Metal laminate sheet and printed circuit board comprising same

Abstract

The present invention relates to a metal laminate sheet and a printed circuit board, the metal laminate sheet comprising: a resin layer formed of a resin composition; and a metal foil disposed on at least one surface of the resin layer, the resin composition comprising: (a) a perfluoroalkoxy alkane (PFA); (b) at least one elastomer selected from the group consisting of styrene-based elastomers and fluorine-based elastomers; and (c) at least two inorganic fillers, wherein each of the at least two inorganic fillers satisfies specific relational expressions 1 and 2.

Description

Metal laminated sheet and printed circuit board comprising the same

[0001] The present invention relates to a metal laminate sheet and a printed circuit board including the same.

[0002] With the advent of hyper-connected intelligence driven by artificial intelligence, big data, and autonomous vehicles, the development and proliferation of various electronic devices, such as smartphones, has accelerated. This has led to the full-fledged adoption of next-generation 5G communications, capable of transmitting high-speed, large-capacity data wirelessly, replacing existing 4G LTE. In particular, the proliferation of autonomous vehicles, smart cities, and smart factories has made next-generation 5G communications technology essential for connecting large amounts of data and processing them in real time without delay. 5G operates at high frequencies (26 GHz and above), known as mmWave 5G, enabling the transmission of massive amounts of data simultaneously and achieving high-resolution, high-precision images. However, higher frequency bands in communication and electronic devices can lead to increased transmission loss of electrical signals, which can lead to issues such as heat generation, signal attenuation, and delays.

[0003] Accordingly, low-roughness copper foil was used in the past to minimize transmission loss of communication and electronic devices in the high-frequency to ultra-high-frequency range. However, when low-roughness copper foil was used, the adhesive strength between the copper foil and the resin layer was too low. Therefore, in the past, inorganic fillers with large average particle diameters were used to increase the adhesive strength between the copper foil and the resin layer. However, when the particle diameter of the inorganic filler was large, the filler in the resin layer increased the roughness of the copper foil surface due to heat and pressure during the lamination molding process with the copper foil, causing a problem in which signal transmission loss became uneven or increased, and the advantage of low-roughness copper foil disappeared. In addition, when processing into a printed circuit board, an inorganic filler with a large average particle diameter increased the inner wall roughness during the hole formation process, causing the plating surface to be uneven, resulting in a problem in reduced reliability.

[0004] The present invention seeks to provide a metal laminate sheet having low signal transmission loss while maintaining low permittivity and low dielectric loss.

[0005] In addition, the present invention seeks to provide a printed circuit board including the aforementioned metal laminate sheet.

[0006] In order to achieve the above object, the present invention provides a metal laminate sheet comprising: a resin layer formed of a resin composition; and a metal foil disposed on at least one surface of the resin layer; wherein the resin composition comprises (a) perfluoroalkoxy alkane (PFA), (b) at least one elastomer selected from the group consisting of a styrene-based elastomer and a fluorine-based elastomer, and (c) at least two inorganic fillers, wherein each of the at least two inorganic fillers satisfies the following relationships 1 and 2:

[0007] [Relationship 1]

[0008]

[0009] [Relationship 2]

[0010]

[0011] (In the above equations 1 and 2,

[0012] D1 is the average particle size of each weapon filler,

[0013] T1 is the thickness of the above resin layer,

[0014] D 90 (is the cumulative 90% particle size of each inorganic filler in the volume-based particle size distribution by laser diffraction particle size distribution measurement method).

[0015] Additionally, according to an example of the present invention, the metal laminate sheet may have a passive intermodulation distortion (PIMD) of -150 dBc or less.

[0016] In addition, according to another example of the present invention, the metal laminate sheet may have a roughness (Rz) of the inner wall surface of the via hole of 20 ㎛ or less after via hole processing and metal plating.

[0017] In addition, according to another example of the present invention, the rate of change in surface roughness of the metal foil before and after hot press processing (ΔRz / Rz1) may be in the range of 0 to 0.5. (Here, ΔRz = Rz1 - Rz2 and Rz1 are the surface roughness of the metal foil before hot press processing, and Rz2 is the surface roughness of the metal foil after hot press processing.

[0018] In addition, according to another example of the present invention, the perfluoroalkoxy alkane includes a tetrafluoroethylene repeating unit and a perfluoroether repeating unit, and the tetrafluoroethylene repeating unit and the perfluoroether repeating unit may be included in a molar ratio range of 1:10 to 1:10000.

[0019] In addition, according to another example of the present invention, the thickness of the resin layer may be in the range of 25 ㎛ to 760 ㎛.

[0020] In addition, according to another example of the present invention, the two or more types of inorganic fillers may each have an average particle diameter in the range of 0.1 to 5 μm.

[0021] In addition, according to an example of the present invention, the two or more types of inorganic fillers may include (c1) a first inorganic filler having an average particle diameter of 0.1 µm or more and less than 3 µm, and (c2) a second inorganic filler having an average particle diameter of 3 to 5 µm.

[0022] In addition, according to another example of the present invention, the first inorganic filler and the second inorganic filler may be included in a weight ratio of 99:1 to 50:50.

[0023] In addition, according to another example of the present invention, the resin composition may include 29 to 70 wt% of a perfluoroalkoxy alkane, 1 to 10 wt% of an elastomer, and 29 to 70 wt% of an inorganic filler, based on 100 wt% of the composition.

[0024] In addition, according to another example of the present invention, the metal foil may have a roughness (Rz) of the matte side in the range of 0.1 to 7 ㎛.

[0025] In addition, the present invention provides a printed circuit board including the aforementioned metal laminate sheet.

[0026] The metal laminated sheet according to the present invention has excellent adhesion to metal foil and low signal transmission loss while maintaining low permittivity and low dielectric loss characteristics, and can therefore be usefully used in printed circuit boards used in various electric, electronic, and communication devices such as mobile communication devices handling high-frequency to ultra-high-frequency signals, base station devices thereof, network-related electronic devices such as servers and routers, automotive radar devices, and large computers.

[0027] FIG. 1 is a cross-sectional view schematically showing a metal laminate sheet according to an example of the present invention.

[0028] <Explanation of symbols>

[0029] 10: Resin matrix,

[0030] 20: Weapon Filler,

[0031] 100: Metal laminated sheet,

[0032] 110: Resin layer,

[0033] 121: Metal foil, first metal foil,

[0034] 122: Second metal foil

[0035] Hereinafter, the present invention will be described.

[0036] All terms (including technical and scientific terms) used in this specification, unless otherwise defined, may be used in their common sense by those of ordinary skill in the art to which the present invention pertains. Furthermore, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless explicitly and specifically defined otherwise.

[0037] Throughout this specification, whenever a part is said to "include" a component, this should be understood as an open-ended term implying the possibility of including other components, rather than excluding other components, unless otherwise stated.

[0038] Additionally, throughout the specification, “above” or “on” means not only the case where the target part is located directly above or directly below it, but also the case where there is another part in between, and does not necessarily mean the position above with respect to the direction of gravity.

[0039] In addition, the terms “first”, “second”, etc. in this specification are not used to indicate any order or importance, but are used to distinguish components from each other.

[0040]

[0041] The metal laminate sheet according to the present invention can be applied to a printed circuit board, particularly a printed circuit board usable in a high frequency to ultra-high frequency band, and comprises a resin layer and a metal foil disposed on at least one surface of the resin layer.

[0042] According to an example, the metal laminate sheet (100) includes a resin layer (110) and first and second metal foils (121, 122) respectively disposed on both sides of the resin layer (110), as illustrated in FIG. 1.

[0043] However, in the present invention, it is intended to secure stability of signal transmission loss while maintaining the low permittivity and low dielectric loss characteristics of the resin layer (110). To this end, the present invention forms the resin layer (110) with a resin composition including (a) perfluoroalkoxy alkane (PFA), (b) at least one elastomer selected from the group consisting of styrene-based elastomers and fluorine-based elastomers, and (c) at least two inorganic fillers having different average particle diameters, while controlling the ratio of the average particle diameter of each inorganic filler to the thickness of the resin layer to be very small, and D of each inorganic filler 90 Also, it is adjusted very small. For this reason, the metal laminated sheet (100) of the present invention not only has a low dielectric constant and dielectric loss tangent in the frequency band of about 1 to 100 ㎓, but also has low signal transmission loss. Therefore, the metal laminated sheet of the present invention can minimize the transmission loss of a printed circuit board for high frequency to ultra-high frequency.

[0044] (1) Resin layer

[0045] In the metal laminate sheet of the present invention, the resin layer (110) is an insulating support member in which the resin composition is cured, and includes a resin matrix component (10) including a perfluoroalkoxy alkane and an elastomer; and two or more types of inorganic fillers (20). At this time, each inorganic filler in the two or more types of inorganic fillers (20) has a very small ratio of the average particle diameter of the inorganic filler to the thickness of the resin layer, and D 90 It is also very small.

[0046] Hereinafter, each component of the resin composition according to the present invention will be described.

[0047] (a) perfluoroalkoxy alkanes

[0048] In the resin composition of the present invention, perfluoroalkoxy alkane is a type of fluorine-containing fluorine (F)-based resin, which can realize low dielectric constant and low dielectric loss characteristics of the resin layer. This perfluoroalkoxy alkane is a solid particle-shaped filler at room temperature, and is bound by an elastomer when the resin composition is dried and incorporated into the resin layer. In a hot press process at about 310°C or higher, it melts to form a matrix component of the resin layer together with the elastomer. In addition, since perfluoroalkoxy alkane does not contain a dispersant, unlike a fluorine resin dispersion, it can improve the heat resistance and adhesiveness of the metal laminate sheet.

[0049] In one example, the perfluoroalkoxy alkane comprises a tetrafluoroethylene (C2F4) repeating unit and a perfluoroether (C2F3OR 1 , where R 1 Silver C1~C 12 It contains repeating units of perfluoroalkyl group.

[0050] At this time, the ratio of the tetrafluoroethylene repeating unit and the perfluoroether repeating unit is not particularly limited, and may be, for example, a molar ratio of 1:10 to 1:10000. However, when the ratio of the tetrafluoroethylene repeating unit and the perfluoroether repeating unit is within the above-mentioned range, the perfluoroalkoxy alkane may have a dielectric constant (Dk) of 2.2 or less and a dielectric loss tangent (Df) of 0.0003 or less.

[0051] The above perfluoroalkoxy alkane may have a melt flow rate (MFR) of about 1 to 30 g / 10 min at about 372°C and about 2 kg according to the ISO 1133-1 test method.

[0052] The more uniformly dispersed these perfluoroalkoxy alkanes are within the resin composition, the more they can improve the dielectric properties of the resin composition. Furthermore, they are suitable for manufacturing metal-laminated sheets through a simple coating process without high-temperature extrusion molding or high-temperature firing. Accordingly, in the present invention, it is preferable to control the shape, size (average particle diameter), and content of the perfluoroalkoxy alkanes within specific ranges.

[0053] Specifically, the shapes of perfluoroalkoxy alkanes include spherical, flake, dendrite, cone, pyramidal, and amorphous. Among these, when a spherical perfluoroalkoxy alkane is used, the surface area of ​​the filler is minimized, so the processing characteristics of the resin composition can be improved, and isotropic properties can be imparted to the resin layer.

[0054] In addition, the perfluoroalkoxy alkane may have an average particle size of about 0.1 to 100 μm, specifically, a range of 1 to 70 μm, and more specifically, a range of 5 to 50 μm. If the perfluoroalkoxy alkane has the above-described average particle size, the perfluoroalkoxy alkane is uniformly dispersed within the resin composition without agglomeration, making it suitable for producing a resin layer for a printed circuit board.

[0055] In the resin composition of the present invention, the content of perfluoroalkoxy alkane is not particularly limited. However, if the content of perfluoroalkoxy alkane is too low, the adhesive strength between the resin layer in the metal laminate sheet and the metal foil (e.g., copper foil) may decrease, resulting in peeling of the metal foil. On the other hand, if the content of perfluoroalkoxy alkane is too high, the coefficient of thermal expansion (CTE) of the resin layer may increase because the content of the inorganic filler is relatively low. Therefore, it is appropriate to adjust the content of perfluoroalkoxy alkane to a range of about 29 to 70 wt% based on the total amount (100 wt%) of the resin composition. In this case, the resin composition of the present invention can form a resin layer having excellent heat resistance and adhesiveness, as well as low permittivity and dielectric loss.

[0056] (b) elastomer

[0057] In the resin composition of the present invention, the elastomer is a binder capable of binding both the inorganic filler and the perfluoroalkoxy alkane. For example, the resin composition may include a thermoplastic elastomer. In this case, the thermoplastic elastomer melts during high-temperature pressing, facilitating the formation of a resin layer.

[0058] The elastomer according to the present invention comprises at least one selected from the group consisting of fluorine-based elastomers and styrenic elastomers. The fluorine-based elastomers and styrenic elastomers not only readily bind inorganic fillers and perfluoroalkoxy alkanes, but also have low dielectric properties. Specifically, the elastomer of the present invention has a dielectric loss tangent (Df) of 0.0005 to 0.0020 at 10 ㎓. In addition, the elastomer of the present invention has a dielectric constant (Dk) of 2.0 to 3.0 at 10 ㎓.

[0059] When the elastomer of the present invention having a low dielectric constant and a low dielectric tangent is used as a binder, a resin layer having a low dielectric loss can be easily formed by directly coating and drying the resin composition on a metal foil without a high-temperature extrusion molding process and a high-temperature firing process.

[0060] The fluorine-based elastomer of the present invention is a type of thermoplastic elastomer, and is an elastomer containing one or more fluorine (F) atoms in at least one repeating unit. This fluorine-based elastomer has a dielectric loss tangent (Df) of 0.0005 to 0.0020 and a permittivity of 2.0 to 3.0 at 10 ㎓, as well as a low modulus.

[0061] Examples of fluorinated elastomers usable in the present invention include, but are not limited to, copolymers comprising two or more selected from the group consisting of vinylidene fluoride (VDF), hexafluoropropylene (HFP), and tetrafluoroethylene (TFE); tetrafluoroethylene-propylene copolymers; vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymers; and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers. These may be used alone or in combination of two or more.

[0062] For example, the fluoroelastomer may be at least one selected from the group consisting of fluorocarbon-based fluoroelastomers (FKM) and perfluoroelastomers (FFKM), and specifically, a copolymer of hexafluoropropylene (HFP) and vinylidene fluoride (VDF), a copolymer of tetrafluoroethylene (TFE), hexafluoropropylene (HFP) and vinylidene fluoride (VDF), a copolymer of tetrafluoroethylene (TFE), fluorinated vinyl ether and vinylidene fluoride (VDF), a copolymer of tetrafluoroethylene (TFE), propylene and vinylidene fluoride (VDF), or a copolymer of tetrafluoroethylene (TFE), hexafluoropropylene (HFP), ethylene, fluorinated vinyl ether and vinylidene It may be at least one selected from the group consisting of a copolymer of fluorofluoroethylene (VDF), and a copolymer of tetrafluoroethylene (TFE) and fluorinated vinyl ether (e.g., perfluoromethylvinylether, PMVE).

[0063] The fluorine (F) content in the fluorine-based elastomer of the present invention is not particularly limited, but when it is in the range of about 60 to 80 wt% per molecule of the fluorine-based elastomer, the fluorine-based elastomer may have a dielectric constant at 10 GHz in the range of about 0.0005 to 0.0020.

[0064] The styrene-based elastomer of the present invention is a type of thermoplastic elastomer, and is an elastomer containing one or more styrene groups in at least one repeating unit. Such a styrene-based elastomer can have a dielectric loss tangent (Df) of 0.0005 to 0.0020 and a permittivity of 2.0 to 3.0 at 10 ㎓.

[0065] The styrene-based elastomer usable in the present invention is styrene and C2~C 10 It may be a copolymer elastomer of an aliphatic unsaturated hydrocarbon. Specifically, examples of styrenic elastomers include, but are not limited to, styrene-butadiene-styrene binary copolymer (SBS), styrene-ethylene-butylene-styrene terpolymer (SEBS), styrene-ethylene-ethylene-propylene-styrene terpolymer (SEEPS), styrene-isoprene-styrene binary copolymer, and styrene-ethylene-propylene-styrene terpolymer. These may be used alone or as a mixture of two or more.

[0066] The styrene group content in the styrene-based elastomer of the present invention is not particularly limited, but when it is in the range of about 10 to 40 wt% per molecule of the styrene-based elastomer, the styrene-based elastomer may have a dielectric constant at 10 GHz in the range of about 0.0005 to 0.0020.

[0067] The elastomer of the present invention may have a melt flow rate (MFR) of about 0.1 g / 10 min or less under conditions of 230°C and 2 kg according to the ISO 1133-1 test method. In addition, the viscosity of a solution in which 5 wt% of the elastomer of the present invention is dissolved in toluene is about 50 to 100 cps. Therefore, the resin composition of the present invention can improve processability when manufacturing a metal laminate sheet by controlling the viscosity within a range of about 150 to 500 cps.

[0068] The elastomer of the present invention has a high thermal decomposition temperature (Td) of about 350°C or higher. Therefore, the resin composition of the present invention can form a resin layer having excellent thermal stability at high temperatures.

[0069] In the resin composition of the present invention, the content of the elastomer is not particularly limited, and may be, for example, in the range of about 1 to 10 wt% based on the total amount of the resin composition. If the content of the elastomer is less than about 1 wt%, the binding effect of the inorganic filler and perfluoroalkoxy alkane may be reduced, and on the other hand, if the content of the elastomer exceeds about 10 wt%, the adhesion between the resin layer and the metal foil (e.g., copper foil) may be reduced, causing the metal foil to peel off during the manufacture and use of the metal laminated sheet.

[0070] (c) Weapon filler

[0071] The resin composition according to the present invention comprises an inorganic filler. The inorganic filler can effectively improve the warpage properties, low expansion, mechanical strength (toughness), and low stress of the final product by reducing the difference in coefficient of thermal expansion (CTE) between the resin layer formed from the resin composition and another layer (e.g., metal foil).

[0072] However, in the present invention, in order to minimize the change in surface roughness of the metal foil before and after the hot press process during the manufacture of the metal laminated sheet while minimizing the generation of parasitic frequencies and the occurrence of burrs on the inner wall of the via hole, two or more types of inorganic fillers having different average particle diameters are included, and each inorganic filler in the two or more types of inorganic fillers satisfies the following relationships 1 and 2.

[0073] [Relationship 1]

[0074]

[0075] [Relationship 2]

[0076]

[0077] (In the above equations 1 and 2,

[0078] D1 is the average particle size of each weapon filler,

[0079] T1 is the thickness of the above resin layer,

[0080] D 90(is the cumulative 90% particle size of each inorganic filler in the volume-based particle size distribution by laser diffraction particle size distribution measurement method).

[0081] The metal laminated sheet including two or more types of inorganic fillers can minimize the generation of parasitic frequencies with a passive intermodulation distortion (PIMD) of -150 dBc or less. In addition, since the metal laminated sheet of the present invention has a low roughness (Rz) of 20 ㎛ or less on the inner wall surface of the via hole during via hole processing and metal plating, a plating layer of uniform thickness can be formed. In addition, the metal laminated sheet of the present invention has a low rate of change in surface roughness of the metal foil before and after hot press processing (ΔRz / Rz1) in the range of 0 to 0.5, so that unevenness or increase in signal transmission loss is not caused. Here, ΔRz = Rz1 - Rz2, Rz1 is the surface roughness of the metal foil before hot press processing, and Rz2 is the surface roughness of the metal foil after hot press processing.

[0082] Specifically, the thickness (T1) of the resin layer is not particularly limited, and may be, for example, in the range of about 25 to 760 μm, specifically in the range of about 40 to 300 μm, and more specifically in the range of about 50 to 200 μm. Considering the thickness of the cured product of the resin composition, the two or more types of inorganic fillers may all have an average particle diameter in the range of about 0.1 to 5 μm.

[0083] The above two or more types of inorganic fillers may include inorganic fillers having different average particle sizes and / or components.

[0084] According to an example, the two or more types of inorganic fillers may include (a) a first inorganic filler having an average particle diameter of 0.1 μm or more and less than 3 μm, and (b) a second inorganic filler having an average particle diameter of 3 to 5 μm. In this case, the components of the first inorganic filler and the second inorganic filler may be the same or different.

[0085] The mixing ratio of the first and second inorganic fillers is not particularly limited. For example, the first and second inorganic fillers may be included in a weight ratio of 99:1 to 50:50, specifically, a weight ratio of 95:5 to 65:35. In this case, a resin layer having excellent electrical properties and excellent low dielectric loss characteristics at high frequencies in the mmWave range can be formed.

[0086] The above first inorganic filler may include at least one selected from the group consisting of (a1) a first A inorganic filler having an average particle diameter of 0.1 to 1 μm, and (a2) a first B inorganic filler having an average particle diameter of more than 1 μm and less than 5 μm. At this time, the components of the first A inorganic filler and the first B inorganic filler may be the same or different.

[0087] If the first inorganic filler includes both the first A inorganic filler and the first B inorganic filler, the mixing ratio of the first A inorganic filler and the first B inorganic filler is not particularly limited. For example, the first A inorganic filler and the first B inorganic filler may be included in a weight ratio of 99:1 to 50:50, specifically, a weight ratio of 70:30 to 50:50. In this case, the resin composition of the present invention may further improve adhesion to a metal foil (e.g., copper foil).

[0088] Non-limiting examples of inorganic fillers usable in the present invention include silica such as natural silica, fused silica, amorphous silica, crystalline silica, etc.; boehmite, alumina, talc, glass (e.g., spherical glass), calcium carbonate, magnesium carbonate, magnesia, clay, calcium silicate, titanium oxide, antimony oxide, glass fiber, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titania (e.g., TiO2), barium zirconate, calcium zirconate, boron nitride, silicon nitride, talc, mica, etc.

[0089] In one example, the first inorganic filler may contain a silicon-based filler. Specifically, the first inorganic filler may be silica (e.g., SiO2) such as natural silica, fused silica, amorphous silica, crystalline silica, or silicon nitride (Si3N4). In this case, the second inorganic filler may be a second silicon-based filler having a different composition and / or average particle size from the first inorganic filler. For example, the second inorganic filler may contain at least one selected from the group consisting of a second silicon-based filler different from the silicon-based filler, and a non-silicon-based filler.

[0090] Specifically, the two or more inorganic fillers may include (a) silica having an average particle size of 0.1 μm or more and less than 3 μm, and (b) alumina or titania having an average particle size of 3 to 5 μm.

[0091] These inorganic fillers can be used singly or in combination of two or more. Among them, silica, alumina, and titania have low dielectric loss factors, which can lower the permittivity and dielectric loss tangent of the resin layer while reducing the difference in thermal expansion coefficient between the resin layer and the metal foil.

[0092] In addition, the shape of the inorganic filler is not particularly limited, and includes, for example, spheres, flakes, dendrites, cones, pyramids, and amorphous shapes.

[0093] In the resin composition of the present invention, the content of the inorganic filler is not particularly limited and can be appropriately adjusted considering the aforementioned bending characteristics, mechanical properties, etc. However, excessive content of the inorganic filler may adversely affect formability and reduce the adhesive strength of the resin layer. For example, the content may be approximately 29 to 70 wt% based on the total weight of the resin composition.

[0094] Meanwhile, the resin composition of the present invention may further include additives such as flame retardants, other thermosetting resins or thermoplastic resins, ultraviolet absorbers, antioxidants, polymerization initiators, dyes, pigments, dispersants, thickeners, leveling agents, colorants, etc. known in the art, in addition to the aforementioned elastomer, perfluoroalkoxy alkanes, and inorganic fillers, as needed, within a range that does not impair the physical properties thereof. The content of the additives may be used as known in the art, and may be, for example, about 0.0001 to 10 wt% based on the total amount of the resin composition.

[0095] The viscosity of the resin composition according to the present invention can be adjusted depending on the type or content of the elastomer, perfluoroalkoxy alkane, and inorganic filler in the composition, and may be, for example, about 150 to 500 cps. In one example, when the resin composition has the viscosity described above, a resin layer can be directly formed on a metal foil by a roll-to-roll coating method.

[0096] As described above, the resin composition of the present invention can easily form a metal laminate sheet having a low dielectric constant and low dielectric loss, and including a resin layer having excellent stability of signal transmission loss, by directly coating and drying on a metal foil without a film forming process (paste extrusion, via hole processing) and a high-temperature firing process during the manufacture of the metal laminate sheet. In addition, the resin composition of the present invention can be applied to substrates of various materials, and for example, can be applied to a polyimide (PI) substrate material to manufacture a flexible metal laminate sheet.

[0097] The resin layer (110) of the present invention may have a dielectric constant (Dk) of about 1.0 to 10.0 and a dielectric loss tangent (Df) of about 0.0001 to 0.0100 at 10 ㎓.

[0098] In addition, the adhesive strength of the resin layer (110) with the first and second metal foils (121, 122) is approximately 0.4 to 1.0 kgf / cm, which is higher than the standard (0.35 kgf / cm) required in the industry. Therefore, even if the surface roughness of the metal foil in contact with the resin layer is low, the present invention can reduce the peeling between the resin layer and the metal foil.

[0099] In addition, the resin layer (110) may have a coefficient of thermal expansion (CTE) of about 15 to 50 ppm / ℃. Therefore, the metal laminated sheet of the present invention can effectively improve the bending characteristics, low expansion, mechanical strength (toughness), and low stress of a printed circuit board.

[0100] In addition, the thickness of the resin layer (110) is not particularly limited, and may be, for example, about 25 to 760 μm, specifically about 40 to 300 μm, and more specifically about 50 to 200 μm. At this time, it is appropriate to adjust the thickness of the resin layer in consideration of the thickness of the metal foil and the metal laminate sheet.

[0101] (2) First and second metal foils

[0102] In the metal laminate sheet of the present invention, the first metal foil (121) is disposed on one surface of the resin layer (110), and the second metal foil (122) may optionally be disposed on the other surface of the resin layer (110). At this time, the first metal foil (121) and the second metal foil (122) may be the same or different from each other.

[0103] In the present invention, the first and second metal foils (121, 122) can be used without any particular limitation as long as they are conventional metal components in the art that can be applied to metal laminate sheets or printed circuit boards. For example, each metal foil can be a metal thin film selected from the group consisting of copper (Cu), iron (Fe), nickel (Ni), titanium (Ti), aluminum (Al), silver (Ag), and gold (Au), or an alloy thin film of two or more types. For example, the first and second metal foils (121, 122) can be copper foils that have excellent electrical conductivity and are inexpensive. At this time, the copper foil can be used without limitation as a conventional copper foil known in the art, and all copper foils manufactured by a rolling method and an electrolytic method can be used.

[0104] In addition, the first and second metal foils have a matte side in contact with the resin layer, and the roughness (Rz) of the matte side may be about 0.1 to 7 ㎛, specifically about 0.3 to 5 ㎛, and more specifically about 0.3 to 3 ㎛. In this case, the present invention exhibits excellent transmission characteristics in the high frequency to ultra-high frequency range.

[0105] The thickness of the above metal foil is not particularly limited, and may be in the range of about 9 to 70 ㎛ in consideration of the thickness and mechanical properties of the final metal laminate sheet.

[0106] The metal laminate sheet of the present invention described above may have a passive intermodulation distortion (PIMD) of -150 dBc or less, specifically, in the range of -170 dBc to -150 dBc. Here, the passive intermodulation distortion is measured according to Experimental Example 1 below. Therefore, a printed circuit board using the metal laminate sheet of the present invention may have minimized signal transmission loss.

[0107] In addition, the metal laminated sheet of the present invention has a low burr generation on the inner wall of the via hole when the via hole is processed. For example, the roughness (Rz) of the inner wall surface of the via hole may be about 20 ㎛ or less, specifically 3 to 20 ㎛. Here, the roughness of the inner wall surface of the via hole is measured according to Experimental Example 5 below. Therefore, the metal laminated sheet of the present invention can form a plating layer of uniform thickness when metal plating is performed after the via hole is processed. In addition, the present invention does not require an additional deburring process to remove the burr.

[0108] In addition, the metal laminated sheet of the present invention may have a change rate (ΔRz / Rz1) of the roughness of the metal foil before and after the hot press processing in the range of 0 to 0.5 (wherein, ΔRz= Rz1-Rz2, Rz1 is the surface roughness of the metal foil before the hot press processing, and Rz2 is the surface roughness of the metal foil after the hot press processing). Here, the surface roughness of the metal foil before the hot press processing is the roughness of the matte surface of the metal foil as a raw material, and the surface roughness of the metal foil after the hot press processing was measured by micro-sectioning the metal laminated sheet itself and observing the cross-section with an optical microscope to measure the roughness of the matte surface of the metal foil, and calculating the difference in roughness after the hot press processing compared to before the hot press processing.

[0109] Meanwhile, the metal laminated sheet of the present invention described above can be manufactured by various methods known in the art.

[0110] For example, a metal laminated sheet (e.g., a copper foil laminated sheet) can be manufactured by a method including a step of directly applying the above-described resin composition onto one surface of a metal substrate (e.g., a copper thin film) and drying it to manufacture two resin-attached metal foils having a resin layer formed on one surface of the metal substrate; and a step of laminating and hot-pressing the two resin-attached metal foils so that the resin layers are in contact with each other. However, the present invention is not limited to the above-described manufacturing method, and the steps of each process may be modified or selectively mixed and performed as needed.

[0111] The method for applying the above resin composition is not particularly limited, and includes, for example, a roll-to-roll coating method, and specifically, comma coating, slot die coating, curtain coating, etc.

[0112] The drying process of the above resin composition is performed at a temperature of about 50 to 200°C for about 2 to 20 minutes, thereby forming a resin layer on the metal substrate. In this way, the present invention only dries the resin composition before the pressing process, and does not perform a high-temperature firing process of 350°C or higher.

[0113] The two resin-attached metal foils described above may be identical or different, and include a metal substrate and a resin layer disposed on one surface of the metal substrate. In this case, the metal substrate and / or resin layer of each resin-attached metal foil may be identical or different.

[0114] The lamination and hot press process between the above resin-attached metal foils can be performed at a temperature of about 280 to 370°C and a pressure of about 10 to 50 kgf / cm2 for about 3 to 60 minutes. For example, by hot-pressing the laminated resin-attached metal foils under the above-described conditions using a hot press device equipped with a heating plate having the above-described temperature conditions, a metal laminate sheet in which the resin layers are pressed can be obtained. In particular, when laminating and pressing at a temperature of about 280 to 370°C, since the perfluoroalkoxy alkane in the resin layer of each resin-attached metal foil melts, the interlayer adhesive force between the resin layers increases, so that the resin layers can be integrated.

[0115] Before and after the hot press process, the change in surface roughness of the metal foil is low. For example, the change rate of surface roughness of the metal foil before and after the hot press process (ΔRz / Rz1) can be in the range of 0 to 0.5 (where ΔRz = Rz1 - Rz2, Rz1 is the surface roughness of the metal foil before hot pressing, and Rz2 is the surface roughness of the metal foil after hot pressing). As such, the resin composition of the present invention has a very small ratio of the average particle diameter of the inorganic filler to the thickness of the resin layer. Therefore, the metal foil is not locally pressed by the inorganic filler, and therefore, there is almost no change in the roughness of the metal foil, so the metal foil in the metal laminated sheet of the present invention can maintain a low roughness before and after hot pressing, and therefore, no unevenness or increase in transmission loss is caused.

[0116]

[0117] Printed circuit board

[0118] Meanwhile, the present invention provides a printed circuit board including the aforementioned metal laminate sheet.

[0119] For example, a printed circuit board includes the metal laminate sheet, and a circuit pattern may be formed on a metal foil (first metal foil and / or second metal foil) included in the metal laminate sheet. In this case, a resin layer included in the metal laminate sheet serves as an insulating support member.

[0120] As another example, a printed circuit board includes the metal laminate sheet; and one or more unit laminates disposed on the metal laminate sheet, wherein the unit laminates include a second resin layer and a third metal foil disposed on the second resin layer. In this case, the second resin layer is an interlayer resin layer, and may be a resin layer formed of the resin composition described above, or a resin layer formed of a resin known in the art, such as polyimide.

[0121] The printed circuit board of the present invention can be manufactured by a conventional method known in the art. For example, it can be manufactured by opening a hole in the aforementioned metal laminate sheet, performing through-hole plating, and then etching a metal foil including the plating film to form a circuit.

[0122] Since the printed circuit board of the present invention described above includes a metal laminate sheet having a low permittivity and dielectric loss tangent in a frequency band of about 1 GHz to 100 GHz, the dielectric loss in the frequency band of about 1 GHz to 100 GHz is small, and thus the transmission loss is also low. Therefore, the printed circuit board of the present invention can be usefully applied to various electric, electronic, and communication devices such as mobile communication devices handling high-frequency or ultra-high-frequency signals, base station devices thereof, network-related electronic devices such as servers and routers, large computers, and automotive radar devices.

[0123]

[0124] Hereinafter, the present invention will be described in detail through examples, but the following examples and experimental examples are merely illustrative of one form of the present invention, and the scope of the present invention is not limited to the following examples and experimental examples.

[0125] <Example 1> - Manufacturing of copper-clad laminated sheet

[0126] The resin composition of Example 1 having the composition shown in Table 1 below was applied to one side of a copper foil [roughness of matte surface (Rz): 6 ㎛] to a thickness of 75 ㎛, and then dried at 140°C for 10 minutes to obtain a resin-coated copper (RCC). Thereafter, two resin-coated copper foils were laminated so that the resin layers were in contact with each other, and then hot-pressed (temperature of the hot plate: 340°C, pressure: 30 kgf / cm2) for 30 minutes to produce a copper-coated laminated sheet. In Tables 1 and 2 below, the content unit of each component is wt%, based on the total amount of the resin composition (100 wt%). In Tables 1 and 2 below, D1 / T1 means the ratio of the average particle diameter (D1) of each inorganic filler to the thickness (T1) of the resin layer. In addition, the average particle diameter of the above-mentioned inorganic filler was measured according to the ASTM D4464 test standard, and the roughness of the matte surface of the above-mentioned copper foil was measured according to the IPC-TM-650 2.2.17 test standard.

[0127]

[0128] <Examples 2-3>

[0129] A copper-clad laminated sheet was manufactured in the same manner as in Example 1, except that the resin compositions of Examples 2 and 3 having the compositions shown in Table 1 below were used instead of the resin composition used in Example 1.

[0130]

[0131] <Example 4>

[0132] A copper-clad laminated sheet was manufactured in the same manner as in Example 1, except that the resin composition of Example 4 having the composition of Table 2 below was used instead of the resin composition used in Example 1, and the copper foil [roughness of matte surface (Rz): 6 ㎛] used in Example 1 was used instead of the copper foil [roughness of matte surface (Rz): 1.7 ㎛] described in Table 2 below.

[0133]

[0134] <Examples 5-6>

[0135] A copper-clad laminated sheet was manufactured in the same manner as in Example 1, except that the resin compositions of Examples 5 and 6 having the compositions shown in Table 2 below were used instead of the resin composition used in Example 1, and the copper foil [roughness of matte surface (Rz): 6 ㎛] used instead of the copper foil used in Example 1 [roughness of matte surface (Rz): 1.7 ㎛] described in Table 2 below was used.

[0136]

[0137] Comparative Examples 1-5

[0138] A copper-clad laminated sheet was manufactured in the same manner as in Example 1, except that the resin compositions of Comparative Examples 1 to 5 having the compositions shown in Table 1 below were used instead of the resin composition used in Example 1.

[0139]

[0140] Comparative Examples 6-10

[0141] A copper-clad laminated sheet was manufactured in the same manner as in Example 1, except that the resin compositions of Comparative Examples 6 to 10 having the compositions shown in Table 2 below were used instead of the resin composition used in Example 1, and the copper foil [roughness of matte surface (Rz): 6 ㎛] used instead of the copper foil used in Example 1 [roughness of matte surface (Rz): 1.7 ㎛] described in Table 2 below was used.

[0142]

[0143] Comparative Example 12312345 Resin layer Resin composition PFA404040404040404040 FKM22222222 Inorganic filler SiO2 (D1 / T1) * 100 (%) Approximately 0.2754-27-----D 90 (㎛)0.9SiO2(D1 / T1)*100 (%)about 2.7-5427--271854D 90 (㎛)5SiO2(D1 / T1)*100 (%)about 13-----2718-D 90 (㎛)30SiO2(D1 / T1)*100 (%)about 33---545418--D 90 (㎛)53TiO2(D1 / T1)*100 (%)44444--4-D 90 (㎛)9.5TiO2(D1 / T1)*100 (%)about 27----44-4D 90 (㎛)40Thickness(T1)(㎛)7575757575757575Roughness(Rz)of matte surface of copper foil layer(㎛)66666666* PFA: perfluoroalkoxy alkane [Tm: 315 ℃, MFR: 1~30 g / 10min, average particle size: 30 ㎛, Df(10 GHz): 0.0002, Dk(10 GHz): 2.1]* FKM: fluorocarbon-based fluoroelastomer [Df(10 GHz): about 0.0020, Dk(10 GHz): about 3.0, F content: 66 wt% per molecule, thermal decomposition temperature: about 390 ℃]

[0144] Comparative Example 456678910 Resin layer Resin composition PFA404040404040404040 FKM22222222 Inorganic filler SiO2 (D1 / T1) * 100 (%) Approximately 0.2754-27-----D 90 (㎛)0.9SiO2(D1 / T1)*100 (%)about 2.7-5427--271854D 90 (㎛)5SiO2(D1 / T1)*100 (%)about 13-----2718-D 90 (㎛)30SiO2(D1 / T1)*100 (%)about 33---5454-18-D 90 (㎛)53TiO2(D1 / T1)*100 (%)44444-4--D 90(㎛)9.5TiO2(D1 / T1)*100 (%)about 27----4-44D 90 (㎛)40Thickness(T1)(㎛)7575757575757575Roughness(Rz)of matte surface of copper foil layer(㎛)1.71.71.71.71.71.71.71.71.7* PFA: perfluoroalkoxy alkane [Tm: 315 ℃, MFR: 1~30 g / 10min, average particle size: 30 ㎛, Df(10 GHz): 0.0002, Dk(10 GHz): 2.1]* FKM: fluorocarbon-based fluoroelastomer [Df(10 GHz): about 0.0020, Dk(10 GHz): about 3.0, F content: 66 wt% per molecule, thermal decomposition temperature: about 390 ℃]

[0145]

[0146] <Experimental Example 1> - Passive Intermodulation Distortion (PIMD)

[0147] The passive intermodulation distortion of printed circuit boards including the copper-clad laminated sheets of Examples 1 to 6 and Comparative Examples 1 to 10 was measured as follows, and the results are shown in Tables 3 and 4, respectively.

[0148] A printed circuit board was formed by forming a Cu circuit layer (impedance: 50 Ω) on a copper-clad laminated sheet. After inputting frequencies of 3630 MHz and 3660 MHz to the printed circuit board, the magnitude of the reflected signal of 43 dBm was measured.

[0149] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PIMD (dBc) - 154 - 151 - 153 - 133 - 131 - 134 - 138 - 140

[0150] Example 4 Example 5 Example 6 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 PIMD (dBc) - 168 - 158 - 160 - 132 - 131 - 136 - 137 - 145

[0151] As can be seen in Tables 3 and 4, the printed circuit boards including the copper-clad laminate sheets of Examples 1 to 6 had a PIMd of -150 dBc or less, whereas the printed circuit boards including the copper-clad laminate sheets of Comparative Examples 1 to 10 had a PIMd of -145 dBc or more. Thus, it was confirmed that when the resin composition according to the present invention is applied as a resin layer to a copper-clad laminate sheet and a printed circuit board, the occurrence of parasitic frequencies is low, thereby preventing deterioration in transmission and reception quality.

[0152]

[0153] <Experimental Example 2> - Peel Strength (P / S)

[0154] The peel strength between the resin layer and the copper foil in the copper foil laminated sheets of Examples 1 to 6 and Comparative Examples 1 to 10 was measured according to the test standard of IPC TM-650.2.4.8, and the measurement results are shown in Tables 5 and 6 below.

[0155] Standard implementation preliminary comparison example 12312345P / S (kgf / cm) 0.35 or more 0.6 1.0 0.7 1.5 1.5 1.5 1.3 1.1

[0156] Standard implementation preliminary comparison example 456678910P / S (kgf / cm) 0.35 or more 0.40.90.61.31.41.11.31.0

[0157] As can be seen in Tables 5 and 6, the copper-clad laminate sheets of Examples 1 to 6 had lower peel strength between the resin layer and the copper foil than the copper-clad laminate sheets of Comparative Examples 1 to 10. However, the specifications required by the industry were satisfied.

[0158]

[0159] <Experimental Example 3> - Dielectric constant and dielectric loss tangent

[0160] The dielectric constant (Dk) and dielectric loss tangent (Df) of the resin layer in the copper-clad laminated sheets of Examples 1 to 3 and Comparative Examples 1 to 5 were measured according to the test standards of IEC 61189-2-721:2015, and the results are shown in Table 7.

[0161] At this time, the copper foil laminated sheet was immersed in an etching solution (hydrochloric acid: hydrogen peroxide = 1:2 volume ratio) to remove the copper foil, and then the dielectric constant (Dk) and dielectric loss tangent (Df) of the resin layer at a frequency of 10 ㎓ were measured using a dielectric constant measuring device (RF Impedence / Material Analyzer; Agilent).

[0162] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Dielectric constant (Dk, @10㎓) 2.97 3.00 3.02 3.03 3.08 3.07 3.03 3.06 Dielectric factor (Df, @10㎓) 0.0012 0.0013 0.0013 0.0013 0.0017 0.0016 0.0013 0.0015

[0163] As can be seen in Table 7, the dielectric constant and dielectric loss tangent of the resin layer in the copper-clad laminated sheets of Examples 1 to 3 were the same or similar to those of the resin layer in the copper-clad laminated sheets of Comparative Examples 1 to 5. As such, it was confirmed that the resin composition of the present invention has excellent low dielectric loss characteristics even if it includes two or more types of inorganic fillers having small average particle diameters.

[0164]

[0165] <Experimental Example 4> - Signal Loss

[0166] A circuit layer (impedance: 50 Ω) was formed on each of the copper-clad laminate sheets manufactured in Examples 1 to 6 and Comparative Examples 1 to 10. Thereafter, the transmission loss at a frequency of 77 GHz was measured for the copper-clad laminate sheets on which the circuit layers were formed using a dielectric constant measuring device (Vector Network Analyzer, Keysight N5225B) according to the test standard of IPC TM 2.5.5.14. At this time, the dB (Log magnitude) values ​​were calculated using the S-Parameter values ​​of S21 and S12, and are shown in Tables 8 and 9.

[0167] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Signal Loss (dB / inch) - 2.09 - 2.10 - 2.10 - 2.11 - 2.15 - 2.18 - 2.12 - 2.15

[0168] Example 4 Example 5 Example 6 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Signal Loss (dB / inch) - 1.58 - 1.60 - 1.62 - 1.63 - 1.70 - 1.61 - 1.70 - 1.68

[0169] As shown in Tables 8 and 9, the copper-clad laminated sheets of Examples 1 to 3 had lower signal loss than the copper-clad laminated sheets of Comparative Examples 1 to 5 that used the same copper foil. In addition, the copper-clad laminated sheets of Examples 4 to 6 had lower signal loss than the copper-clad laminated sheets of Comparative Examples 6 to 10 that used the same copper foil. In addition, the copper-clad laminated sheets of Examples 4 to 6 had lower signal loss than the copper-clad laminated sheets of Examples 1 to 3 that used copper foil with a higher roughness of the matte surface.

[0170] In this way, it was confirmed that when the resin composition according to the present invention is applied to a copper-clad laminated sheet, stability of signal transmission loss can be secured.

[0171]

[0172] <Experimental Example 5> - Hole Wall Roughness

[0173] The copper-clad laminate sheets of Examples 4 to 6 and Comparative Examples 6 to 10 were processed with laser via holes and then copper (Cu) plated. Thereafter, the surface roughness (Rz) of the inner wall of the formed hole was measured as follows, and the results are shown in Table 10.

[0174] The surface roughness (Rz) of the inner wall of a hole in a plated copper-clad laminate sheet was quantified by micro-sectioning the hole using an optical microscope. The hole was an inverted trapezoid, and when the upper and lower starting points of the hole were drawn in a straight line, the degree (height) (㎛) at which a burr protruded into the hole was measured, and the surface roughness (Rz) of the inner wall of the hole was obtained using this.

[0175] Example 4 Example 5 Example 6 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Hole wall roughness (㎛) 5663132263028

[0176] As can be seen in Table 10, the copper-clad laminated sheets of Examples 4 to 6 had much lower surface roughness of the inner wall of the hole compared to the copper-clad laminated sheets of Comparative Examples 6 to 10. As such, it was confirmed that when the resin composition of the present invention was applied to the copper-clad laminated sheet, a plating layer was formed with a uniform thickness on the inner wall of the hole when the hole was drilled, and further, there was no need to additionally perform a deburring process to remove burrs.

[0177]

[0178] <Experimental Example 6> - Changes in the surface roughness of metal foil before and after hot press processing

[0179] The surface roughness of the metal foil in the copper-clad laminated sheets of Examples 1 to 6 and Comparative Examples 1 to 3 and 6 to 10 was measured to determine whether there was a change before and after hot press processing, as follows, and the results are shown in Table 11.

[0180] The copper foil laminate sheets manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 and 6 to 10 were micro-sectioned and the cross-sections were observed with an optical microscope to measure the surface roughness (Rz) of the copper foil after hot press processing, and the difference (ΔRz) with the roughness of the copper foil before processing was calculated. Here, the surface roughness (Rz) is the ten-point average roughness.

[0181] Surface roughness of copper foil before processing (Rz1) (㎛) Surface roughness of copper foil after processing (Rz2) (㎛) ΔRz / Rz1 Example 1660.00 Example 266.50.08 Example 366.50.08 Comparative example 16110.83 Comparative example 26121.00 Comparative example 36100.67 Example 41.71.70.00 Example 51.72.50.47 Example 61.72.20.29 Comparative example 61.783.71 Comparative example 71.794.29 Comparative example 81.751.94 Comparative example 91.773.12 Comparative example 101.762.53

Claims

1. A resin layer formed of a resin composition; and a metal foil disposed on at least one surface of the resin layer; The above resin composition (a) perfluoroalkoxy alkane (PFA); (b) at least one elastomer selected from the group consisting of styrenic elastomers and fluoroelastomers; and (c) Two or more types of inorganic fillers Including, but not limited to, A metal laminated sheet in which each of the two or more types of inorganic fillers satisfies the following relationships 1 and 2: [Relationship 1] [Relationship 2] (In the above equations 1 and 2, D1 is the average particle size of each weapon filler, T1 is the thickness of the above resin layer, D 90 (is the cumulative 90% particle size of each inorganic filler in the volume-based particle size distribution by laser diffraction particle size distribution measurement method).

2. In paragraph 1, A metal laminate sheet having a passive intermodulation distortion (PIMD) of -150 dBc or less.

3. In paragraph 1, A metal laminate sheet, wherein the roughness (Rz) of the inner wall of the via hole is 20 ㎛ or less after via hole processing and metal plating.

4. In paragraph 1, When manufacturing the metal laminated sheet, the change rate of the surface roughness of the metal foil before and after hot press processing (ΔRz / Rz1) is in the range of 0 to 0.5, the metal laminated sheet (wherein, ΔRz = Rz1 - Rz2 and Rz1 are the surface roughness of the metal foil before hot press processing, and Rz2 is the surface roughness of the metal foil after hot press processing.

5. In paragraph 1, The above perfluoroalkoxy alkane contains tetrafluoroethylene repeating units and perfluoroether repeating units, A metal laminated sheet, wherein the tetrafluoroethylene repeating unit and the perfluoroether repeating unit are included in a molar ratio range of 1:10 to 1:10000.

6. In paragraph 1, A metal laminated sheet, wherein the thickness of the resin layer is in the range of 25 to 760 ㎛.

7. In paragraph 1, A metal laminated sheet, wherein the two or more types of inorganic fillers each have an average particle diameter in the range of 0.1 to 5 ㎛.

8. In paragraph 1, The above two or more types of inorganic fillers (a) a first inorganic filler having an average particle diameter of 0.1 ㎛ or more and less than 3 ㎛, and (b) a second inorganic filler having an average particle diameter of 3 to 5 μm; A metal laminate sheet comprising:

9. In paragraph 8, The above first weapon filler A first A inorganic filler having an average particle size of 0.1 to 1 ㎛, and Type 1B inorganic filler having an average particle size of more than 1 ㎛ and less than 3 ㎛ A metal laminate sheet comprising:

10. In paragraph 8, A metal laminate sheet, wherein the first inorganic filler contains a silicon-based filler.

11. In paragraph 8, A metal laminated sheet, wherein the second inorganic filler contains at least one selected from the group consisting of a silicon-based filler different from the first inorganic filler and a non-silicon-based filler.

12. In paragraph 8, A metal laminate sheet comprising the first inorganic filler and the second inorganic filler in a weight ratio of 99:1 to 50:

50.

13. In paragraph 1, The above resin composition Based on 100% by weight of the composition 29-70 wt% perfluoroalkoxy alkane, 1 to 10 wt% of an elastomer, and 29~70 wt% inorganic filler A metal laminate sheet comprising:

14. In paragraph 1, The above metal foil is a metal laminate sheet having a roughness (Rz) of the matte side in the range of 0.1 to 7 ㎛.

15. A printed circuit board comprising a metal laminate sheet according to any one of claims 1 to 14.

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