Multilayer body and method for manufacturing a multilayer body

Abstract

To solve the problems, the present application provides a multilayer body having a metal plate (1) and a prepreg (2) directly or indirectly bonded to the metal plate (1) in a plane direction, the prepreg (2) impregnated with a polyamide resin in continuous reinforcing fibers aligned in one direction, and containing 5 to 300 parts by mass of the continuous reinforcing fibers per 100 parts by mass of the polyamide resin, the metal plate having a tensile strength of 300 MPa or more and 1400 MPa or less as measured according to JIS Z2241.

Description

Technical Field

[0001] This invention relates to multilayer bodies and methods for manufacturing multilayer bodies. Background Technology

[0002] Currently, multilayer structures combining metal sheets (metal layers) and prepregs are being researched. Such multilayer structures are advantageous when it is desirable to maintain high strength while reducing weight.

[0003] As an example of such a multilayer, Patent Document 1 discloses a laminate having a metal layer and a carbon fiber reinforced polyamide resin layer on the surface of the metal layer. The carbon fiber reinforced polyamide resin layer contains 5 to 300 parts by mass of carbon fiber (B) relative to 100 parts by mass of polyamide resin (A) composed of diamine units and dicarboxylic acid units. More than 70 mol% of the diamine units are derived from phenylenediamine, and more than 70 mol% of the dicarboxylic acid units are derived from sebacic acid.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2016-043526 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] For multilayer bodies with metal sheets and prepregs, high bending strength is desirable for molded products with high strength, but they become difficult to process when the bending load is high.

[0009] The purpose of this invention is to solve the above-mentioned problems and provide a multilayer body with high bending strength and excellent processability, as well as a method for manufacturing the above-mentioned multilayer body.

[0010] Methods for solving problems

[0011] Based on the above-mentioned issues, the inventors conducted research and found that the above problems can be solved by producing a multilayer body of a metal plate with a given tensile strength and a prepreg containing polyamide resin impregnated in continuous reinforcing fibers stretched in one direction.

[0012] Specifically, the above problems can be solved in the following ways.

[0013] <1> A multilayer body comprising a metal plate and a prepreg that is directly or indirectly bonded to the metal plate in the surface direction.

[0014] The prepreg is impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction, and contains 5 to 300 parts by weight of continuous reinforcing fibers relative to 100 parts by weight of the polyamide resin.

[0015] The tensile strength of the metal plate, as determined according to JIS Z2241, is 300 MPa or more and 1400 MPa or less.

[0016] <2> According to the multi-layered structure described in <1>, among which,

[0017] The tensile strength of the metal plate, as determined according to JIS Z2241, is less than 1200 MPa.

[0018] <3> According to the multi-layered structure described in <1> or <2>, among which,

[0019] The continuous reinforcing fiber comprises at least one selected from carbon fiber and glass fiber.

[0020] <4> Based on any one of <1> to <3>, the multi-layered structure described therein,

[0021] The thickness of the metal plate is less than 2.0 mm.

[0022] <5> Based on any one of <1> to <4>, the multi-layered structure described therein,

[0023] The content of continuous reinforcing fibers in the prepreg is 30-70% by volume.

[0024] <6> The multilayer body according to any one of <1> to <5> comprises a polyamide resin, the polyamide resin comprising structural units derived from a diamine and structural units derived from a dicarboxylic acid, wherein more than 70 mol% of the structural units derived from the diamine are derived from phenylenediamine, and more than 70 mol% of the structural units derived from the dicarboxylic acid are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0025] <7> According to the multi-layered structure described in <1>, among which,

[0026] The continuous reinforcing fiber comprises at least one selected from carbon fiber and glass fiber, and the thickness of the metal plate is less than 2.0 mm.

[0027] The content of continuous reinforcing fibers in the prepreg is 30-70% by volume.

[0028] The multilayer comprises a polyamide resin, the polyamide resin comprising structural units derived from a diamine and structural units derived from a dicarboxylic acid, wherein more than 70 mol% of the structural units derived from the diamine are derived from phenylenediamine, and more than 70 mol% of the structural units derived from the dicarboxylic acid are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0029] <8> A method for manufacturing a multilayer body, which is a method for manufacturing a multilayer body described in any one of <1> to <7>, the method comprising:

[0030] The metal sheet and the prepreg are hot-melt bonded together, the prepreg being impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction.

[0031] <9> A method for manufacturing a multilayer body, which is a method for manufacturing a multilayer body described in any one of <1> to <7>, the method comprising:

[0032] The metal sheet and prepreg are subjected to vibration cladding, ultrasonic cladding, or laser cladding, wherein the prepreg is impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction.

[0033] <10> A method for manufacturing a multilayer body, the multilayer body having a metal plate and a prepreg fused together with the metal plate in the surface direction.

[0034] The prepreg is impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction.

[0035] The prepreg contains 5 to 300 parts by weight of continuous reinforcing fibers per 100 parts by weight of polyamide resin.

[0036] The tensile strength of the metal plate, as determined according to JIS Z2241, is 300 MPa or higher and 1400 MPa or lower.

[0037] The manufacturing method of this multilayer body includes:

[0038] The metal plate, the phthalamide resin film, and the prepreg are stacked in the order described above, and then further heated to melt and coat the metal plate, the phthalamide resin film, and the prepreg.

[0039] The phenylenediamine-based polyamide resin film comprises a polyamide resin containing structural units derived from a diamine and structural units derived from a dicarboxylic acid, wherein more than 70 mol% of the structural units derived from the diamine are derived from phenylenediamine, and more than 70 mol% of the structural units derived from the dicarboxylic acid are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0040] <11> According to the manufacturing method of the multilayer body described in <10>, wherein,

[0041] The thickness of the phenylenediamine polyamide resin film is 15–50 μm.

[0042] <12> According to the manufacturing method of the multilayer body described in <10> or <11>, wherein,

[0043] The prepreg comprises a polyamide resin containing structural units derived from a diamine and structural units derived from a dicarboxylic acid, wherein more than 70 mol% of the structural units derived from the diamine are derived from phenylenediamine, and more than 70 mol% of the structural units derived from the dicarboxylic acid are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0044] <13> According to any one of <10> to <12>, the method for manufacturing a multilayer body, wherein,

[0045] The welding is performed by laser welding, which involves irradiating the prepreg side with a laser.

[0046] <14> According to any one of <10> to <13>, the method for manufacturing a multilayer body, wherein,

[0047] The continuous reinforcing fiber comprises at least one selected from carbon fiber and glass fiber.

[0048] <15> According to any one of <10> to <14>, the method for manufacturing a multilayer body, wherein,

[0049] The thickness of the metal plate is less than 2.0 mm.

[0050] <16> According to any one of <10> to <15>, the manufacturing method of the multilayer body, wherein,

[0051] The content of continuous reinforcing fibers in the prepreg is 30-70% by volume.

[0052] <17> According to any one of <10> to <16>, the method for manufacturing a multilayer body, wherein,

[0053] The multi-layered structure is a vehicle's support pillar or a component thereof.

[0054] <18> According to the manufacturing method of the multilayer body described in <10>, wherein,

[0055] The thickness of the phenylenediamine polyamide resin film is 15–50 μm.

[0056] The prepreg comprises a polyamide resin containing structural units derived from diamines and structural units derived from dicarboxylic acids, wherein at least 70 mol% of the structural units derived from diamines are derived from phenylenediamine, and at least 70 mol% of the structural units derived from dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0057] The welding is performed by laser welding, which involves irradiating the prepreg side with a laser.

[0058] The continuous reinforcing fiber comprises at least one selected from carbon fiber and glass fiber.

[0059] The thickness of the metal plate is less than 2.0 mm.

[0060] The content of continuous reinforcing fibers in the prepreg is 30-70% by volume.

[0061] The multi-layered structure is a vehicle's support pillar or a component thereof.

[0062] <19> According to any one of <10> to <18>, the method for manufacturing a multilayer body, wherein,

[0063] The tensile strength of the metal plate, as determined according to JIS Z2241, is 300 MPa or more and 1200 MPa or less.

[0064] <20> A multilayer body, wherein,

[0065] Metal sheets, phthalamide resin films, and prepreg impregnated with polyamide resin in continuous reinforcing fibers stretched in one direction are stacked together in the order described above.

[0066] The tensile strength of the metal plate, as determined according to JIS Z2241, is 300 MPa or higher and 1400 MPa or lower.

[0067] The phenylenediamine-based polyamide resin film comprises a polyamide resin containing structural units derived from a diamine and structural units derived from a dicarboxylic acid, wherein more than 70 mol% of the structural units derived from the diamine are derived from phenylenediamine, and more than 70 mol% of the structural units derived from the dicarboxylic acid are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0068] Invention Effects

[0069] This invention provides a multilayer body with high bending strength and excellent processability, as well as a method for manufacturing the aforementioned multilayer body. Attached Figure Description

[0070] Figure 1 This is a cross-sectional schematic diagram showing the layer structure of the multilayer body according to the first embodiment.

[0071] Figure 2 This is a cross-sectional schematic diagram showing the layer structure of the multilayer body according to the second embodiment.

[0072] Symbol Explanation

[0073] 1 Metal plate

[0074] 2 Prepreg

[0075] 11 Metal Plate

[0076] 12. Phenylenediamine polyamide resin film

[0077] 13 Prepreg Detailed Implementation

[0078] The following describes in detail a method for implementing the present invention (hereinafter referred to as "this embodiment"). It should be noted that the following embodiment is merely an example for illustrating the present invention, and the present invention is not limited to this embodiment.

[0079] It should be noted that in this specification, "~" is used to encompass the values ​​recorded before and after it as the lower and upper limits.

[0080] Unless otherwise specified, all physical property values ​​and characteristic values ​​in this specification are set to values ​​at 23°C.

[0081] In this specification, the number-average molecular weight is the polystyrene equivalent value obtained by GPC (gel permeation chromatography).

[0082] Unless otherwise specified, where the testing methods, etc., differ according to the year, the standards expressed in this instruction manual are based on the standards of January 1, 2021.

[0083] The multilayer body of the first embodiment is characterized in that it has a metal plate and a prepreg that is directly or indirectly bonded to the metal plate in the surface direction. The prepreg contains polyamide resin impregnated in continuous reinforcing fibers that are aligned in one direction, and contains 5 to 300 parts by weight of continuous reinforcing fibers relative to 100 parts by weight of polyamide resin. The tensile strength of the metal plate, as measured according to JIS Z2241, is 300 MPa or more and 1400 MPa or less.

[0084] Metal sheets have high tensile strength and excellent overall strength, but they tend to have lower ductility as tensile strength increases. During pressing processes, metal sheets are prone to defects such as cracking.

[0085] It can be deduced that, in the first embodiment, by forming a multilayer of a metal sheet and a prepreg containing polyamide resin impregnated in continuous reinforcing fibers stretched in one direction, the strength of the multilayer can be reduced when the prepreg is partially heated, thereby improving processability. On the other hand, in the first embodiment, by laminating a metal sheet with a tensile strength of 300 MPa or more and 1400 MPa or less as measured according to JIS Z2241 and a prepreg containing continuous reinforcing fibers stretched in one direction, the flexural strength at room temperature can be improved.

[0086] For example, such as Figure 1As shown, the multilayer body of the first embodiment includes a metal plate 1 and a prepreg 2 that is directly or indirectly bonded to the metal plate 1 in the surface direction. The metal plate 1 and the prepreg 2 can be directly bonded together or indirectly bonded together. Direct bonding is preferred. In addition, as in the case of indirect bonding, sometimes an adhesive layer or a resin layer (preferably a polyamide resin layer, more preferably a phenylenediamine polyamide resin layer) is provided between the metal plate 1 and the prepreg 2.

[0087] It should be noted that, in Figure 1 The thickness ratio of each layer is not shown in the image.

[0088] exist Figure 1 In this process, the prepreg 2 may consist of only one layer (1 sheet, 1 ply), but it can also consist of two or more layers (2 sheets, 2 ply). When there are two or more layers, the continuous reinforcing fibers can be stacked together with different orientations. For example, the continuous reinforcing fibers of the second layer can be stacked at a 90° angle relative to the direction of the continuous reinforcing fibers of the first layer.

[0089] The metal sheet used in the first embodiment has a tensile strength of 300 MPa or more and 1400 MPa or less, as measured according to JIS Z2241. By using such a metal sheet, a multilayer with excellent strength can be obtained. The tensile strength of the aforementioned metal sheet is preferably 400 MPa or more, more preferably 550 MPa or more, even more preferably 590 MPa or more, even more preferably 600 MPa or more, even more preferably 800 MPa or more, even more preferably 900 MPa or more, and particularly preferably 1000 MPa or more. Furthermore, as an upper limit, for example, it can be 1200 MPa or less.

[0090] The thickness of the metal sheet in the first embodiment is preferably 2.0 mm or less, more preferably 1.8 mm or less, even more preferably 1.6 mm or less, even more preferably 1.3 mm or less, and still more preferably 1.1 mm or less. By setting it to the upper limit value or below, there is a tendency to further improve processing characteristics such as bending. Furthermore, the thickness of the metal sheet in the first embodiment is preferably 0.1 mm or more, more preferably 0.3 mm or more, even more preferably 0.6 mm or more, and even more preferably 0.8 mm or more. By setting it to the lower limit value or above, there is a tendency to further improve the strength of the multilayer.

[0091] A metal sheet is a sheet whose main component is metal. Here, a sheet whose main component is metal means that 70% or more by mass of the metal sheet is metal; typically, 90% or more by mass of the metal sheet is metal, and preferably 98% or more by mass of the metal sheet is metal. The metal sheet may contain one type of metal or two or more types. When two or more types of metal are contained, their total amount is the amount of metal contained in the aforementioned metal sheet.

[0092] The metal plate in the first embodiment contains low-carbon steel with silicon and manganese as the main components, and copper, chromium, nickel, molybdenum, etc. as needed.

[0093] The metal plate used in the first embodiment is preferably a so-called high-tensile steel.

[0094] The metal sheet in the first embodiment preferably has an uneven surface. By having an uneven surface, the bonding strength with the prepreg can be further improved in the resulting multilayer body.

[0095] The unevenness can be formed by roughening the surface of the metal sheet. There are no particular limitations on the roughening process; examples include cutting and / or polishing. Cutting and / or polishing are any operations that remove a portion of the metal surface and are not particularly limited. Specific examples of cutting and / or polishing include using a file such as sandpaper, sandblasting using a polishing agent, and surface treatments that form nanoscale indentations on the metal sheet surface. Details of these processes can be found in paragraphs 0018 to 0021 of Japanese Patent Application Publication No. 2003-103563, which are incorporated herein by reference.

[0096] The roughening treatment in the first embodiment refers to a so-called physical treatment. In addition to roughening treatment, or as an alternative to roughening treatment, the surface of the metal sheet can also be treated by applying a compound that reacts with the metal. As a method for treating the metal sheet by applying a compound that reacts with the metal, please refer to paragraphs 0021 to 0026 of Japanese Patent Application Publication No. 2003-103563, the contents of which are incorporated herein by reference.

[0097] Next, the prepreg of the first embodiment will be described.

[0098] In the first embodiment, the prepreg is impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction, and contains 5 to 300 parts by weight of continuous reinforcing fibers relative to 100 parts by weight of polyamide resin. By using a prepreg containing continuous reinforcing fibers pulled in one direction, the bending strength along the fiber length can be improved. Therefore, a material capable of withstanding bending processes can be manufactured. In particular, although ultra-high tensile steel has a high modulus of elasticity, bending processes require high stress when its thickness increases, significantly reducing its processability. The multilayer structure of the first embodiment achieves good bending processability and improves strength.

[0099] The polyamide resin can be an aliphatic polyamide resin, a semi-aromatic polyamide resin, or a mixture of both. In the first embodiment, the polyamide resin contained in the prepreg preferably comprises at least a semi-aromatic polyamide resin.

[0100] Here, a semi-aromatic polyamide resin refers to a resin composed of structural units derived from diamines and structural units derived from dicarboxylic acids, wherein 20 to 80 mol% of the total structural units derived from diamines and dicarboxylic acids are structural units containing aromatic rings. By using such a semi-aromatic polyamide resin, the mechanical strength of the resulting molded article can be improved. Examples of semi-aromatic polyamide resins include polyamide 6T, polyamide 9T, polyamide 10T, polyamide 6I, polyamide 9I, polyamide 6T / 6I, polyamide 9T / 9I, and the phenylene dimethylamine polyamide resins described later, with phenylene dimethylamine polyamide resins being preferred.

[0101] Examples of aliphatic polyamide resins include polyamide 6, polyamide 66, polyamide 666, polyamide 10, polyamide 610, polyamide 11, and polyamide 12, with polyamide 6, polyamide 66, and polyamide 666 being preferred, and polyamide 66 being more preferred.

[0102] In a first embodiment, the prepreg preferably comprises a phenylenediamine-based polyamide resin, which contains structural units derived from diamines and structural units derived from dicarboxylic acids. At least 70 mol% of the structural units derived from the diamine are derived from phenylenediamine, and at least 70 mol% of the structural units derived from the dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. By using a phenylenediamine-based polyamide resin, the adhesion to the metal sheet can be further improved.

[0103] The diamine-derived structural units of the phenylenediamine-based polyamide resin are more preferably 75 mol% or more, further preferably 80 mol% or more, even more preferably 85 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more derived from phenylenediamine. The dicarboxylic acid-derived structural units of the phenylenediamine-derived polyamide resin are more preferably 75 mol% or more, further preferably 80 mol% or more, even more preferably 90 mol% or more, and even more preferably 95 mol% or more derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms.

[0104] As diamines that can be used as raw material components in phenylenediamine polyamide resins, examples of diamines other than m-phenylenediamine and p-phenylenediamine include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, etc. (aliphatic diamines), and 1,3-bis( Alicyclic diamines such as aminomethylcyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decahydronaphthalene, and bis(aminomethyl)tricyclodecane, as well as diamines with aromatic rings such as bis(4-aminophenyl)ether, p-phenylenediamine, and bis(aminomethyl)naphthalene, can be used in one or a mixture of two or more.

[0105] The preferred dicarboxylic acid component used as a raw material in phenylene dimethylamine polyamide resins is an α,ω-linear aliphatic dicarboxylic acid with 4 to 20 carbon atoms. Examples include succinic acid, glutaric acid, pimelic acid, octanoic acid, azelaic acid, adipic acid, sebacic acid, undecanoic acid, and dodecanoic acid. One or more of these dicarboxylic acids can be used. Adipic acid or sebacic acid is more preferred from the perspective of ensuring the melting point of the polyamide resin is within a range suitable for molding and processing, and adipic acid is even more preferred. By using adipic acid, the weld strength with the metal sheet can be further improved.

[0106] As dicarboxylic acid components other than the aforementioned α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms, examples include phthalic acid compounds such as isophthalic acid, terephthalic acid, and phthalic acid, and isomers of naphthalenedicarboxylic acid such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. One or a mixture of two or more can be used.

[0107] For the phenylenediamine polyamide resin of the first embodiment, preferably 0 to 100 mol% of the diamine structural unit is from p-phenylenediamine, 100 to 0 mol% is from m-phenylenediamine, and 70 mol% or more (preferably 80 mol% or more, more preferably 90 mol% or more) of the dicarboxylic acid structural unit is from sebacic acid and / or adipic acid.

[0108] As a more preferred embodiment of the phenylenediamine polyamide resin, an example is a phenylenediamine polyamide resin in which 70 mol% or more (preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more) of the structural units derived from diamine are derived from m-phenylenediamine, and 70 mol% or more (preferably 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, even more preferably 99 mol% or more) of the structural units derived from dicarboxylic acid are derived from dicarboxylic acid.

[0109] The phenylene dimethylamine polyamide resin of the first embodiment is mainly composed of structural units derived from diamine and structural units derived from dicarboxylic acids, but does not completely exclude structural units other than these. It may also include structural units derived from lactams such as ε-caprolactam and laurolactam, and aliphatic aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid. Here, "main component" refers to the structural units of the phenylene dimethylamine polyamide resin in which the total number of structural units derived from diamine and dicarboxylic acids is the largest among all structural units. In the first embodiment, the total number of structural units derived from diamine and dicarboxylic acids in the phenylene dimethylamine polyamide resin preferably accounts for 90% or more by mass of all structural units, more preferably 95% or more by mass, and even more preferably 98% or more by mass.

[0110] In the first embodiment, the polyamide resin constituting the prepreg preferably comprises 90-100% by weight of a phenylenediamine polyamide resin, 10-0% by weight of polyamide 66, and 3-0% by weight of other polyamide resins.

[0111] The melting point of the polyamide resin contained in the prepreg is preferably 150-350°C, more preferably 180-330°C, and even more preferably 200-300°C.

[0112] The melting point can be determined according to differential scanning calorimetry based on JIS K7121 and K7122.

[0113] The lower limit of the number average molecular weight (Mn) of the polyamide resin contained in the prepreg is preferably 6,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The upper limit of the above-mentioned Mn is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 18,000 or less. When it is within such a range, the heat resistance, elastic modulus, dimensional stability, and processability are better.

[0114] The prepreg used in the first embodiment may contain various components without departing from the resin of the first embodiment. Specifically, elastomers, antioxidants, heat stabilizers and other stabilizers, hydrolysis resistance modifiers, weather stabilizers, matting agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, anti-coloring agents, gelling inhibitors, colorants, release agents, lubricants and other additives may be added. Details of these components can be found in paragraphs 0130 to 0155 of Japanese Patent No. 4894982, which are incorporated herein by reference. The total amount of these components is preferably 10% by mass or less of the polyamide resin contained in the prepreg, more preferably 5% by mass or less, even more preferably 3% by mass or less, and may also be 1% by mass or less.

[0115] Typically, these components are preferably impregnated in continuous reinforcing fibers in a manner consistent with the polyamide resin.

[0116] The prepreg of the first embodiment comprises continuous reinforcing fibers.

[0117] Continuous fibers refer to fibers longer than 50 mm, specifically fibers longer than 50 cm. The cross-section of the reinforcing fibers in this invention can be circular or flat. Only one type of continuous reinforcing fiber can be used, or two or more types can be used. The average fiber length of the continuous reinforcing fibers used in the first embodiment is not particularly limited; for example, it is preferably in the range of 10 cm to 1000 m, more preferably 50 cm to 700 m, and even more preferably 1 to 500 m.

[0118] The continuous reinforcing fibers used in the first embodiment can include inorganic fibers such as glass fiber, carbon fiber, alumina fiber, boron fiber, ceramic fiber, and metal fiber (steel fiber), as well as plant fibers (including kenaf, bamboo fiber, etc.), aromatic polyamide fibers, polyoxymethylene fibers, and poly(p-phenylenebenzodioxane) fibers. Organic fibers such as azole fiber and ultra-high molecular weight polyethylene fiber. Preferably, it includes at least one selected from carbon fiber, aramid fiber and glass fiber, more preferably at least one selected from carbon fiber and glass fiber, and even more preferably at least one selected from carbon fiber.

[0119] The continuous reinforcing fiber used in the first embodiment is preferably a fiber that has been treated with a treatment agent. Examples of such treatment agents include bundling agents and surface treatment agents, and the treatment agents described in paragraphs 0093 and 0094 of Japanese Patent No. 4894982 are preferred, as these contents are incorporated herein by reference.

[0120] As a surface treatment agent, examples include surface treatment agents containing functional compounds such as epoxy compounds, acrylic compounds, isocyanate compounds, silane compounds, and titanate compounds, such as silane coupling agents and titanate coupling agents, with silane coupling agents being preferred.

[0121] Furthermore, as a binding agent, it is preferably at least one of epoxy resin, urethane resin, silane compound, isocyanate compound, titanate compound, and polyamide resin, more preferably at least one of epoxy resin, urethane resin, silane coupling agent, water-insoluble polyamide resin, and water-soluble polyamide resin, even more preferably at least one of epoxy resin, urethane resin, water-insoluble polyamide resin, and water-soluble polyamide resin, and even more preferably water-soluble polyamide resin.

[0122] The amount of the above-mentioned treatment agent is preferably 0.001 to 1.5% by mass of the continuous reinforcing fiber, more preferably 0.1 to 1.2% by mass, and even more preferably 0.3 to 1.1% by mass.

[0123] Treatment methods for continuous reinforcing fibers based on treatment agents can employ known methods. For example, one method involves impregnating the continuous reinforcing fibers in a liquid formed by dissolving the treatment agent in a solution, thereby adhering the treatment agent to the surface of the continuous reinforcing fibers. Alternatively, the treatment agent can be blown onto the surface of the continuous reinforcing fibers. Furthermore, continuous reinforcing fibers that have already been treated with a surface treatment agent can be used, or a commercially available surface treatment agent can be washed off and then re-treated with a desired dosage.

[0124] In the first embodiment, the content of continuous reinforcing fibers in the prepreg is preferably 30% by volume or more, more preferably 35% by volume or more, and preferably 70% by volume or less, more preferably 65% ​​by volume or less, even more preferably 60% by volume or less, even more preferably 55% by volume or less, even more preferably 50% by volume or less, or possibly 45% by volume or less.

[0125] In the first embodiment, the content of continuous reinforcing fibers in the prepreg is 5 parts by weight or more, preferably 10 parts by weight or more, more preferably 20 parts by weight or more, more preferably 30 parts by weight or more, more preferably 35 parts by weight or more, and even more preferably 40 parts by weight or more, and also 300 parts by weight or less, preferably 250 parts by weight or less, more preferably 200 parts by weight or less, even more preferably 160 parts by weight or less, and even more preferably 140 parts by weight or less, relative to 100 parts by weight of polyamide resin.

[0126] The prepreg described above may contain only one type of continuous reinforcing fiber, or it may contain two or more types of continuous reinforcing fibers. When two or more types are included, the total volume or total mass is preferably within the range described above.

[0127] In the aforementioned prepreg, the continuous reinforcing fibers and polyamide resin preferably account for 90% or more of the total mass, more preferably 95% or more of the total mass, and even more preferably 97% or more of the total mass. The upper limit is when the total mass of the continuous reinforcing fibers and polyamide resin reaches 100%.

[0128] Regarding the thickness of the prepreg, the average thickness of each layer is preferably 15 μm or more, more preferably 20 μm or more, even more preferably 25 μm or more, and even more preferably 30 μm or more. In addition, it is preferably 300 μm or less, more preferably 250 μm or less, and even more preferably 200 μm or less.

[0129] In the first embodiment, the prepreg is preferably stacked in 1 to 5 layers.

[0130] The maximum bending load of the multilayer body in the first embodiment is preferably 800 N or more, preferably 900 N or more, and more preferably 1000 N or more. Furthermore, the upper limit of the maximum bending load is preferably 2500 N or less. The maximum bending load can be measured according to the embodiments described later.

[0131] Such maximum bending load can be achieved by using a metal plate and aligning the continuous reinforcing fibers in the prepreg in one direction.

[0132] The multilayer body of the first embodiment can be manufactured by known methods.

[0133] The manufacturing method of the multilayer body according to the first embodiment preferably includes hot-melt bonding of a metal sheet and a prepreg impregnated with polyamide resin in continuous reinforcing fibers stretched in one direction. Hot-melt bonding is preferably performed by hot pressing. By hot pressing, the metal sheet and the prepreg can be firmly bonded together.

[0134] In addition, the manufacturing method of the multilayer body in the first embodiment preferably includes vibration welding, ultrasonic welding or laser welding of a metal plate and a prepreg impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction.

[0135] In the first embodiment, when cladding is performed by laser cladding, it is preferable to clad from the prepreg side, for example... Figure 1 The arrow is illuminated by a laser.

[0136] In addition, the metal sheet can be heated separately during the lamination of the metal sheet and the prepreg. The heating temperature at this time can be determined according to the thickness of the prepreg and the number of layers, for example, preferably 50 to 200°C.

[0137] In the first embodiment, as described above, the metal sheet 1 and the prepreg 2 are stacked and further heated to fuse the metal sheet 1 and the prepreg 2. Here, the surface of the metal sheet may be smooth, but it typically has irregularities. By having irregularities, the contact area between the metal sheet and the polyamide resin contained in the prepreg is increased, thereby improving the fusion strength. In addition, the molten polyamide resin solidifies in the form of recesses entering the surface of the metal sheet, enabling a stronger bond.

[0138] In the first embodiment, the metal sheet and the prepreg can be stacked separately, or multiple sheets can be stacked. When multiple sheets of prepreg are stacked, they can be stacked with the continuous reinforcing fibers of each prepreg in the same direction, or they can be stacked with different directions. For example, the fiber length direction of the continuous reinforcing fibers in the second layer of prepreg can be set at a 90° angle relative to the fiber length direction of the continuous reinforcing fibers in the first layer of prepreg, or it can be set at an angle of 45°, 30°, etc.

[0139] The second embodiment is a method for manufacturing multilayer bodies.

[0140] Furthermore, the manufacturing method of the multilayer body according to the second embodiment is characterized in that the multilayer body has a metal plate and a prepreg fused together with the metal plate in the surface direction, the prepreg being impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction, the prepreg containing 5 to 300 parts by weight of continuous reinforcing fibers relative to 100 parts by weight of polyamide resin, and the metal plate being manufactured according to JIS... The tensile strength measured by Z2241 is 300 MPa or more and 1400 MPa or less (preferably 1200 MPa or less). The manufacturing method of the multilayer includes: stacking the above-mentioned metal plate, the above-mentioned phenylenediamine polyamide resin film and the above-mentioned prepreg in the above-mentioned order, and further heating to melt the above-mentioned metal plate, the above-mentioned phenylenediamine polyamide resin film and the above-mentioned prepreg. The above-mentioned phenylenediamine polyamide resin film contains polyamide resin, which contains structural units from diamine and structural units from dicarboxylic acid. More than 70 mol% of the above-mentioned structural units from diamine are from phenylenediamine, and more than 70 mol% of the above-mentioned structural units from dicarboxylic acid are from α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms.

[0141] With this configuration, the metal sheet and prepreg can be firmly welded together. In particular, even with welding methods such as laser welding, which are difficult to achieve high welding strength, the metal sheet and prepreg can be properly welded together.

[0142] Especially in the manufacture of multilayer bodies like the above, metal sheets and prepregs are typically fused together. There are various methods for fusing metal sheets and prepregs, and hot pressing is known as a method that can achieve a relatively strong fusion. However, in cases such as manufacturing vehicle pillars, it is sometimes difficult to use a strong fusion method like hot pressing. By using the above-described multilayer body manufacturing method, even fusion methods like laser fusion, which are difficult to achieve high fusion strength, can appropriately fuse metal sheets and prepregs together.

[0143] In the second embodiment, for example, such as Figure 2 As shown, the metal plate 11, the diphenylene diamine polyamide resin film 12, and the prepreg 13 are stacked together in the order described above. In this way, by fusing the metal plate 11 and the prepreg 13 through the diphenylene diamine polyamide resin film 12, even when using a fusing method that is difficult to achieve high fusing strength, the metal plate 11 and the prepreg 13 can be firmly fused. This is based on the fact that the diphenylene diamine polyamide resin is a resin with excellent adhesion to the metal plate 11, and that the diphenylene diamine polyamide resin is a resin with excellent adhesion to the prepreg containing the polyamide resin.

[0144] It should be noted that, in Figure 2The thickness ratio of each layer is not shown in the figure. Furthermore, in the multilayer obtained by the manufacturing method of the second embodiment, sometimes the diphenylene diamine polyamide resin film and prepreg melt, blurring the boundaries between the layers.

[0145] In addition, the metal sheet and prepreg in the second embodiment are welded together by means of a phenylenediamine polyamide resin film. Typically, the metal sheet and prepreg are welded together by means of a phenylenediamine polyamide resin film.

[0146] In the second embodiment, as described above, the metal plate 11, the phenylene diamine polyamide resin film 12, and the prepreg 13 are stacked in the order described above, and further heated to fuse the metal plate 11, the phenylene diamine polyamide resin film 12, and the prepreg 13. Through this heating-based fusion, a portion or all of the phenylene diamine polyamide resin film and a portion or all of the polyamide resin contained in the prepreg melt. Furthermore, the molten phenylene diamine polyamide resin fuses with the metal plate and the prepreg. Here, the surface of the metal plate may be smooth, but it typically has irregularities. By having irregularities, the contact area between the metal plate and the phenylene diamine polyamide resin increases, thereby improving the fusion strength. Additionally, the molten phenylene diamine polyamide resin solidifies in the form of recesses into the surface of the metal plate, enabling a more robust fusion.

[0147] In the second embodiment, the metal plate, the phthalamide resin film, and the prepreg can be stacked individually, or multiple sheets can be stacked. When multiple sheets of prepreg are stacked, the directions of the continuous reinforcing fibers in each prepreg can be the same or different. For example, the fiber length direction of the continuous reinforcing fibers in the second layer of prepreg can be set at a 90° angle relative to the fiber length direction of the continuous reinforcing fibers in the first layer of prepreg, or it can be set at an angle of 45°, 30°, etc.

[0148] The heating-based welding method can be any type, including vibration welding, ultrasonic welding, and laser welding, with laser welding being preferred. In welding methods where it is difficult to increase welding strength, this invention achieves sufficient welding strength, and from this perspective, it is highly valuable. However, the welding method of the second embodiment can, of course, employ welding methods that can already achieve high welding strength, such as hot pressing.

[0149] In the second embodiment, when cladding is performed by laser cladding, it is preferable to clad from the prepreg side, for example... Figure 2The laser is irradiated from one side of the arrow. By configuring it in this way, it is possible to control the irradiation to be limited to the prepreg, limited to the metal, or to be applied to both the prepreg and the metal, depending on the light source intensity, the light source position (distance from the prepreg and the metal), and the light source angle.

[0150] Alternatively, it is preferable to heat the metal plate separately. The heating temperature at this time can be determined according to the thickness of the diphenylene amide resin film and the prepreg, for example, preferably 50 to 200°C.

[0151] During laser cladding, it is preferable to apply pressure while cladding using a pressure roller. The temperature of the roller can be determined based on the softening temperature and melting point of the thermoplastic resin contained in the prepreg. For example, it can be set to the melting point of the thermoplastic resin contained in the prepreg +10 to 40°C. Furthermore, the pressure applied by the heating roller can be set, for example, to 1 to 10 kgf.

[0152] Next, the metal plate of the second embodiment will be described.

[0153] The metal plate used in the second embodiment contains the same components as the metal plate described in the first embodiment, and the preferred range is also the same.

[0154] Next, the prepreg of the second embodiment will be described.

[0155] In the second embodiment, the prepreg is fused to the metal sheet in the planar direction. By using the prepreg, high strength can be achieved, and it is also significantly lighter compared to using only the metal sheet.

[0156] In the second embodiment, the prepreg is impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction. By using polyamide resin, the adhesion to the phenylene diamine polyamide resin film can be improved, and the weld strength of the multilayer can be increased. Furthermore, by using continuous reinforcing fibers pulled in one direction, the bending load in the fiber length direction can be increased. Therefore, a material that can adequately withstand bending processes can be manufactured. In particular, although ultra-high tensile steel has a high modulus of elasticity, bending processes require high stress when its thickness increases, significantly reducing its workability. The multilayer obtained by the manufacturing method of the second embodiment achieves good bending workability and improved strength.

[0157] The details of the prepreg in the second embodiment are preferably the same as those of the prepreg described in the first embodiment.

[0158] The phenylene dimethylamine polyamide resin film used in the second embodiment comprises a polyamide resin containing structural units derived from diamines and structural units derived from dicarboxylic acids. At least 70 mol% of the structural units derived from the diamines are derived from phenylene dimethylamine, and at least 70 mol% of the structural units derived from the dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. Phenylene dimethylamine polyamide resins are resins with excellent weldability to metals, and can improve the weld strength between prepreg and metal sheet.

[0159] The details of the phenylenediamine polyamide resin are the same as those of the phenylenediamine polyamide resin described in the first embodiment, and the preferred range is also the same.

[0160] The proportion of phthalamide polyamide resin in the above-mentioned phthalamide polyamide resin film is preferably 90% or more by mass of the total film, more preferably 95% or more by mass, and even more preferably 97% or more by mass. The upper limit is when the total amount of phthalamide polyamide resin is 100% by mass.

[0161] The aforementioned phenylenediamine polyamide resin film may contain only one type of phenylenediamine polyamide resin, or it may contain two or more types. When two or more types are contained, the total amount is preferably within the range described above.

[0162] Phthalic diamine polyamide resin films may also contain polyamide resins other than phthalic diamine polyamide resins and additives.

[0163] Polyamide resins other than phenylenediamine polyamide resins can be aliphatic polyamide resins, semi-aromatic polyamide resins, or mixtures of both.

[0164] The preferred semi-aromatic polyamide resins are polyamide 6T, polyamide 9T, polyamide 10T, polyamide 6I, polyamide 9I, polyamide 6T / 6I, and polyamide 9T / 9I.

[0165] Examples of aliphatic polyamide resins include polyamide 6, polyamide 66, polyamide 666, polyamide 10, polyamide 610, polyamide 11, and polyamide 12, with polyamide 6, polyamide 66, and polyamide 666 being preferred, and polyamide 66 being more preferred.

[0166] As additives, fillers, elastomers, antioxidants, heat stabilizers and other stabilizers, hydrolysis resistance modifiers, weather stabilizers, matting agents, ultraviolet absorbers, nucleating agents, plasticizers, dispersants, flame retardants, antistatic agents, anti-coloring agents, gelling inhibitors, colorants, release agents, lubricants and other additives can be added. Details of these additives can be found in paragraphs 0130 to 0155 of Japanese Patent No. 4894982, which are incorporated herein by reference. The total amount of these components is preferably 10% by mass or less of the phenylenediamine polyamide resin, more preferably 5% by mass or less, even more preferably 3% by mass or less, and may also be 1% by mass or less.

[0167] The thickness of the aforementioned phenylene dimethylamine polyamide resin film is preferably 15 μm or more, more preferably 17 μm or more, and even more preferably 19 μm or more. Furthermore, the thickness of the aforementioned phenylene dimethylamine polyamide resin film is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 35 μm or less, even more preferably 30 μm or less, and still even more preferably 25 μm or less. By setting the thickness to the upper limit or lower limit mentioned above, there is a tendency to further improve the weld strength between the metal sheet and the prepreg.

[0168] The multilayer body of the first embodiment and the multilayer body manufactured by the manufacturing method of the second embodiment are suitable for molded articles having concave and convex portions, molded articles having curved portions, substrates that cannot be hot-pressed, and small-sized molded articles.

[0169] Specifically, the aforementioned multilayer bodies can be appropriately used in components of electrical / electronic equipment such as automobiles, aircraft, ships, personal computers, OA equipment, AV equipment, and mobile phones, as well as optical equipment, precision equipment, toys, and household / office appliances.

[0170] In particular, the aforementioned multi-layered structure is preferably a vehicle pillar or a component thereof.

[0171] Example

[0172] The present invention will be described in more detail below with examples. The materials, amounts, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0173] If the measuring equipment used in the embodiments is difficult to obtain due to production stoppage or other reasons, other equipment with the same performance can be used for measurement.

[0174] 1. Raw materials

[0175] MXD6: A polyamide resin synthesized from m-phenylenediamine and adipic acid, manufactured by Mitsubishi Gas Chemical Co., Ltd., product number: #6000

[0176] PA66: Polyamide 66, manufactured by Toray Industries, product number: CM3001-N

[0177] MP10: A polyamide resin synthesized from phenylenediamine and sebacic acid through the following synthesis example.

[0178] <Example of MP10 synthesis>

[0179] Sebacic acid was dissolved by heating in a reaction vessel under a nitrogen atmosphere. While stirring the contents, a mixture of diamines (3:7 molar ratio of p-phenylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and m-phenylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was gradually added dropwise under pressure (0.35 MPa) at a molar ratio of approximately 1:1, and the temperature was raised to 235°C. After the addition was complete, the reaction was continued for 60 minutes, and the amount of components with a molecular weight below 1000 was adjusted. After the reaction was complete, the contents were removed in a thread and granulated using a granulator to obtain a polyamide resin (MP10, M / P = 7:3).

[0180] PA6: Polyamide 6, manufactured by Ube Industries, Ltd., product number: 1022B

[0181] Carbon fiber: Carbon fiber roving manufactured by Toray Corporation, which has undergone surface treatment with epoxy resin.

[0182] Talc: MS Talc, manufactured by Japan Talc Co., Ltd.

[0183] StCa: Calcium stearate, manufactured by Nitto Kasei Corporation.

[0184] High-tensile steel (metal sheet): The tensile strength and thickness of the steel listed in Tables 1 to 3 are the values ​​measured according to JIS Z2241.

[0185] <Manufacturing Example 1: Manufacturing of Prepreg (MXD6-CF)>

[0186] 90 parts by weight of MXD6, 9 parts by weight of PA66, 0.9 parts by weight of talc, and 0.1 parts by weight of StCa were weighed separately and dry-mixed. The mixture was fed from the top feed port of a twin-screw extruder (trade name: TEM26SS, manufactured by Shibaura Machinery Co., Ltd.). The drum temperature was set to 280°C and the mixture was melt-mixed at a screw speed of 200 pm to obtain the MXD6 composition.

[0187] Ten spools of roving-like carbon fiber are arranged at equal intervals and spread to a width of approximately 100 mm using a spreader. Molten MXD6 composition is supplied as the spread carbon fiber is fed between two impregnation rollers, impregnating the carbon fiber with the molten MXD6 composition. Then, while being cooled using cooling rollers, the carbon fiber is drawn and wound into a cylindrical core material to create a tape.

[0188] The volume percentage of carbon fiber in the prepreg is 38% (92 parts by mass relative to 100 parts by mass of polyamide resin).

[0189] <Manufacturing Example 2: Manufacturing of Prepreg (MP10-CF)>

[0190] Except that the resins (PAMXD6 and PA66) used in Manufacturing Example 1 were replaced with an equal amount of MP10, a prepreg formed from MP10-CF was manufactured using the same method.

[0191] The volume percentage of carbon fiber in the prepreg is 40% by volume (116 parts by mass relative to 100 parts by mass of polyamide resin).

[0192] <Manufacturing Example 3: Manufacturing of Prepreg (PA6-CF)>

[0193] Except that the resins (MXD6 and PA66) used in Manufacturing Example 1 were changed to an equal amount of PA6, a prepreg formed from PA6-CF was manufactured by the same method.

[0194] The volume percentage of carbon fiber in the prepreg is 44 vol% (125 parts by mass relative to 100 parts by mass of polyamide resin).

[0195] <Manufacturing Example 4: Manufacturing of phenylenediamine polyamide resin film (MXD6)>

[0196] Polyamide resin MXD6 was supplied to a single-screw extruder with a screw of 30 mm φ and a T-die. The extrusion temperature was 260 °C and 50 rpm, and the resin was cooled by a cooling roller at 80 °C to obtain a 20 μm thick cast film.

[0197] 2. Examples 1-1 to 1-8

[0198] <Manufacturing of Multilayer Bodies>

[0199] The surface of the high-tensile steel (metal sheet) was sandblasted using Alumina #180 (manufacturer: Monota RO).

[0200] Multiple sheets of prepreg (shown in Tables 1-3) were stacked on the treated surface of the high-tensile steel after the above sandblasting treatment.

[0201] Then, the mixture was hot-pressed at 280℃ and 2.0MPa for 15 minutes to obtain a multilayer body.

[0202] <Maximum Bending Load>

[0203] Using a universal testing machine (INSTRON "CAEAST 9350"), bending tests were conducted at 23°C and 80°C according to ISO 178, with a span distance of 32 mm and a test speed of 1.7 mm / min. The maximum bending load was determined. The unit of maximum bending load is expressed in N.

[0204] In addition, Tables 1-3 show the displacement (mm) from the start of the bending test to the point where the metal sheet and prepreg peel off during the bending test at 80°C. It can be considered that the larger the value, the less likely the metal sheet is to peel off from the prepreg during processing, indicating excellent processability.

[0205] Comparative Examples 1-1 to 1-3, 1-5

[0206] For the metal plates with given thicknesses and tensile strengths shown in Tables 1-3, the test piece weights and maximum bending loads were determined.

[0207] Comparative Examples 1-4

[0208] <The Making of Random Pieces>

[0209] Except that the resins (PAMXD6 and PA66) used in Manufacturing Example 1 were replaced with an equal amount of PA6, a prepreg formed from PA6-CF was manufactured using the same method. The volume percentage of carbon fibers in the prepreg was 44% by volume (125 parts by mass relative to 100 parts by mass of polyamide resin).

[0210] The obtained prepreg was cut into pieces 12.5cm wide and 25cm long. The randomly cut prepreg was spread across a 200mm square with a thickness of 1.0mm after hot pressing. The pieces were then hot-pressed at 250℃ and 2.0MPa for 15 minutes to produce random sheets.

[0211] In Examples 1-4, instead of prepreg, a random sheet obtained above was laminated, and the process was otherwise identical to obtain a multilayer body. The weight and maximum bending load of the resulting multilayer bodies were measured.

[0212]

[0213]

[0214] [Table 3]

[0215]

[0216] The results in Tables 1 to 3 above demonstrate that, compared to the case of a metal sheet alone, the multilayer structure of the present invention is lightweight and achieves a maximum bending load comparable to that of a metal sheet. On the other hand, metal sheets have poor processability, but the multilayer structure of the present invention exhibits excellent heat processability at 80°C. Furthermore, by using a prepreg having continuous reinforcing fibers aligned in one direction, the multilayer structure of the present invention achieves a very high maximum bending load compared to fiber-reinforced resins with fibers dispersed in random directions.

[0217] 3. Examples 2-1 and 2-2

[0218] The surface of high-tensile steel (metal sheet, tensile strength 1180 MPa, thickness 1.0 mm, tensile strength as measured according to JIS Z2241) was sandblasted using Alumina#180 (manufacturer: MonotaRO).

[0219] One sheet of polyamide resin film and one layer of prepreg of the types shown in Table 4 are stacked on the treated surface of the high-tensile steel after sandblasting in the order described above.

[0220] Then, laser cladding was performed from the prepreg side under the following conditions to obtain a multilayer body.

[0221] <Laser cladding conditions>

[0222] Laser cladding equipment: AFP device HUMM3

[0223] Transfer speed: 24mm / sec

[0224] Temperature near the pressure roller: 260℃

[0225] Roller pressure: 4 kgf

[0226] Temperature for high-tensile steel: Temperatures listed in Table 1

[0227] The shear strength of the resulting multilayer was measured as described below. Additionally, the delamination mode—whether it is base material failure or interfacial delamination—is also shown. It can be assumed that a stronger weld is formed in the case of base material failure.

[0228] <Determination of Shear Strength>

[0229] For the fused metal sheet and resin composition, the joint strength (unit: N) was determined by using a tensile testing machine (INSTRON "5544" model) with chucks clamped at both ends along the long axis using tensile clamps according to ISO 19095, under the conditions of tensile speed of 5 mm / min and chuck distance of 80 mm.

[0230] [Table 4]

[0231]

[0232] Based on the above results, in the manufacturing method of the multilayer body of the present invention, the metal plate (high-tensile steel) and the prepreg are fully fused together (Examples 2-1, 2-2).

Claims

1. A multilayer body comprising a metal plate and a prepreg directly or indirectly bonded to the metal plate in a planar direction. The prepreg is impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction, and contains 5 to 300 parts by weight of continuous reinforcing fibers relative to 100 parts by weight of polyamide resin. The polyamide resin comprises structural units derived from diamines and structural units derived from dicarboxylic acids, wherein more than 90 mol% of the structural units derived from diamines are derived from m-phenylenediamine, and more than 90 mol% of the structural units derived from dicarboxylic acids are derived from dicarboxylic acids. The tensile strength of the metal plate, as determined according to JIS Z2241, is 300 MPa or more and 1400 MPa or less.

2. The multilayer body according to claim 1, wherein, The tensile strength of the metal plate, as determined according to JIS Z2241, is less than 1200 MPa.

3. The multilayer body according to claim 1 or 2, wherein, The continuous reinforcing fiber comprises at least one selected from carbon fiber and glass fiber.

4. The multilayer body according to claim 1 or 2, wherein, The thickness of the metal plate is less than 2.0 mm.

5. The multilayer body according to claim 1 or 2, wherein, The content of continuous reinforcing fibers in the prepreg is 30-70% by volume.

6. The multilayer body according to claim 1, wherein, The continuous reinforcing fiber comprises at least one selected from carbon fiber and glass fiber, and the thickness of the metal plate is less than 2.0 mm. The content of continuous reinforcing fibers in the prepreg is 30-70% by volume.

7. A method for manufacturing a multilayer body, which is the method for manufacturing a multilayer body according to any one of claims 1, 2, and 6, the method comprising: The metal sheet and the prepreg are hot-melt bonded together, the prepreg being impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction.

8. A method for manufacturing a multilayer body, which is the method for manufacturing a multilayer body according to any one of claims 1, 2 and 6, the method comprising: The metal sheet and prepreg are subjected to vibration cladding, ultrasonic cladding, or laser cladding, wherein the prepreg is impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction.

9. A method for manufacturing a multilayer body, the multilayer body having a metal plate and a prepreg fused together with the metal plate in a surface direction. The prepreg is impregnated with polyamide resin in continuous reinforcing fibers pulled in one direction. The prepreg contains 5 to 300 parts by weight of continuous reinforcing fibers per 100 parts by weight of polyamide resin. The tensile strength of the metal plate, as determined according to JIS Z2241, is 300 MPa or higher and 1400 MPa or lower. The manufacturing method of this multilayer body includes: The metal plate, the phthalamide resin film, and the prepreg are stacked in the order described above, and then further heated to melt and coat the metal plate, the phthalamide resin film, and the prepreg. The phenylenediamine-based polyamide resin film comprises a polyamide resin containing structural units derived from diamines and structural units derived from dicarboxylic acids. More than 70 mol% of the structural units derived from the diamines are derived from phenylenediamine, and more than 70 mol% of the structural units derived from the dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. The prepreg comprises a polyamide resin containing structural units derived from a diamine and structural units derived from a dicarboxylic acid, wherein more than 90 mol% of the structural units derived from the diamine are derived from m-phenylenediamine and more than 90 mol% of the structural units derived from the dicarboxylic acid are derived from dicarboxylic acid.

10. The method for manufacturing a multilayer body according to claim 9, wherein, The thickness of the phenylenediamine polyamide resin film is 15~50μm.

11. The method for manufacturing a multilayer body according to claim 9 or 10, wherein, The welding is performed by laser welding, which involves irradiating the prepreg side with a laser.

12. The method for manufacturing a multilayer body according to claim 9 or 10, wherein, The continuous reinforcing fiber comprises at least one selected from carbon fiber and glass fiber.

13. The method for manufacturing a multilayer body according to claim 9 or 10, wherein, The thickness of the metal plate is less than 2.0 mm.

14. The method for manufacturing a multilayer body according to claim 9 or 10, wherein, The content of continuous reinforcing fibers in the prepreg is 30-70% by volume.

15. The method for manufacturing a multilayer body according to claim 9 or 10, wherein, The multi-layered structure is a vehicle's support pillar or a component thereof.

16. The method for manufacturing a multilayer body according to claim 9, wherein, The thickness of the phenylenediamine polyamide resin film is 15~50μm. The welding is performed by laser welding, which involves irradiating the prepreg side with a laser. The continuous reinforcing fiber comprises at least one selected from carbon fiber and glass fiber. The thickness of the metal plate is less than 2.0 mm. The content of continuous reinforcing fibers in the prepreg is 30-70% by volume. The multi-layered structure is a vehicle's support pillar or a component thereof.

17. The method for manufacturing a multilayer body according to any one of claims 9, 10, and 16, wherein, The tensile strength of the metal plate, as determined according to JIS Z2241, is 300 MPa or more and 1200 MPa or less.

18. A multilayer body, wherein, Metal sheets, phthalamide resin films, and prepreg impregnated with polyamide resin in continuous reinforcing fibers stretched in one direction are stacked together in the order described above. The tensile strength of the metal plate, as determined according to JIS Z2241, is 300 MPa or higher and 1400 MPa or lower. The phenylenediamine-based polyamide resin film comprises a polyamide resin containing structural units derived from diamines and structural units derived from dicarboxylic acids. More than 70 mol% of the structural units derived from the diamines are derived from phenylenediamine, and more than 70 mol% of the structural units derived from the dicarboxylic acids are derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. The prepreg comprises a polyamide resin containing structural units derived from a diamine and structural units derived from a dicarboxylic acid, wherein more than 90 mol% of the structural units derived from the diamine are derived from m-phenylenediamine and more than 90 mol% of the structural units derived from the dicarboxylic acid are derived from dicarboxylic acid.

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