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WO2022168329A1 - Plastique souple de carénage et son procédé de production - Google Patents

Plastique souple de carénage et son procédé de production Download PDF

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Publication number
WO2022168329A1
WO2022168329A1 PCT/JP2021/004664 JP2021004664W WO2022168329A1 WO 2022168329 A1 WO2022168329 A1 WO 2022168329A1 JP 2021004664 W JP2021004664 W JP 2021004664W WO 2022168329 A1 WO2022168329 A1 WO 2022168329A1
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WO
WIPO (PCT)
Prior art keywords
resin member
resin
thermoplastic resin
bumper fascia
resin material
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/JP2021/004664
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English (en)
Japanese (ja)
Inventor
正広 佐藤
和男 大谷
信行 高橋
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.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
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 Showa Denko KK filed Critical Showa Denko KK
Priority to PCT/JP2021/004664 priority Critical patent/WO2022168329A1/fr
Priority to JP2022579312A priority patent/JPWO2022168329A1/ja
Publication of WO2022168329A1 publication Critical patent/WO2022168329A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R19/00—Wheel guards; Radiator guards, e.g. grilles; Obstruction removers; Fittings damping bouncing force in collisions
    • B60R19/02—Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects
    • B60R19/04—Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects formed from more than one section in a side-by-side arrangement

Definitions

  • the present disclosure relates to a bumper fascia provided on the front and rear parts of the vehicle body of an automobile and a manufacturing method thereof.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2012-166634 discloses a bumper for a vehicle and a molding method thereof.
  • the plate thickness of the bumper center where a plurality of gates are concentrated, is set small during injection molding, while the plate thickness of the bumper side is set large to create a different plate thickness distribution. It is said that it is possible to achieve both overall weight reduction and avoidance of deterioration in appearance due to occurrence of weld lines.
  • the present disclosure provides a bumper fascia that can achieve the desired stiffness and good appearance even when weight is reduced, and a method that can inexpensively manufacture such a bumper fascia.
  • the task is to
  • the present disclosure includes the following aspects.
  • the first resin member is a reinforcing rib and/or a bracket
  • the second resin member is a bumper fascia main body
  • the first resin member and the second resin member are welded via the primer layer
  • a bumper fascia wherein at least one of the primer layers is a polymer composition layer formed from the following polymer composition (A) or (B).
  • B The following (1) A polymer of a polymerizable composition containing at least one of (7), a maleic anhydride-modified polypropylene or a modified polyphenylene ether, and a thermoplastic resin different from the thermoplastic resin constituting the thermoplastic resin material, (1) Combination of difunctional isocyanate compound and diol (2) Combination of difunctional isocyanate compound and difunctional amino compound (3) Combination of difunctional isocyanate compound and difunctional thiol compound (4) Bifunctional Combination of epoxy compound and diol (5) Combination of bifunctional epoxy compound and bifunctional carboxy compound (6) Combination of bifunctional epoxy compound and bifunctional thiol compound (7) Monofunctional radically polymerizable monomer [2] Polymer composition The bumper fascia according to [1], wherein the
  • thermoplastic resin constituting the thermoplastic resin material is at least one selected from the group consisting of polypropylene, modified polyphenylene ether, and polybutylene terephthalate, according to any one of [1] to [5].
  • bumper facia [7] Both the first resin member and the second resin member have the primer layer, and the primer layer of the first resin member and the primer layer of the second resin member are welded together. [1] The bumper fascia according to any one of [6].
  • a monomer occupying the maximum content and the thermoplastic resin material of the first resin member are Among the monomers constituting the thermoplastic resin, the monomers occupying the maximum content are the same, and the content of each of the monomers is 70% by mass or more, [1] to [7 ].
  • the aspect ratio (height/thickness) of the height and thickness of the first resin member is 5 or more, and the ratio of the height of the first resin member to the thickness of the second resin member is 5.
  • the thermoplastic resin material of the first resin member or the second resin member includes polypropylene and at least one reinforcing material selected from the group consisting of talc, glass fiber, and carbon fiber, and The bumper fascia according to any one of [1] to [9], wherein the first resin member or the second resin member has a tensile strength of 40 MPa or more and a Young's modulus of 3 GPa or more.
  • the thermoplastic resin material of the first resin member or the second resin member contains polyetherimide and at least one reinforcing material selected from the group consisting of talc, glass fiber, and carbon fiber.
  • a method of manufacturing a bumper fascia, comprising welding the first resin member and the second resin member by crimping the first resin member and the second resin member so as to be interposed therebetween.
  • FIG. 1 is a vehicle front view showing the position of a bumper fascia (dotted line portion limited to the front bumper) in the vehicle.
  • FIG. 2 is a schematic diagram showing each component of the bumper fascia.
  • FIG. 3 is a schematic diagram of the bumper fascia showing other components joined to the bumper fascia body.
  • FIG. 4 is a schematic cross-sectional view showing a state in which one primer layer is laminated on a thermoplastic resin material in the first resin member of one embodiment.
  • FIG. 5 is a schematic cross-sectional view showing a state in which a plurality of primer layers are laminated on a thermoplastic resin material in a first resin member of another embodiment.
  • FIG. 6 is a schematic cross-sectional view of a state in which the first resin member and the second resin member are welded together.
  • Adhesion means bonding two adherends (objects to be adhered) via an organic material (hardening resin, thermoplastic resin, etc.) such as tape or adhesive.
  • Welding means melting the surface of an adherend such as a thermoplastic resin by heat, and forming a joined state by entanglement and crystallization due to molecular diffusion by contact pressure and cooling.
  • (meth)acrylic means acrylic or methacrylic
  • (meth)acrylate means acrylate or methacrylate
  • FIG. 1 is a vehicle front view showing the position of a bumper fascia 10 (dotted line portion limited to the front bumper) in the vehicle.
  • a bumper fascia is a part (outer panel) that is positioned on the outermost side of the vehicle body among the parts that make up the bumper and that can be visually recognized as the exterior of the vehicle.
  • FIG. 2 is a schematic diagram showing each component of the bumper fascia 10
  • FIG. 3 is a schematic diagram of the bumper fascia showing a state in which other components are joined to the bumper fascia main body 12.
  • the bumper fascia main body 12 shows the inner surface of the vehicle body.
  • the bumper fascia 10 is joined to a bumper fascia main body 12, reinforcing ribs 14 for reinforcing a thin center portion of the bumper fascia main body 12, and both outer portions of the bumper fascia main body 12 to provide a vehicle. and a bracket 16 that houses sensors or the like for detecting obstacles ahead.
  • the weight thereof need not be excessively large.
  • the reinforcing ribs 14 the weight thereof need not be excessively large.
  • the desired rigidity of the bumper fascia 10 can be achieved even if the central portion of the bumper fascia main body 12 is thinned.
  • the reinforcing rib 14 and/or the bracket 16 are also referred to as the "first resin member 1", and the bumper fascia main body 12 is also referred to as the "second resin member 4".
  • the first resin member 1 of one embodiment is a laminate having a thermoplastic resin material 2 and one or more primer layers 3 laminated on the thermoplastic resin material.
  • at least one layer of the primer layer 3 is a polymer composition layer 3a formed from a specific polymerizable composition.
  • the polymerizable composition is a combination of specific bifunctional compounds, by polyaddition reaction in the presence of a catalyst, or by radical polymerization reaction of specific monofunctional monomers, a thermoplastic structure, That is, it means a composition that forms a linear polymer structure.
  • a catalyst or by radical polymerization reaction of specific monofunctional monomers
  • the polymerizable composition does not form a three-dimensional network with a crosslinked structure and has thermoplasticity.
  • a polymer composition means a composition containing a polymer (linear polymer) having a thermoplastic structure as a main component (90% by mass or more in total).
  • the polymer includes a polymer obtained from a polymerizable composition containing a combination of the specific bifunctional compounds and/or a specific monofunctional monomer, and a polymer obtained by adding maleic anhydride-modified polypropylene to the polymer. , maleic anhydride-modified polypropylene, modified polyphenylene ether, and the like.
  • the polymer composition layer 3a is formed from a polymer composition containing a polymer of the polymerizable composition, a polymer obtained by adding maleic anhydride-modified polypropylene to the polymer, a maleic anhydride-modified polypropylene, a modified polyphenylene ether, and the like. It is the layer where The polymerizable composition has a thermoplastic structure, i.e., a combination of the specific bifunctional compounds undergoing a polyaddition reaction in the presence of a catalyst, or a radical polymerization reaction of the specific monofunctional monomers. , forming a linear polymer structure.
  • the primer layer 3 includes the thermoplastic resin material 2 of the first resin member 1 and the second resin material having the thermoplastic resin material, which is the other bonding object, as shown in FIG. 6 to be described later. Interposed between the thermoplastic resin material 2 of the first resin member 1 and the thermoplastic resin material of the second resin member 4 when the bumper fascia 10 (resin-resin joint) is obtained by joining and integrating the member 4 and a layer that improves the bonding strength between the thermoplastic resin material 2 of the first resin member 1 and the thermoplastic resin material of the second resin member 4 .
  • the second resin member 4 when the second resin member 4 has a thermoplastic resin material made of the same thermoplastic resin as the thermoplastic resin forming the thermoplastic resin material 2, the first resin member 1 and the second resin The member 4 can be firmly welded.
  • the second resin member 4 has a thermoplastic resin material made of a thermoplastic resin different from the thermoplastic resin forming the thermoplastic resin material 2, generally, the thermoplastic resin material 2 of the first resin member 1 and the second
  • the present disclosure also allows such dissimilar thermoplastic resin materials to be strongly welded together.
  • the “same type of thermoplastic resin” means that the monomers constituting the thermoplastic resin have the same monomer that accounts for the maximum content, and the content of each of the monomers is 70 mass. % or more means a thermoplastic resin.
  • “Different thermoplastic resin” means a thermoplastic resin other than “the same type of thermoplastic resin”. In the monomer, a thermoplastic resin in which the monomers occupying the maximum content are different, or the monomers occupying the maximum content are the same, and the content of at least one of the monomers occupying the maximum content is 70 mass % less than the thermoplastic resin.
  • thermoplastic resin material 2 The thermoplastic resin forming the thermoplastic resin material 2 is not particularly limited.
  • thermoplastic resins examples include polypropylene (PP, SP value: 8.0 (J/cm 3 ) 1/2 ), polyamide 6 (PA6, SP value: 12.7 to 13.6 (J/cm 3 ) 1 /2 ), polyamide 66 (PA66, SP value: 13.6 (J/cm 3 ) 1/2 ), polyimide (PI), modified polyphenylene ether (m-PPE), polyphenylene sulfide (PPS, SP value: 19 .8 (J/cm 3 ) 1/2 ), polyetherimide (PEI), polycarbonate (PC, SP value: 9.7 (J/cm 3 ) 1/2 ), polybutylene terephthalate (PBT, SP value: 20.5 (J/cm 3 ) 1/2 ) and the like. From the viewpoint of obtaining the effects of the present invention, the thermoplastic resin is preferably at least one selected from the group consisting of polypropylene, modified polyphenylene ether, and polybutylene terephthalate.
  • a solubility parameter is a value ( ⁇ ) that provides a numerical prediction of the degree of interaction between materials, defined by the regular solution theory introduced by Hildebrand.
  • ⁇ ( ⁇ E coh / ⁇ V) 1/2 (1)
  • ⁇ is the solubility parameter (J 0.5 /cm 1.5 )
  • E coh is the cohesive energy density (J/mol)
  • V is the molar molecular volume (cm 3 /mol)
  • ⁇ is for each atomic group. is the sum of all the atomic groups constituting the monomer.
  • the values of E coh and V for each atomic group are listed, for example, in Table 7.3 of "Properties of Polymers, Third completely revised edition".
  • the thermoplastic resin material 2 may further contain at least one selected from the group consisting of fillers and fibers.
  • the thermoplastic resin material 2 may be of a high-rigidity type containing the above thermoplastic resin and at least one reinforcing material selected from the group consisting of talc, glass fiber, and carbon fiber.
  • examples of talc-containing polypropylene include TRC104N (trade name) manufactured by SunAllomer Co., Ltd.
  • glass fiber-containing polypropylene include PP-GF40- (trade name) manufactured by Daicel Miraise Co., Ltd. 01 F02
  • examples of the carbon fiber-containing polypropylene include PP-CF40-11 F008 (trade name) manufactured by Daicel Miraise Co., Ltd.
  • a glass fiber-containing thermoplastic resin material is a type of glass fiber reinforced resin (GFRP), and a carbon fiber-containing thermoplastic resin material is a type of carbon fiber reinforced resin (CFRP).
  • the thermoplastic resin material containing reinforcing fibers such as glass fiber and carbon fiber may be in the form of molded articles such as sheet molding compounds (SMC) and bulk molding compounds (BMC).
  • SMC is a sheet-shaped molding obtained by impregnating reinforcing fibers such as glass fibers and carbon fibers with a resin composition containing a thermoplastic resin, a low shrinkage agent, a filler, and the like.
  • Primer layer 3 A primer layer 3 is laminated on the thermoplastic resin material 2 .
  • At least one layer of the primer layer 3 is a polymer composition layer 3a formed from a specific polymer composition.
  • the polymer composition layer 3a can be obtained by coating the thermoplastic resin material 2 with the specific polymer composition or a solution containing the specific polymer composition.
  • the polymerizable composition layer 3a can be formed by volatilizing the solvent after application.
  • the polymer composition layer 3a preferably contains 90% by mass or more, more preferably 95% by mass or more, of the polymer of the specific polymerizable composition.
  • the specific polymer composition is the following polymer composition (A) or (B).
  • a polymer composition containing a polymer of a polymerizable composition containing at least one of the following (1) to (7), and a maleic anhydride-modified polypropylene or a modified polyphenylene ether (B) The following (1) A polymer of a polymerizable composition containing at least one of (7), a maleic anhydride-modified polypropylene or a modified polyphenylene ether, and a thermoplastic resin different from the thermoplastic resin constituting the thermoplastic resin material 2, (1) Combination of difunctional isocyanate compound and diol (2) Combination of difunctional isocyanate compound and difunctional amino compound (3) Combination of difunctional isocyanate compound and difunctional thiol compound (4) Bifunctional Combination of epoxy compound and diol (5) Combination of bifunctional epoxy compound and bifunctional carboxy compound (6) Combination of bifunctional epoxy compound and bifunctional thiol compound (7) Monofunctional radically polymerizable monomer
  • the polymer composition of (A) and (B) preferably contains a polymer of a polymerizable composition containing the above (4), and the above (4) is a bifunctional epoxy resin and a bifunctional phenol A combination with a compound is more preferred.
  • the compounding ratio of the bifunctional isocyanate compound and the diol in (1) is preferably set so that the molar equivalent ratio of the isocyanate group to the hydroxyl group is 0.7 to 1.5, more preferably 0.5. 8 to 1.4, more preferably 0.9 to 1.3.
  • the compounding ratio of the bifunctional isocyanate compound and the bifunctional amino compound in (2) is preferably set so that the molar equivalent ratio of the isocyanate group to the amino group is 0.7 to 1.5, and more It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
  • the compounding ratio of the bifunctional isocyanate compound and the bifunctional thiol compound in (3) is preferably set so that the molar equivalent ratio of the isocyanate group to the thiol group is 0.7 to 1.5, and more It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
  • the compounding ratio of the difunctional epoxy compound and the diol in (4) is preferably set so that the molar equivalent ratio of the epoxy group to the hydroxyl group is 0.7 to 1.5, more preferably 0.5. 8 to 1.4, more preferably 0.9 to 1.3.
  • the compounding ratio of the bifunctional epoxy compound and the bifunctional carboxy compound in (5) is preferably set so that the molar equivalent ratio of the epoxy group to the carboxy group is 0.7 to 1.5, more preferably It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
  • the compounding ratio of the bifunctional epoxy compound and the bifunctional thiol compound in (6) is preferably set so that the molar equivalent ratio of the epoxy group to the thiol group is 0.7 to 1.5, and more It is preferably 0.8 to 1.4, more preferably 0.9 to 1.3.
  • the bifunctional isocyanate compound is a compound having two isocyanato groups, such as hexamethylene diisocyanate, tetramethylene diisocyanate, dimer acid diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI) or a mixture thereof, Examples include diisocyanate compounds such as p-phenylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI). From the viewpoint of primer strength, the bifunctional isocyanate compound is preferably TDI or MDI.
  • the diol is a compound having two hydroxy groups, and examples thereof include aliphatic glycols such as ethylene glycol, propylene glycol, diethylene glycol and 1,6-hexanediol, and bisphenols such as bisphenol A, bisphenol F and bisphenol S. mentioned.
  • the diol is preferably propylene glycol or diethylene glycol from the viewpoint of the toughness of the primer.
  • the bifunctional amino compound is a compound having two amino groups, and examples thereof include bifunctional aliphatic diamines and aromatic diamines.
  • Aliphatic diamines include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, 1,6-hexamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminocyclohexane, N-aminoethylpiperazine and the like.
  • aromatic diamines examples include diaminodiphenylmethane, diaminodiphenylpropane, and the like.
  • the bifunctional amino compound is preferably 1,3-propanediamine, 1,4-diaminobutane, and 1,6-hexamethylenediamine from the viewpoint of primer toughness.
  • the bifunctional thiol compound is a compound having two mercapto groups in the molecule. manufactured by Karenz MT (registered trademark) BD1).
  • the bifunctional epoxy compound is a compound having two epoxy groups in one molecule.
  • aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, naphthalene type bifunctional epoxy resin, and 1,6-hexanediol diglycidyl ether, etc.
  • Aliphatic epoxy compounds may be mentioned.
  • the bifunctional epoxy compounds may be used alone, or two or more of them may be used in combination.
  • the bifunctional carboxy compound is a compound having two carboxy groups, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, isophthalic acid, and terephthalic acid.
  • the bifunctional carboxy compound is preferably isophthalic acid, terephthalic acid, and adipic acid from the viewpoint of primer strength or toughness.
  • the monofunctional radically polymerizable monomer is a monomer having one ethylenically unsaturated bond.
  • styrene monomers ⁇ -, o-, m- or p-alkyl, nitro, cyano, amide or ester derivatives of styrene, styrenic monomers such as chlorostyrene, vinyltoluene, divinylbenzene; and ethyl (meth)acrylate.
  • the monofunctional radically polymerizable monomers may be used alone or in combination of two or more.
  • the monofunctional radically polymerizable monomer is styrene, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, or phenoxyethyl (meth)acrylate, and two of these. A combination of the above is preferred.
  • the monofunctional radically polymerizable monomer is preferably the main component among the components other than the solvent of the radically polymerizable composition.
  • the main component means that the content of the monofunctional radically polymerizable monomer is 50 to 100% by mass.
  • the content is preferably 60% by mass or more, more preferably 80% by mass or more.
  • the polymerization initiator for the radical polymerization reaction for example, known organic peroxides, photoinitiators and the like are preferably used.
  • a room-temperature radical polymerization initiator that combines an organic peroxide with a cobalt metal salt or an amine may also be used.
  • Organic peroxides include those classified as ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, or peroxydicarbonates.
  • the photoinitiator it is desirable to use one capable of initiating polymerization within the wavelength range from ultraviolet rays to visible rays.
  • the radical polymerization reaction is preferably carried out by heating at room temperature to 200°C for 5 to 90 minutes, although this depends on the type of reaction compound.
  • a polymerization reaction is carried out by irradiating ultraviolet rays or visible light.
  • the polymer composition layer 3a is preferably a layer in direct contact with the thermoplastic resin material 2. As shown in FIG.
  • thermoplastic resin material 2 it is preferable to select a composition containing a thermoplastic resin that is the same as or similar to the thermoplastic resin that constitutes the thermoplastic resin material 2 .
  • the thermoplastic resin material 2 is polypropylene
  • stronger welding can be achieved by using a polymer composition containing maleic anhydride-modified polypropylene.
  • the thermoplastic resin material 2 is modified polyphenylene ether
  • stronger welding can be achieved by using a polymer composition containing modified polyphenylene ether.
  • the primer layer 3 can also be composed of multiple layers including the polymer composition layer 3a.
  • the primer layer 3 is composed of a plurality of layers, it is preferable to laminate such that the essential polymer composition layer 3a is the outermost surface on the side opposite to the thermoplastic resin material 2 .
  • the polymer composition layer A which is one embodiment of the polymer composition layer 3a, is formed from the polymer composition (A).
  • the polymer constituting the polymer composition layer A is obtained by polyaddition reaction of at least one of the above (1) to (6) in the presence of a catalyst in a solution of maleic anhydride-modified polypropylene or modified polyphenylene ether.
  • a catalyst for example, tertiary amines such as triethylamine and 2,4,6-tris(dimethylaminomethyl)phenol, and phosphorus compounds such as triphenylphosphine are preferably used.
  • the polyaddition reaction is preferably carried out by heating at room temperature to 200° C. for 5 to 120 minutes, depending on the composition of the composition.
  • the polymer composition layer A is a mixture of a polymerizable composition containing at least one of the above (1) to (6) and maleic anhydride-modified polypropylene or modified polyphenylene ether, and a thermoplastic resin.
  • a polyaddition reaction may be preformed prior to application to the material 2 , and a mixture containing the reactants may be applied onto the thermoplastic resin material 2 to form the mixture.
  • the polymer constituting the polymer composition layer A is obtained by subjecting the composition containing the monofunctional radically polymerizable monomer (7) to a radical polymerization reaction in a solution of maleic anhydride-modified polypropylene or modified polyphenylene ether.
  • the radical polymerization reaction is preferably carried out by heating at room temperature to 200° C. for 5 to 90 minutes, depending on the composition of the composition.
  • a polymerization reaction is carried out by irradiating ultraviolet rays or visible light.
  • the polymer composition layer A is formed by mixing the polymerizable composition containing the monofunctional radically polymerizable monomer (7) with maleic anhydride-modified polypropylene or modified polyphenylene ether and heating the mixture.
  • the resulting mixture containing the radically polymerized reaction product can be applied onto the thermoplastic resin material 2 to form a coating.
  • maleic anhydride-modified polypropylene The maleic anhydride-modified polypropylene is polypropylene graft-modified with maleic anhydride. Examples thereof include Kayabrid 002PP, 002PP-NW, 003PP, 003PP-NW manufactured by Kayaku Akzo Co., Ltd., and Modic series manufactured by Mitsubishi Chemical Corporation. BYK SCONA TPPP2112GA, TPPP8112GA, or TPPP9212GA may also be used as a maleic anhydride functionalized polypropylene additive.
  • modified polyphenylene ether A known modified polyphenylene ether can be used. Modified polyphenylene ether is a blend of polystyrene, polyamide, polyphenylene sulfide, polypropylene, etc., in polyphenylene ether. Zylon series (PPE/PS, PP/PPE, PA/PPE, PPS/PPE, PPA/PPE), Mitsubishi Engineering-Plastics Epiace series, Lemalloy series (PPE/PS, PPE/PA), etc. be done.
  • the total amount of (1) to (7) used when obtaining the polymer composition layer A is 5 to 100 parts by mass when maleic anhydride-modified polypropylene or modified polyphenylene ether is 100 parts by mass. is preferred, 10 to 60 parts by weight is more preferred, and 20 to 40 parts by weight is even more preferred.
  • Polymer composition layer B The polymer composition layer B, which is one embodiment of the polymer composition layer 3a, is formed from the polymer composition (B).
  • the polymer composition layer B is formed by polyaddition reaction of at least one of the above (1) to (6) in the presence of a catalyst in a solution of maleic anhydride-modified polypropylene or modified polyphenylene ether, and then the thermoplastic resin material 2. It can be obtained by mixing with a thermoplastic resin different from the thermoplastic resin constituting the. In a solution containing a thermoplastic resin different from the thermoplastic resin constituting the thermoplastic resin material 2, at least one of (1) to (6) is subjected to a polyaddition reaction in the presence of a catalyst, and then maleic anhydride is added. It can also be obtained by mixing with modified polypropylene or modified polyphenylene ether.
  • catalysts for the polyaddition reaction for example, tertiary amines such as triethylamine and 2,4,6-tris(dimethylaminomethyl)phenol, and phosphorus compounds such as triphenylphosphine are preferably used.
  • the polyaddition reaction is preferably carried out by heating at room temperature to 200° C. for 5 to 120 minutes, depending on the composition of the composition.
  • the polymer composition layer B includes maleic anhydride-modified polypropylene or modified polyphenylene ether, a thermoplastic resin different from the thermoplastic resin constituting the thermoplastic resin material 2, and the above (1) to ( A mixture containing a reaction product obtained by heating a mixture with a polymerizable composition containing at least one of 6) can be applied onto the thermoplastic resin material 2 to form the mixture.
  • the polymer composition layer B comprises a composition containing the monofunctional radically polymerizable monomer (7), maleic anhydride-modified polypropylene or modified polyphenylene ether, and a thermoplastic resin that constitutes the thermoplastic resin material 2. It can also be obtained by a radical polymerization reaction in a solution containing different thermoplastic resins.
  • the radical polymerization reaction is preferably carried out by heating at room temperature to 200° C. for 5 to 90 minutes, depending on the composition of the composition.
  • photocuring a polymerization reaction is carried out by irradiating ultraviolet rays or visible light.
  • the polymer composition layer B comprises a polymer of the polymerizable composition containing the monofunctional radically polymerizable monomer (7), maleic anhydride-modified polypropylene or modified polyphenylene ether, and a thermoplastic resin.
  • the thermoplastic resin material 2 can be formed by mixing a thermoplastic resin different from the thermoplastic resin constituting the material 2 and applying a mixture containing a reactant obtained by heating onto the thermoplastic resin material 2 .
  • the manner of reaction occurring when obtaining the polymer composition forming the polymer composition layer is reaction of maleic anhydride-modified polypropylene or modified polyphenylene ether with bifunctional epoxy resin, maleic anhydride-modified polypropylene or modified polyphenylene. It is also not possible to comprehensively express specific aspects based on a wide variety of combinations, such as reactions between ethers and bifunctional phenol compounds. Therefore, it may be impossible or impractical to directly characterize the polymer composition by structure or properties.
  • the composition containing the curable resin contains a solvent and, if necessary, an additive such as a coloring agent in order to allow the curing reaction of the curable resin to proceed sufficiently to form a desired curable resin layer.
  • the curable resin is preferably the main component among the components other than the solvent of the composition.
  • the main component means that the content of the curable resin is 40 to 100% by mass.
  • the content is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
  • curable resin examples include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.
  • the curable resin layer 3b may be made of one of these resins, or may be made of a mixture of two or more.
  • the curable resin layer 3b may be composed of a plurality of layers, and each layer may be made of a composition containing different types of curable resins.
  • the coating method for forming the curable resin layer 3b with the composition containing the curable resin monomer is not particularly limited, examples thereof include a spray coating method and an immersion method.
  • the curable resin broadly means a resin that cures by cross-linking, and is not limited to the heat-curing type, and also includes the normal-temperature curing type and the light-curing type.
  • the photo-curing type can also be cured in a short time by irradiation with visible light or ultraviolet rays.
  • the photo-curing type may be used in combination with a heat-curing type and/or a normal temperature-curing type.
  • Examples of the photocurable type include vinyl ester resins such as “Lipoxy (registered trademark) LC-760” and “Lipoxy (registered trademark) LC-720” manufactured by Showa Denko K.K.
  • the urethane resin is usually a resin obtained by reacting an isocyanate group of an isocyanate compound with a hydroxyl group of a polyol compound, and is defined in ASTM D16 as "a coating containing polyisocyanate with a non-volatile content of 10% by weight or more in a vehicle".
  • a urethane resin corresponding to a material is preferable.
  • the urethane resin may be of a one-pack type or a two-pack type.
  • one-liquid type urethane resin examples include oil-modified type (those cured by oxidation polymerization of unsaturated fatty acid groups), moisture-curable type (those cured by reaction between isocyanato groups and water in the air), block type ( isocyanato groups, which are dissociated and regenerated by heating the blocking agent, react with hydroxyl groups to cure), lacquer type (cures by drying after the solvent evaporates), and the like.
  • moisture-curable one-liquid urethane resins are preferably used from the viewpoint of ease of handling and the like. Specifically, "UM-50P" manufactured by Showa Denko K.K.
  • Examples of two-component urethane resins include catalyst-curing type (isocyanato groups and water in the air react with each other in the presence of a catalyst to cure), polyol-curing type (reaction of isocyanato groups with hydroxyl groups of polyol compounds, hardened by) and the like.
  • polyol compounds in the polyol curing type examples include polyester polyols, polyether polyols, and phenol resins.
  • the isocyanate compound having an isocyanato group in the polyol curable type includes, for example, hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, aliphatic isocyanate such as dimer acid diisocyanate; 2,4- or 2,6-tolylene diisocyanate (TDI ) or mixtures thereof, aromatic isocyanates such as p-phenylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) or polynuclear mixtures thereof such as polymeric MDI; alicyclic isocyanates such as isophorone diisocyanate (IPDI).
  • HDI hexamethylene diisocyanate
  • TDI 2,4- or 2,6-tolylene diisocyanate
  • aromatic isocyanates such as p-phenylene diisocyanate, xylylene diisocyanate, diphenylme
  • the compounding ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably such that the hydroxyl group/isocyanate group molar equivalent ratio is in the range of 0.7 to 1.5.
  • Examples of the urethanization catalyst used in the two-component urethane resin include triethylenediamine, tetramethylguanidine, N,N,N',N'-tetramethylhexane-1,6-diamine, dimethyl etheramine, N, Amine catalysts such as N,N',N'',N''-pentamethyldipropylene-triamine, N-methylmorpholine, bis(2-dimethylaminoethyl) ether, dimethylaminoethoxyethanol, triethylamine; Organic tin catalysts such as acetate, dibutyltin dilaurate, dibutyltin thiocarboxylate, and dibutyltin dimaleate are included.
  • the epoxy resin is a resin having at least two epoxy groups in one molecule.
  • Prepolymers of the epoxy resin before curing include, for example, ether-based bisphenol-type epoxy resins, novolac-type epoxy resins, polyphenol-type epoxy resins, aliphatic-type epoxy resins, ester-type aromatic epoxy resins, and cycloaliphatic epoxy resins. , ether-ester type epoxy resins, and the like.
  • bisphenol A type epoxy resins are preferably used.
  • An epoxy resin may be used independently and may use 2 or more types together.
  • bisphenol A type epoxy resins include “jER (registered trademark) 828” and “jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Corporation.
  • novolak-type epoxy resins include "D.E.N. (registered trademark) 438 (registered trademark)” manufactured by The Dow Chemical Company.
  • Examples of the curing agent used for the epoxy resin include known curing agents such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, thiols, imidazoles, and cationic catalysts.
  • curing agent such as aliphatic amines, aromatic amines, acid anhydrides, phenol resins, thiols, imidazoles, and cationic catalysts.
  • thiols include the same compounds as exemplified as thiol compounds for forming the functional group-containing layer described later.
  • pentaerythritol tetrakis(3-mercaptobutyrate) for example, "Karenzu MT (registered trademark) PE1” manufactured by Showa Denko KK
  • Karenzu MT registered trademark
  • PE1 Showa Denko KK
  • the vinyl ester resin is obtained by dissolving a vinyl ester compound in a polymerizable monomer (such as styrene). Also called epoxy (meth)acrylate resins, in the present disclosure, the vinyl ester resins also include urethane (meth)acrylate resins.
  • vinyl ester resin for example, those described in "Polyester Resin Handbook” (Nikkan Kogyo Shimbun, 1988), “Paint Glossary” (Shikizai Kyokai, 1993), etc. may also be used. can be done. Specific examples include “Lipoxy (registered trademark) R-802", “Lipoxy (registered trademark) R-804" and “Lipoxy (registered trademark) R-806" manufactured by Showa Denko KK.
  • urethane (meth)acrylate resin for example, after reacting an isocyanate compound and a polyol compound, radicals obtained by reacting a hydroxyl group-containing (meth)acrylic monomer (and optionally a hydroxyl group-containing allyl ether monomer)
  • a polymerizable unsaturated group-containing oligomer is mentioned. Specific examples include “Lipoxy (registered trademark) R-6545” manufactured by Showa Denko K.K.
  • the vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide.
  • organic peroxide examples include, but are not limited to, ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, peroxy oxydicarbonates and the like. By combining these with a cobalt metal salt or the like, curing at room temperature is also possible.
  • the cobalt metal salt is not particularly limited, but examples thereof include cobalt naphthenate, cobalt octylate, and cobalt hydroxide. Among these, cobalt naphthenate and cobalt octylate are preferred.
  • the unsaturated polyester resin is a condensation product (unsaturated polyester) obtained by an esterification reaction between a polyol compound and an unsaturated polybasic acid (and saturated polybasic acid if necessary) and a polymerizable monomer (such as styrene). ).
  • polyester resin those described in "Polyester Resin Handbook” (Nikkan Kogyo Shimbun, 1988), “Paint Glossary” (Shikizai Kyokai, 1993), etc. can also be used. can. Specifically, “RIGOLAC (registered trademark)” manufactured by Showa Denko K.K.
  • the unsaturated polyester resin can be cured by radical polymerization by heating in the presence of the same catalyst as the vinyl ester resin.
  • a primer layer 3 is formed on the surface of the thermoplastic resin material 2 .
  • the primer layer 3 can provide excellent bondability with the second resin member 4 to be bonded. It is also possible to obtain the first resin member 1 capable of maintaining the bondability for a long period of several months. In addition, the surface of the thermoplastic resin material 2 is protected by the primer layer 3, and deterioration such as adhesion of dirt and oxidation can be suppressed.
  • thermoplastic resin forming the thermoplastic resin material of the second resin member 4 may be of the same type as or different from the thermoplastic resin forming the thermoplastic resin material 2 of the first resin member 1 . From the viewpoint of strong welding, these thermoplastic resins are preferably of the same type.
  • thermoplastic resin constituting one thermoplastic resin material and the thermoplastic resin constituting the other thermoplastic resin material are of the same type, one or both If the thermoplastic resin contains fillers or fibers, or if the thermoplastic resin is blended with other thermoplastic resins, according to the prior art, the bond strength between the two thermoplastic resin materials will be inadequate. may be sufficient. According to the present disclosure, even in these cases, the first resin member 1 and the second resin member 4 can be strongly welded via the primer layer 3 (included in the first resin member 1). .
  • thermoplastic resin constituting the thermoplastic resin material 2 of the first resin member 1 and the thermoplastic resin constituting the thermoplastic resin material of the second resin member 4 are of the same kind, a monomer constituting the thermoplastic resin , the ratio of the monomers occupying the maximum content is 70% by mass or more, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 85 to 100% by mass. .
  • the content is preferably 5. to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass. When the content is within the above range, the bonding strength between the first resin member 1 and the second resin member 4 can be increased.
  • thermoplastic resin constituting the thermoplastic resin material 2 of the first resin member 1 and/or the thermoplastic resin constituting the thermoplastic resin material of the second resin member 4 is a blend of the main thermoplastic resin and the secondary thermoplastic resin.
  • the content of the secondary thermoplastic resin is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 5 to 20% by mass. When the content is within the range, the bonding strength between the first resin member 1 and the second resin member 4 can be increased.
  • thermoplastic resin forming the thermoplastic resin material of the second resin member 4 and the thermoplastic resin forming the thermoplastic resin material 2 of the first resin member 1 are different types, the second The resin member 4 and the first resin member 1 can be strongly welded together. Furthermore, even when the SP value of the thermoplastic resin constituting the thermoplastic resin material of the second resin member 4 and the SP value of the thermoplastic resin constituting the thermoplastic resin material 2 of the first resin member 1 are separated, , the second resin member 4 and the first resin member 1 can be firmly welded.
  • FIG. 6 is a schematic cross-sectional view of a state in which the first resin member 1 and the second resin member 4 are welded together, and is a view showing, for example, the encircled portion A in FIG.
  • the bumper fascia 10 (resin-resin bonded body) is formed by welding the first resin member 1 and the second resin member 4 via the primer layer 3 (included in the first resin member 1).
  • thermoplastic resin material of the bumper fascia body 4 (12), the thermoplastic resin material 2 of the reinforcing rib 1 (14), and the thermoplastic resin material 2 of the bracket 1 (16) are are welded through the primer layer 3 (included in the reinforcing rib 1 and the bracket 1).
  • the desired rigidity of the bumper fascia 10 can be achieved even if the central portion of the bumper fascia main body 12(4) is thinned.
  • the bumper fascia 10 of the present embodiment is manufactured by the above-described method (i.e., bonding via the primer layer (3)) without injection molding the reinforcing ribs 14 (1) and the like on the bumper fascia main body 4 (12). Therefore, the exterior surface of the obtained bumper fascia 10 does not have an appearance defect called a sink mark.
  • the bumper fascia 10 of the present embodiment differs from the case where separately formed reinforcing ribs are adhered to the inside of the bumper fascia using an adhesive, and a plurality of processes (frame treatment of the resin surface, plasma treatment, etc.) are performed. Since it is produced by the above-described method without going through surface treatment, primer coating, adhesive application, adhesive curing, etc., it can be produced at low cost.
  • the aspect ratio (height/thickness) of the height and thickness of the first resin member 1 is 5 or more, and the ratio of the height of the first resin member 1 to the thickness of the second resin member 4 is 5 or more.
  • thermoplastic resin material of the first resin member 1 or the second resin member 4 contains polypropylene and at least one reinforcing material selected from the group consisting of talc, glass fiber, and carbon fiber, and the first resin member 1 Alternatively, it is preferable that the second resin member 4 has properties such as a tensile strength of 40 MPa or more and a Young's modulus of 3 GPa or more.
  • the thermoplastic resin material of the first resin member 1 or the second resin member 4 contains polyetherimide and at least one reinforcing material selected from the group consisting of talc, glass fiber, and carbon fiber, and the first resin It is preferable that the member 1 or the second resin member 4 have properties such as a tensile strength of 90 MPa or more and a Young's modulus of 3 GPa or more.
  • the thickness of the primer layer 3 depends on the materials of the first resin member 1 and the second resin member 4 and the contact area of the joint portion, but from the viewpoint of obtaining excellent joint strength, it is 1 ⁇ m to 1 ⁇ m. It is preferably 500 ⁇ m, more preferably 3 ⁇ m to 100 ⁇ m, still more preferably 5 ⁇ m to 70 ⁇ m.
  • the thickness (thickness after drying) of the polymer composition layer 3a is preferably 1 to 60 ⁇ m. When the primer layer 3 has a plurality of layers, the thickness of the primer layer 3 (thickness after drying) is the total thickness of each layer.
  • the primer layer 3 of the first resin member 1 is subjected to ultrasonic welding, vibration welding, electromagnetic induction, high frequency, laser, hot plate welding.
  • a second resin member 4 is welded by at least one method selected from the group consisting of a method and a hot press method, and a second resin member is formed on the primer layer 3 of the first resin member 1 by injection molding. 4, a method of molding a thermoplastic resin material.
  • the bumper fascia 10 (resin-resin bonded body) by a hot press method.
  • the primer layer 3 is heated, and the first resin member 1 and the second resin member 4 are crimped so that the heated primer layer 3 is interposed between the first resin member 1 and the second resin member 4.
  • the heating temperature of the primer layer depends on the melting point and softening point of the resin to be bonded, and is preferably 100°C to 350°C. For example, when the resin is nylon 6, the heating temperature is preferably 230°C.
  • the primer layer having a melting point is preferably heated at a melting point ⁇ 5°C
  • the primer layer having a softening point is preferably heated at a softening point ⁇ 15°C.
  • the pressure during crimping is preferably 0.01 MPa to 10 MPa.
  • the second resin member 4 instead of the first resin member 1 may have one or more primer layers laminated on the thermoplastic resin material.
  • the primer layer 3 ′ of the second resin member 4 the same material as the primer layer 3 described above can be used.
  • the welding of the first resin member 1 and the second resin member 4 is performed by replacing the above-described "first resin member 1" with the "second resin member 4" in this embodiment and the above-described "second resin member 4". 4” can be read as “first resin member 1” in this embodiment.
  • both the first resin member 1 and the second resin member 4 have the primer layers 3, 3' described above, and the primer layer 3 of the first resin member 1 and the primer layer of the second resin member 4 layer 3' is welded.
  • the thermoplastic resin forming the thermoplastic resin material 2 of the first resin member 1 and the thermoplastic resin forming the thermoplastic resin material of the second resin member 4 may be of the same type. It may be heterogeneous.
  • the bumper fascia 10 (resin-resin joint) is formed by at least one method selected from the group consisting of ultrasonic welding, vibration welding, electromagnetic induction, high frequency, laser, and heat press. It can be manufactured by welding the primer layer 3 of the first resin member 1 and the primer layer 3' of the second resin member 4 using a method, preferably a hot press method.
  • thermoplastic resin material for test piece Under the conditions shown in Table 1 below, using an injection molding machine (SE100V manufactured by Sumitomo Heavy Industries, Ltd.), a thermoplastic resin material for a test piece for a tensile test (width 10 mm, length 45 mm, thickness 3 mm) ): Talc-containing PP resin, m-PPE resin, PC resin, and glass fiber-containing PBT resin were obtained.
  • bifunctional epoxy resin (jER (registered trademark) 1001 manufactured by Mitsubishi Chemical Corporation) (bisphenol A type epoxy resin, molecular weight about 900): 1.01 g, bisphenol A: 0.24 g, 2,4,6-tris (Dimethylaminomethyl)phenol: 0.006 g was put into a flask and stirred at 125° C. for 30 minutes to carry out a polyaddition reaction between the bifunctional epoxy resin and bisphenol A.
  • a composition-1 hereinafter simply referred to as composition-1) containing maleic anhydride-modified polypropylene and a polymer (thermoplastic epoxy resin) of the bifunctional epoxy resin and bisphenol A was obtained. .
  • composition-2 for forming primer layer
  • a flask was charged with 3.77 g of modified polyphenylene ether (NOLYL731 manufactured by SABIC) and 95 g of xylene, and the temperature was raised to 125° C. with stirring to dissolve.
  • bifunctional epoxy resin Mitsubishi Chemical Corporation jER (registered trademark) 1001: 1.0 g, bisphenol A: 0.22 g, 2,4,6-tris (dimethylaminomethyl) phenol: 0.005 g
  • the mixture was put into a flask and stirred at 125° C. for 30 minutes to carry out a polyaddition reaction between the bifunctional epoxy resin and bisphenol A.
  • composition-2 hereinafter simply referred to as composition- 2 was obtained.
  • composition-1 is applied to the surface of one side of the thermoplastic resin material for the test piece, PP (30% by mass of talc) or PBT (30% by mass of glass fiber), so that the thickness after drying is 80 ⁇ m. It was applied by a spray method. After volatilizing the solvent (xylene) by leaving it in the air at room temperature for 30 minutes, heating it in a furnace at 150 ° C. for 30 minutes and allowing it to cool to room temperature. Test piece having composition-1 as a primer layer. PP-1 and PBT-1 were obtained.
  • Composition-2 was applied by spraying to the surface of one side of the m-PPE of the thermoplastic resin material for the test piece so that the thickness after drying was 80 ⁇ m. After volatilizing the solvent (xylene) by leaving it in the air at room temperature for 30 minutes, heating it in a furnace at 150 ° C. for 30 minutes, allowing it to cool to room temperature, and using Composition-2 as a primer layer. m-PPE-1 was obtained.
  • the surface on which the primer layer is formed on the test piece is referred to as the primer surface, and the surface on which the primer layer is not formed is referred to as the non-primer surface.
  • the primer surface the surface on which the primer layer is not formed
  • the non-primer surface the surface on which the primer layer is not formed.
  • a surface having a primer layer is indicated as (present), and a surface having no primer layer is indicated as (absent).
  • ⁇ Test Example 1> (welding) The primer surface of PP-1 and the primer surface of m-PPE-1 are overlapped so that the joint portion overlaps so that the length is 5 mm and the width is 10 mm. - Ultrasonic welding was performed using JII430T-M (28.5 KHz) to obtain a test piece 1 (resin-resin bonded body).
  • the joint portion means a portion where the thermoplastic resin material for the test piece is superimposed.
  • Test Pieces 4-1 and 4-2> A thermoplastic resin material m-PPE-1 or PP-1 with a primer is inserted into a mold, PBT is injection molded on the primer surface under the same conditions as in Table 1, and the primer surface and PBT (width 10 mm, length A test piece (2 types) having a length of 5 mm and a width of 10 mm was obtained.
  • the present invention can be used for a bumper fascia and its manufacturing method.
  • first resin member 2 thermoplastic resin material 3 primer layer 3a polymer composition layer 3b curable resin layer 4 second resin member 10 bumper fascia (resin-resin joint) REFERENCE SIGNS LIST 12 Bumper fascia body 14 Reinforcement rib 14a Trunk 14b Branch 16 Bracket A Circled portion

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

Sont divulgués : un plastique souple de carénage qui possède une rigidité souhaitée même s'il est conçu pour être plus léger et qui peut présenter un aspect favorable ; et un procédé permettant de produire à bas coût ledit plastique souple de carénage. Un premier élément en résine (1) est un support et/ou une nervure de renfort. Un second élément en résine (4) est un corps de plastique souple de carénage. Le premier élément en résine et le second élément en résine sont soudés, et au moins une couche d'une couche d'apprêt est une couche d'une composition du type à polymérisation in situ, qui est formée par polymérisation d'une composition du type à polymérisation in situ sur le matériau de résine thermoplastique.
PCT/JP2021/004664 2021-02-08 2021-02-08 Plastique souple de carénage et son procédé de production Ceased WO2022168329A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62153160U (fr) * 1986-03-24 1987-09-29
JP2020199899A (ja) * 2019-06-11 2020-12-17 昭和電工株式会社 クラッシュボックス及びその製造方法
WO2020256038A1 (fr) * 2019-06-19 2020-12-24 昭和電工株式会社 Corps multicouche composite et corps lié métal-polyoléfine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62153160U (fr) * 1986-03-24 1987-09-29
JP2020199899A (ja) * 2019-06-11 2020-12-17 昭和電工株式会社 クラッシュボックス及びその製造方法
WO2020256038A1 (fr) * 2019-06-19 2020-12-24 昭和電工株式会社 Corps multicouche composite et corps lié métal-polyoléfine

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