WO2022168329A1 - Bumper fascia and production method therefor - Google Patents
Bumper fascia and production method therefor Download PDFInfo
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- 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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- resin member
- resin
- thermoplastic resin
- bumper fascia
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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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Abstract
Description
本開示は、自動車の車体前後部に設けられるバンパーフェイシア及びその製造方法に関する。 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.
近年、製品の軽量化及び低コスト化等の観点より、自動車部品を樹脂化して樹脂成形品とすることが頻繁に行われている。車体の前後部に必ず取り付けられるバンパーについても例外ではなく、樹脂化による軽量化が行われている。 In recent years, from the viewpoint of weight reduction and cost reduction of products, it is frequently practiced to make automobile parts into resin molded products. Bumpers, which are always attached to the front and rear of the vehicle body, are no exception, and weight reduction is being carried out by using resin.
特許文献1(特開2012-166634号公報)は、車両用バンパー及びその成形方法を開示している。この車両用バンパーでは、射出成形の際に複数のゲートが集中するバンパーセンターの板厚を小さく設定する一方、前記バンパーサイドの板厚を大きく設定して異なる板厚分布とすることで、バンパーの全体的な軽量化と、ウエルドラインの発生による外見低下の回避との両立を図ることができる、とされている。 Patent Document 1 (Japanese Patent Application Laid-Open No. 2012-166634) discloses a bumper for a vehicle and a molding method thereof. In this vehicle bumper, 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.
特許文献1のバンパーフェイシアのように、バンパーセンターの板厚を小さくした場合には、本来バンパーに要求される剛性を実現できないおそれがある。また、近年ではバンパーについて軽量化のみならず良好な外観を実現することも要請されている。しかし、極端に板厚の小さい部分が存在する場合には、剛性を高める目的でバンパーフェイシアの内側に補強リブなどを射出成形などにより一体成形すると、射出成形された樹脂が冷却時に収縮することにより生じる内部応力により、バンパーフェイシアの外装面にヒケと呼ばれる外観不良を生ずるおそれもある。
As with the bumper fascia in
さらに、別体で成形した補強リブをバンパーフェイシアの内側に接着剤を用いて接着する方法では、樹脂面のフレーム処理、プラズマ処理などの下地処理、プライマー塗工、接着剤塗布、接着剤硬化などの複数の工程を複雑な形状を有する接着面に対して実施する必要があり、コストの点で不利であった。 Furthermore, in the method of bonding reinforcing ribs molded separately to the inside of the bumper fascia with adhesive, frame treatment of the resin surface, base treatment such as plasma treatment, primer coating, adhesive application, adhesive curing, etc. It is necessary to carry out a plurality of steps for bonding surfaces having complicated shapes, which is disadvantageous in terms of cost.
本開示は、軽量化を図った場合であっても所望の剛性を実現するととともに、良好な外観を実現し得るバンパーフェイシア、及びそのようなバンパーフェイシアを安価に製造することのできる方法を提供することを課題とする。 SUMMARY OF THE DISCLOSURE 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
本開示は以下の態様を包含する。 The present disclosure includes the following aspects.
〔1〕 熱可塑性樹脂材を有する第1樹脂部材と、
熱可塑性樹脂材を有する第2樹脂部材と、
前記第1樹脂部材の前記熱可塑性樹脂材及び前記第2樹脂部材の前記熱可塑性樹脂材の少なくとも1つに積層された1層又は複数層のプライマー層と
を備えるバンパーフェイシアであって、
前記第1樹脂部材が補強リブ及び/又はブラケットであり、
前記第2樹脂部材がバンパーフェイシア本体であり、
前記第1樹脂部材と前記第2樹脂部材とが前記プライマー層を介して溶着されており、
前記プライマー層の少なくとも1層が、下記(A)又は(B)の重合物組成物から形成された重合物組成物層である、バンパーフェイシア。
(A)下記(1)~(7)の少なくとも一種を含有する重合型組成物の重合物と、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、を含む重合物組成物
(B)下記(1)~(7)の少なくとも一種を含有する重合型組成物の重合物と、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、前記熱可塑性樹脂材を構成する熱可塑性樹脂とは異種の熱可塑性樹脂と、を含む重合物組成物
(1)2官能イソシアネート化合物とジオールの組み合わせ
(2)2官能イソシアネート化合物と2官能アミノ化合物の組み合わせ
(3)2官能イソシアネート化合物と2官能チオール化合物の組み合わせ
(4)2官能エポキシ化合物とジオールの組み合わせ
(5)2官能エポキシ化合物と2官能カルボキシ化合物の組み合わせ
(6)2官能エポキシ化合物と2官能チオール化合物の組み合わせ
(7)単官能ラジカル重合性モノマー
〔2〕 前記重合物組成物層が、前記熱可塑性樹脂材に直接に接する層である、〔1〕に記載のバンパーフェイシア。
〔3〕 前記重合物組成物が、前記(4)を含有する重合型組成物の重合物を含有し、かつ、前記(4)のジオールが2官能フェノール化合物である、〔1〕又は〔2〕のいずれかに記載のバンパーフェイシア。
〔4〕 前記プライマー層が、前記重合物組成物層と前記熱可塑性樹脂材との間に硬化性樹脂を含む組成物から形成された硬化性樹脂層を有する、〔1〕又は〔3〕のいずれかに記載のバンパーフェイシア。
〔5〕 前記硬化性樹脂が、ウレタン樹脂、エポキシ樹脂、ビニルエステル樹脂、及び不飽和ポリエステル樹脂からなる群より選ばれる少なくとも1種である、〔4〕に記載のバンパーフェイシア。
〔6〕 前記熱可塑性樹脂材を構成する熱可塑性樹脂が、ポリプロピレン、変性ポリフェニレンエーテル、及びポリブチレンテレフタレートからなる群より選ばれる少なくとも1種である、〔1〕~〔5〕のいずれかに記載のバンパーフェイシア。
〔7〕 前記第1樹脂部材及び前記第2樹脂部材の両方が前記プライマー層を有し、前記第1樹脂部材の前記プライマー層と前記第2樹脂部材の前記プライマー層とが溶着されている、〔1〕~〔6〕のいずれかに記載のバンパーフェイシア。
〔8〕 前記第2樹脂部材の前記熱可塑性樹脂材を構成する熱可塑性樹脂を構成する単量体において、最大含有量を占める単量体と、前記第1樹脂部材の前記熱可塑性樹脂材を構成する熱可塑性樹脂を構成する単量体において、最大含有量を占める単量体とが同一であり、該単量体の含有量がいずれも70質量%以上である、〔1〕~〔7〕のいずれかに記載のバンパーフェイシア。
〔9〕 前記第1樹脂部材の高さと厚さのアスペクト比(高さ/厚さ)が5以上であり、前記第2樹脂部材の厚さに対する前記第1樹脂部材の高さの比が5以上である、〔1〕~〔8〕のいずれかに記載のバンパーフェイシア。
〔10〕 前記第1樹脂部材又は前記第2樹脂部材の前記熱可塑性樹脂材が、ポリプロピレンと、タルク、ガラス繊維、及び炭素繊維からなる群より選ばれる少なくとも1種の補強材とを含み、前記第1樹脂部材又は前記第2樹脂部材が引張強度40MPa以上及びヤング率3GPa以上の特性を有する、〔1〕~〔9〕のいずれかに記載のバンパーフェイシア。
〔11〕 前記第1樹脂部材又は前記第2樹脂部材の前記熱可塑性樹脂材が、ポリエーテルイミドと、タルク、ガラス繊維、及び炭素繊維からなる群より選ばれる少なくとも1種の補強材とを含み、前記第1樹脂部材又は前記第2樹脂部材が引張強度90MPa以上及びヤング率3GPa以上の特性を有する、〔1〕~〔9〕のいずれかに記載のバンパーフェイシア。
〔12〕 〔1〕~〔11〕のいずれかに記載のバンパーフェイシアの製造方法であって、前記プライマー層を加熱し、加熱された前記プライマー層が前記第1樹脂部材と前記第2樹脂部材の間に介在するように前記第1樹脂部材と前記第2樹脂部材を圧着することにより、前記第1樹脂部材と前記第2樹脂部材を溶着することを含む、バンパーフェイシアの製造方法。
[1] A first resin member having a thermoplastic resin material;
a second resin member having a thermoplastic resin material;
A bumper fascia comprising one or more primer layers laminated on at least one of the thermoplastic resin material of the first resin member and the thermoplastic resin material of the second resin member,
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).
(A) 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, (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 material layer is a layer in direct contact with the thermoplastic resin material.
[3] [1] or [2], wherein the polymer composition contains a polymer of a polymerizable composition containing (4), and the diol of (4) is a bifunctional phenol compound; ].
[4] The primer layer of [1] or [3], wherein the primer layer has a curable resin layer formed from a composition containing a curable resin between the polymer composition layer and the thermoplastic resin material. A bumper fascia as described in any of the preceding paragraphs.
[5] The bumper fascia according to [4], wherein the curable resin is at least one selected from the group consisting of urethane resins, epoxy resins, vinyl ester resins, and unsaturated polyester resins.
[6] 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].
[8] Among the monomers constituting the thermoplastic resin constituting the thermoplastic resin material of the second resin member, 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 ].
[9] 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 bumper fascia according to any one of the above [1] to [8].
[10] 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.
[11] 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. , 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 90 MPa or more and a Young's modulus of 3 GPa or more.
[12] The method for manufacturing a bumper fascia according to any one of [1] to [11], wherein the primer layer is heated, and the heated primer layer forms the first resin member and the second resin member. 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.
本開示によれば、軽量化を図った場合であっても所望の剛性を実現するととともに、良好な外観を実現し得るバンパーフェイシアを提供することができ、そのようなバンパーフェイシアを安価に製造することができる。 ADVANTAGE OF THE INVENTION According to the present disclosure, it is possible to provide a bumper fascia that achieves a desired rigidity and a good appearance even when weight is reduced, and to manufacture such a bumper fascia at a low cost. be able to.
次に、本開示の実施形態について図面を参照して以下に説明する。 Next, embodiments of the present disclosure will be described below with reference to the drawings.
本開示において、接合とは、物と物を繋ぎ合わせることを意味し、接着及び溶着はその下位概念である。接着とは、テープ、接着剤などの有機材料(硬化性樹脂、熱可塑性樹脂等)を介して、2つの被着材(接着しようとするもの)を接合状態とすることを意味する。溶着とは、被着材である熱可塑性樹脂等の表面を熱によって溶融し、接触加圧と冷却により分子拡散による絡み合いと結晶化で接合状態とすることを意味する。 In the present disclosure, "joining" means joining things together, and adhesion and welding are subordinate concepts. 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.
本開示において、「(メタ)アクリル」とは、アクリル又はメタクリルを意味し、「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。 In the present disclosure, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.
[バンパーフェイシア]
図1は、車両におけるバンパーフェイシア10(点線部分であって、フロントバンパーに限る)の位置を示す車両正面図である。バンパーフェイシアとは、バンパーを構成する部品のうち、車体の最も外側に位置する部品であって、車両外観として視認できる部品(アウターパネル)である。
[Bumper Facia]
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.
図2は、バンパーフェイシア10の各構成要素を示す概略図であり、図3は、バンパーフェイシア本体12に他の構成要素を接合した状態を示すバンパーフェイシアの概略図である。なお、これらのいずれの図においても、バンパーフェイシア本体12は車体内側の面を示している。これらの図に示すように、バンパーフェイシア10は、バンパーフェイシア本体12と、バンパーフェイシア本体12の薄肉中央部分を補強するための補強リブ14と、バンパーフェイシア本体12の両外側部分に接合され、車両前方にある障害物を検知するためのセンサー等を収容するブラケット16と、を含む。
FIG. 2 is a schematic diagram showing each component of the
補強リブ14については、その重量が過度に大きくなければよく、例えば図2、3に示すようにバンパーフェイシア本体12の長手方向に沿って延びる幹部14aと、幹部14aの両側に延びて幹部14aの長手方向において互いに等間隔で存在する複数の枝部14bとを含む。補強リブ14の存在により、バンパーフェイシア本体12の中央部分が薄肉化されていても、バンパーフェイシア10としての所望の剛性を実現することができる。
As for the reinforcing
以下では、補強リブ14及び/又はブラケット16を「第1樹脂部材1」とも記載し、バンパーフェイシア本体12を「第2樹脂部材4」とも記載する。
In the following, the reinforcing
[第1樹脂部材1]
一実施形態の第1樹脂部材1は、図4に示すように、熱可塑性樹脂材2と、前記熱可塑性樹脂材に積層された1層又は複数層のプライマー層3とを有する積層体である。図4において、前記プライマー層3の少なくとも1層は、特定の重合型組成物から形成された重合物組成物層3aである。
[First resin member 1]
As shown in FIG. 4, the
本開示において、重合型組成物とは、特定の2官能の化合物の組み合わせを、触媒存在下で重付加反応することにより、あるいは、特定の単官能のモノマーのラジカル重合反応により、熱可塑構造、すなわち、リニアポリマー構造を形成する組成物を意味する。重合型組成物は、重合すると架橋構造による3次元ネットワークを構成する硬化性樹脂とは異なり、架橋構造による3次元ネットワークを構成せず、熱可塑性を有する。 In the present disclosure, 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. Unlike curable resins that form a three-dimensional network with a crosslinked structure when polymerized, the polymerizable composition does not form a three-dimensional network with a crosslinked structure and has thermoplasticity.
本開示において、重合物組成物とは、熱可塑構造を有する重合物(リニアポリマー)を主成分(合計90質量%以上)とする組成物を意味する。前記重合物には、前記特定の2官能の化合物の組み合わせ及び/又は特定の単官能のモノマーを含む重合型組成物から得られた重合物、前記重合物に無水マレイン酸変性ポリプロピレンが付加したもの、無水マレイン酸変性ポリプロピレン、変性ポリフェニレンエーテル等が含まれる。 In the present disclosure, 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.
前記重合物組成物層3aは、前記重合型組成物の重合物、前記重合物に無水マレイン酸変性ポリプロピレンが付加したもの、無水マレイン酸変性ポリプロピレン、変性ポリフェニレンエーテル等を含む重合物組成物から形成される層である。前記重合型組成物は、前記特定の2官能の化合物の組み合わせが触媒存在下で重付加反応することにより、あるいは、前記特定の単官能のモノマーがラジカル重合反応することにより、熱可塑構造、すなわち、リニアポリマー構造を形成する。
The
本開示において、プライマー層3とは、後述する図6に示すように、第1樹脂部材1の熱可塑性樹脂材2と、もう一方の接合対象物である、熱可塑性樹脂材を有する第2樹脂部材4とを接合一体化してバンパーフェイシア10(樹脂-樹脂接合体)を得る際に、第1樹脂部材1の熱可塑性樹脂材2と第2樹脂部材4の熱可塑性樹脂材との間に介在し、第1樹脂部材1の熱可塑性樹脂材2と第2樹脂部材4の熱可塑性樹脂材との接合強度を向上させる層を意味する。
In the present disclosure, the
本開示によれば、第2樹脂部材4が、熱可塑性樹脂材2を構成する熱可塑性樹脂と同種の熱可塑性樹脂からなる熱可塑性樹脂材を有する場合に、第1樹脂部材1と第2樹脂部材4とを強固に溶着することができる。第2樹脂部材4が、熱可塑性樹脂材2を構成する熱可塑性樹脂とは異種の熱可塑性樹脂からなる熱可塑性樹脂材を有する場合、一般に、第1樹脂部材1の熱可塑性樹脂材2と第2樹脂部材4の熱可塑性樹脂材のSP値は離れていることが多いが、本開示によれば、そのような異種の熱可塑性樹脂材を強固に溶着することもできる。
According to the present disclosure, when the
本開示において、「同種の熱可塑性樹脂」とは、熱可塑性樹脂を構成する単量体において、最大含有量を占める単量体が同一であり、該単量体の含有量がいずれも70質量%以上である熱可塑性樹脂を意味する。「異種の熱可塑性樹脂」とは、「同種の熱可塑性樹脂」以外の熱可塑性樹脂を意味し、具体的には、共通する単量体が存在しない熱可塑性樹脂、熱可塑性樹脂を構成する単量体において、最大含有量を占める単量体が異なる熱可塑性樹脂、又は最大含有量を占める単量体が同一であり、かつ少なくとも一方の最大含有量を占める単量体の含有量が70質量%未満である熱可塑性樹脂を意味する。 In the present disclosure, 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.
<熱可塑性樹脂材2>
熱可塑性樹脂材2を構成する熱可塑性樹脂は特に限定されるものではない。
<
The thermoplastic resin forming the
熱可塑性樹脂として、例えば、ポリプロピレン(PP、SP値:8.0(J/cm3)1/2)、ポリアミド6(PA6、SP値:12.7~13.6(J/cm3)1/2)、ポリアミド66(PA66、SP値:13.6(J/cm3)1/2)、ポリイミド(PI)、変性ポリフェニレンエーテル(m-PPE)、ポリフェニレンスルファイド(PPS、SP値:19.8(J/cm3)1/2)、ポリエーテルイミド(PEI)、ポリカーボネート(PC、SP値:9.7(J/cm3)1/2)、ポリブチレンテレフタレート(PBT、SP値:20.5(J/cm3)1/2)等が挙げられる。熱可塑性樹脂は、本発明の効果を得る観点から、ポリプロピレン、変性ポリフェニレンエーテル、及びポリブチレンテレフタレートからなる群より選ばれる少なくとも1種であることが好ましい。 Examples of thermoplastic resins 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.
本開示において、溶解パラメータ(SP値)とは、ヒルデブランドによって導入された正則溶液論により定義された、材料間の相互作用の程度の数値予測を提供する値(δ)である。 In the present disclosure, a solubility parameter (SP value) is a value (δ) that provides a numerical prediction of the degree of interaction between materials, defined by the regular solution theory introduced by Hildebrand.
SP値の算出法は種々提案されているが、例えば、Fedors(Polym.Eng.Sci.1974年、14巻、p.147)によって提案された手法に従い、下記式(1)を用いて求めることができる。
δ=(ΣEcoh/ΣV)1/2 ・・・(1)
ここで、δは溶解パラメータ(J0.5/cm1.5)、Ecohは凝集エネルギー密度(J/mol)、Vはモル分子容(cm3/mol)を表し、Σは原子団ごとに与えられているこれらの数値を、モノマーを構成する原子団すべてについて和を取る意味である。原子団ごとのEcoh及びVの数値は、例えば“Properties of Polymers, Third completely revised edition”のTable7.3等に挙げられている。
Various methods for calculating the SP value have been proposed. can be done.
δ=(ΣE coh /ΣV) 1/2 (1)
Here, δ 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), and Σ 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".
熱可塑性樹脂材2は、フィラー及び繊維からなる群より選ばれる少なくとも1種を更に含んでもよい。例えば、熱可塑性樹脂材2は、上記熱可塑性樹脂と、タルク、ガラス繊維、及び炭素繊維からなる群より選ばれる少なくとも1種の補強材とを含む高剛性タイプであってもよい。熱可塑性樹脂がポリプロピレンである実施形態において、タルク含有ポリプロピレンとしては、例えば、サンアロマー株式会社製商品名TRC104Nが挙げられ、ガラス繊維含有ポリプロピレンとしては、例えば、ダイセルミライズ株式会社製商品名PP-GF40-01 F02が挙げられ、炭素繊維含有ポリプロピレンとしては、例えば、ダイセルミライズ株式会社製商品名PP-CF40-11 F008が挙げられる。
The
ガラス繊維含有熱可塑性樹脂材は、ガラス繊維強化樹脂(GFRP)の一種であり、炭素繊維含有熱可塑性樹脂材は、炭素繊維強化樹脂(CFRP)の一種である。ガラス繊維、炭素繊維などの補強繊維を含む熱可塑性樹脂材は、シートモールディングコンパウンド(SMC)、バルクモールディングコンパウンド(BMC)などの成形体の形態であってもよい。SMCとは、熱可塑性樹脂、低収縮剤、充填剤などを混合した樹脂組成物を、ガラス繊維、炭素繊維などの補強繊維に含浸させることによって得られるシート状成形体である。 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.
<プライマー層3>
プライマー層3は、熱可塑性樹脂材2の上に積層される。
<
A
〔重合物組成物層3a〕
プライマー層3の少なくとも1層は、特定の重合物組成物から形成される重合物組成物層3aである。
[
At least one layer of the
重合物組成物層3aは、前記特定の重合物組成物又は該特定の重合物組成物を含む溶液を熱可塑性樹脂材2の上に塗布して得ることができる。熱可塑性樹脂材2の上に前記特定の重合物組成物を含む溶液を塗布する場合には、塗布後に溶剤を揮発させることにより重合性組成物層3aを形成することができる。
The
重合物組成物層3aは前記特定の重合型組成物の重合物を90質量%以上含むことが好ましく、95質量%以上含むことがより好ましい。
The
前記特定の重合物組成物は、下記(A)又は(B)の重合物組成物である。
(A)下記(1)~(7)の少なくとも一種を含有する重合型組成物の重合物と、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、を含む重合物組成物
(B)下記(1)~(7)の少なくとも一種を含有する重合型組成物の重合物と、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、熱可塑性樹脂材2を構成する熱可塑性樹脂とは異種の熱可塑性樹脂と、を含む重合物組成物
(1)2官能イソシアネート化合物とジオールの組み合わせ
(2)2官能イソシアネート化合物と2官能アミノ化合物の組み合わせ
(3)2官能イソシアネート化合物と2官能チオール化合物の組み合わせ
(4)2官能エポキシ化合物とジオールの組み合わせ
(5)2官能エポキシ化合物と2官能カルボキシ化合物の組み合わせ
(6)2官能エポキシ化合物と2官能チオール化合物の組み合わせ
(7)単官能ラジカル重合性モノマー
The specific polymer composition is the following polymer composition (A) or (B).
(A) 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
前記(A)及び(B)の重合物組成物は、前記(4)を含有する重合型組成物の重合物を含有することが好ましく、前記(4)としては2官能エポキシ樹脂と2官能フェノール化合物との組み合わせがより好ましい。 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.
(1)における2官能イソシアネート化合物とジオールとの配合量比は、水酸基に対するイソシアネート基のモル当量比が、0.7~1.5となるように設定されることが好ましく、より好ましくは0.8~1.4、更に好ましくは0.9~1.3とする。 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.
(2)における2官能イソシアネート化合物と2官能アミノ化合物との配合量比は、アミノ基に対するイソシアネート基のモル当量比が、0.7~1.5となるように設定されることが好ましく、より好ましくは0.8~1.4、更に好ましくは0.9~1.3とする。 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.
(3)における2官能イソシアネート化合物と2官能チオール化合物との配合量比は、チオール基に対するイソシアネート基のモル当量比が、0.7~1.5となるように設定されることが好ましく、より好ましくは0.8~1.4、更に好ましくは0.9~1.3とする。 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.
(4)における2官能エポキシ化合物とジオールとの配合量比は、水酸基に対するエポキシ基のモル当量比が、0.7~1.5となるように設定されることが好ましく、より好ましくは0.8~1.4、更に好ましくは0.9~1.3とする。 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.
(5)における2官能エポキシ化合物と2官能カルボキシ化合物との配合量比は、カルボキシ基に対するエポキシ基のモル当量比が、0.7~1.5となるように設定されることが好ましく、より好ましくは0.8~1.4、更に好ましくは0.9~1.3とする。 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.
(6)における2官能エポキシ化合物と2官能チオール化合物との配合量比は、チオール基に対するエポキシ基のモル当量比が、0.7~1.5となるように設定されることが好ましく、より好ましくは0.8~1.4、更に好ましくは0.9~1.3とする。 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.
(2官能イソシアネート化合物)
前記2官能イソシアネート化合物は、イソシアナト基を2個有する化合物であり、例えば、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、ダイマー酸ジイソシアネート、2,4-若しくは2,6-トリレンジイソシアネート(TDI)又はその混合物、p-フェニレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート(MDI)等のジイソシアネート化合物が挙げられる。前記2官能イソシアネート化合物は、プライマーの強度の観点から、TDI及びMDIが好ましい。
(Bifunctional isocyanate compound)
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.
(ジオール)
前記ジオールは、ヒドロキシ基を2個有する化合物であり、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、1,6-ヘキサンジオール等の脂肪族グリコール、及びビスフェノールA、ビスフェノールF、ビスフェノールS等のビスフェノール類が挙げられる。前記ジオールは、プライマーの強靭性の観点から、プロピレングリコール、及びジエチレングリコールが好ましい。
(diol)
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.
(2官能アミノ化合物)
前記2官能アミノ化合物は、アミノ基を2個有する化合物であり、例えば、2官能の脂肪族ジアミン、及び芳香族ジアミンが挙げられる。脂肪族ジアミンとしては、エチレンジアミン、1,2-プロパンジアミン、1,3-プロパンジアミン、1,4-ジアミノブタン、1,6-ヘキサメチレンジアミン、2,5-ジメチル-2,5-ヘキサンジアミン、2,2,4-トリメチルヘキサメチレンジアミン、イソホロンジアミン、ビス(4-アミノ-3-メチルシクロヘキシル)メタン、1,3-ジアミノシクロヘキサン、N-アミノエチルピペラジン等が挙げられる。芳香族ジアミンとしては、ジアミノジフェニルメタン、ジアミノジフェニルプロパン等が挙げられる。前記2官能アミノ化合物は、プライマーの強靭性の観点から、1,3-プロパンジアミン、1,4-ジアミノブタン、及び1,6-ヘキサメチレンジアミンが好ましい。
(Bifunctional amino compound)
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. Examples of aromatic diamines 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.
(2官能チオール化合物)
前記2官能チオール化合物は、分子内にメルカプト基を2つ有する化合物であり、例えば、2官能2級チオール化合物の1,4-ビス(3-メルカプトブチリルオキシ)ブタン(例えば、昭和電工株式会社製「カレンズMT(登録商標)BD1」)が挙げられる。
(Bifunctional thiol compound)
The bifunctional thiol compound is a compound having two mercapto groups in the molecule. manufactured by Karenz MT (registered trademark) BD1).
(2官能エポキシ化合物)
前記2官能エポキシ化合物は、1分子中に2個のエポキシ基を有する化合物である。例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビフェノール型エポキシ樹脂、ナフタレン型2官能エポキシ樹脂等の芳香族エポキシ樹脂、及び1,6-ヘキサンジオールジグリシジルエーテル等の脂肪族エポキシ化合物が挙げられる。
(Bifunctional epoxy compound)
The bifunctional epoxy compound is a compound having two epoxy groups in one molecule. For example, 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.
前記2官能エポキシ化合物は、単独で用いてもよく、2種以上を併用してもよい。 The bifunctional epoxy compounds may be used alone, or two or more of them may be used in combination.
具体的には、三菱ケミカル株式会社製「jER(登録商標)828」、同「jER(登録商標)834」、同「jER(登録商標)1001」、同「jER(登録商標)1004」、同「jER(登録商標)YX-4000」等が挙げられる。その他2官能であれば特殊な構造のエポキシ化合物も使用可能である。 Specifically, Mitsubishi Chemical Corporation "jER (registered trademark) 828", "jER (registered trademark) 834", "jER (registered trademark) 1001", "jER (registered trademark) 1004", "jER (registered trademark) YX-4000" and the like. In addition, an epoxy compound with a special structure can be used as long as it is bifunctional.
(2官能カルボキシ化合物)
前記2官能カルボキシ化合物は、カルボキシ基を2つ有する化合物であり、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、イソフタル酸、テレフタル酸等が挙げられる。前記2官能カルボキシ化合物は、プライマーの強度又は強靭性の観点から、イソフタル酸、テレフタル酸、及びアジピン酸が好ましい。
(Bifunctional carboxy compound)
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.
(単官能ラジカル重合性モノマー)
前記単官能ラジカル重合性モノマーは、エチレン性不飽和結合を1個有するモノマーである。例えば、スチレンモノマー、スチレンのα-、o-、m-又はp-アルキル、ニトロ、シアノ、アミド又はエステル誘導体、クロロスチレン、ビニルトルエン、ジビニルベンゼン等のスチレン系モノマー;及び(メタ)アクリル酸エチル、(メタ)アクリル酸メチル、(メタ)アクリル酸n-プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ドデシル、(メタ)アクリル酸シクロペンチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸テトラヒドロフリル、アセトアセトキシエチル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、グリシジル(メタ)アクリレート等の(メタ)アクリル酸エステルが挙げられる。前記単官能ラジカル重合性モノマーは、単独で用いてもよく、2種以上を併用してもよい。前記単官能ラジカル重合性モノマーは、プライマーの強度又は強靭性の観点から、スチレン、(メタ)アクリル酸メチル、(メタ)アクリル酸2-エチルヘキシル、又はフェノキシエチル(メタ)アクリレート、及びこれらの2種以上の組み合わせが好ましい。
(Monofunctional radically polymerizable monomer)
The monofunctional radically polymerizable monomer is a monomer having one ethylenically unsaturated bond. For example, styrene monomers, α-, o-, m- or p-alkyl, nitro, cyano, amide or ester derivatives of styrene, styrenic monomers such as chlorostyrene, vinyltoluene, divinylbenzene; and ethyl (meth)acrylate. , (meth)methyl acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylate dodecyl acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, acetoacetoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate , glycidyl (meth)acrylate and other (meth)acrylic acid esters. The monofunctional radically polymerizable monomers may be used alone or in combination of two or more. From the viewpoint of the strength or toughness of the primer, 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.
単官能ラジカル重合性モノマーのラジカル重合物を得る際には、ラジカル重合反応を十分に進行させ、所望の重合物を得るため、溶剤、及び必要に応じて着色剤等の添加剤を含んでいてもよい。この場合、前記ラジカル重合性組成物の溶剤以外の含有成分中、前記単官能ラジカル重合性モノマーが主成分であることが好ましい。前記主成分とは、前記単官能ラジカル重合性モノマーの含有率が50~100質量%であることを意味する。前記含有率は、好ましくは60質量%以上、より好ましくは80質量%以上である。 When obtaining a radically polymerized product of a monofunctional radically polymerizable monomer, a solvent and, if necessary, an additive such as a coloring agent are included in order to allow the radical polymerization reaction to proceed sufficiently to obtain a desired polymerized product. good too. In this case, 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.
ラジカル重合反応のための重合開始剤としては、例えば、公知の有機過酸化物、光開始剤等が好適に用いられる。有機過酸化物にコバルト金属塩又はアミンを組み合わせた常温ラジカル重合開始剤を使用してもよい。有機過酸化物としては、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアリルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、又はパーオキシジカーボネートに分類されるものが挙げられる。光開始剤としては、紫外線から可視線の波長範囲内で重合が開始できるものを使用することが望ましい。 As 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. As the photoinitiator, it is desirable to use one capable of initiating polymerization within the wavelength range from ultraviolet rays to visible rays.
ラジカル重合反応は、反応化合物等の種類にもよるが、常温~200℃で、5~90分間加熱して行うことが好ましい。光硬化の場合は紫外線又は可視光を照射して重合反応を行う。 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. In the case of photocuring, a polymerization reaction is carried out by irradiating ultraviolet rays or visible light.
熱可塑性樹脂材2上に、プライマー層3として重合物組成物層3aが積層されていることにより、熱可塑性樹脂材2と、同種の熱可塑性樹脂材又は異種の熱可塑性樹脂材とを強固に溶着することができる。特に、重合物組成物層3aは、熱可塑性樹脂材2に直接に接する層であることが好ましい。
By laminating the
前記重合物組成物としては、熱可塑性樹脂材2を構成する熱可塑性樹脂と同種又は類似の熱可塑性樹脂を含む組成物を選択することが好ましい。例えば、熱可塑性樹脂材2がポリプロピレンの場合、無水マレイン酸変性ポリプロピレンを含む重合物組成物を用いることにより、より強固な溶着が可能となる。熱可塑性樹脂材2が変性ポリフェニレンエーテルの場合、変性ポリフェニレンエーテルを含む重合物組成物を用いることにより、より強固な溶着が可能となる。
As the polymer composition, 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
プライマー層3を、重合物組成物層3aを含む複数層で構成することもできる。プライマー層3が複数層からなる場合、必須となる重合物組成物層3aが、熱可塑性樹脂材2と反対側の最表面となるように積層することが好ましい。
The
(重合物組成物層A)
重合物組成物層3aの実施形態の一つである重合物組成物層Aは、前記(A)重合物組成物から形成される。
(Polymer composition layer A)
The polymer composition layer A, which is one embodiment of the
重合物組成物層Aを構成する重合物は、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルの溶液中で、前記(1)~(6)の少なくとも一種を触媒存在下で重付加反応させて得ることができる。重付加反応のための触媒としては、例えば、トリエチルアミン、2,4,6-トリス(ジメチルアミノメチル)フェノール等の3級アミン、及びトリフェニルホスフィン等のリン系化合物が好適に用いられる。前記重付加反応は、組成物の組成にもよるが、常温~200℃で、5~120分間加熱して行うことが好ましい。 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. can be done. As 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.
具体的には、重合物組成物層Aは、前記(1)~(6)の少なくとも一種を含有する重合型組成物と、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルとの混合物を、熱可塑性樹脂材2に塗布する前に予め重付加反応させ、その反応物を含む混合物を、熱可塑性樹脂材2の上に塗布して形成することができる。
Specifically, 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
重合物組成物層Aを構成する重合物は、前記(7)の単官能ラジカル重合性モノマーを含有する組成物を、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルの溶液中でラジカル重合反応させて得ることもできる。前記ラジカル重合反応は、組成物の組成にもよるが、常温~200℃で、5~90分間加熱して行うことが好ましい。光硬化の場合は紫外線又は可視光を照射して重合反応を行う。 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. can also 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. In the case of photocuring, a polymerization reaction is carried out by irradiating ultraviolet rays or visible light.
具体的には、重合物組成物層Aは、前記(7)の単官能ラジカル重合性モノマーを含有する重合型組成物と、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルとを混合し、加熱して得たラジカル重合反応物を含む混合物を、熱可塑性樹脂材2の上に塗布して形成することができる。
Specifically, 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
(無水マレイン酸変性ポリプロピレン)
前記無水マレイン酸変性ポリプロピレンは、無水マレイン酸でグラフト変性されたポリプロピレンである。例えば、化薬アクゾ社製カヤブリッド002PP、002PP-NW、003PP、003PP-NW、三菱ケミカル株式会社製Modicシリーズ等が挙げられる。無水マレイン酸で機能化させたポリプロピレン添加剤としてBYK社製SCONA TPPP2112GA、TPPP8112GA、又はTPPP9212GAを併用してもよい。
(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.
(変性ポリフェニレンエーテル)
前記変性ポリフェニレンエーテルとしては公知のものが使用できる。変性ポリフェニレンエーテルは、ポリフェニレンエーテルにポリスチレン、ポリアミド、ポリフェニレンサルファイド、ポリプロピレン等をブレンドしたものであり、例えば、SABIC社製NORYLシリーズ(PPS/PS):731、7310、731F、7310F、旭化成ケミカルズ株式会社製ザイロンシリーズ(PPE/PS、PP/PPE、PA/PPE、PPS/PPE、PPA/PPE)、三菱エンジニアリングプラスチックス株式会社製エピエースシリーズ、レマロイシリーズ(PPE/PS、PPE/PA)等が挙げられる。
(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.
前記重合物組成物層Aを得る際に使用する前記(1)~(7)の合計量は、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルを100質量部としたとき、5~100質量部であることが好ましく、10~60質量部であることがより好ましく、20~40質量部であることが更に好ましい。 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.
(重合物組成物層B)
重合物組成物層3aの実施形態の一つである重合物組成物層Bは、前記(B)重合物組成物から形成される。
(Polymer composition layer B)
The polymer composition layer B, which is one embodiment of the
重合物組成物層Bは、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルの溶液中で、前記(1)~(6)の少なくとも一種を触媒存在下で重付加反応させた後、熱可塑性樹脂材2を構成する熱可塑性樹脂とは異種の熱可塑性樹脂と混合して得ることができる。熱可塑性樹脂材2を構成する熱可塑性樹脂とは異種の熱可塑性樹脂を含む溶液中で、前記(1)~(6)の少なくとも一種を触媒存在下で重付加反応させた後、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと混合して得ることもできる。無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、熱可塑性樹脂材2を構成する熱可塑性樹脂とは異種の熱可塑性樹脂と、前記(1)~(6)の少なくとも一種を触媒存在下で重付加反応させて得ることもできる。重付加反応のための触媒としては、例えば、トリエチルアミン、2,4,6-トリス(ジメチルアミノメチル)フェノール等の3級アミン、及びトリフェニルホスフィン等のリン系化合物が好適に用いられる。前記重付加反応は、組成物の組成にもよるが、常温~200℃で、5~120分間加熱して行うことが好ましい。
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
具体的には、重合物組成物層Bは、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、熱可塑性樹脂材2を構成する熱可塑性樹脂とは異種の熱可塑性樹脂と、前記(1)~(6)の少なくとも一種を含有する重合型組成物との混合物を加熱して得た反応物を含む混合物を、熱可塑性樹脂材2の上に塗布して形成することができる。
Specifically, the polymer composition layer B includes maleic anhydride-modified polypropylene or modified polyphenylene ether, a thermoplastic resin different from the thermoplastic resin constituting the
重合物組成物層Bは、前記(7)の単官能ラジカル重合性モノマーを含有する組成物を、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、熱可塑性樹脂材2を構成する熱可塑性樹脂とは異種の熱可塑性樹脂を含む溶液中でラジカル重合反応させて得ることもできる。前記ラジカル重合反応は、組成物の組成にもよるが、常温~200℃で、5~90分間加熱して行うことが好ましい。光硬化の場合は紫外線又は可視光を照射して重合反応を行う。
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
具体的には、重合物組成物層Bは、前記(7)の単官能ラジカル重合性モノマーを含有する重合型組成物の重合物に、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、熱可塑性樹脂材2を構成する熱可塑性樹脂とは異種の熱可塑性樹脂とを混合し、加熱して得た反応物を含む混合物を、熱可塑性樹脂材2の上に塗布して形成することができる。
Specifically, 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
なお、前記重合物組成物層を形成する重合物組成物を得る際に生じる反応の仕方は、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと2官能エポキシ樹脂の反応、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと2官能フェノール化合物との反応など、多岐にわたり、かつ、その組み合わせに基づく具体的態様を包括的に表現することもできない。よって、前記重合物組成物を構造又は特性により直接特定することは不可能又は非実際的といえる。 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.
〔硬化性樹脂層3b〕
プライマー層3を、重合物組成物層3aを含む複数層で構成する場合、図5に示すように、プライマー層3は、重合物組成物層3aと熱可塑性樹脂材2との間に、硬化性樹脂を含む組成物から形成された硬化性樹脂層3bを含むこともできる。
[
When the
前記硬化性樹脂を含む組成物は、前記硬化性樹脂の硬化反応を十分に進行させ、所望の硬化性樹脂層を形成させるため、溶剤、及び必要に応じて着色剤等の添加剤を含んでいてもよい。この場合、前記組成物の溶剤以外の含有成分中、前記硬化性樹脂が主成分であることが好ましい。前記主成分とは、前記硬化性樹脂の含有率が40~100質量%であることを意味する。前記含有率は、好ましくは60質量%以上、より好ましくは70質量%以上、更に好ましくは80質量%以上である。 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. You can In this case, 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.
前記硬化性樹脂としては、例えば、ウレタン樹脂、エポキシ樹脂、ビニルエステル樹脂、及び不飽和ポリエステル樹脂が挙げられる。 Examples of the curable resin include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.
硬化性樹脂層3bは、これらの樹脂のうちの1種で形成されていてもよく、2種以上が混合されて形成されていてもよい。硬化性樹脂層3bを複数層で構成し、各層を異なる種類の硬化性樹脂を含む組成物で形成することもできる。
The
前記硬化性樹脂のモノマーを含む組成物により、硬化性樹脂層3bを形成するコーティング方法は、特に限定されるものではないが、例えば、スプレー塗布法、浸漬法等が挙げられる。
Although the coating method for forming the
本開示において、硬化性樹脂は、広く、架橋硬化する樹脂を意味し、加熱硬化タイプに限られず、常温硬化タイプ及び光硬化タイプも包含する。前記光硬化タイプは、可視光又は紫外線の照射によって短時間での硬化も可能である。前記光硬化タイプを、加熱硬化タイプ及び/又は常温硬化タイプと併用してもよい。前記光硬化タイプとしては、例えば、昭和電工株式会社製「リポキシ(登録商標)LC-760」、同「リポキシ(登録商標)LC-720」等のビニルエステル樹脂が挙げられる。 In the present disclosure, 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.
(ウレタン樹脂)
前記ウレタン樹脂は、通常、イソシアネート化合物のイソシアナト基とポリオール化合物の水酸基との反応によって得られる樹脂であり、ASTM D16において、「ビヒクル不揮発成分10重量%以上のポリイソシアネートを含む塗料」と定義されるものに該当するウレタン樹脂が好ましい。前記ウレタン樹脂は、一液型であっても、二液型であってもよい。
(urethane resin)
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.
一液型ウレタン樹脂としては、例えば、油変性型(不飽和脂肪酸基の酸化重合により硬化するもの)、湿気硬化型(イソシアナト基と空気中の水との反応により硬化するもの)、ブロック型(ブロック剤が加熱により解離し再生したイソシアナト基と水酸基が反応して硬化するもの)、ラッカー型(溶剤が揮発して乾燥することにより硬化するもの)等が挙げられる。これらの中でも、取り扱い容易性等の観点から、湿気硬化型一液ウレタン樹脂が好適に用いられる。具体的には、昭和電工株式会社製「UM-50P」等が挙げられる。 Examples of one-liquid type urethane resin 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. Among these, 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.
二液型ウレタン樹脂としては、例えば、触媒硬化型(イソシアナト基と空気中の水等とが触媒存在下で反応して硬化するもの)、ポリオール硬化型(イソシアナト基とポリオール化合物の水酸基との反応により硬化するもの)等が挙げられる。 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.
前記ポリオール硬化型におけるポリオール化合物としては、例えば、ポリエステルポリオール、ポリエーテルポリオール、フェノール樹脂等が挙げられる。 Examples of polyol compounds in the polyol curing type include polyester polyols, polyether polyols, and phenol resins.
前記ポリオール硬化型におけるイソシアナト基を有するイソシアネート化合物としては、例えば、ヘキサメチレンジイソシアネート(HDI)、テトラメチレンジイソシアネート、ダイマー酸ジイソシアネート等の脂肪族イソシアネート;2,4-若しくは2,6-トリレンジイソシアネート(TDI)又はその混合物、p-フェニレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート(MDI)又はその多核体混合物であるポリメリックMDI等の芳香族イソシアネート;イソホロンジイソシアネート(IPDI)等の脂環族イソシアネート等が挙げられる。 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).
前記ポリオール硬化型の二液型ウレタン樹脂における前記ポリオール化合物と前記イソシアネート化合物の配合比は、水酸基/イソシアナト基のモル当量比が0.7~1.5の範囲であることが好ましい。 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.
前記二液型ウレタン樹脂において使用されるウレタン化触媒としては、例えば、トリエチレンジアミン、テトラメチルグアニジン、N,N,N’,N’-テトラメチルヘキサン-1,6-ジアミン、ジメチルエーテルアミン、N,N,N’,N’’,N’’-ペンタメチルジプロピレン-トリアミン、N-メチルモルフォリン、ビス(2-ジメチルアミノエチル)エーテル、ジメチルアミノエトキシエタノール、トリエチルアミン等のアミン系触媒;ジブチルスズジアセテート、ジブチルスズジラウレート、ジブチルスズチオカルボキシレート、ジブチルスズジマレエート等の有機スズ系触媒等が挙げられる。 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.
前記ポリオール硬化型においては、一般に、前記ポリオール化合物100質量部に対して、前記ウレタン化触媒が0.01~10質量部配合されることが好ましい。 In the polyol-curing type, it is generally preferred that 0.01 to 10 parts by mass of the urethanization catalyst be blended with 100 parts by mass of the polyol compound.
(エポキシ樹脂)
前記エポキシ樹脂は、1分子中に少なくとも2個のエポキシ基を有する樹脂である。前記エポキシ樹脂の硬化前のプレポリマーとしては、例えば、エーテル系ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、ポリフェノール型エポキシ樹脂、脂肪族型エポキシ樹脂、エステル系の芳香族エポキシ樹脂、環状脂肪族エポキシ樹脂、エーテル・エステル系エポキシ樹脂等が挙げられる。これらの中でも、ビスフェノールA型エポキシ樹脂が好適に用いられる。エポキシ樹脂は、単独で用いてもよく、2種以上を併用してもよい。
(Epoxy resin)
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. Among these, bisphenol A type epoxy resins are preferably used. An epoxy resin may be used independently and may use 2 or more types together.
ビスフェノールA型エポキシ樹脂としては、具体的には、三菱ケミカル株式会社製「jER(登録商標)828」、同「jER(登録商標)1001」等が挙げられる。 Specific examples of bisphenol A type epoxy resins include "jER (registered trademark) 828" and "jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Corporation.
ノボラック型エポキシ樹脂としては、具体的には、ザ・ダウ・ケミカル・カンパニー製「D.E.N.(登録商標)438(登録商標)」等が挙げられる。 Specific examples of novolak-type epoxy resins include "D.E.N. (registered trademark) 438 (registered trademark)" manufactured by The Dow Chemical Company.
前記エポキシ樹脂に使用される硬化剤としては、例えば、脂肪族アミン、芳香族アミン、酸無水物、フェノール樹脂、チオール類、イミダゾール類、カチオン触媒等の公知の硬化剤が挙げられる。前記硬化剤を、長鎖脂肪族アミン又は/及びチオール類と併用することにより、伸び率が大きく、耐衝撃性に優れる硬化性樹脂層を形成することができる。 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. By using the curing agent together with a long-chain aliphatic amine and/or thiols, it is possible to form a curable resin layer having a large elongation and excellent impact resistance.
前記チオール類の具体例としては、後述する官能基含有層を形成するためのチオール化合物として例示したものと同じ化合物が挙げられる。これらの中でも、硬化性樹脂層の伸び率及び耐衝撃性の観点から、ペンタエリスリトールテトラキス(3-メルカプトブチレート)(例えば、昭和電工株式会社製「カレンズMT(登録商標)PE1」)が好ましい。 Specific examples of the thiols include the same compounds as exemplified as thiol compounds for forming the functional group-containing layer described later. Among these, pentaerythritol tetrakis(3-mercaptobutyrate) (for example, "Karenzu MT (registered trademark) PE1" manufactured by Showa Denko KK) is preferable from the viewpoint of elongation and impact resistance of the curable resin layer.
(ビニルエステル樹脂)
前記ビニルエステル樹脂は、ビニルエステル化合物を重合性モノマー(例えば、スチレン等)に溶解したものである。エポキシ(メタ)アクリレート樹脂とも呼ばれるが、本開示において、前記ビニルエステル樹脂には、ウレタン(メタ)アクリレート樹脂も包含される。
(vinyl ester resin)
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.
前記ビニルエステル樹脂としては、例えば、「ポリエステル樹脂ハンドブック」(日刊工業新聞社、1988年発行)、「塗料用語辞典」(色材協会、1993年発行)等に記載されているものも使用することができる。具体的には、昭和電工株式会社製「リポキシ(登録商標)R-802」、同「リポキシ(登録商標)R-804」、同「リポキシ(登録商標)R-806」等が挙げられる。 As the 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.
前記ウレタン(メタ)アクリレート樹脂としては、例えば、イソシアネート化合物とポリオール化合物とを反応させた後、水酸基含有(メタ)アクリルモノマー(及び必要に応じて水酸基含有アリルエーテルモノマー)を反応させて得られるラジカル重合性不飽和基含有オリゴマーが挙げられる。具体的には、昭和電工株式会社製「リポキシ(登録商標)R-6545」等が挙げられる。 As the 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.
前記ビニルエステル樹脂は、有機過酸化物等の触媒存在下での加熱によるラジカル重合で硬化させることができる。 The vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide.
前記有機過酸化物としては、特に限定されるものではないが、例えば、ケトンパーオキサイド類、パーオキシケタール類、ハイドロパーオキサイド類、ジアリルパーオキサイド類、ジアシルパーオキサイド類、パーオキシエステル類、パーオキシジカーボネート類等が挙げられる。これらをコバルト金属塩等と組み合わせることにより、常温での硬化も可能となる。 Examples of the organic peroxide 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.
前記コバルト金属塩としては、特に限定されるものではないが、例えば、ナフテン酸コバルト、オクチル酸コバルト、水酸化コバルト等が挙げられる。これらの中でも、ナフテン酸コバルト及びオクチル酸コバルトが好ましい。 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.
(不飽和ポリエステル樹脂)
前記不飽和ポリエステル樹脂は、ポリオール化合物と不飽和多塩基酸(及び、必要に応じて飽和多塩基酸)とのエステル化反応による縮合生成物(不飽和ポリエステル)を重合性モノマー(例えば、スチレン等)に溶解したものである。
(unsaturated polyester resin)
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). ).
前記不飽和ポリエステル樹脂としては、「ポリエステル樹脂ハンドブック」(日刊工業新聞社、1988年発行)、「塗料用語辞典」(色材協会、1993年発行)等に記載されているものも使用することができる。具体的には、昭和電工株式会社製「リゴラック(登録商標)」等が挙げられる。 As the unsaturated 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.
前記不飽和ポリエステル樹脂は、前記ビニルエステル樹脂と同様の触媒存在下での加熱によるラジカル重合で硬化させることができる。 The unsaturated polyester resin can be cured by radical polymerization by heating in the presence of the same catalyst as the vinyl ester resin.
〔プライマー層3の作用〕
プライマー層3は、熱可塑性樹脂材2の表面に形成される。
[Action of Primer Layer 3]
A
プライマー層3によって、接合対象である第2樹脂部材4との優れた接合性が付与され得る。数ヶ月間の長期にわたって、前記の接合性を維持し得る第1樹脂部材1を得ることもできる。また、プライマー層3により熱可塑性樹脂材2の表面が保護され、汚れの付着、酸化等の変質を抑制することができる。
The
[第2樹脂部材4]
第2樹脂部材4の熱可塑性樹脂材を構成する熱可塑性樹脂は、第1樹脂部材1の熱可塑性樹脂材2を構成する熱可塑性樹脂と同種であってもよく、異種であってもよい。強固に溶着する観点から、これらの熱可塑性樹脂は同種であることが好ましい。
[Second resin member 4]
The thermoplastic resin forming the thermoplastic resin material of the
2つの熱可塑性樹脂材を接合しようとする場合、一方の熱可塑性樹脂材を構成する熱可塑性樹脂と、他方の熱可塑性樹脂材を構成する熱可塑性樹脂とが同種であっても、一方又は双方の熱可塑性樹脂にフィラー又は繊維が含有されていたり、該熱可塑性樹脂が他の熱可塑性樹脂とのブレンドであったりすると、従来技術によれば、2つの熱可塑性樹脂材間の接合強度が不十分となる場合がある。本開示によれば、これらの場合であっても、第1樹脂部材1と第2樹脂部材4とを(第1樹脂部材1に含まれる)プライマー層3を介して強固に溶着することができる。
When trying to join two thermoplastic resin materials, even if the 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
第1樹脂部材1の熱可塑性樹脂材2を構成する熱可塑性樹脂と第2樹脂部材4の熱可塑性樹脂材を構成する熱可塑性樹脂とが同種である場合、熱可塑性樹脂を構成する単量体において、最大含有量を占める単量体の割合は、いずれも70質量%以上であり、好ましくは70~100質量%、より好ましくは80~100質量%、更に好ましくは85~100質量%である。
When the thermoplastic resin constituting the
第1樹脂部材1の熱可塑性樹脂材2及び/又は第2樹脂部材4の熱可塑性樹脂材がフィラー及び繊維からなる群より選ばれる少なくとも1種を含有する場合、その含有量は、好ましくは5~50質量%、より好ましくは5~40質量%、更に好ましくは5~30質量%である。前記含有量が前記範囲内であると第1樹脂部材1と第2樹脂部材4との接合強度を高めることができる。
When the
第1樹脂部材1の熱可塑性樹脂材2を構成する熱可塑性樹脂及び/又は第2樹脂部材4の熱可塑性樹脂材を構成する熱可塑性樹脂が、主たる熱可塑性樹脂と従たる熱可塑性樹脂のブレンドである場合、従たる熱可塑性樹脂の含有率は、好ましくは5~40質量%、より好ましくは5~30質量%、更に好ましくは5~20質量%である。前記含有率が前記範囲内であると第1樹脂部材1と第2樹脂部材4との接合強度を高めることができる。
The thermoplastic resin constituting the
前記含有率は下記式により求めることができる。
含有率(質量%)=[B/(A+B)]×100
(式中、Aは第1樹脂部材1の熱可塑性樹脂材2を構成する熱可塑性樹脂及び/又は第2樹脂部材4の熱可塑性樹脂材を構成する熱可塑性樹脂のうち主たる熱可塑性樹脂の質量(g)であり、Bは第1樹脂部材1の熱可塑性樹脂材2を構成する熱可塑性樹脂及び/又は第2樹脂部材4の熱可塑性樹脂材を構成する熱可塑性樹脂のうち従たる熱可塑性樹脂の質量(g)である。)
The content rate can be determined by the following formula.
Content rate (mass%) = [B / (A + B)] × 100
(In the formula, A is the mass of the main thermoplastic resin among the thermoplastic resin constituting the
本開示によれば、第2樹脂部材4の熱可塑性樹脂材を構成する熱可塑性樹脂と第1樹脂部材1の熱可塑性樹脂材2を構成する熱可塑性樹脂とが異種である場合でも、第2樹脂部材4と第1樹脂部材1とを強固に溶着することができる。更に、第2樹脂部材4の熱可塑性樹脂材を構成する熱可塑性樹脂のSP値と、第1樹脂部材1の熱可塑性樹脂材2を構成する熱可塑性樹脂のSP値とが離れている場合でも、第2樹脂部材4と第1樹脂部材1とを強固に溶着することができる。
According to the present disclosure, even if the thermoplastic resin forming the thermoplastic resin material of the
[バンパーフェイシア10(樹脂-樹脂接合体)]
図6は、第1樹脂部材1と第2樹脂部材4とが溶着された状態の概略断面図であり、例えば、図3の丸囲み部分Aを示す図である。バンパーフェイシア10(樹脂-樹脂接合体)は、第1樹脂部材1と第2樹脂部材4とを(第1樹脂部材1に含まれる)プライマー層3を介して溶着させることにより形成される。
[Bumper fascia 10 (resin-resin bonded body)]
FIG. 6 is a schematic cross-sectional view of a state in which the
図6に示すように、バンパーフェイシア10では、バンパーフェイシア本体4(12)の熱可塑性樹脂材と、補強リブ1(14)の熱可塑性樹脂材2及びブラケット1(16)の熱可塑性樹脂材2とが、(補強リブ1及びブラケット1に含まれる)プライマー層3を介して溶着されている。
As shown in FIG. 6, in the
上述したように、補強リブ14(1)の存在により、バンパーフェイシア本体12(4)の中央部分が薄肉化されていても、バンパーフェイシア10としての所望の剛性を実現することができる。また、本実施形態のバンパーフェイシア10は、バンパーフェイシア本体4(12)に補強リブ14(1)等を射出成形せずに、上述の方法(即ちプライマー層(3)を介する接合)によって製造されるものであるため、得られたバンパーフェイシア10の外装面にヒケと呼ばれる外観不良は存在しない。さらに、本実施形態のバンパーフェイシア10は、別体で成形した補強リブをバンパーフェイシアの内側に接着剤を用いて接着する場合とは異なり、複数の工程(樹脂面のフレーム処理、プラズマ処理などの下地処理、プライマー塗工、接着剤塗布、接着剤硬化など)を経ずに上述の方法によって製造されるものであるため、安価に製造することができる。
As described above, due to the presence of the reinforcing rib 14(1), the desired rigidity of the
以上により、本実施形態では、軽量化を図った場合であっても所望の剛性を実現するととともに、良好な外観を実現し得るバンパーフェイシアを提供することができるとともに、そのようなバンパーフェイシアを安価で製造することができる。 As described above, in the present embodiment, it is possible to provide a bumper fascia that achieves a desired rigidity even when the weight is reduced and that can achieve a good appearance. can be manufactured in
一実施形態では、第1樹脂部材1の高さと厚さのアスペクト比(高さ/厚さ)が5以上であり、第2樹脂部材4の厚さに対する第1樹脂部材1の高さの比が5以上である。
In one embodiment, the aspect ratio (height/thickness) of the height and thickness of the
第1樹脂部材1又は第2樹脂部材4の熱可塑性樹脂材が、ポリプロピレンと、タルク、ガラス繊維、及び炭素繊維からなる群より選ばれる少なくとも1種の補強材とを含み、第1樹脂部材1又は第2樹脂部材4が引張強度40MPa以上及びヤング率3GPa以上の特性を有することが好ましい。
The thermoplastic resin material of the
第1樹脂部材1又は第2樹脂部材4の熱可塑性樹脂材が、ポリエーテルイミドと、タルク、ガラス繊維、及び炭素繊維からなる群より選ばれる少なくとも1種の補強材とを含み、第1樹脂部材1又は第2樹脂部材4が引張強度90MPa以上及びヤング率3GPa以上の特性を有することが好ましい。
The thermoplastic resin material of the
プライマー層3の厚さ(乾燥後の厚さ)は、第1樹脂部材1及び第2樹脂部材4の材質及び接合部分の接触面積にもよるが、優れた接合強度を得る観点から、1μm~500μmであることが好ましく、より好ましくは3μm~100μm、更に好ましくは5μm~70μmである。重合物組成物層3aの厚さ(乾燥後の厚さ)は、好ましくは1~60μmである。プライマー層3が複数層の場合、プライマー層3の厚さ(乾燥後の厚さ)は、各層合計の厚さとする。
The thickness of the primer layer 3 (thickness after drying) depends on the materials of the
バンパーフェイシア10(樹脂-樹脂接合体)を製造する方法としては、第1樹脂部材1のプライマー層3に、超音波溶着法、振動溶着法、電磁誘導法、高周波法、レーザー法、熱板溶着法、及び熱プレス法からなる群より選ばれる少なくとも1種の方法で、第2樹脂部材4を溶着する方法、及び第1樹脂部材1のプライマー層3の上に、射出成形によって第2樹脂部材4の熱可塑性樹脂材を成形する方法が挙げられる。
As a method for manufacturing the bumper fascia 10 (resin-resin bonded body), the
製造装置への要求の軽減、製造工程の簡略化、及び樹脂部材の設計自由度の観点から、バンパーフェイシア10(樹脂-樹脂接合体)は、熱プレス法により製造されることが有利である。具体的には、プライマー層3を加熱し、加熱されたプライマー層3が第1樹脂部材1と第2樹脂部材4の間に介在するように第1樹脂部材1と第2樹脂部材4を圧着することにより、バンパーフェイシア10(樹脂-樹脂接合体)を製造することができる。プライマー層の加熱温度は、接合させる樹脂の融点、軟化点に依存し、100℃~350℃であることが好ましい。例えば樹脂がナイロン6である場合、加熱温度は230℃であることが好ましい。また、融点を持つプライマー層は、加熱温度を融点±5℃とすることが好ましく、軟化点を持つプライマー層は、加熱温度を軟化点±15℃にすることが好ましい。圧着時の圧力は、0.01MPa~10MPaであることが好ましい。
From the viewpoints of reducing requirements for manufacturing equipment, simplifying the manufacturing process, and designing the resin members, it is advantageous to manufacture the bumper fascia 10 (resin-resin bonded body) by a hot press method. Specifically, the
別の実施形態では、第1樹脂部材1ではなく、第2樹脂部材4が、熱可塑性樹脂材に積層された1層又は複数層のプライマー層を有してもよい。第2樹脂部材4のプライマー層3’として、上述したプライマー層3と同様のものを使用することができる。この実施形態において、第1樹脂部材1と第2樹脂部材4の溶着は、上述の「第1樹脂部材1」をこの実施形態における「第2樹脂部材4」に、上述の「第2樹脂部材4」をこの実施形態における「第1樹脂部材1」と読み替えることより、実施することができる。
In another embodiment, the
更に別の実施形態では、第1樹脂部材1及び第2樹脂部材4の両方が上述のプライマー層3、3’を有し、第1樹脂部材1のプライマー層3と第2樹脂部材4のプライマー層3’とが溶着されている。この実施形態において、第1樹脂部材1の熱可塑性樹脂材2を構成する熱可塑性樹脂と、第2樹脂部材4の熱可塑性樹脂材を構成する熱可塑性樹脂とは、同種であってもよく、異種であってもよい。この実施形態において、バンパーフェイシア10(樹脂-樹脂接合体)は、超音波溶着法、振動溶着法、電磁誘導法、高周波法、レーザー法、及び熱プレス法からなる群より選ばれる少なくとも1種の方法、好ましくは熱プレス法を用いて、第1樹脂部材1のプライマー層3と第2樹脂部材4のプライマー層3’とを溶着することによって製造することができる。
In yet another embodiment, both the
本発明のいくつかの実施形態について説明したが、本発明は上述した実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲で様々に変更可能である。 Although several embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, and can be variously modified without departing from the gist of the present invention.
本発明に関連した実施試験例及び比較試験例を以下に示すが、本発明は下記実施試験例に限定されるものではない。 Examples of practical tests and comparative test examples related to the present invention are shown below, but the present invention is not limited to the following practical test examples.
<試験片用熱可塑性樹脂材>
以下に示す表1の条件で、射出成形機(住友重機械工業株式会社製 SE100V)を使用して、引張試験のための試験片用熱可塑性樹脂材(幅10mm、長さ45mm、厚さ3mm):タルク入りPP樹脂、m-PPE樹脂、PC樹脂、及びガラス繊維入りPBT樹脂を得た。
<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 (
<試験片の作製:実施試験例1~3、及び比較試験例1~2>
(プライマー層形成用の組成物-1の作製)
フラスコに無水マレイン酸変性ポリプロピレン(三菱ケミカル株式会社製Modic(登録商標)ER321P):5g、キシレン:95gを仕込み、撹拌しながら125℃に昇温して溶解した。次に、2官能エポキシ樹脂(三菱ケミカル株式会社製jER(登録商標)1001)(ビスフェノールA型エポキシ樹脂、分子量約900):1.01g、ビスフェノールA:0.24g、2,4,6-トリス(ジメチルアミノメチル)フェノール:0.006gをフラスコ中に投入し、125℃で30分間撹拌し、前記2官能エポキシ樹脂とビスフェノールAの重付加反応を行った。このようにして、無水マレイン酸変性ポリプロピレン、及び前記2官能エポキシ樹脂とビスフェノールAとの重合物(熱可塑性エポキシ樹脂)を含む組成物-1(以下、単に組成物-1ともいう)を得た。
<Preparation of test pieces: Examples 1 to 3 and Comparative Examples 1 to 2>
(Preparation of composition-1 for forming primer layer)
A flask was charged with maleic anhydride-modified polypropylene (Modic (registered trademark) ER321P manufactured by Mitsubishi Chemical Corporation): 5 g and xylene: 95 g, and heated to 125° C. with stirring to dissolve. Next, 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. Thus, 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. .
(プライマー層形成用の組成物-2の作製)
フラスコに変性ポリフェニレンエーテル(SABIC社製NOLYL731):3.77g、キシレン:95gを仕込み、撹拌しながら125℃に昇温して溶解した。次に、2官能エポキシ樹脂(三菱ケミカル株式会社製jER(登録商標)1001):1.0g、ビスフェノールA:0.22g、2,4,6-トリス(ジメチルアミノメチル)フェノール:0.005gをフラスコ中に投入し、125℃で30分間撹拌し、前記2官能エポキシ樹脂とビスフェノールAの重付加反応を行った。このようにして、前記変性ポリフェニレンエーテル100質量部に対して32質量部の前記2官能エポキシ樹脂とビスフェノールAとの重合物(熱可塑性エポキシ樹脂)を含む組成物-2(以下、単に組成物-2ともいう)を得た。
(Preparation of 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. Next, 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. Thus, composition-2 (hereinafter simply referred to as composition- 2) was obtained.
(プライマー層の形成)
次に、前記試験片用熱可塑性樹脂材のPP(タルク30質量%)、又はPBT(ガラス繊維30質量%)の片側の表面に乾燥後の厚さが80μmになるように組成物-1をスプレー法にて塗布した。空気中に常温で30分間放置することによって溶剤(キシレン)を揮発させた後、150℃の炉中に30分間加熱し、常温まで放冷して、組成物-1をプライマー層として有する試験片PP-1、及びPBT-1を得た。
(Formation of primer layer)
Next, 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 μm. 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.
前記試験片用熱可塑性樹脂材のm-PPEの片側の表面に乾燥後の厚さが80μmになるように組成物-2をスプレー法にて塗布した。空気中に常温で30分間放置することによって溶剤(キシレン)を揮発させた後、150℃の炉中に30分間加熱し、常温まで放冷して、組成物-2をプライマー層とする試験片m-PPE-1を得た。 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 μm. 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.
以下、試験片においてプライマー層を形成した面をプライマー面、プライマー層を形成していない面をプライマー無し面という。また、下記表2において、プライマー層を有する面を(有)、プライマー層を有さない面を(無)と表記する。 Hereinafter, 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. In addition, in Table 2 below, a surface having a primer layer is indicated as (present), and a surface having no primer layer is indicated as (absent).
<実施試験例1>
(溶着)
PP-1のプライマー面とm-PPE-1のプライマー面とを接合部が重なり長さ5mm、幅10mmとなるように重ね合わせた状態で、精電舎電子工業株式会社製超音波溶着機SONOPET-JII430T-M(28.5KHz)を使用して超音波溶着し、試験片1(樹脂-樹脂接合体)を得た。ここで接合部とは、試験片用熱可塑性樹脂材を重ね合わせた箇所を意味する。
<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). Here, the joint portion means a portion where the thermoplastic resin material for the test piece is superimposed.
(引張りせん断強度)
試験片1について、常温で1日間放置後、ISO19095 1-4に準拠して、引張試験機(株式会社島津製作所製万能試験機オートグラフ「AG-IS」、ロードセル10kN、引張速度10mm/min、温度23℃、50%RH)にて、引張りせん断強度試験を行い、接合強度を測定した。測定結果を下記表2に示す。
(Tensile shear strength)
After leaving the
<実施試験例2>
(溶着)
PP-1のプライマー面とPBT-1のプライマー面とを接合部が重なり長さ5mm、幅10mmとなるように重ね合わせた状態で、精電舎電子工業株式会社製超音波溶着機SONOPET-JII430T-M(28.5KHz)を使用して超音波溶着し、試験片2(樹脂-樹脂接合体)を得た。
<Test Example 2>
(welding)
The primer surface of PP-1 and the primer surface of PBT-1 are overlapped so that the joint overlaps with a length of 5 mm and a width of 10 mm, and an ultrasonic welding machine SONOPET-JII430T manufactured by Seidensha Electronics Industry Co., Ltd. -M (28.5 KHz) was used for ultrasonic welding to obtain a test piece 2 (resin-resin bonded body).
(引張りせん断強度)
試験片2について、実施試験例1と同じ手法で引張りせん断強度試験を行った。測定結果を下記表2に示す。
(Tensile shear strength)
For the
<実施試験例3>
(溶着)
m-PPE-1のプライマー面と前記試験片用熱可塑性樹脂材のPCの片面(プライマー無し面)とを接合部が重なり長さ5mm、幅10mmとなるように重ね合わせた状態で、精電舎電子工業株式会社製超音波溶着機SONOPET-JII430T-M(28.5KHz)を使用して超音波溶着し、試験片3(樹脂-樹脂接合体)を得た。
<Test Example 3>
(welding)
In a state in which the primer surface of m-PPE-1 and one side of the PC of the thermoplastic resin material for the test piece (the surface without primer) are overlapped so that the joint overlaps so that the length is 5 mm and the width is 10 mm, Seiden Ultrasonic welding was performed using an ultrasonic welding machine SONOPET-JII430T-M (28.5 kHz) manufactured by Sha Denshi Kogyo Co., Ltd. to obtain a test piece 3 (resin-resin bonded body).
(引張りせん断強度)
試験片3について、実施試験例1と同じ手法で引張りせん断強度試験を行った。測定結果を下記表2に示す。
(Tensile shear strength)
A tensile shear strength test was performed on the
<比較試験例1>
PP-1のプライマー無し面とPBT-1のプライマー無し面とを接合部が重なり長さ5mm、幅10mmとなるように重ね合わせた状態で、精電舎電子工業株式会社製超音波溶着機SONOPET-JII430T-M(28.5KHz)を使用して超音波溶着を試みたが溶着できなかった。
<Comparative Test Example 1>
The unprimed surface of PP-1 and the unprimed surface of PBT-1 are overlapped so that the joint overlaps with a length of 5 mm and a width of 10 mm. - Ultrasonic welding was attempted using JII430T-M (28.5 KHz), but welding failed.
<比較試験例2>
m-PPE-1のプライマー無し面と前記試験片用熱可塑性樹脂材のPCの片面(プライマー無し面)とを接合部が重なり長さ5mm、幅10mmとなるように重ね合わせた状態で、精電舎電子工業株式会社製超音波溶着機SONOPET-JII430T-M(28.5KHz)を使用して超音波溶着を試みたが溶着できなかった。
<Comparative Test Example 2>
The non-primer side of m-PPE-1 and one side (the non-primer side) of the PC of the thermoplastic resin material for the test piece are overlapped so that the joints overlap so that the length is 5 mm and the width is 10 mm. Ultrasonic welding was attempted using an ultrasonic welding machine SONOPET-JII430T-M (28.5 KHz) manufactured by Densha Denshi Kogyo Co., Ltd., but welding was not possible.
<実施試験例4:試験片4-1及び4-2>
プライマー付き熱可塑性樹脂材m-PPE-1又はPP-1を金型にインサートして、そのプライマー面にPBTを表1と同一条件で射出成形して、前記プライマー面とPBT(幅10mm、長さ45mm、厚さ3mm)との接合部が重なり長さ5mm、幅10mmとなる試験片(2種)を得た。
<Test Example 4: 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 (
(引張りせん断強度)
各試験片について、実施試験例1と同じ手法で引張りせん断強度試験を行った。測定結果を下記表3に示す。
(Tensile shear strength)
Each test piece was subjected to a tensile shear strength test in the same manner as in Practical Test Example 1. The measurement results are shown in Table 3 below.
本発明は、バンパーフェイシア及びその製造方法に利用可能である。 The present invention can be used for a bumper fascia and its manufacturing method.
1 第1樹脂部材
2 熱可塑性樹脂材
3 プライマー層
3a 重合物組成物層
3b 硬化性樹脂層
4 第2樹脂部材
10 バンパーフェイシア(樹脂-樹脂接合体)
12 バンパーフェイシア本体
14 補強リブ
14a 幹部
14b 枝部
16 ブラケット
A 丸囲み部分
1
REFERENCE SIGNS
Claims (12)
熱可塑性樹脂材を有する第2樹脂部材と、
前記第1樹脂部材の前記熱可塑性樹脂材及び前記第2樹脂部材の前記熱可塑性樹脂材の少なくとも1つに積層された1層又は複数層のプライマー層と
を備えるバンパーフェイシアであって、
前記第1樹脂部材が補強リブ及び/又はブラケットであり、
前記第2樹脂部材がバンパーフェイシア本体であり、
前記第1樹脂部材と前記第2樹脂部材とが前記プライマー層を介して溶着されており、
前記プライマー層の少なくとも1層が、下記(A)又は(B)の重合物組成物から形成された重合物組成物層である、バンパーフェイシア。
(A)下記(1)~(7)の少なくとも一種を含有する重合型組成物の重合物と、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、を含む重合物組成物
(B)下記(1)~(7)の少なくとも一種を含有する重合型組成物の重合物と、無水マレイン酸変性ポリプロピレン又は変性ポリフェニレンエーテルと、前記熱可塑性樹脂材を構成する熱可塑性樹脂とは異種の熱可塑性樹脂と、を含む重合物組成物
(1)2官能イソシアネート化合物とジオールの組み合わせ
(2)2官能イソシアネート化合物と2官能アミノ化合物の組み合わせ
(3)2官能イソシアネート化合物と2官能チオール化合物の組み合わせ
(4)2官能エポキシ化合物とジオールの組み合わせ
(5)2官能エポキシ化合物と2官能カルボキシ化合物の組み合わせ
(6)2官能エポキシ化合物と2官能チオール化合物の組み合わせ
(7)単官能ラジカル重合性モノマー a first resin member having a thermoplastic resin material;
a second resin member having a thermoplastic resin material;
A bumper fascia comprising one or more primer layers laminated on at least one of the thermoplastic resin material of the first resin member and the thermoplastic resin material of the second resin member,
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).
(A) 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, (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
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2021/004664 WO2022168329A1 (en) | 2021-02-08 | 2021-02-08 | Bumper fascia and production method therefor |
| JP2022579312A JPWO2022168329A1 (en) | 2021-02-08 | 2021-02-08 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2021/004664 WO2022168329A1 (en) | 2021-02-08 | 2021-02-08 | Bumper fascia and production method therefor |
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| Publication Number | Publication Date |
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| WO2022168329A1 true WO2022168329A1 (en) | 2022-08-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2021/004664 Ceased WO2022168329A1 (en) | 2021-02-08 | 2021-02-08 | Bumper fascia and production method therefor |
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| Country | Link |
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| JP (1) | JPWO2022168329A1 (en) |
| WO (1) | WO2022168329A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62153160U (en) * | 1986-03-24 | 1987-09-29 | ||
| JP2020199899A (en) * | 2019-06-11 | 2020-12-17 | 昭和電工株式会社 | Crash box and production method of the same |
| WO2020256038A1 (en) * | 2019-06-19 | 2020-12-24 | 昭和電工株式会社 | Composite multilayer body and metal-polyolefin bonded body |
-
2021
- 2021-02-08 JP JP2022579312A patent/JPWO2022168329A1/ja active Pending
- 2021-02-08 WO PCT/JP2021/004664 patent/WO2022168329A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62153160U (en) * | 1986-03-24 | 1987-09-29 | ||
| JP2020199899A (en) * | 2019-06-11 | 2020-12-17 | 昭和電工株式会社 | Crash box and production method of the same |
| WO2020256038A1 (en) * | 2019-06-19 | 2020-12-24 | 昭和電工株式会社 | Composite multilayer body and metal-polyolefin bonded body |
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|---|---|
| JPWO2022168329A1 (en) | 2022-08-11 |
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