Laminate, coating material or exterior material, electrical / electronic apparatus, and method for producing laminate

Abstract

Provided is a laminate having good environmental resistance. The laminate has at least one metal layer and at least one resin layer being laminated, and the crystallinity of the at least one resin layer as measured at a diffraction angle from 10° to 35° by X-ray diffraction measurements is 85.0% or less.

Description

Laminates, covering materials or exterior materials, and electrical and electronic equipment, as well as methods for manufacturing laminates.

[0001] This disclosure relates to laminates, covering materials or exterior materials, electrical and electronic equipment, and methods for manufacturing laminates.

[0002] In recent years, global concern for environmental issues has increased, and the adoption of environmentally friendly vehicles equipped with secondary batteries, such as electric vehicles and hybrid vehicles, is progressing. These vehicles use many electronic components and systems, and electromagnetic shielding is used to prevent malfunctions caused by electromagnetic interference. As these electronic components and systems are miniaturized and highly integrated, the problem of temperature rise due to increased heat generation has arisen. For example, Patent Document 1 discloses an electromagnetic shielding material for vehicles, in which an aluminum layer and a pair of resin layers sandwiching the aluminum layer are laminated.

[0003] Japanese Patent Publication No. 2013-071702

[0004] However, when an electromagnetic shielding material consisting of a laminated metal layer and a resin layer, as shown in Patent Document 1, is used in a vehicle, the metal layer and the resin layer may delaminate due to poor environmental resistance such as weather resistance, heat cycle resistance, and heat resistance.

[0005] Therefore, the objective of one embodiment of the present invention is to provide a laminate with good environmental resistance.

[0006] The inventors of the present invention have conducted diligent research to solve the above problems and have found that by controlling the degree of crystallinity of at least one resin layer laminated in a laminate to a relatively low level, the adhesion between the resin layer and the metal layer is improved, resulting in good environmental resistance. The present invention was completed based on the above findings and is illustrated below. [1] A laminate comprising at least one metal layer and at least one resin layer, wherein the degree of crystallinity of at least one of the resin layers, as measured by X-ray diffraction at diffraction angles of 10° to 35°, is 85.0% or less. [2] The laminate of [1], wherein the degree of crystallinity is 83.0% or less. [3] The laminate of [1] or [2], wherein the arithmetic mean roughness Ra of the surface of at least one of the resin layers is 0.1 μm or more and 1.5 μm or less. [4] The laminate of [3], wherein the arithmetic mean roughness Ra is 0.2 μm or more and 1.2 μm or less. [5] A laminate according to any of [1] to [4], wherein the maximum height roughness RzD of the surface of at least one resin layer is 0.1 μm or more and 8.0 μm or less. [6] A laminate according to any of [1] to [5], wherein the arithmetic mean roughness Ra of the surface of at least one metal layer is 0.03 μm or more and 0.20 μm or less. [7] The laminate according to [6], wherein the arithmetic mean roughness Ra is 0.05 μm or more and 0.15 μm or less. [8] A laminate according to any of [1] to [7], wherein the maximum height roughness RzD of the surface of at least one metal layer is 0.15 μm or more and 1.50 μm or less. [9] The resin layer is a laminate according to any of [1] to [8], containing one or more selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyamides (PA), modified polyphenylene ether (m-PPE), polypropylene (PP), polycarbonate (PC), polyimides (PI), fluororesins (such as PFA and PTFE), liquid crystal polymer (LCP), and polyphenylene sulfide (PPS).

[10] The laminate of [9] wherein the resin layer contains one or more selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamides (PA), modified polyphenylene ether (m-PPE), polyimides (PI), fluororesins (such as PFA and PTFE), liquid crystal polymer (LCP), and polyphenylene sulfide (PPS).

[11] The laminate of any of [1] to

[10] wherein the resin layer is an unoriented film.

[12] The laminate of any of [1] to

[11] wherein the metal layer contains one or more selected from the group consisting of copper, copper alloys, aluminum, aluminum alloys, iron, and iron alloys.

[13] The laminate of

[12] wherein the metal layer contains copper.

[14] The laminate of any of [1] to

[13] having a thickness of 16 μm or more and 900 μm or less.

[15] A covering or exterior material for electrical and electronic equipment comprising a laminate of any of [1] to

[14] .

[16] An electrical or electronic device equipped with the covering or exterior material of

[15] .

[17] A method for manufacturing a laminate, comprising a lamination step of laminating at least one metal layer and at least one resin layer, wherein the lamination step uses at least one resin layer having a crystallinity of 85.0% or less as measured by X-ray diffraction at diffraction angles of 10° to 35°.

[18] The method for manufacturing a laminate of

[17] , wherein the crystallinity is 60.0% or less.

[19] A method for manufacturing a laminate according to

[17] or

[18] , wherein the value obtained by subtracting the crystallinity of at least one resin layer used in the lamination, measured by X-ray diffraction at a diffraction angle of 10° to 35°, from the crystallinity of at least one resin layer of the laminate measured by X-ray diffraction at a diffraction angle of 10° to 35°, is -20.0% or more and 60.0% or less.

[20] A method for manufacturing a laminate according to any one of

[17] to

[19] , wherein in the lamination step, at least one resin layer having an arithmetic mean roughness Ra of 0.1 μm or more and 1.5 μm or less is used for lamination.

[0007] In one embodiment of the present invention, a laminate with good environmental resistance can be provided.

[0008] This is a cross-sectional view showing an example of a laminate according to the present invention. This is a cross-sectional view showing another example of a laminate according to the present invention. This is a cross-sectional view showing another example of a laminate according to the present invention. This is a table showing the main amorphous and crystalline peaks of the resin material that occur in the diffraction angle range of 10° to 35° measured by X-ray diffraction measurement. Figures 5(A) to (B) are diagrams showing an example of a method for adjusting the background in X-ray diffraction measurement. These are top views showing molded bodies obtained by cutting the laminates of Examples 1 to 15 and Comparative Examples 1 to 6. Figures 7(A) to (C) are cross-sectional views for illustrating the procedure for manufacturing the molded bodies of Examples 1 to 15 and Comparative Examples 1 to 6.

[0009] Preferred embodiments of the present invention will be described below in detail, but the present invention should not be construed as being limited thereto, and various modifications and improvements can be made based on the knowledge of those skilled in the art, without departing from the spirit of the invention. The multiple components disclosed in each embodiment can be combined in appropriate ways to form various inventions. For example, some components may be removed from all the components shown in each embodiment, or components from different embodiments may be combined in appropriate ways.

[0010] [1. Laminates] The laminate 100 shown in Figure 1 is constructed by laminating a resin layer 110 and a metal layer 160 in that order. The laminate 200 shown in Figure 2 is constructed by laminating a resin layer 210, a metal layer 260, a resin layer 220, and a metal layer 270 in that order. The laminate 300 shown in Figure 3 is constructed by laminating a resin layer 310, a metal layer 360, a resin layer 320, a metal layer 370, and a resin layer 330 in that order. In other words, these laminates 100, 200, and 300 have at least one resin layer and at least one metal layer laminated together, and have a structure in which at least one resin layer and at least one metal layer are laminated alternately. Laminates 100, 200, and 300 having such a structure have electromagnetic shielding effects and heat dissipation properties, and can therefore be used as electromagnetic shielding materials and heat dissipation members. Furthermore, since the laminates 100, 200, and 300 are constructed by alternately laminating at least one resin layer and one metal layer, they can be made lighter compared to a single metal layer of the same thickness.

[0011] (Laminated Structure) Examples of laminated structures include the following: (1) When the laminated structure consists of two layers, for example, the metal layer / resin layer shown in Figure 1 is an example. (2) When the laminated structure consists of three layers, for example, the metal layer / resin layer / metal layer, resin layer / metal layer / resin layer, resin layer / metal layer / metal layer, and metal layer / resin layer / resin layer are examples. (3) When the laminated structure consists of four layers, in addition to the metal layer / resin layer / metal layer / resin layer shown in Figure 2, for example, the metal layer / metal layer / metal layer / resin layer, metal layer / metal layer / resin layer / metal layer, metal layer / metal layer / resin layer / resin layer, and metal layer / resin layer / resin layer / metal layer are examples. (4) If the laminate is composed of three layers, for example, in addition to the resin layer / metal layer / resin layer / metal layer / resin layer shown in Figure 3, for example, metal layer / resin layer / metal layer / resin layer / metal layer, metal layer / metal layer / metal layer / metal layer / metal layer / resin layer, metal layer / metal layer / metal layer / resin layer / metal layer, metal layer / metal layer / metal layer / resin layer / resin layer / metal layer, metal layer / metal layer / resin layer / metal layer / metal layer, metal layer / metal layer / resin layer / resin layer / metal layer, metal layer / Resin layer / metal layer / metal layer / resin layer, metal layer / resin layer / metal layer / resin layer / metal layer, metal layer / resin layer / metal layer / resin layer / resin layer, metal layer / resin layer / resin layer / metal layer / resin layer, metal layer / resin layer / resin layer / resin layer / metal layer, metal layer / resin layer / resin layer / resin layer / resin layer, resin layer / metal layer / metal layer / resin layer / resin layer, resin layer / resin layer / metal layer / resin layer / resin layer, resin layer / resin layer / metal layer / resin layer / resin layer, resin layer / resin layer / resin layer / metal layer / resin layer.(3) The laminate is composed of six layers, for example, metal layer / resin layer / metal layer / resin layer / metal layer / resin layer, metal layer / metal layer / metal layer / metal layer / metal layer / metal layer / resin layer, metal layer / metal layer / metal layer / metal layer / resin layer / metal layer, metal layer / metal layer / metal layer / metal layer / resin layer / resin layer, metal layer / metal layer / metal layer / resin layer / metal layer / metal layer, metal layer / metal layer / metal layer / resin layer / metal layer / resin layer, metal layer / metal layer / metal layer / resin layer / resin layer / metal layer, metal layer / metal layer / metal layer / resin layer / resin layer / resin layer, metal layer / metal layer / resin layer / metal layer / metal layer / resin layer, metal layer / metal layer / resin layer / metal layer / resin layer / metal layer, metal layer / metal layer / resin layer / metal layer / resin layer / resin layer, metal layer / metal layer / resin layer / resin layer / metal layer / metal layer, metal layer / metal layer / resin layer / resin layer / metal layer / resin layer, metal layer / metal layer / resin layer / Resin layer / resin layer / metal layer, metal layer / metal layer / resin layer / resin layer / resin layer / resin layer, metal layer / resin layer / metal layer / metal layer / metal layer / resin layer, metal layer / resin layer / metal layer / metal layer / resin layer / metal layer, metal layer / Resin layer / metal layer / resin layer / resin layer / metal layer, metal layer / resin layer / resin layer / resin layer / resin layer / metal layer, resin layer / metal layer / metal layer / metal layer / metal layer / resin layer, resin layer / metal layer / metal layer / metal layer / resin layer / tree Examples include a resin layer, a resin layer / metal layer / metal layer / resin layer / resin layer / resin layer, a resin layer / metal layer / metal layer / resin layer / metal layer / resin layer, a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer / resin layer, a resin layer / metal layer / resin layer / metal layer / resin layer / resin layer, a resin layer / metal layer / resin layer / resin layer / resin layer / resin layer, a resin layer / metal layer / resin layer / resin layer / metal layer / resin layer, a resin layer / resin layer / metal layer / resin layer / resin layer. (6) When the composite structure of the composite body consists of seven layers, for example, a resin layer / metal layer / resin layer / resin layer / resin layer / metal layer / resin layer, a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, a resin layer / resin layer / metal layer / resin layer / metal layer, etc.

[0012] (Overall Thickness) From the viewpoint of moldability, the thickness of the laminates 100, 200, and 300 is preferably 16 μm or more, more preferably 50 μm or more, and even more preferably 100 μm or more. However, from the viewpoint of lightness and processability, the thickness of the laminates 100, 200, and 300 is preferably 900 μm or less, more preferably 600 μm or less, and even more preferably 550 μm or less. The thickness of the laminates 100, 200, and 300 can be measured using a constant pressure thickness tester (THICKNESS METER B-1, manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with Method A in JIS K 6250:2019, by clamping four points on the surface of the sheet sample with an indenter with a measuring force of 1.22 N, measuring the thickness at each point, and then averaging the measured values.

[0013] The ratio (M / R) of the total thickness (M) of the metal layers 160, 260, 270, 360, and 370 to the total thickness (R) of the resin layers 110, 210, 220, 310, 320, and 330 can be set as appropriate, but from the viewpoint of moldability, it is, for example, between 0.03 and 15.00.

[0014] <Resin Layer> Conventionally, laminates have used materials with a relatively high degree of crystallinity (especially biaxially oriented films) as their resin layer. However, the inventors have confirmed that molded articles obtained by molding such laminates did not have good environmental resistance. As a result of diligent research, the inventors have found that by controlling the degree of crystallinity of at least one resin layer within the laminate to a relatively low level, environmental resistance can be improved. Although this is not theoretically certain, the following can be inferred. That is, in resins with a relatively low degree of crystallinity (especially unoriented films), crystalline molecules are randomly distributed, so functional groups (such as hydroxyl groups) that are effective for bonding with adhesives and metals can easily move due to the pressure and heat during bonding, making it easier to obtain high adhesion strength between the resin and the metal. Therefore, it is possible to obtain laminates that are less likely to peel off in environments such as high temperature, high humidity, or thermal cycling.

[0015] In one embodiment, from the viewpoint of having good environmental resistance, when at least one resin layer 110, 210, 220, 310, 320, 330 of the laminate 100, 200, 300 is measured by X-ray diffraction at a diffraction angle of 10° to 35°, the degree of crystallinity of the resin layer 110, 210, 220, 310, 320, 330 is 85.0% or less, preferably 83.0% or less, more preferably 80.0%, and even more preferably 70.0% or less. On the other hand, there is no particular lower limit set for this degree of crystallinity, but from the viewpoint of dimensional stability in a heat-resistant environment, if a limit were to be set, it would be, for example, 5.0% or more, and for example, 10.0% or more. Furthermore, as shown in Figures 1 and 2, for laminates 100 and 200, from the viewpoint of ensuring adhesion with injection resin during or after molding, it is preferable that the resin layers 110 and 210 arranged on at least one of the outermost layers satisfy the above crystallinity range, and it is desirable that each resin layer 110, 210, and 220 satisfies the above crystallinity range. Furthermore, as shown in Figure 3, for laminate 300, from the viewpoint of ensuring adhesion with injection resin during or after molding, it is preferable that the resin layers 310 and 330 arranged on at least one of the outermost layers satisfy the above crystallinity range, it is more preferable that both of the outermost resin layers 310 and 330 satisfy the above crystallinity range, and it is particularly preferable that each resin layer 310, 320, and 330 satisfies the above crystallinity range. Although not shown, in laminates where no resin layer is arranged on any of the outermost layers, it is preferable that the resin layer sandwiched between the metal layers satisfies the above crystallinity range. To measure the crystallinity of a resin layer sandwiched between two metal layers, the measurement can be performed by peeling off at least one of the metal layers and exposing the resin layer.

[0016] (Method for measuring crystallinity) First, the laminate is cut into pieces of a suitable size for measurement. The crystallinity is measured using a SmartLab manufactured by Rigaku Corporation or an equivalent device. The measurement conditions are shown below. <Measurement Conditions> Measurement target: Resin layer X-ray source: CuKα X-ray output: 45kV-200mA Optical system: Focused method Scanning axis: θ / 2θ (Continuous scan) Scanning range: 5° to 80° Evaluation range: 10° to 35° Step: 0.01° Scan speed: 20° / min Analysis Peak search method: Peak top method (If the peak is not automatically detected, refer to Figure 4 and manually add the peak) Peak shape: Symmetric pseudo-Voigt function Background type: A straight line connecting the endpoints of 10° and 35° within the evaluation range as shown in Figure 5(A) (If the background is higher than the bottom of the peak, adjust the evaluation range to take up the background within a range of ±5° (a straight line connecting the endpoints of 15° and 30° within the evaluation range as shown in Figure 5(B))) After setting the background as described above, crystalline peaks were identified as peaks whose peak tops were obtained within ±1.5° of the peak position obtained from known literature within the evaluation range. Peaks other than crystalline peaks within the evaluation range were identified as amorphous peaks and were identified to be broader than the crystalline peaks. Crystallinity was defined as the value obtained by dividing the peak area of ​​all crystalline peaks within the evaluation range by the sum of the areas of all amorphous and all crystalline peaks.

[0017] (Surface Roughness) The arithmetic mean roughness Ra of the surfaces 111, 112, 211, 212, 221, 222, 311, 312, 321, 322, 331, and 332 of at least one resin layer 110, 210, 220, 310, 320, and 330 is not particularly limited, but is preferably 0.1 μm or more and 1.5 μm or less, and more preferably 0.2 μm or more and 1.2 μm or less. For example, as shown in Figures 1 to 3, if the arithmetic mean roughness Ra of the surfaces (outer surfaces) 111, 211, 311, and 332 of the outermost resin layer 110, 210, 310, and 330 is within the above range, good moldability can be ensured. Furthermore, as shown in Figures 1 to 3, for example, if the arithmetic mean roughness Ra of the surfaces 112, 212, 221, 222, 312, 321, 322, 331 of the resin layers 110, 210, 220, 310, 320, 330 on the metal layer 160, 260, 270, 360, 370 side is within the above range, good adhesion to the metal layer can be ensured. Here, in this specification, "Ra" means the surface roughness Ra measured in accordance with JIS B 0601-1982.

[0018] (Method for measuring surface roughness Ra) First, the laminate is cut to a suitable size for measurement. The arithmetic surface roughness Ra is measured using a Surfcoder SE600 manufactured by Kosaka Laboratory Co., Ltd. or an equivalent device. The measurement conditions are as follows: <Measurement conditions> Target of measurement: Surface of the resin layer (contact type) Stylus diameter: R2 60° Magnification: 10,000x Transverse magnification: 100x Measurement method: 0.1 mm / S Standard: JIS '82 Cutoff value: 0.25 Leveling: Linear (entire area) Evaluation length: 0.8 mm Calculation parameter: Ra Filter: 2CR

[0019] The maximum height roughness RzD of the surfaces 111, 112, 211, 212, 221, 222, 311, 312, 321, 322, 331, and 332 of at least one resin layer 110, 210, 220, 310, 320, and 330 is not particularly limited, but is preferably 0.1 μm or more and 8.0 μm or less, and more preferably 0.2 μm or more and 5.0 μm or less. For example, as shown in Figures 1 to 3, if the RzD of the surfaces (outer surfaces) 111, 211, 311, and 332 of the outermost resin layer 110, 210, 310, and 330 is within the above range, good moldability can be ensured. Furthermore, as shown in Figures 1 to 3, for example, if the maximum height roughness RzD of the surfaces 112, 212, 221, 222, 312, 321, 322 of the resin layers 110, 210, 220, 310, 320, 330 on the metal layers 160, 260, 270, 360, 370 side is within the above range, good adhesion to the metal layers can be ensured. Here, in this specification, "RzD" means the maximum height roughness RzD measured in accordance with JIS B 0601-1982.

[0020] First, the laminate is cut to a suitable size for measurement. The maximum height roughness RzD is measured using a Surfcoder SE600 manufactured by Kosaka Laboratory Co., Ltd. or an equivalent device. The measurement conditions are as follows: <Measurement Conditions> Measurement target: Surface of the resin layer (contact type) Stylus diameter: R2 60° Measurement magnification: 10000x Transverse magnification: 100x Measurement method: 0.1 mm / S Standard: JIS '82 Cutoff value: 0.25 Leveling: Linear (entire area) Evaluation length: 0.8 mm Calculation parameter: RzD Filter: 2CR

[0021] (Shape) The resin layers 110, 210, 220, 310, 320, and 330 are not particularly limited in shape, but for example, they can be in the form of a film. When the resin layers 110, 210, 220, 310, 320, and 330 are in the form of a film, the film is not particularly limited, but it is preferable that it be an unoriented film. Since an unoriented film is not subjected to stretching treatment during film formation, it has a relatively lower degree of crystallinity compared to a uniaxially oriented film or a biaxially oriented film.

[0022] (Resin material) The resin layers 110, 210, 220, 310, 320, and 330 are not particularly limited as resin materials as long as they satisfy the above crystallinity range, but it is preferable that they contain one or more selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyamides (PA), modified polyphenylene ether (m-PPE), polypropylene (PP), polycarbonate (PC), polyimides (PI), fluororesins (such as PFA and PTFE), liquid crystal polymer (LCP), and polyphenylene sulfide (PPS). Among these, it is more preferable that the resin layer contains one or more selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamides (PA), modified polyphenylene ether (m-PPE), polyimides (PI), fluororesins (such as PFA and PTFE), liquid crystal polymers (LCP), and polyphenylene sulfide (PPS). In this case, each layer may be made of the same type of resin material or different resin materials. Furthermore, from the viewpoint of heat dissipation, the resin may contain metal powders such as copper and aluminum, fillers, and inorganic powders such as carbon and graphite. The content of inorganic powder in the resin is not particularly limited, but is, for example, 95% by volume or less.

[0023] When forming multiple resin layers, all resin layers may be made of the same material, or different materials may be used for each layer. Furthermore, all resin layers may have the same thickness, or different thicknesses may be used for each layer.

[0024] (Thickness) The thickness of each layer of the above resin layers 110, 210, 220, 310, 320, and 330 is, for example, 10 μm or more at the lower limit and 25 μm or more at the upper limit. On the other hand, the thickness of each layer is, for example, 300 μm or less and 200 μm or less at the upper limit. The thickness of the resin layers 110, 210, 220, 310, 320, and 330 can be measured using the same method as the thickness of the laminates 100, 200, and 300. If the thickness of the resin layers 110, 210, 220, 310, 320, and 330 in the laminates 100, 200, and 300 is to be measured by observing the thickness cross-section with an SEM or similar device.

[0025] <Metal Layer> (Surface Roughness) The arithmetic mean roughness Ra of the surfaces 161, 162, 261, 262, 271, 272, 361, 362, 371, and 372 of at least one metal layer 160, 260, 270, 360, and 370 is not particularly limited, but is preferably 0.03 μm or more and 0.20 μm or less, and more preferably 0.05 μm or more and 0.15 μm or less. For example, as shown in Figures 1 and 2, if the arithmetic mean roughness Ra of the surfaces (outer surfaces) 162 and 272 of the outermost metal layers 160 and 270 arranged in the laminates 100 and 200 is within the above range, contact resistance can be reduced when attaching to substrates or metal housings when applying to products such as ECUs and inverters, thereby ensuring good shielding performance. For example, as shown in Figures 1-3, for laminates 100, 200, and 300, if the arithmetic mean roughness Ra of the surfaces 161, 261, 262, 271, 361, 362, 371, and 372 of the metal layers 160, 260, 270, 360, and 370 on the resin layers 110, 210, 220, 310, 320, and 330 is within the above range, good adhesion to the resin layers 110, 210, 220, 310, 320, and 330 can be ensured. Here, in this specification, "Ra" can be measured in the same way as the arithmetic mean roughness Ra of the resin layer surface. The measurement conditions can be the same as the measurement conditions for the resin layer surface described above, except that the metal layer surface is the measurement target.

[0026] The maximum height roughness RzD of the surfaces 161, 162, 261, 262, 271, 272, 361, 362, 371, and 372 of at least one metal layer 160, 260, 270, 360, and 370 is not particularly limited, but is preferably 0.15 μm or more and 1.50 μm or less, and more preferably 0.30 μm or more and 1.20 μm or less. For example, as shown in Figures 1 and 2, if the maximum height roughness RzD of the surfaces (outer surfaces) 162 and 272 of the outermost metal layers 160 and 270 is within the above range, contact resistance can be reduced when attaching to substrates or metal housings when applying to products such as ECUs and inverters, thereby ensuring good shielding performance. For example, as shown in Figures 1-3, for laminates 100, 200, and 300, if the maximum height roughness RzD of the surfaces 161, 261, 262, 271, 361, 362, 371, and 372 of the metal layers 160, 260, 270, 360, and 370 on the resin layers 110, 210, 220, 310, 320, and 330 is within the above range, good adhesion to the resin layers 110, 210, 220, 310, 320, and 330 can be ensured. Here, in this specification, "RzD" can be measured in the same way as the maximum height roughness RzD of the resin layer surface described above. The measurement conditions can be the same as the measurement conditions for the resin layer surface described above, except that the surface of the metal layer is the target of measurement.

[0027] The surface roughness RzD of at least one metal layer used during lamination is not particularly limited, but is preferably 0.1 μm or more and 1.5 μm or less, and more preferably 0.25 μm or more and 1.0 μm or less. For example, in the laminates 100 and 200 shown in Figures 1 and 2, if the surface roughness RzD of the outermost metal layers 160 and 270 (outer surfaces) 162 and 272 is within the above range, good adhesion and moldability can be ensured. For example, in the laminates 100, 200, and 300 shown in Figures 1 to 3, if the roughness RzD of the surfaces 161, 261, 262, 271, 361, 362, 371, and 372 of the metal layers 160, 260, 270, 360, and 370 used during lamination, on the resin layers 110, 210, 220, 310, 320, and 330, is within the above range, then good adhesion to the resin layers 110, 210, 220, 310, 320, and 330 can be ensured. Here, in this specification, "RzD" can be measured in the same way as the maximum height roughness RzD of the metal layer surface of the laminate. The measurement conditions can be the same as the measurement conditions for the metal layer surface of the laminate described above, except that the measurement target is the surface of the metal layer used during lamination.

[0028] (Thickness) The thickness of each metal layer 160, 260, 270, 360, and 370 is, for example, 6 μm or more at the lower limit and 9 μm or more at the upper limit. On the other hand, the thickness of each metal layer is, for example, 150 μm or less and 50 μm or less at the upper limit. The thickness of metal layers 160, 260, 270, 360, and 370 can be measured using the same method as the thickness of laminates 100, 200, and 300. If the thickness of a metal layer in a laminate is to be measured, the thickness can be measured by observing the cross-section using an SEM or similar device.

[0029] (Shape) The shape of the metal layers 160, 260, 270, 360, and 370 is not particularly limited, but examples include metal foil. When copper foil is used as the metal foil, a high purity of copper is preferred because it improves the shielding properties, and the purity is preferably 99.5% by mass or more, and more preferably 99.8% by mass or more. Rolled copper foil, electrolytic copper foil, metallized copper foil, etc. can be used as the copper foil, but rolled copper foil, which has excellent formability, is preferred. When alloying elements are added to the copper foil to make a copper alloy foil, the total content of these elements and unavoidable impurities should be less than 0.5% by mass. In particular, it is preferable to include at least one selected from tin, manganese, chromium, zinc, zirconium, magnesium, nickel, silicon, and silver in a total of 50 to 2000 ppm by mass, and / or phosphorus in 10 to 50 ppm by mass, as this improves the elongation compared to pure copper foil of the same thickness.

[0030] (Heat Treatment) Metal layers 160, 260, 270, 360, and 370 exhibit excellent formability upon heat treatment. The heat treatment should preferably be carried out under vacuum or in a deoxygenated atmosphere such as nitrogen at a temperature of 200 to 400°C for 30 minutes to 24 hours.

[0031] (Treatment Film) From the viewpoint of improving heat dissipation, the treatment film is formed on at least one surface 161, 162, 261, 262, 271, 272, 361, 362, 371, 372 of the metal layers 160, 260, 270, 360, 370. For example, it may further include one or more selected from an electromagnetic wave absorption auxiliary film, a heat-resistant film, a rust-preventive film, and a weather-resistant film made of an alloy containing copper. Examples of heat-treated heat-resistant films include plating films and vapor-deposited films containing cobalt and nickel. Examples of rust-preventive films include inorganic plating films and vapor-deposited films such as zinc and chromium, organic films such as benzotriazole, and examples of silane-coupled weather-resistant films include organic coating films containing a silane coupling agent. In other words, the treatment film may further contain one or more elements selected from zinc, molybdenum, tin, phosphorus, tungsten, chromium, and silicon, in addition to copper, cobalt, and nickel. The treated film may be interposed between the resin layers 110, 210, 220, 310, 320, and 330 and the metal layers 160, 260, 270, 360, and 370. Such a treated film can also improve the adhesion between the resin layers 110, 210, 220, 310, 320, and 330 and the metal layers 160, 260, 270, 360, and 370. Furthermore, the treated film can also improve the shielding properties.

[0032] Electromagnetic wave absorbing auxiliary films can be manufactured by known methods, such as plating, metal deposition, and sputtering. Among these, a method of forming an electromagnetic wave absorbing auxiliary film made of copper, cobalt, and nickel by applying a plating treatment to the surfaces 161, 162, 261, 262, 271, 361, 362, 371, and 372 of metal layers 160, 260, 270, 360, and 370 is described below as an example. In the plating treatment for forming the electromagnetic wave absorbing auxiliary film, a particle film made of copper, cobalt, and nickel is formed on at least one surface 161, 162, 261, 262, 271, 361, 362, 371, and 372 of metal layers 160, 260, 270, 360, and 370.

[0033] (Plating Conditions (Rough Plating): Copper, Cobalt, and Nickel Alloy Plating) An example of the plating conditions for copper, cobalt, and nickel is as follows: Liquid Composition: 10 - 20 g / L of copper, 5 - 15 g / L of cobalt, 5 - 15 g / L of nickel pH: 2 - 3 Liquid Temperature: 30 - 50 °C Current Density: 10 - 60 A / dm 2 , Coulomb Quantity: 10 - 48 As / dm 2

[0034] At this time, under the above plating conditions, the rough plating process can also be carried out in multiple stages.

[0035] In the heat treatment, at least one film of the following heat-resistant films 1 - 2 can be further formed on the electromagnetic wave absorption auxiliary film described above. The plating conditions and deposition conditions are shown below.

[0036] (Plating Conditions for Heat-Resistant Film 1) (Co-Ni Plating: Cobalt-Nickel Alloy Plating) Liquid Composition: 5 - 20 g / L of nickel, 1 - 8 g / L of cobalt pH: 2 - 3 Liquid Temperature: 40 - 60 °C Current Density: 10 - 30 A / dm 2 Coulomb Quantity: 2 - 20 As / dm 2

[0037] (Plating Conditions for Heat-Resistant Film 2) (Ni-Zn Plating: Nickel-Zinc Alloy Plating) Liquid Composition: 2 - 30 g / L of nickel, 2 - 30 g / L of zinc pH: 3 - 4 Liquid Temperature: 30 - 50 °C Current Density: 1 - 10 A / dm 2 Coulomb Quantity: 0.5 - 2 As / dm 2

[0038] In the rust prevention treatment, the following rust prevention film and / or weather resistance film can be further formed on the electromagnetic wave absorption auxiliary film or heat-resistant film described above. The conditions are shown below.

[0039] (Plating Conditions for Rust Prevention Film) Liquid Composition: 1 - 10 g / L of potassium dichromate, 0.2 - 0.5 g / L of zinc pH: 3 - 4 Liquid Temperature: 50 - 70 °C Current Density: 0 - 2 A / dm 2 (0 A / dm 2This is the case of immersion chromate treatment.) Coulomb amount: 0 to 2 As / dm 2 (0 As / dm 2 This is the case of immersion chromate treatment.)

[0040] (Type of weather-resistant film (silane coupling film)) As an example, application of a diaminosilane aqueous solution or an epoxy silane aqueous solution can be cited. In addition, when a metal film such as a heat-resistant film or a plating film is provided by vapor deposition (dry plating) such as sputtering, and when a metal film such as a heat-resistant film or a plating film is provided by plating (wet plating), and when the metal film such as a heat-resistant film or a plating film is normal plating (smooth plating, that is, plating performed at a current density less than the limiting current density), the metal film and the plating film do not affect the surface shape of the copper foil. The limiting current density varies depending on the metal concentration, pH, supply rate of the plating solution, interelectrode distance, and plating solution temperature. In the present invention, the current density at the boundary between normal plating (the state where the plated metal is deposited in a film form) and roughening plating (burned plating, the state where the plated metal is deposited in a crystalline form (such as spherical, needle-like, or dendritic), with irregularities) is defined as the limiting current density, and the current density (visual judgment) at the limit (immediately before becoming burned plating) where normal plating is achieved in the Hull cell test is taken as the limiting current density. Specifically, the metal concentration, pH, and plating solution temperature are set as the plating production conditions, and the Hull cell test is performed. Then, the formation state of the metal layer (whether the plated metal is deposited in a layer form or formed in a crystalline form) in the plating solution composition and plating solution temperature is investigated. Then, based on the current density quick reference table manufactured by Yamamoto Plating Tester Co., Ltd., the current density at the boundary of the test piece is obtained from the position of the test piece at the boundary between normal plating and roughening plating of the test piece. Then, the current density at the boundary position is defined as the limiting current density. Thereby, the limiting current density at the plating solution composition and plating solution temperature can be known. Generally, when the interelectrode distance is short, the limiting current density tends to be high. The method of the Hull cell test is described, for example, on pages 157 to 160 of "Practical Guide to Plating" by Kiyoshi Maruyama, published by Nihon Keizai Shimbunsha on June 30, 1983. In addition, in order to perform the plating treatment at a current density less than the limiting current density, the current density during the plating treatment is 20 A / dm 2It is preferably as follows, 10 A / dm 2 It is more preferably as follows, 8 A / dm 2 It is even more preferably as follows. Further, since the thicknesses of the rust preventive film and the weather resistant film are extremely thin, they do not affect the shape of the surface of the copper foil.

[0041] (Metal Material) The metal layers 160, 260, 270, 360, 370 are not particularly limited as the material, but it is preferable that they contain one or more selected from the group consisting of copper, copper alloy, aluminum, aluminum alloy, iron, and iron alloy. Among them, it is more preferable to contain copper. From the viewpoint of electromagnetic wave shielding properties, a material having a conductivity of 1.0×10 6 S / m or more is desirable.

[0042] When forming a plurality of metal layers, all the metal layers may be composed of the same material, or different materials may be used for each layer. Also, all the metal layers may have the same thickness, or the thicknesses may be different for each layer.

[0043] [2. Manufacturing Method of the Laminate] In one embodiment, the manufacturing method of the laminate according to the present invention includes a laminating step of laminating at least one metal layer and at least one resin layer.

[0044] In the lamination process, from the viewpoint of improving the environmental resistance of the electromagnetic wave shielding material, at least one resin layer is used for lamination, wherein the crystallinity measured by X-ray diffraction at diffraction angles of 10° to 35° is 85.0% or less. At this time, the upper limit of the crystallinity is 60.0% or less, more preferably 55.0%, and even more preferably 50.0% or less. On the other hand, there is no particular lower limit set for the crystallinity, but from the viewpoint of dimensional stability in a heat-resistant environment, if a lower limit were to be set, it would be 5.0% or more as an example, and also 10.0% or more as an example. Furthermore, as shown in Figures 1 and 2, from the viewpoint of ensuring adhesion with the injection resin at the same time as molding or after molding, it is preferable that the resin layer before being laminated to one of the outermost layers satisfies the above crystallinity range, and it is desirable that each resin layer satisfies the above crystallinity range. Furthermore, as shown in Figure 3, from the viewpoint of ensuring adhesion with the injection resin at the same time as molding or after molding, it is preferable that the resin layer before being laminated to one of the outermost layers satisfies the above crystallinity range, more preferably that the resin layer before being laminated to either of the outermost layers satisfies the above crystallinity range, and particularly preferably that each resin layer satisfies the above crystallinity range. Although not shown in the figures, in a laminate where no resin layer is placed on any of the outermost layers, it is preferable that the resin layer before being laminated sandwiched between the metal layers satisfies the above crystallinity range.

[0045] (Degree of change) From the viewpoint of dimensional stability during warm molding, the value obtained by subtracting the degree of crystallinity of at least one resin layer used in lamination, measured by X-ray diffraction at a diffraction angle of 10° to 35°, from the degree of crystallinity of at least one resin layer in the laminate, measured by X-ray diffraction at a diffraction angle of 10° to 35°, is preferably -20.0% to 60.0%, and more preferably 0% to 25.0%.

[0046] From the viewpoint of improving adhesion to the metal layer, at least one surface of the resin layer used in lamination of the laminate can be subjected to chemical treatments such as corona treatment, ozone treatment, surface elution by coating with organic solvents or adhesives, and catalyst treatment by embedding a catalyst on the surface to express functionalities such as hydroxyl groups.

[0047] The thickness of the manufactured laminate, the surface roughness, shape, resin material and thickness of the resin layer used in the lamination process, and the surface roughness, shape, metal material and thickness of the metal layer used in the lamination process are the same as those of the laminate described above, so no further explanation is provided.

[0048] (Lamination Method) As a means of laminating the resin layer and the metal layer, an adhesive may be used between the resin layer and the metal layer, or the resin layer may be heat-pressed to the metal layer without using an adhesive. A method of simply stacking without using an adhesive is also acceptable, but considering the integrity of the laminate, it is preferable to join at least the edges (for example, each side if the laminate is rectangular) with tape, adhesive, or by heat pressing. There are no particular restrictions on the adhesive, but examples include acrylic resin, epoxy resin, urethane, polyester, polycarbonate, silicone resin, vinyl acetate, styrene-butadiene rubber, nitrile rubber, phenolic resin, and cyanoacrylate. Urethane, polyester, and vinyl acetate are preferred for ease of manufacture and cost reasons. From the viewpoint of heat dissipation, the adhesive may contain thermally conductive inorganic powders such as alumina, metal powders, powders such as carbon and graphite, or fillers. The content of inorganic powder in the adhesive is not particularly limited, but for example, it is 95% by mass or less.

[0049] The means for forming the above-mentioned laminate are not particularly limited, but examples include bending, press molding, deep drawing, injection molding, and vacuum pressure forming.

[0050] (Applications) In one embodiment, it can be used for various electromagnetic shielding applications, particularly as a covering or exterior material for electrical and electronic equipment (e.g., inverters, communication devices, resonators, electron tubes / discharge lamps, electric heating equipment, electric motors, generators, electronic components, printed circuits, medical devices, etc.), covering material for harnesses and communication cables connected to electrical and electronic equipment, electromagnetic shielding sheets, electromagnetic shielding panels, electromagnetic shielding bags, electromagnetic shielding boxes, electromagnetic shielding rooms, etc.

[0051] The present invention will be specifically described based on examples and comparative examples. The following descriptions of examples and comparative examples are merely specific examples to facilitate understanding of the technical content of the present invention, and the technical scope of the present invention is not limited by these examples.

[0052] [Fabrication of Laminates] In Examples 1 to 15 and Comparative Examples 1 to 6, the materials shown in Tables 1 to 2 were prepared, and laminates were fabricated according to the configuration shown in Table 3. The specific fabrication method is described below. The thickness, arithmetic mean roughness Ra, and maximum height roughness RzD of each material shown in Tables 1 to 2 were measured. The results are shown in Tables 1 to 2. At this time, the thickness, arithmetic mean roughness Ra, and maximum height roughness RzD of each material were measured by the method described above.

[0053] First, in the preparation of the laminates in Examples 1-12 and 14-15, resin layers A-D were treated so that their back surfaces were bonded to the surface of the metal layer, so that resin layers A-D would be the outermost layers. In other words, in the laminates of Examples 1-12 and 14-15, the front surfaces of resin layers A-D became the outer surfaces. Next, in the preparation of the laminate in Example 13, resin layer F was treated so that its front surface was bonded to the front surface of metal layer A, so that resin layer F would be the outermost layer. In other words, in the laminate of Example 13, the back surface of resin layer F became the outer surface. Next, in the preparation of the laminates in Comparative Examples 1-5, resin layers E, G, and H were treated so that their front surfaces were bonded to the front surface of the metal layer, so that resin layers E, G, and H would be the outermost layers. In other words, in the laminates of Comparative Examples 1-5, the back surfaces of resin layers E, G, and H became the outer surfaces. Next, in the preparation of the laminate of Comparative Example 6, the resin layer E was treated so that it became the outermost layer, and the back surface of the resin layer E was bonded to the back surface of the metal layer. In other words, in the laminate of Comparative Example 6, the front surface of the resin layer E became the outer surface.

[0054] Next, in the preparation of the laminates in Examples 1 to 15 and Comparative Examples 1 to 6, the resin layer and the metal layer were laminated using a two-component mixed adhesive (main component: SD2, curing agent: H-5) manufactured by Rock Paint Co., Ltd.

[0055] The laminates of Examples 1 to 15 and Comparative Examples 1 to 6 prepared above were subjected to the following characteristic evaluations.

[0056] <Surface Roughness Ra, RzD> Surface roughness measurements were performed at one arbitrary location selected from the outer surface of the resin layer and the outer surface of the metal layer, which are located in the outermost layer of the laminates in Examples 1 to 15 and Comparative Examples 1 to 6. The arithmetic mean roughness Ra and maximum height roughness RzD at these measurement points are shown in Table 3. The arithmetic mean roughness Ra and maximum height roughness RzD were measured using the method described above.

[0057] <Crystallization> For the outermost resin layer of the laminates used in Examples 1-12, 14, 15 and Comparative Examples 1-6, four arbitrarily selected locations were measured, and the average crystallinity at these measurement points is shown in Table 4. On the other hand, for the outermost resin layer of the laminate used in Example 13, one arbitrarily selected location was measured, and the crystallinity at that measurement point is shown in Table 4. Furthermore, for the outermost resin layer of the laminates in Examples 1-2, 8-12, 14, 15 and Comparative Example 1, four arbitrarily selected locations were measured, and the average crystallinity at these measurement points is shown in Table 4. On the other hand, for Examples 3-7, 13 and Comparative Examples 2-6, one arbitrarily selected location was measured from the outer surface of the outermost resin layer of the laminate, and the average crystallinity at that measurement point is shown in Table 4. The crystallinity was measured using the method described above.

[0058] <Changes in Crystallinity> In Examples 1 to 15 and Comparative Examples 1 to 6, the crystallinity of the surface of the resin layer used in lamination that was not laminated to the metal layer was subtracted from the crystallinity of the outer surface of the outermost resin layer of the laminate. The resulting values ​​are shown in Table 4.

[0059] [Method for manufacturing molded bodies] Three molded bodies 500 were prepared by cutting the laminates obtained in Examples 1 to 15 and Comparative Examples 1 to 6 using scissors or the like to obtain the shape shown in Figure 6, and molded bodies were manufactured according to the following procedure. (1) The molded body 500 was clamped between the die 610 and the holder 620 of the processing machine 600 shown in Figure 7(A). At this time, the outermost metal layer of the molded body 500 was clamped so as to be in contact with the punch 630. (2) As shown in Figure 7(B), the punch 630 was moved vertically downward along the die 610 and the holder 620 at a speed of 900 m / sec and pushed into the die hole 640. The clearance between the die 610 and the punch 630 was set to 0.5 mm, and the punch indentation amount (the change obtained by subtracting the height of the outer surface of the molded body 550 in contact with the punch 630 after indentation from the height of the outer surface of the molded body 500 in contact with the punch 630 in the vertical direction) was set to 2 mm. Three molded bodies 550 were then produced as shown in Figure 7(C). In comparative examples 4 and 5, although molded bodies 550 were produced as described above, one molded body in each case had already demolished.

[0060] The molded articles of Examples 1 to 15 and Comparative Examples 1 to 6, which were prepared as described above, were subjected to the following characteristic evaluations.

[0061] <Moldability (Flatness)> For flatness, a VR series ONE-SHOT 3D manufactured by Keyence Corporation, or an equivalent device, was used to measure the difference between the maximum and minimum heights within a 2 mm x 2 mm plane on the flange portion 650 (Figure 7(C)) of a 10 mm x 10 mm (R1) 2 mm high drawn-out molded body. The difference between the maximum and minimum heights within a 2 mm x 2 mm plane was measured using a VR series ONE-SHOT 3D manufactured by Keyence Corporation, or an equivalent device (see Table 4 below). The measurement conditions are shown below. For samples with tilt throughout the molded body, tilt correction was performed at two points of imaging. <Measurement Conditions> Measurement target: 10 mm x 10 mm (R1) drawn-out molded body with a 2 mm stroke Imaging conditions: Full auto Magnification: 12x Evaluation area: 2 mm x 2 mm flange portion of the molded body 3 points Evaluation analysis conditions: Surface measurement (flatness) Calculation parameters: Maximum height and minimum height (mm)

[0062] <Weather Resistance> The weather resistance of the molded bodies of Examples 1 to 15 and Comparative Examples 1 to 6 was evaluated by placing them in a constant temperature and humidity chamber at a temperature of 85°C and a humidity of 85% Rh using an ESPEC PL-3J or equivalent apparatus, and checking the appearance of the molded bodies after 100 hours (after standing). At this time, the molded bodies were removed from the constant temperature and humidity chamber at 24 hours, 48 ​​hours, 72 hours, and immediately after 100 hours from the time they were placed in the chamber, and the presence or absence of delamination and blistering was checked visually. Note that a "-" in the durability time shown in Table 4 means that delamination was confirmed from at least one layer of each layer at the time the molded body was manufactured.

[0063] <Heat Cycle Resistance> The molded bodies of Examples 1 to 15 and Comparative Examples 1 to 6 were placed in an ESPEC TSE-12-A or equivalent apparatus under cycle conditions of -40°C and 120°C, and the number of cycles they could withstand was measured as follows. First, the process started at the high temperature side of 120°C, with 100 cycles consisting of 20 minutes at 120°C and 20 minutes at -40°C. Movement from the high temperature layer to the low temperature layer was limited to within 1 minute. Immediately after 100 cycles, the molded bodies were removed from the apparatus and visually inspected for delamination and blistering (see Table 4 below).

[0064] <Heat Resistance> The molded bodies of Examples 1 to 15 and Comparative Examples 1 to 6 were placed in a constant temperature chamber at a temperature of 120°C using a DNE600 manufactured by Yamato Scientific Co., Ltd. or an equivalent device, and their weather resistance was evaluated by checking the appearance of the molded bodies after 100 hours (after standing). At this time, the molded bodies were removed from the constant temperature chamber at 24 hours, 48 ​​hours, 72 hours, and immediately after 100 hours from the time they were placed in the chamber, and visually inspected. The molded bodies were removed from the constant temperature chamber immediately after 100 hours, and the presence or absence of delamination and blistering was checked visually (Table 4 below).

[0065]

[0066]

[0067]

[0068]

[0069] As can be seen from the above results, according to the embodiments of the present invention, a laminate with good environmental resistance can be provided.

[0070] (Potential Contribution to SDGs) According to the above embodiment, a laminate for manufacturing electromagnetic shielding material with good environmental resistance can be provided, and therefore it may contribute to the reliability of electronic devices. Reliability of electronic devices is required for the realization of an AI / IoT society. For this reason, one embodiment of the present invention may contribute to Goal 9 of the United Nations-led Sustainable Development Goals (SDGs), "Build resilient infrastructure, promote inclusive and sustainable industrialization and foster technological innovation."

[0071] 100, 200, 300 Laminate 110, 210, 220, 310, 320, 330 Resin layer 160, 260, 270, 360, 370 Metal layer 111, 162, 211, 272, 311, 332 Surface (outer surface) 112, 161, 212, 221, 222, 261, 262, 271, 312, 321, 322, 331, 361, 362, 371, 372 Surface 500 Molded object 550 Molded object 600 Processing machine 610 Die 620 Holder 630 Punch 640 Die hole 650 Flange

Claims

1. A laminate comprising at least one metal layer and at least one resin layer, wherein the crystallinity of at least one of the resin layers, as measured by X-ray diffraction at diffraction angles of 10° to 35°, is 85.0% or less.

2. The laminate according to claim 1, wherein the degree of crystallinity is 83.0% or less.

3. The laminate according to claim 1 or 2, wherein the arithmetic mean roughness Ra of the surface of at least one of the resin layers is 0.1 μm or more and 1.5 μm or less.

4. The laminate according to claim 3, wherein the arithmetic mean roughness Ra is 0.2 μm or more and 1.2 μm or less.

5. The laminate according to any one of claims 1 to 4, wherein the maximum height roughness RzD of the surface of at least one of the resin layers is 0.1 μm or more and 8.0 μm or less.

6. The laminate according to any one of claims 1 to 5, wherein the arithmetic mean roughness Ra of the surface of at least one of the metal layers is 0.03 μm or more and 0.20 μm or less.

7. The laminate according to claim 6, wherein the arithmetic mean roughness Ra is 0.05 μm or more and 0.15 μm or less.

8. The laminate according to any one of claims 1 to 7, wherein the maximum height roughness RzD of the surface of at least one of the metal layers is 0.15 μm or more and 1.50 μm or less.

9. The laminate according to any one of claims 1 to 8, wherein the resin layer contains one or more selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyamides (PA), modified polyphenylene ether (m-PPE), polypropylene (PP), polycarbonate (PC), polyimides (PI), fluororesins, liquid crystal polymers (LCP), and polyphenylene sulfide (PPS).

10. The laminate according to claim 9, wherein the resin layer contains one or more selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyamides (PA), modified polyphenylene ether (m-PPE), polyimides (PI), fluororesins, liquid crystal polymers (LCP), and polyphenylene sulfide (PPS).

11. The laminate according to any one of claims 1 to 10, wherein the resin layer is an unstretched film.

12. The laminate according to any one of claims 1 to 11, wherein the metal layer contains one or more selected from the group consisting of copper, copper alloys, aluminum, aluminum alloys, iron, and iron alloys.

13. The laminate according to claim 12, wherein the metal layer contains copper.

14. A laminate according to any one of claims 1 to 13, having a thickness of 16 μm or more and 900 μm or less.

15. A covering or exterior material for electrical and electronic equipment, comprising the laminate described in any one of claims 1 to 14.

16. An electrical or electronic device comprising the covering material or exterior material described in claim 15.

17. A method for manufacturing a laminate, comprising a lamination step of laminating at least one metal layer and at least one resin layer, wherein the lamination step involves laminating at least one resin layer having a crystallinity of 85.0% or less as measured by X-ray diffraction at diffraction angles of 10° to 35°.

18. The method for producing a laminate according to claim 17, wherein the degree of crystallinity is 60.0% or less.

19. The method for manufacturing a laminate according to claim 17 or 18, wherein the value obtained by subtracting the crystallinity of at least one resin layer used in the laminate, measured by X-ray diffraction at a diffraction angle of 10° to 35°, from the crystallinity of at least one resin layer of the laminate, measured by X-ray diffraction at a diffraction angle of 10° to 35°, is -20.0% or more and 60.0% or less.

20. The method for manufacturing a laminate according to any one of claims 17 to 19, wherein the lamination step involves laminating using at least one resin layer having a surface with an arithmetic mean roughness Ra of 0.1 μm or more and 1.5 μm or less.

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