming the surface layer and the protective layer, particularly between the FScs top face of the surface layer and the protective layer.

[0048] In one particular embodiment, the surface layer may be a multilayer of several thermoplastic polymer films, 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.

[0049] Protective layer

[0050] As previously mentioned, the multilayer system includes a protective layer facing the top face of the surface layer. This protective layer is based on cross-linked polyurethane and has a polyurethane content ranging from 1 to 40 g / m². 2 advantageously between 15 and 25 g / m 2 The person skilled in the art will adjust the weight of the protective layer to ensure a sufficient level of abrasion resistance.

[0051] According to one 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.

[0052] According to another variant 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.

[0053] The primary layer has a surface mass advantageously between 1 and 10 g / m² 2 , for example 5 g / m 2 .

[0054] The surface layer can be treated, for example by a process (plasma, corona, etc.), before the primary layer is deposited. This treatment improves the alignment of the primary layer.

[0055] In addition, the primer layer helps to improve the bond between the surface layer and the protective layer, acting as a binder.

[0056] Multilayer and its use

[0057] According to a particular embodiment, the multilayer comprises (is advantageously constituted) the following layers:

[0058] - protective layer with a weight between 1 and 40 g / m 2 ,

[0059] - surface layer with a basis weight of less than 450 g / m² 2 , for example less than 300 g / m 2 ,

[0060] - main layer with a basis weight of less than 700 g / m² 2 ,

[0061] - layer of glue,

[0062] - textile underlayer.

[0063] According to another particular embodiment, the multilayer comprises (is advantageously constituted) the following layers:

[0064] - protective layer with a weight between 1 and 40 g / m 2 ,

[0065] - surface layer with a basis weight of less than 400 g / m² 2, for example less than 300 g / m 2

[0066] - main layer with a basis weight of less than 700 g / m² 2 .

[0067] 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.

[0068] The multilayer may also have a structure comprising at least the following layers: protective layer / primary layer / surface layer / main layer / optionally adhesive layer / textile underlayer / optionally adhesive layer / foam underlayer, the primary layer or the surface layer being advantageously printed.

[0069] According to another particular embodiment, the multilayer comprises (is advantageously made up of the following layers:

[0070] - protective layer with a weight between 1 and 40 g / m 2 ,

[0071] - surface layer with a basis weight of less than 450 g / m² 2 , for example less than 300 g / m 2 ,

[0072] - main layer with a basis weight of less than 700 g / m² 2 ,

[0073] - textile underlayer.

[0074] According to another particular embodiment, the multilayer comprises (is advantageously made up of the following layers:

[0075] - protective layer with a weight between 1 and 40 g / m 2 ,

[0076] - surface layer with a basis weight of less than 450 g / m² 2 , for example less than 300 g / m 2 ,

[0077] - main layer with a basis weight of less than 700 g / m² 2 ,

[0078] - a textile underlayer,

[0079] - layer of glue,

[0080] - foam underlay.

[0081] The multilayer can include one or more intermediate layers, for example made of polyolefin.

[0082] The multilayer material can be textured and / or printed. 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.

[0083] Multilayer preparation process

[0084] The present invention also relates to a method for manufacturing the multilayer. This method includes 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 upper face FSCP, the surface layer having a lower face Fies opposite the upper face FSCP of the main layer, and an upper face F Scs, the protective layer being deposited on the upper face F Scs of the surface layer.

[0085] Optionally, the multilayer can be grained, advantageously in line in a calender.

[0086] During the extrusion assembly process, the graining cylinder can press the material to give it its final shape.

[0087] 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.

[0088] 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.

[0089] The textile underlayer is advantageously combined with the main layer by calendering.

[0090] The textile underlayer can also be joined to the main layer by gluing, for example by means of a layer of glue or dots of glue.

[0091] According to another particular embodiment, the main layer is associated with the textile underlayer by direct calendering (without glue) or indirect calendering (with glue).

[0092] According to another particular embodiment, the main layer is advantageously prepared by extruding thermoplastic granules. As already mentioned, the invention also relates to the use of this multilayer in the leather goods industry.

[0093] Example

[0094] According to one example, the multilayer was prepared as follows:

[0095] - Extrusion of the main layer (220°C, 350 g / m²) 2 , 700pm, density: 0.5) (single layer of expanded polyolefin + dye and UV stabilizer) on the surface of the fabric underlayer (composed of 100% polypropylene, 200g / m 2 ),

[0096] - Association (by extrusion) of the surface layer (220°C, 300 g / m 2, 0.330 mm, density: 0.9) (polyolefin formulation) on the upper surface of the main layer,

[0097] - Corona treatment,

[0098] - Application of a primer layer (5g / m²) 2 cross-linked polyurethane) on the upper surface of the surface layer,

[0099] - Printing on the primary layer (1 g / m 2 colored polyurethane),

[0100] - Application of a protective layer (4x5g / m 2 of cross-linked polyurethane) on the printing layer,

[0101] - Consolidation and post-graining of the multilayer by passing through a calender (rubber / steel).

[0102] The main layer comprises (by mass) 100% fine polyol (of which 4.5% is cross-linked fine polyol).

Claims

Demands 1. Multilayer comprising at least: a) a main layer having a FICP lower face and an FSCP upper 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 2 , 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 2 and greater than 60 g / m 2the surface layer being a thermoplastic polymer film, preferably selected from: polyolefin; polyurethane and mixtures thereof, the surface layer having a lower face Fies opposite the upper face FSCP of the main layer, and an upper face F Scs, 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 basis weight of between 1 and 40 g / m² 2 , d) a textile underlayer opposite the lower FICP face 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 2 .

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 / foam underlayer, the primary layer or the 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 chosen from: stabilizers, antioxidants, flame retardants, anti-UV agents, lubricants, fillers, expanding agents, hot melt adhesives, mineral fillers, vegetable fillers, crosslinking agents, colorants, pigments and mixtures thereof, the linear polyolefin being chosen from the group including polyethylenes, polypropylenes, polybutenes, polypentenes, poly(4-methylpentene), olefin copolymers, polyolefin elastomers and mixtures thereof, the crosslinked polyolefin being chosen from the group including polyethylenes, polypropylenes, polybutenes, olefin copolymers, plastomers, styrenic resins, elastomers and mixtures thereof.

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 plant 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 an upper face FSCP, the surface layer having a lower face Fies opposite the upper face FSCP of the main layer, and an upper face F Scs, the protective layer being deposited on the upper face F Scs 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 layer of surface and a protective layer, the main layer having a lower face FICP and an upper face FSCP, the surface layer having a lower face Fies opposite the upper face FSCP of the main layer, and an upper face F Scs, the protective layer being deposited on the upper face F Scs 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.