WO2021024223A1 - A multilayer structure for automotive components - Google Patents

A multilayer structure for automotive components Download PDF

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Publication number
WO2021024223A1
WO2021024223A1 PCT/IB2020/057448 IB2020057448W WO2021024223A1 WO 2021024223 A1 WO2021024223 A1 WO 2021024223A1 IB 2020057448 W IB2020057448 W IB 2020057448W WO 2021024223 A1 WO2021024223 A1 WO 2021024223A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
multilayer structure
polyurethane
range
structure according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2020/057448
Other languages
English (en)
French (fr)
Inventor
Francesco Gastaldi
Giorgio Lesage
Roberto PEROO'
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Adler Evo SRL
Original Assignee
Adler Evo SRL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Adler Evo SRL filed Critical Adler Evo SRL
Priority to EP20764772.8A priority Critical patent/EP4010185B1/en
Priority to BR112022002300A priority patent/BR112022002300A8/pt
Priority to US17/632,673 priority patent/US20220281206A1/en
Priority to MX2022001453A priority patent/MX2022001453A/es
Publication of WO2021024223A1 publication Critical patent/WO2021024223A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00Layered products having a non-planar shape
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022Non-woven fabric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/04Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by at least one layer folded at the edge, e.g. over another layer ; characterised by at least one layer enveloping or enclosing a material
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    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
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    • B32B5/18Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
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    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02Physical, chemical or physicochemical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
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    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02Physical, chemical or physicochemical properties
    • B32B7/022Mechanical properties
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/33Agglomerating foam fragments, e.g. waste foam
    • GPHYSICS
    • G10MUSICAL INSTRUMENTS; ACOUSTICS
    • G10KSOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
    • G10K11/00Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/16Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
    • G10K11/162Selection of materials
    • G10K11/168Plural layers of different materials, e.g. sandwiches
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/044 layers
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2250/00Layers arrangement
    • B32B2250/055 or more layers
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2250/00Layers arrangement
    • B32B2250/40Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • B32B2260/023Two or more layers
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
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    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60RVEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/08Insulating elements, e.g. for sound insulation
    • CCHEMISTRY; METALLURGY
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    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

Definitions

  • the present invention relates to a multilayer structure that achieves desired sound absorption, thermal insulation, structural-stiffness performances, lightness while being at the same time environmentally sustainable.
  • This novel multilayer structure is suitable for preparing several automotive components, placed in different vehicle locations.
  • the multilayer structure is made by using automotive production scraps, cut-outs, off spec products, having therefore a positive impact on environmental footprint as it will be evident below. Moreover, it reduces the weight of vehicle itself, decreasing energy consumption, while maintaining valid structural and mechanical properties.
  • Such components are normally made by inorganic compounds bound with thermosetting resins, usually combined with layers of different area/weight of organic material with glass fibers/fillers (SMC) or even rubber (filled with inorganic materials).
  • SMC glass fibers/fillers
  • engine “bonnets” are available. They are manufactured with inorganic compounds combined with natural fibers, reinforced with thermosetting polymer injection moulding parts. The latter are treated for oil/fluids/fire resistance before assembling.
  • the materials employed for the structural layer are usually natural fibers, sometimes bound with thermosetting powders or with thermoplastic fibers, sometimes polyurethane foams are applied for the same function.
  • a typical weight value of the present shielding components (with respect to the surface), obtained via injection moulding is between 3.0 and 4.0 kg/m 2 and the material density is between 1400-1500 kg/m 3 .
  • Automotive suppliers are therefore demanded to find a compromise and develop lighter, structurally resistant and flexible structures, to meet these challenging requests. Together with the above targets it is necessary to find sustainable solutions, able to combine an environmentally friendly material together with high performance structures.
  • the main object of the present invention consists in providing automotive components made of high-performance light structures as well as recycling automotive wastes materials, avoiding their landfill or incineration.
  • the inventors of the present invention have surprisingly found that automotive polyurethane scraps can be used by assembling them together with other materials, avoiding car polyurethane component waste disposal.
  • Said polyurethane scraps can be used to manufacture a multilayer structure for preparing further car components.
  • the present invention concerns a multilayer structure comprising:
  • the multilayer structure according to the invention has the following layer sequence:
  • the layers 2) and 3) of the preferred embodiments of the invention are repeated at least twice.
  • the present invention further relates to a process for preparing the multilayer structure of the invention, said process comprising the following steps: a) providing polyurethane automotive scraps having a density value in the range from 20 to 30 g/l; b) cutting a glass wool fiber into sheets having a bidimensional shape suitable for a molding step f), thus obtaining at least one sheet of layer b, made of a glass wool fiber; c) cutting the polyurethane automotive scraps of step a) into sheets having a bidimensional shape suitable for a molding step f), thus obtaining at least one sheet of layer g, made of polyurethane scraps having a density value in the range from 20 to 30 g/l; d) cutting a non-woven material into sheets having a bidimensional shape twice of the bidimensional shape of layer b or of layer g, thus obtaining at least one non- woven sheet; e) folding the at least one non-woven sheet of step d), thus obtaining two outer layers a1 ; f) inserting the
  • the inserting step f) allow to obtain different sandwich assemblies for preparing different multilayer structures as it will be evident from the figures and the examples reported below.
  • the multilayer structure of the invention achieves desired sound absorption, valid structural and mechanical performances, while at the same time being lighter and more sustainable, with respect to the known structures for automotive purposes.
  • the multilayer structure of the invention has hence at the same time balanced integration of functions, i.e. thermal, acoustical, and mechanical functions.
  • the properties of the multilayer are also allowed by the sandwich assembly of materials of the multilayer structure of the invention, which achieves at the same time the scope to be lighter than the known structures, avoiding the problem of materials “sandwich fragility” with respect to the known structures, increasing also overall resiliency, flexibility and resistance over them.
  • the multilayer structure comprises the at least one intermediate layer b and the at least one intermediate layer g repeated alternately at least 2 times.
  • the present invention provides an automotive component made of the multilayer structure of the invention.
  • Said automotive component encloses optimal technical features together with the possibility of reducing byproducts and production discarded materials as well as recycling automotive wastes materials.
  • Figure 1 shows a multilayer structure of the invention as prepared in Examples 1-4;
  • Figure 2 shows an alternative multilayer structure of the invention as prepared in Examples 9, 10;
  • Figure 3 shows a comparison of acoustic tests of the samples of the invention, as prepared in Examples 9 and 10 without airgap;
  • Figure 4 shows a comparison of acoustic tests of the samples of the invention, as prepared in Examples 9 and 10 with 10 mm airgap;
  • Figure 5 shows a stone chipping test picture of the multilayer structure of the invention, prepared according to Example 9.
  • Figure 6 shows a stone chipping test picture of the multilayer structure of the invention, prepared according to Example 10.
  • the present invention therefore relates to a multilayer structure comprising:
  • the at least one intermediate polyurethane layer g is made of polyurethane deriving from polyurethane automotive scraps, and wherein the at least one intermediate polyurethane layer g has a density value in the range from 20 to 30 g/l.
  • scraps or “automotive scraps” it is meant any scraps, wastes, discarded polyurethane materials, deriving from polyurethane automotive pieces and having a density value in the range from 20 to 30 g/l;
  • outer it is meant any external layer, acting as top and bottom layers, employed in the multilayer structure
  • intermediate it is meant any internal layer, placed in between the outer layers, present in the multilayer structure.
  • the multilayer structure comprises at least one intermediate polyurethane layer g deriving from automotive scraps and having a density value in the range from 20 to 30 g/l, which therefore combines lightness, remarkable mechanical and structural properties, as will be clear from the detailed description and the examples, and allows a sustainable polyurethane wastes recycling.
  • the multilayer structure comprises the at least one intermediate layer b made of a glass wool fiber and/or the at least one intermediate layer g, wherein the at least one intermediate layer b and/or the at least one intermediate layer g are repeated, independently each other, at least twice.
  • the multilayer structure comprises the at least one intermediate layer g with the at least one intermediate layer b made of a glass wool fiber in between.
  • an outer layer a1 made of a non-woven material
  • At least one intermediate polyurethane layer g made of polyurethane automotive scraps having a density value in the range from 20 to 30 g/l;
  • an outer layer a1 made of a non-woven material.
  • an outer layer a1 made of a non-woven material
  • the layers 2) and 3) of the preferred embodiments of the invention are repeated at least twice.
  • the intermediate layer g is made of polyurethane deriving from polyurethane automotive scraps.
  • Said polyurethane of the layer y is a lightweight material, having a density value in the range from 20 to 30 g/l, preferably from 22 to 25 g/l.
  • the density value of the polyurethane scraps can be measured according to well known measurement in the art, for example ISO 845.
  • the polyurethane of the layer g has a density of 25 g/l, even more preferably of 22 g/l.
  • the at least one intermediate polyurethane layer g has preferably an elongation value at break in both directions in a range from 40 to 150 % (according to EN ISO 9073-3).
  • the at least one intermediate polyurethane layer g has preferably a compression set of 1000-1200 g/cm 2 (according to DIN EN ISO 1856).
  • the at least one intermediate polyurethane layer g has also sound-absorption and self-extinguishing, not burnable characteristics.
  • the flammability value of the layer g is surprisingly 100 mm/min.
  • the layer g has more preferably a tear resistance in both directions of 14 N/cm 2 (according to EN ISO 1798) and an elongation value in both directions of 40%.
  • the multilayer structure comprises two outer layers a1 , which are placed one as top layer and the other as bottom layer.
  • the material of the two outer layers a1 made of a non-woven material, might be chosen on the basis of the final use of the automotive component made of the multilayer structure of the invention. Through different combinations it is possible to change the area of the vehicle where the component can be placed, ensuring a flexible application of the novel materials solution.
  • the non-woven material of layer a1 is made of preferably viscose and polyester, more preferably of total weight of 100-120 g/m 2 according to EN ISO 9073-1.
  • the non-woven material is made of viscose/polyester-PET based fibers, covered with a phenolic coating.
  • the two outer layers a1 made of viscose-polyester-PET based fibers are preferably thin layers more preferably having:
  • the two outer layers a1 made of viscose-polyester-PET based fibers have preferably good flexibility, having an elongation at maximal breaking strength in the machine direction, at a speed of 100 mm/min, according to EN ISO 9073-3, of about 46.7%, and an elongation at maximal breaking strength in the cross direction, at a speed of 100 mm/min, according to EN ISO 9073-3, of about 77.6%. They further possess advantageously oil/water/gasoil repellency, having a value of flammability approximately about 0.
  • the outer layers a1 are preferably made of a carbon non- woven material, more preferably a needle-punched carbon non-woven material, still more preferably they are made of a PANO (pre-oxidized polyacrylonitrile C-fibers)- polyester fiber, covered with a phenolic coating.
  • a carbon non- woven material more preferably a needle-punched carbon non-woven material, still more preferably they are made of a PANO (pre-oxidized polyacrylonitrile C-fibers)- polyester fiber, covered with a phenolic coating.
  • PANO pre-oxidized polyacrylonitrile C-fibers
  • the outer layer a1 made of a carbon non-woven material has preferably a total surface weight in the range from 100 to 120 g/m 2 , according to EN ISO 9073-1.
  • the two outer layers a1 comprising a carbon non-woven material are preferably thin layers more preferably having:
  • the two outer layers a1 comprising a carbon non-woven material have preferably good flexibility, having an elongation at maximal breaking strength in the machine direction, at a speed of 100 mm/min, according to EN ISO 9073-3, of minimum 30%, and an elongation at maximal breaking strength in the cross direction, at a speed of 100 mm/min, according to EN ISO 9073-3, of minimum 60%.
  • the multilayer structure comprises at least one intermediate layer b, made of a glass wool fiber. This layer gives good performances in thermal and acoustical insulation of the car engine compartment.
  • the glass wool fiber is preferably bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission.
  • the intermediate layer b can further comprise a flame retardant additive.
  • the at least intermediate layer b containing the flame retardant additive has preferably a compression load deflection in the range from 3 to 5 kPa at 40% deformation (according to DIN EN ISO 3386/1), a compression set of maximum 8% at 50% deformation (according to DIN EN ISO 1856), an elongation at break of minimum 150% (according to DIN EN ISO 1798) and a tensile strength of minimum 150 kPa (according to DIN EN ISO 1798).
  • the multilayer structure comprises:
  • - two outer layers a1 made of a non-woven material consisting in a blend of 50/50 viscose-polyester-PET based fibers covered with a phenolic coating, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100cm 2 and a thickness of 0.78 mm.
  • At least one intermediate glass wool layer b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • the multilayer structure comprises:
  • - two carbon non-woven outer layers a1 made of a PANO (pre-oxidized polyacrylonitrile C-fibers)-polyester fiber covered with a phenolic coating, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100 cm 2 and a thickness at 1 KPa of 1 mm.
  • PANO pre-oxidized polyacrylonitrile C-fibers
  • At least one intermediate glass wool layer b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and comprising a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • the multilayer structure comprises:
  • - two outer layers a1 made of a non-woven material consisting in a blend of 50/50 viscose-polyester-PET based fibers covered with a phenolic coating, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100cm 2 and a thickness of 0.78 mm.
  • At least one intermediate glass wool layer b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and comprising a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • the multilayer structure comprises:
  • - two carbon non-woven outer layer a1 made of a PANO (pre-oxidized polyacrylonitrile C-fibers)-polyester fiber covered with a phenolic coating, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100cm 2 and a thickness at 1 kPa of 1 mm.
  • PANO pre-oxidized polyacrylonitrile C-fibers
  • At least one intermediate glass wool layer b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and comprising a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • - three layers b can be stacked, to obtain a multilayer structure, in between the two intermediate layers g and inside the two outer layers a1 , and
  • the multilayer structures of the invention showed very good performances, preferably they showed:
  • E - flexural modulus
  • E from 380 to 1600 N/mm 2 , preferably 550-950 N/mm 2 measured according to IS0179 via 3 points flexural method (Charpy method), using 10 rectangular samples of the multilayer structure (50 x 160 mm), through a 10 mm diameter punch at a load speed of 10 mm/min, with a distance between the supports of 100 mm and with a press pressure of 150 bar.
  • - tensile resistance from 4 to 16 N/mm 2 according to IS0179, using 10 rectangular samples of the multilayer structure according to the invention (50 x 160 mm) and pulling the samples with 100 mm/min of advancing speed till breaking.
  • the invention concerns an automotive component made of the multilayer structure of the invention.
  • automotive components the following can be cited: wheelarch, air ducting, rectractable, hard top, trunk floor cover and underbody covers. All the automotive components can be placed on different vehicles and in different locations of the vehicle.
  • the invention hence concerns a process for preparing the multilayer structure of the invention, said process comprising the following steps: a) providing polyurethane automotive scraps having a density value in the range from 20 to 30 g/l; b) cutting a glass wool fiber into sheets having a bidimensional shape suitable for a molding step f), thus obtaining at least one sheet of layer b, made of a glass wool fiber; c) cutting the polyurethane automotive scraps of step a) into sheets having a bidimensional shape suitable for a molding step f), thus obtaining at least one sheet of layer g, made of polyurethane scraps, having a density value in the range from 20 to 30 g/l; d) cutting a non-woven material into sheets having a bidimensional shape twice of the bidimensional shape of layer b or of layer g, thus obtaining at least one non- woven sheet; e) folding the at least one non-woven sheet of step d), thus obtaining two outer layers a1 ; f) inserting
  • the inserting step f) provides for inserting the layers b and g, of steps b) and c) in a desired sandwich assembly having a layer sequence as above indicated in the preferred embodiments of the invention.
  • - two outer layers a1 made of non-woven viscose-polyester layers comprising polyester, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100cm 2 , a thickness of 0.78 mm and made of a blend 50/50 of viscose/black polyester-PET fibers, covered with a phenolic coating.
  • intermediate glass wool layers b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • polyurethane automotive scraps were firstly provided.
  • a glass wool fiber was cut into sheets having a rectangular shape suitable for fitting in the molding device, thus obtaining three sheets of layer b, made of a glass wool fiber.
  • polyurethane automotive scraps were cut into sheets having the same rectangular shape of the sheet of glass wool fiber, thus obtaining two sheets of layer g.
  • the polyurethane sheet had a compression set in the range from 1000 to 1200 g/cm 3 , a tear resistance in both directions of 14 N/cm 2 and an elongation value in both directions between 40-150%.
  • a non-woven material was cut into sheets having a shape twice of the rectangular shape of layer b, thus obtaining one non-woven sheet. The latter was then folded thus obtaining two outer layers a1 .
  • the three layers b and two layers g were inserted alternatively according to the layer sequence reported in Figure 1.
  • the final sandwich assembly was hence uploaded into the heat mold device and molded via thermocompression, at a temperature 190-20CTC for a time equal or below 60 seconds, thus obtaining the multilayer structure of the invention of Figure 1.
  • - two carbon non-woven outer layers a1 made of PANO (pre-oxidized polyacrylonitrile C-fibers)-polyester fibers covered with a phenolic coating, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100 cm 2 and a thickness at 1 Kpa of 1 mm.
  • PANO pre-oxidized polyacrylonitrile C-fibers
  • intermediate glass wool layers b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and comprising a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • the polyurethane layer g had a compression set in the range from 1000 to 1200 g/cm 3 , a tear resistance in both directions of 14 N/cm 2 and an elongation value in both directions between 40-150%.
  • - two outer layers a1 made of needle punched non-woven layers comprising viscose-polyester, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100cm 2 , a thickness of 0.78 mm and made of a blend 50/50 of viscose/black polyester-PET fibers, covered with a phenolic coating.
  • intermediate glass wool layers b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and comprising a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • the polyurethane layer g had a compression set in the range from 1000 to 1200 g/cm 3 , a tear resistance in both directions of 14 N/cm 2 and an elongation value in both directions between 40-150%.
  • - two carbon non-woven outer layer a1 made of PANO (pre-oxidized polyacrylonitrile C-fibers)-polyester fibers covered with a phenolic coating, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100cm 2 and a thickness at 1 kPa of 1 mm.
  • PANO pre-oxidized polyacrylonitrile C-fibers
  • intermediate glass wool layers b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and comprising a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • the polyurethane layer g had a compression set in the range from 1000 to 1200 g/cm 3 , a tear resistance in both directions of 14 N/cm 2 and an elongation value in both directions between 40-150%.
  • a prior art material employed in the production of automotive components, such as wheelarch, airducting retractable hard top, trunk floor cover and underbody covers, is polyamide reinforced with 30% glass fibers (FCA STANDARD MS.50017).
  • Said material is available on the market as PA GF30 (i.e. Durethan BKV 30H produced by Bayer, Zytel 73G30 produced by Dupont and TECFINYL C218 V30 produced by NYLTECFI) and it is obtained with the known technology injection molding.
  • the prior art material (PA GF30) and the multilayer structure of the invention were tested for evaluating the density and the weight.
  • the prior art material resulted to have a density of 1400 kg/m 2 and a weight of 3.0 kg
  • the multilayer structure of the invention resulted to have a density of 543 kg/m 2 and a weight of 1 .2 kg.
  • the weight reduction achieved with the multilayer of the invention was around 61 .2% with respect to the known prior art material. It is evident that the multilayer structure of the invention allows to prepare lighter automotive components, decreasing therefore their weight and the final vehicle mass.
  • the automotive components namely wheelarch, airducting retractable hard top, trunk floor cover and underbody covers, were prepared by using the same prior art material of Example 5. The obtained samples were used as comparative samples.
  • the multilayer structure of Example 1 was used for preparing the same automotive components namely wheelarch, airducting retractable hard top, trunk floor cover and underbody covers.
  • the automotive components made of the prior art material and the automotive components, made of the multilayer structure of the invention, were evaluated for the following properties: Lightweight, acoustic insulation, acoustic absorption, esthetical property, mechanical property, structural property, impact resistance- stone, resilience and flame resistance.
  • the evaluation consisted in giving a score in a scale from “ — ” to “+ + +” with respect to the reference.
  • samples of the invention showed better acoustic absorption and better aesthetical, mechanical and structural properties.
  • Example 7 Evaluation of Flexural Modulus (E) of the multilayer structures of the invention
  • the multilayer structure 1 prepared according to Example 1 , the multilayer structure 3, prepared according to Example 3, were evaluated by measuring the Flexural Modulus E via 3 points flexural method (Charpy Method, according to IS0179 - plane sheets).
  • All the samples of the invention were tested through a 10 mm diameter punch with a load speed of 10 mm/min, with a distance between the supports 16 times the multilayer structure thickness (100 mm) and with a press pressure of 150 bar.
  • the Flexural Modulus (E) was evaluated according to Formula (I): wherein P is the load (N) b is the test tube width (mm)
  • / is the distance between supports (mm) s is the test tubes thickness (mm)
  • / is the distance between supports (mm) s is the test tubes thickness
  • the average tensile resistance values have been calculated for both multilayer structures 1 and 3, thus obtaining the following results: Both multilayer structures of the invention showed good tensile resistance properties.
  • the multilayer structure 1 showed good tensile resistance.
  • Example 9 Preparation of the multilayer structure 5 of the invention, as represented in Figure 2 By following the same procedure as in Example 1 by using the layers indicated below the multilayer structure 5, having a different layer sequence, has been prepared.
  • two outer layers a1 made of needle punched non-woven layers comprising viscose-polyester, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100 cm 2 , a thickness of 0.78 mm and made of a blend 50/50 of viscose/black polyester-PET fibers, covered with a phenolic coating.
  • intermediate glass wool layers b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and comprising a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • - two carbon non-woven outer layers a1 made of PANO (pre-oxidized polyacrylonitrile C-fibers)-polyester fibers covered with a phenolic coating, having a total surface weight in the range from 100 to 120 g/m 2 with respect to a multilayer structure sample of 100 cm 2 and a thickness at 1 Kpa of 1 mm.
  • PANO pre-oxidized polyacrylonitrile C-fibers
  • intermediate glass wool layers b made of a glass wool fiber bonded with a thermosetting phenolic resin binder (R225) in an amount of 10% with respect to the total weight of the layer b, with very low formaldehyde emission, and comprising a flame retardant additive.
  • R225 thermosetting phenolic resin binder
  • the multilayer structure 5 had a weight of 3.43 g, a weight per area of 2157 g/m 2 , a thickness of 2.7 mm and a density of 811 kg/m 3
  • the multilayer structure 6 had a weight of 3.66 g, a weight per area of 2301 g/m 2 , a thickness of 3.0 mm and a density of 767 kg/m 3
  • the multilayer structure 6, showed better noise absorption without airgap, while the multilayer structure 5, absorbed effectively the acoustic waves in presence of a 10 mm airgap.
  • Test conditions used were according to a Global Automotive Customer specification.
  • the rocks were loaded in a Gravelometerfor launching towards the test multilayers.
  • the experiment goal is to test the material resistance to gravel impact, thus establishing the material reliability against corrosion. Therefore, after the rock treatment, there shall be no holes, cracking or peeling on the specimen and no water flowed through the sample.
  • the conditions for the exposure test and chipping resistance were the following: 10 cycles of 500g Basalt (7 rocks) were used at a pressure of 0.4 MPa.
  • the multilayer structure sample was 150 x 100 mm, 4mm thick.
  • the angle used for the experiment was 90 ° C and the distance between the launching area and the test specimens was 35 cm.
  • the multilayer structure 5 of the invention showed very good resistance towards stone impact. No holes were formed after the treatment, indicating high stiffness and therefore protection against corrosion, as shown in Figure 5.
  • the multilayer structure showed very good resistance towards stones impact. No holes were formed after the treatment, indicating high stiffness and therefore protection against corrosion, as shown in Figure 6.

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WO2006071464A1 (en) * 2004-12-28 2006-07-06 Owens-Corning Fiberglas Technology Ii, Llc. Polymer/wucs mat for use in automotive applications
JP2007111866A (ja) * 2005-10-18 2007-05-10 Nagoya Oil Chem Co Ltd 染出抑制材及び積層材
US20140124972A1 (en) * 2011-03-23 2014-05-08 Autoneum Management Ag Production process for a moulded multilyer lining

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KR101272551B1 (ko) * 2011-06-27 2013-06-11 엔브이에이치코리아(주) 자동차용 고성능 다층 흡음재 제조방법
US20190329525A1 (en) * 2016-11-18 2019-10-31 Kuraray Co., Ltd. Sound-absorbing thermal-insulating material

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WO2006071464A1 (en) * 2004-12-28 2006-07-06 Owens-Corning Fiberglas Technology Ii, Llc. Polymer/wucs mat for use in automotive applications
JP2007111866A (ja) * 2005-10-18 2007-05-10 Nagoya Oil Chem Co Ltd 染出抑制材及び積層材
US20140124972A1 (en) * 2011-03-23 2014-05-08 Autoneum Management Ag Production process for a moulded multilyer lining

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