Copper-clad laminate film and electronic device including the same

Abstract

Disclosed is a copper-clad laminate film and an electronic device including the same. The copper-clad laminate film includes: a polyimide substrate in which a fluorine layer is provided on at least one surface; a tie layer provided on the polyimide substrate on which the fluorine layer is provided; and a copper layer provided on the tie layer, wherein the tie layer includes at least one selected from the group consisting of Group 4, Group 6, Group 13, and Group 14 metal elements of the periodic table, and a metal-oxygen (M-O) bond dissociation energy of the metal elements is greater than or equal to 400 kJ / mol.

Description

[0001] Cross-references to related applications

[0002] This application claims priority and benefit to Korean Patent Application No. 10-2021-0144004, filed on October 26, 2021, which is incorporated herein by reference for all purposes as fully set forth herein. Technical Field

[0003] The invention relates to a copper-clad laminate and an electronic device comprising the same. Background Technology

[0004] Copper-clad laminates are laminates of a substrate and conductive copper foil. With the trend towards miniaturization and lightweighting of electronic devices, the use of copper-clad laminates has increased. The recent development of 5G mobile communication devices has made GHz band signal transmission speeds increasingly common. There is a need to improve the dielectric properties of substrates used in printed circuits or antenna components and reduce thermal expansion characteristics to meet this trend of higher signal frequencies. Simultaneously, copper-clad laminates need to exhibit excellent chemical resistance in acidic and / or alkaline environments without affecting the etching performance of circuit patterns. Therefore, there remains a need for copper-clad laminates with low coefficients of thermal expansion, low dielectric constants, low dielectric losses, and low transmission losses at high frequencies, while also possessing excellent etching and chemical resistance, and for the electronic devices incorporating them. Summary of the Invention

[0005] On the one hand, a copper-clad laminate is provided, which has a low coefficient of thermal expansion, low dielectric constant, low dielectric loss and low transmission loss at high frequencies, and at the same time has excellent etch resistance and chemical resistance.

[0006] On the other hand, an electronic device is provided that includes the copper-clad laminate.

[0007] According to one aspect, a copper-clad laminate is provided, comprising:

[0008] A polyimide substrate, wherein a fluorine layer is disposed on at least one surface;

[0009] A tie layer disposed on the polyimide substrate on which a fluorine layer is disposed; and

[0010] A copper layer is disposed on the connection layer.

[0011] The connecting layer includes at least one metallic element selected from Groups 4, 6, 13, and 14 of the periodic table.

[0012] The metal-oxygen (M-O) bond dissociation energy of the metal element is greater than or equal to 400 kJ / mol.

[0013] The metal element can include at least one selected from W, Ti, Sn, Cr, Al, and Mo.

[0014] The metal element can further include Ni, and the content of the Ni can be less than or equal to 50 wt%.

[0015] The thickness of the polyimide substrate provided with the fluorine layer can be about 25 μm to about 100 μm.

[0016] The thickness of the fluorine layer can be less than or equal to 50% based on the thickness 100% of the polyimide substrate provided with the fluorine layer.

[0017] The fluorine content of the surface of the polyimide substrate provided with the fluorine layer can be about 60 atomic% to about 75 atomic%.

[0018] The surface energy of the polyimide substrate provided with the fluorine layer can be about 11 dyne / cm to about 19 dyne / cm.

[0019] The polyimide substrate provided with the fluorine layer can have a dielectric constant (D k ) of less than or equal to 2.8 and a dielectric loss (D f ) of less than or equal to 0.003 at a frequency of 20 GHz.

[0020] The coefficient of thermal expansion of the polyimide substrate provided with the fluorine layer can be less than or equal to 25 ppm / °C.

[0021] According to another aspect,

[0022] An electronic device is provided, which includes the above-described copper-clad laminate film.

[0023] The electronic device can include an antenna device or an antenna cable. BRIEF DESCRIPTION OF DRAWINGS

[0024] The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the application and together with the description serve to explain the principles of the application.

[0025] Figure 1 is a schematic cross-sectional view of a copper-clad laminate film according to a specific embodiment.

[0026] Figure 2 is a schematic cross-sectional view of a copper-clad laminate film according to another specific embodiment. DETAILED DESCRIPTION

[0027] Hereinafter, the copper-clad laminate film and the electronic device including the same will be described in detail with reference to the embodiments of the present application and the accompanying drawings. It will be obvious to those skilled in the art that these embodiments are illustrative only and the scope of the present application is not limited to these embodiments.

[0028] Unless otherwise defined, all technical and scientific terms used in the specification have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. If there is a conflict between the definitions in the specification and those in the accompanying claims, the definitions in the accompanying claims shall control.

[0029] Methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, but suitable methods and materials are described in the specification.

[0030] Unless specifically noted, the term "comprising" in the specification is used to mean that other constituents can be added to the composition without excluding other constituents.

[0031] In the specification, the term "and / or" is intended to include any and all combinations of one or more of the associated listed items. In the specification, the term "or" means "and / or". In the specification, the expression "at least one of" or "one or more of" preceding a list of components does not mean that the entire list of components can be supplemented, but each component recited in the above description can be supplemented.

[0032] In the specification, the "polyimide base material" means both "polyimide base material" and "polyimide-containing derived base material".

[0033] In the specification, when a component is said to be "on" another component, it can be directly on the other component, or there can be intervening components between the components. On the other hand, when a component is said to be "directly on" another component, there can be no intervening components.

[0034] In the electronic device, the antenna device is generally manufactured by laminating a metal layer such as a copper foil, which generates a current of a wireless signal, on a base material.

[0035] Losses associated with antenna signal reception include losses due to the dielectric constant of the substrate and signal losses due to resistive physics when the wireless signal (i.e., an electrical signal) flows through the metal layer. Compared to wireless signals with relatively low frequency bands, for wireless signals with higher frequency bands, the current passing through the wireless signal is more concentrated on the surface of the metal layer. Furthermore, in copper-clad laminates with a stacked configuration, physical stress is generated in the copper foil in the curved areas of the antenna device, leading to cracks on its surface. As a result, transmission losses may occur. In addition, substrates with a coefficient of thermal expansion exceeding 25 ppm / °C may experience peeling or cracking due to the difference in thermal expansion coefficients compared to the conductive copper foil. On the other hand, with the trend towards miniaturization and lightweighting of electronic devices, the necessity for realizing microcircuit patterns is increasing. Therefore, properties requiring excellent chemical resistance in acidic and / or alkaline environments are demanded without affecting pattern etchability.

[0036] In order to address these problems and needs, the inventors of this invention intend to propose the following copper-clad laminate.

[0037] A copper-clad laminate according to a specific embodiment may include: a polyimide substrate, wherein a fluorine layer is disposed on at least one surface; a tie layer disposed on the polyimide substrate on which the fluorine layer is disposed; and a copper layer disposed on the tie layer, wherein the tie layer may include at least one metal element selected from Groups 4, 6, 13, and 14 of the periodic table, and the metal-oxygen (MO) bond dissociation energy of the metal element may be greater than or equal to 400 kJ / mol. The copper layer may include a copper seed layer and a copper plating layer disposed sequentially.

[0038] The copper-clad laminate has excellent etch resistance and chemical resistance while having a low coefficient of thermal expansion, low dielectric constant, low dielectric loss and low transmission loss.

[0039] Figure 1 This is a schematic cross-sectional view of a copper-clad laminate 10 according to a specific embodiment. Figure 2 This is a schematic cross-sectional view of the copper-clad laminate 20 according to another specific embodiment.

[0040] Reference Figure 1 In a copper-clad laminate 10 according to a specific embodiment, a polyimide substrate 1 with a fluorine layer 5 disposed on one surface, a tie layer 2 disposed on the polyimide substrate 1 with the fluorine layer 5, a copper seed layer 3, and a copper plating layer 4 may be disposed sequentially. (Refer to...) Figure 2The copper-clad laminate film 20 according to another embodiment is composed of a first surface 21 and a second surface 22, wherein, in the first surface 21, the polyimide base material 11 provided with the fluorine layer 15 on one surface thereof, the connection layer 12 provided on the upper surface of the polyimide base material 11 provided with the fluorine layer 15, the copper seed layer 13, and the plated copper layer 14 are sequentially provided, and, in the second surface 22, the connection layer 12', the copper seed layer 13', and the plated copper layer 14' are sequentially provided on the lower surface of the polyimide base material 11 provided with the fluorine layer 15'.

[0041] Hereinafter, the polyimide base materials 1 and 11 provided with the fluorine layers 5, 15, and 15' constituting the copper-clad laminate films 10 and 20, the connection layers 2, 12, and 12', the copper seed layers 3, 13, and 13', and the plated copper layers 4, 14, and 14' are described.

[0042]

[0043] The polyimide base materials 1 and 11 can be modified polyimide (m-PI) base materials. The modified polyimide base material is a resin base material having a reduced number of substituents having a large polarity. When a wireless signal passes through a circuit, the electric field around the circuit changes. When this electric field change approaches the relaxation time of the internal polarization of the resin base material, the electric displacement is delayed. At this time, heat is generated due to the molecular friction occurring inside the resin base material, and the generated heat affects the dielectric properties. Therefore, a modified polyimide base material having a reduced number of substituents having a large polarity is used as the base material.

[0044] ​The fluorine layers 5, 15, and 15' can be provided on one or both surfaces of the polyimide substrates 1 and 11. The fluorine layers 5, 15, and 15' can include at least one fluororesin selected from polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), fluorinated ethylene propylene copolymer (FEP), chlorotrifluoroethylene polymer (CTFE), tetrafluoroethylene / CTFE copolymer (TFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinylidene fluoride (PVDF). For example, the fluorine layers 5, 15, and 15' can be PFA.

[0045] The thickness of the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15, and 15' can be about 25 µm to about 100 µm. For example, the thickness of the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15, and 15' can be about 25 µm to about 90 µm, about 25 µm to about 80 µm, about 25 µm to about 70 µm, about 25 µm to about 60 µm, or about 25 µm to about 50 µm. The thickness of the fluorine layers 5, 15, and 15' can be less than or equal to 50% based on the thickness 100% of the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15, and 15'. When the thickness of the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15, and 15' is less than 25 µm, productivity in manufacturing the copper-clad laminated films 10 and 20 can be reduced, and when the thickness of the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15, and 15' exceeds 100 µm, thin filmization can not be achieved.

[0046] The fluorine content of the surface of the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15, and 15' can be about 60 atomic % to about 75 atomic %. In the fluorine content range, the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15, and 15' can have a low dielectric constant, a low dielectric loss, and a low transmission loss. The polyimide substrates 1 and 11 provided with the fluorine layers 5, 15, and 15' can have a dielectric constant (D k ) of less than or equal to 2.8 and a dielectric loss (D f). For example, the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15 and 15' can have a dielectric constant (D k ) of 0.01 to 2.8 and a dielectric loss (D f ) of 0.00001 to 0.003 at a frequency of 20 GHz.

[0047] The coefficient of thermal expansion (CTE) of the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15 and 15' can be less than or equal to 25 ppm / °C. For example, the coefficient of thermal expansion (CTE) of the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15 and 15' can be about 0.01 ppm / °C to about 25 ppm / °C. The polyimide substrates 1 and 11 provided with the fluorine layers 5, 15 and 15' having this coefficient of thermal expansion (CTE) do not bend and do not have problems of bending and twisting due to shrinkage when the copper-clad laminated films 10 and 20 are manufactured together with the copper foils including the copper seed layers 3, 13 and 13' and the copper-plated layers 4, 14 and 14' because the difference between the coefficient of thermal expansion (CTE) of the copper layers including the copper seed layers 3, 13 and 13' and the copper-plated layers 4, 14 and 14' (about 16 ppm to about 20 ppm) and the coefficient of thermal expansion (CTE) of the substrates is not large, and the amount of occurrence of residual stress is low.

[0048] If necessary, the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15 and 15' can be surface-treated by irradiating an ion beam that ionizes a reaction gas itself on the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15 and 15' before the connection layers 2, 12 and 12' to be described later are provided. As a result, functional groups such as -OH, -CHO and -COOH can be generated on the surface of the fluorine layers 5, 15 and 15' to provide the copper-clad laminated films 10 and 20 having excellent adhesion even at high temperatures.

[0049] The surface treatment using the ion beam can use a reaction gas including at least one selected from the group consisting of nitrogen (N2), oxygen (O2), argon (Ar), xenon (Xe) and helium (He). For example, the reaction gas can consist of only oxygen (O2), or can be a mixed gas of argon and oxygen (Ar-O2) or argon and nitrogen (Ar-N2), in which case the adhesion between the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15 and 15' and the connection layers 2, 12 and 12' to be described later, the copper seed layers 3, 13 and 13' and the copper-plated layers 4, 14 and 14' can be greatly improved even at high temperatures.

[0050] Further, when argon (Ar) is mixed to be used as the reaction gas, the content of argon (Ar) can be about 0.1 vol% to about 50 vol%, about 0.1 vol% to about 30 vol%, or about 0.1 vol% to about 25 vol% based on the total volume of the total reaction gas. When argon (Ar) is mixed to be used within the above range of volumes, the adhesion between the polyimide substrates 1 and 11 provided with the fluorine layer 5, 15, and 15' and the connection layer 2, 12, and 12' to be described later, the copper seed layer 3, 13, and 13', and the copper-plated layer 4, 14, and 14' can be greatly improved even at high temperatures.

[0051] The injection amount of the reaction gas can be, for example, about 1 sccm (Standard Cubic Centimeter per Minute) to about 100 sccm, about 50 sccm to about 100 sccm, or about 60 sccm to about 80 sccm. Within this range, there is an effect of being able to stably irradiate the ion beam to the surface of the polyimide substrates 1 and 11 provided with the fluorine layer 5, 15, and 15'.

[0052] However, the irradiation amount of the ion beam is not limited thereto, and can be, for example, about 1 x 1010 ions / cm2 to about 1 x 1012 ions / cm2. 2 to about 1 x 1012 17 ions / cm2 2 and within this range, the effect of irradiating the ion beam to the surface of the polyimide layer can be maximized.

[0053] Further, the irradiation time of the ion beam is not limited, and can be appropriately adjusted according to the purpose.

[0054] The method of irradiating the ion beam can be performed by a roll-to-roll process. For example, in the roll-to-roll process, the ion beam can be continuously supplied at about 2 mpm (meters per minute) to about 10 mpm and irradiated on the machine direction (MD) for about 1 to about 50 seconds on the surface of the polyimide substrates 1 and 11 provided with the fluorine layer 5, 15, and 15' in the range of 1 to 50 seconds. Within this range, the adhesion of the copper-clad laminate film 10 and 20 is excellent, and can have excellent efficiency.

[0055] The power for applying the ion beam can be about 0.1 kV to about 5 kV, about 0.1 kV to about 3 kV, or about 0.5 kV to about 2 kV. Within this range, the adhesion between the polyimide substrates 1 and 11 provided with the fluorine layer 5, 15, and 15' and the connection layer 2, 12, and 12' to be described later, the copper seed layer 3, 13, and 13', and the copper-plated layer 4, 14, and 14' can be greatly improved even at high temperatures.

[0056] <Connection layer 2, 12, and 12'>

[0057] A connection layer 2, 12, and 12' is provided on the polyimide substrates 1 and 11 provided with the fluorine layer 5, 15, and 15'. The connection layer 2, 12, and 12' can include at least one selected from the group consisting of Group 4, Group 6, Group 13, and Group 14 metal elements of the periodic table. The connection layer 2, 12, and 12' can include at least one metal or alloy selected from the group consisting of Group 4, Group 6, Group 13, and Group 14 metal elements of the periodic table.

[0058] The metal-oxygen (M-O) bond dissociation energy of the metal element can be greater than or equal to 400 kJ / mol. The metal element having the metal-oxygen (M-O) bond dissociation energy is relatively stable in combination with oxygen. As a result, by securing a stable metal oxide or alloy oxide at the interface between the connection layer 2, 12, and 12' and the fluorine layer 5, 15, and 15' to improve adhesion, and applying the connection layer 2, 12, and 12' having high conductivity, it is possible to minimize transmission loss.

[0059] The metal element can include at least one selected from the group consisting of W, Ti, Sn, Cr, Al, and Mo. The metal element is relatively stable in combination with oxygen and can have low transmission loss compared to only a Ni metal seed layer having a strong magnet property.

[0060] The metal element can further include Ni, and the content of the Ni can be less than or equal to 50 wt%. The metal element forms an alloy with the Ni, and the content of the Ni in the alloy can be less than or equal to 50 wt%. When the content of the Ni exceeds 50 wt%, high transmission loss can occur.

[0061] The thickness of the connection layer 2, 12, and 12' can be about 10 nm to about 100 nm. When the thickness of the connection layer 2, 12, and 12' is less than 10 nm, it is difficult to secure adhesion because a sufficient metal oxide or alloy oxide cannot be formed at the interface with the polyimide substrates 1 and 11 provided with the fluorine layer 5, 15, and 15' due to the thin thickness. When the thickness of the connection layer 2, 12, and 12' exceeds 100 nm, the connection layer 2, 12, and 12' cannot be well etched and remains in the etching process for forming a circuit, and thus can cause a poor circuit.

[0062] <Copper seed layer 3, 13, and 13' and copper plating layer 4, 14, and 14'>

[0063] The copper seed layers 3, 13, and 13' are provided on the connection layers 2, 12, and 12'. The copper seed layers 3, 13, and 13' can be sputtered layers. The copper sputtered seed layers are pleased to maintain the surface roughness of the polyimide substrates 1 and 11 themselves on which the fluorine layers 5, 15, and 15' are provided, and at the same time, to make them have low transmission loss. As a sputtering method, a method of physical vapor deposition (PVD), chemical vapor deposition (CVD), low pressure chemical vapor deposition (LPCVD), vacuum deposition, and the like can be used, but is not limited thereto, and all sputtering methods that can be used as a sputtering method in the art can be used. For example, a PVD method can be used as a sputtering method.

[0064] The thickness of the copper seed layers 3, 13, and 13' can be about 1 nm to about 100 nm. to about 50 nm For example, the thickness of the copper seed layers 3, 13, and 13' can be about 1 nm to about 50 nm. to about 50 nm about 1 nm to about 50 nm to about 50 nm about 1 nm to about 50 nm to about 50 nm about 1 nm to about 50 nm to about 50 nm or about 10 nm to about 50 nm to about 50 nm When the copper seed layers 3, 13, and 13' have the above thickness range, the electrical conductivity can be ensured at the time of film formation, and the copper-clad laminated films 10 and 20 having low transmission loss while having low surface roughness (R z ) can be provided.

[0065] The copper-plated layers 4, 14, and 14' are located on the copper seed layers 3, 13, and 13'. As a method of forming the copper-plated layers 4, 14, and 14', a chemical plating method or an electrolytic plating method can be used. For example, the copper-plated layers 4, 14, and 14' can be formed by using an electrolytic plating method.

[0066] The method of forming the copper-plated electrolytic layer can use all methods available in the technical field. For example, electrolytic plating can be performed by using an electrolytic plating solution with copper sulfate and sulfuric acid as basic substances, thereby forming a copper-plated electrolytic layer on one surface of the copper seed layers 3, 13, and 13'. In addition, for productivity and surface uniformity, an additive such as a gloss agent, a leveling agent, a correction agent, or a buffer, and the like can be added to the electrolytic plating solution.

[0067] The thickness of the copper plating layer 4, 14 and 14' can be less than or equal to 12 μm. For example, the thickness of the copper plating layer 4, 14 and 14' can be about 0.1 μm to about 12.0 μm, about 1.0 μm to about 12.0 μm, about 2.0 μm to about 12.0 μm, about 4.0 μm to about 12.0 μm, or about 6.0 μm to about 12.0 μm.

[0068] < Copper-clad laminated films 10 and 20 >

[0069] The copper-clad laminated films 10 and 20 include polyimide substrates 1 and 11 provided with fluorine layers 5, 15 and 15' on at least one surface thereof, and a connection layer provided on the polyimide substrates 1 and 11 provided with the fluorine layers 5, 15 and 15', the connection layer including at least one selected from the group consisting of Group 4, Group 6, Group 13 and Group 14 metal elements of the periodic table, and the metal element having a metal-oxygen (M-O) bond dissociation energy of greater than or equal to 400 kJ / mol. The copper-clad laminated films 10 and 20 can provide a copper-clad laminated film having a low coefficient of thermal expansion, a low dielectric constant, a low dielectric loss and a low transmission loss while having excellent etching resistance and chemical resistance.

[0070] < Electronic device >

[0071] The electronic device according to another specific embodiment can include the copper-clad laminated films 10 and 20.

[0072] The electronic device can include an antenna device or an antenna cable. For example, the antenna device can be an antenna device for a mobile phone or a display. In addition, the antenna device can include a circuit board such as a network server, an Internet of Things (IoT) home appliance for 5G, a Radar, a USB, etc.

[0073] Hereinafter, the constitution of the present application and the effects according to the constitution will be described in further detail through examples and comparative examples. However, it is obvious that the present application is not limited in scope to these examples only, as the present embodiments are merely for further specifically describing the present application.

[0074] Example 1 : Copper-clad laminate film

[0075] As Figure 2 The copper-clad laminated film 20 was manufactured as follows.

[0076] As a base material, a polyimide film 11 (PI High Tech Materials, total thickness: 50 μm, dielectric constant (Dk) at a frequency of 20 GHz: 2.8, dielectric loss (Df): 0.003, and CTE: ≤ 25 ppm / °C) provided with fluorine coatings 15 and 15' each having a thickness of 12.5 μm on both surfaces thereof was prepared. The first surface 21 of the polyimide film 11 provided with the fluorine coatings 15 and 15' was subjected to ion beam treatment using an ion beam source in a roll-to-roll type sputtering device. The ion beam treatment was performed by injecting 30 seem of inert gas Ar under a pressure condition of 10 -6 Torr and under a condition where electric power of 1.0 kV was applied. Then, on the upper surface of the ion beam-treated fluorine coating 15, a tie layer 12 having a thickness of about 20 nm was formed using molybdenum (Mo, Mo-O bond dissociation energy: 400 kJ / mol) having a purity of 99.995% in a physical vapor deposition method (PVD). Then, a copper seed layer 13 having a thickness of about 100 nm was formed on the upper surface of the tie layer 12 using copper having a purity of 99.995% in a physical vapor deposition method (PVD). Thereafter, ion beam treatment was performed on the second surface 22 of the polyimide film 11 provided with the fluorine coating 15' thereon in the same manner as described above, thereby forming a tie layer 12' and a copper seed layer 13'. Then, a plated copper layer having a thickness of about 12 μm was formed on each of the copper seed layers 13 and 13' by an electrolytic copper plating method. The electrolytic copper plating solution used for the electrolytic copper plating was Cu 2+ Concentrations of 8 g / L and sulfuric acid of 195 g / L, further including 0.01 g / L of 3-N,N-dimethylamino dithiocarbamyl-1-propanesulfonic acid and a brightener (a product of Atotech Corporation) as a brightener. For the electrolytic copper plating, the current density was started at 1.0 A / dm 2 and the current was gradually increased to 2.86 A / dm 2 .

[0077] Example 2: Copper-clad laminate film

[0078] A copper-clad laminate film 20 was manufactured in the same manner as in Example 1, except that, on the upper surface of the ion beam-treated fluorine coating 15, a tie layer 12 having a thickness of about 20 nm was formed using molybdenum (Mo, Mo-O bond dissociation energy: 400 kJ / mol) and titanium (Ti, Ti-O bond dissociation energy: 670 kJ / mol) having a weight ratio of 50:50 (purity: 99.9% or more) in a physical vapor deposition method (PVD).

[0079] Example 3: Copper-clad laminate film

[0080] A copper-clad laminate film 20 was produced in the same manner as in Example 1, except that molybdenum (Mo, Mo-O bond dissociation energy: 400 kJ / mol) and nickel (Ni, Ni-O bond dissociation energy: 360 kJ / mol) were formed into a connecting layer 12 having a thickness of about 20 nm in a weight ratio of 70:30 (purity: 99.9% or more) on the upper surface of the ion-beam-processed fluorine coating 15 by a physical vapor deposition method (PVD).

[0081] Example 4: Copper-clad laminate film

[0082] A copper-clad laminate film 20 was produced in the same manner as in Example 1, except that molybdenum (Mo, Mo-O bond dissociation energy: 400 kJ / mol) and nickel (Ni, Ni-O bond dissociation energy: 360 kJ / mol) were formed into a connecting layer 12 having a thickness of about 20 nm in a weight ratio of 50:50 (purity: 99.9% or more) on the upper surface of the ion-beam-processed fluorine coating 15 by a physical vapor deposition method (PVD).

[0083] Example 5: Copper-clad laminate film

[0084] A copper-clad laminate film 20 was produced in the same manner as in Example 1, except that tungsten (W, W-O bond dissociation energy: 710 kJ / mol) having a purity of 99.995% was used to form a connecting layer 12 having a thickness of about 20 nm on the upper surface of the ion-beam-processed fluorine coating 15 by a physical vapor deposition method (PVD).

[0085] Example 6: Copper-clad laminate film

[0086] A copper-clad laminate film 20 was produced in the same manner as in Example 1, except that tungsten (W, W-O bond dissociation energy: 710 kJ / mol) and titanium (Ti, Ti-O bond dissociation energy: 670 kJ / mol) were formed into a connecting layer 12 having a thickness of about 20 nm in a weight ratio of 90:10 (purity: 99.9% or more) on the upper surface of the ion-beam-processed fluorine coating 15 by a physical vapor deposition method (PVD).

[0087] Example 7: Copper-clad laminate film

[0088] A copper-clad laminate film 20 was produced in the same manner as in Example 3, except that when the ion beam treatment was performed on the first surface 21 of the polyimide film 11 provided with the fluorine coating 15 in the roll-to-roll sputtering device, the ion beam treatment was performed at a pressure of 10 -6 Torr under conditions in which the reaction gas O2 was injected at 9 seem and power of 1.0 kV was applied.

[0089] Example 8: Copper-clad laminate film

[0090] A copper-clad laminate film 20 was produced in the same manner as in Example 3, except that when the first surface 21 of the polyimide film 11 provided with the fluorine coating layer 15 was subjected to ion beam treatment in the roll-to-roll sputtering device, the ion beam treatment was performed at a pressure of 10 -6 Torr under conditions where the reaction gas N2was injected at 9 seem and power of 1.0 kV was applied.

[0091] Comparative Example 1 : Copper-clad laminate film

[0092] A copper-clad laminate film 20 was produced in the same manner as in Example 1, except that on the upper surface of the ion beam-treated fluorine coating layer 15, a connection layer 12 was formed to a thickness of about 20 nm using copper (Cu, Cu-O bond dissociation energy: 280 kJ / mol) having a purity of 99.995% in a physical vapor deposition method (PVD).

[0093] Comparative Example 2: Copper-clad laminate film

[0094] A copper-clad laminate film 20 was produced in the same manner as in Example 3, except that a polyimide film (PI High Tech Materials, total thickness: 25 μm, dielectric constant (D k ) : 3.5, dielectric loss (D f ) : 0.004, and CTE: ≤ 25 ppm / °C) not provided with a fluorine coating layer 15 was used as the base material.

[0095] Comparative Example 3: Copper-clad laminate film

[0096] A copper-clad laminate film 20 was produced in the same manner as in Example 3, except that a liquid crystal polymer (LCP; Liquid crystal polymer) film (manufactured by Chiyoda Corporation, total thickness: 50 μm, dielectric constant (D k ) : 2.7, dielectric loss (D f ) : 0.002, and CTE: ≥ 40 ppm / °C) was used as the base material.

[0097] Comparative Example 4: Copper-clad laminate film

[0098] A copper-clad laminate film 20 was produced in the same manner as in Example 3, except that the first surface 21 and the second surface 22 of the polyimide film 11 provided with the fluorine coating layer 15 were not subjected to ion beam treatment.

[0099] Evaluation Example 1 : Physical property evaluation

[0100] The physical properties of the copper-clad laminate films produced in Examples 1 to 8 and Comparative Examples 1 to 4 were evaluated by the following measurement methods. The results are shown in Table 1 below.

[0101] (1) Fluorine content - X-ray photoelectron spectroscopy (XPS) analysis

[0102] XPS analysis was performed for the fluorine-coated polyimide films with ion beam surface treatment of Example 3, Example 7, Example 8, and Comparative Example 4, or without ion beam surface treatment. For the XPS analysis, a K-Alpha of ThermoFisher was used.

[0103] (2) Transmission loss

[0104] Ten straight line circuits were formed using etching with a width of 40 μm, a length of 50 mm, and a longitudinal direction of 40 mm for the copper-clad laminated films manufactured by Example 3, Comparative Example 2, and Comparative Example 3. Then, each of the signal conductors and the ground conductors forming the transmission path of the straight line circuits were connected to the measurement ports of a measurement device (Vector Network Analyzer), and a signal of up to a frequency of 28 GHz was applied to measure the transmission loss. At this time, the evaluation of the transmission loss was as follows.

[0105] O: In the case where the transmission loss is greater than -0.5 dB / cm

[0106] Δ: In the case where the transmission loss is -0.5 dB / cm to -1.5 dB / cm

[0107] X: In the case where the transmission loss is less than -1.5 dB / cm

[0108] (3) Etching resistance

[0109] For the copper-clad laminated films manufactured by Example 1 to 6, Comparative Example 1, a circuit pattern having a width of 3 mm was formed on the surface thereof, and whether or not the circuit pattern having a width of 3 mm was peeled off by an etching solution, i.e., a ferric chloride (FeCl3) and copper chloride (CuCl2) solution, used when etching the entire surface of the opposite surface of the copper-clad laminated film on which the circuit pattern was formed, was evaluated as follows.

[0110] O: In the case where the circuit pattern was not peeled off and liquid penetration did not occur under the circuit pattern

[0111] Δ: In the case where liquid penetration occurred under the circuit pattern

[0112] X: In the case where the circuit pattern was peeled off

[0113] (4) Chemical resistance

[0114] The copper-clad laminate film formed with a circuit pattern to be used in the (3) etch resistance evaluation was immersed in a 10% hydrochloric acid (HCl) solution for 1 minute or in a 5% or less alkaline solution for 1 minute. The chemical resistance evaluation of the copper-clad laminate film was as follows.

[0115] O: a case where the circuit pattern does not fall off and liquid penetration does not occur under the circuit pattern

[0116] Δ: a case where liquid penetration occurs under the circuit pattern

[0117] X: a case where the circuit pattern falls off

[0118] [Table 1]

[0119]

[0120]

[0121] As shown in Table 1, it can be confirmed that the copper-clad laminate films manufactured by Examples 1 to 6 have excellent etch resistance and chemical resistance while having low dielectric constant, low dielectric loss, low transmission loss, and low thermal expansion coefficient.

[0122] The copper-clad laminate film manufactured by Comparative Example 1 includes a copper connection layer (Cu-O bond dissociation energy: 280 kJ / mol) and the circuit pattern falls off in an acid and alkaline environment. The copper-clad laminate film manufactured by Comparative Example 2 includes a polyimide film on which a fluorine coating layer is not provided and has high dielectric constant, high dielectric loss, and high transmission loss compared to the copper-clad laminate films manufactured by Examples 1 to 8. The copper-clad laminate film manufactured by Comparative Example 3 includes an LCP film and has high thermal expansion coefficient and warpage compared to the copper-clad laminate films manufactured by Examples 1 to 8.

[0123] Thus, since the copper-clad laminate films manufactured by Examples 1 to 8 have a high frequency trend suitable for 5G mobile communication devices and have improved base material dielectric properties and have excellent etch resistance and chemical resistance, they can be applied to electronic devices such as miniaturized 5G mobile communication devices.

[0124] A copper-clad laminate film according to an aspect includes a polyimide substrate in which a fluorine layer is provided on at least one surface, a tie layer provided on the polyimide substrate on which the fluorine layer is provided, and a copper layer provided on the tie layer. The tie layer can include at least one selected from the group consisting of Group 4, Group 6, Group 13, and Group 14 metal elements of the periodic table, and a metal-oxygen (M-O) bond dissociation energy of the metal element can be greater than or equal to 400 kJ / mol. The copper-clad laminate film has excellent etch resistance and chemical resistance while having a low coefficient of thermal expansion, a low dielectric constant, a low dielectric loss, and a low transmission loss.

[0125] While certain example embodiments and implementations have been described herein, other embodiments and modifications will be apparent to those of ordinary skill in the art from the description. The disclosure is not limited to the described embodiments, but rather only limited by the scope of the appended claims, and the variety of possible modifications and equivalent arrangements will be apparent to those of ordinary skill in the art.

Claims

1. A copper-clad laminate film, comprising: a polyimide substrate, wherein a fluorine layer is provided on at least one surface; a connecting layer provided on the polyimide substrate on which the fluorine layer is provided; and a copper layer provided on the connecting layer, wherein, the connecting layer includes at least one selected from the group consisting of Group 4, Group 6, Group 13 and Group 14 metal elements of the periodic table, a metal-oxygen bond dissociation energy of the metal element is greater than or equal to 400 kJ / mol, and the metal element includes at least one selected from the group consisting of W, Ti, Sn, Al and Mo. the connecting layer further includes Ni, and a content of the Ni is less than or equal to 50% by weight.

2. The copper-clad laminate film according to claim 1, wherein, a thickness of the polyimide substrate on which the fluorine layer is provided is 25 μm to 100 μm.

3. The copper-clad laminate film according to claim 1, wherein, a thickness of the fluorine layer is less than or equal to 50% based on 100% of a thickness of the polyimide substrate on which the fluorine layer is provided.

4. The copper-clad laminate film according to claim 1, wherein, a fluorine content of a surface of the polyimide substrate on which the fluorine layer is provided is 60 atom% to 75 atom%.

5. The copper-clad laminate film according to claim 1, wherein, the polyimide substrate on which the fluorine layer is provided has a dielectric constant of less than or equal to 2.8 and a dielectric loss of less than or equal to 0.003 at a frequency of 20 GHz.

6. The copper-clad laminate film according to claim 1, wherein, a coefficient of thermal expansion of the polyimide substrate on which the fluorine layer is provided is less than or equal to 25 ppm / °C.

7. The copper-clad laminate film according to claim 1, wherein, a thickness of the copper layer is less than or equal to 12 μm.

8. The copper-clad laminate film according to claim 1, wherein, 9. An electronic device including the copper-clad laminate film according to any one of claims 1 to 8. the electronic device includes an antenna device or an antenna cable.

10. Electronic device according to claim 9, wherein, ​

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