Copper-clad laminate film, and component and device each comprising same

Abstract

Disclosed are a copper-clad laminate film, and a component and a device each comprising same. The copper-clad laminate film comprises; a non-conductive polymer substrate; a ternary alloy tie layer composed of Cu, Ni, and Ti located on the non-conductive polymer substrate; and a copper layer located on the ternary alloy tie layer, wherein the Ti content may be 1 wt% to 10 wt% relative to the total weight of the ternary alloy. The copper-clad laminate film can exhibit high room-temperature adhesive strength, heat-resistant adhesive strength, and chemical resistance between the substrate and the copper layer, while having a low dielectric constant and a low dielectric loss at a high frequency.

Description

Copper-clad laminated film and components and devices including the same

[0001] The present invention relates to a copper-clad laminate film and components and devices including the same.

[0002] Copper clad laminate (CCL) is a laminate of a substrate and a conductive copper foil. The use of CCL is increasing alongside the trend toward miniaturization and lightweighting of electronic devices. The recent development of 5G mobile communication devices has led to the widespread adoption of GHz-band signal transmission speeds. This trend toward higher frequency signals necessitates improved dielectric properties of substrates used in printed circuits or antenna elements. Furthermore, the accelerated growth of the mobile market and the increasing demand for LCD TV monitors are driving the development of materials that offer thinner, smaller, lighter, more durable, and higher image quality in fields such as electronic products and semiconductor integrated circuits. CCL, used in LCD driver integrated circuits (ICs), is also increasingly demanding fine patterning, thinner, and more durable features.

[0003] Therefore, there is still a need for a copper-clad laminate film having low permittivity and low dielectric loss at high frequencies while simultaneously having improved room temperature adhesion, heat resistance, and chemical resistance between the substrate and the copper layer.

[0004] One aspect is to provide a copper-clad laminate film having low permittivity and low dielectric loss at high frequencies while at the same time having improved room temperature adhesion, heat resistance, and chemical resistance between a substrate and a copper layer.

[0005] Another aspect is to provide a component including the above copper foil laminate film.

[0006] Another aspect is to provide a device including the above copper foil laminate film.

[0007] According to one aspect,

[0008] Non-conductive polymer substrate;

[0009] A ternary alloy tie layer composed of Cu, Ni, and Ti positioned on the non-conductive polymer substrate; and

[0010] A copper layer positioned on the ternary alloy tie layer;

[0011] A copper-clad laminate film is provided, wherein the Ti content is 1 wt% to 10 wt% based on the total weight of the ternary alloy.

[0012] The above non-conductive polymer substrate may include a polyimide-based polymer substrate.

[0013] The above non-conductive polymer substrate has a dielectric constant (D) of 3.5 or less at a frequency of 28 GHz. k ) and dielectric loss (D) of 0.005 or less f ) can have.

[0014] The thickness of the above non-conductive polymer substrate may be 7.5 ㎛ to 100 ㎛.

[0015] The weight ratio of Cu, Ni, and Ti in the above ternary alloy tie layer may be 70:20:10 to 70:29:1.

[0016] The thickness of the above ternary alloy tie layer may be 60 Å to 3500 Å.

[0017] The above copper layer may include a copper seed layer and a copper plating layer.

[0018] The thickness of the above copper plating layer may be 12 ㎛ or less.

[0019] The adhesion of the copper layer to the substrate at room temperature may be 0.9 kgf / cm to 1.5 kgf / cm.

[0020] After two heat treatments at 150°C for 2 hours and an additional heat treatment at 240°C for 10 minutes, the adhesion of the copper layer to the substrate can be 0.9 kgf / cm to 1.5 kgf / cm.

[0021] Depending on other aspects,

[0022] A component including the aforementioned copper foil laminate film is provided.

[0023] According to another aspect,

[0024] A device including the aforementioned copper foil laminate film is provided.

[0025] A copper-clad laminate film according to a side includes a non-conductive polymer substrate, a ternary alloy tie layer composed of Cu, Ni, and Ti positioned on the non-conductive polymer substrate, and a copper layer positioned on the ternary alloy tie layer, wherein the Ti content may be 1 wt% to 10 wt% based on the total weight of the ternary alloy. The copper-clad laminate film may have a low permittivity and a low dielectric loss at high frequencies, while at the same time having improved room temperature adhesion, heat resistance, and chemical resistance between the substrate and the copper layer.

[0026] Figure 1 is a cross-sectional schematic diagram of a copper foil laminate film according to one embodiment.

[0027] Figure 2 is a cross-sectional schematic diagram of a copper foil laminate film according to another embodiment.

[0028] Figure 3a is a photograph showing whether the circuit pattern of the copper foil laminated film manufactured by Example 1 is peeled off.

[0029] Figure 3b is a photograph showing whether the circuit pattern of the copper foil laminated film manufactured by Comparative Example 3 is peeled off.

[0030] Figure 4a is a photograph showing the etchability of the substrate of the copper-clad laminate film manufactured by Example 1.

[0031] Figure 4b is a photograph showing whether the circuit pattern of the copper-clad laminated film manufactured by Comparative Example 2 is peeled off.

[0032] Hereinafter, copper foil laminate films, and articles and devices including the same will be described in detail with reference to embodiments and drawings of the present invention. These embodiments are provided solely as examples to more specifically illustrate the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these embodiments.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In case of conflict, the present specification, including its definitions, shall prevail.

[0034] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

[0035] The term "including" in this specification means that other components may be included rather than excluding other components unless specifically stated to the contrary.

[0036] The term "combination of these" in this specification means a mixture or combination of one or more of the described components.

[0037] As used herein, the term "and / or" is meant to include any and all combinations of one or more of the items described herein. As used herein, the term "or" means "and / or." The expressions "at least one" or "one or more" preceding elements herein may modify the entire list of elements and do not mean that they modify individual elements described above.

[0038] When a component is referred to herein as being "on" or "over" another component, the component may be directly on the other component, or there may be intervening components between the components. Conversely, when a component is referred to as being "directly on" or "directly over" another component, there may not be intervening components.

[0039] In this specification, the term “~-based polymer (resin)” or “~-based copolymer (resin)” is a broad concept that includes all of “~ polymer (resin)”, “~ copolymer (resin)”, and / or “derivatives of ~ polymer (resin) or copolymer (resin)”.

[0040] Among the conventional printed circuit board (PCB) manufacturing methods, the method of sputtering one side of the substrate and then electroplating results in low adhesion between the substrate and the deposited copper layer. This low adhesion between the substrate and the copper layer can lead to the circuit pattern being removed or deformed during PCB manufacturing. To address this issue, a bonding layer, such as nickel or a nickel-chromium alloy, can be placed between the substrate and the copper layer. However, manufacturing processes that include this bonding layer increase the number of processes and use hazardous substances, which poses safety and environmental issues. In circuits that utilize high-frequency signals, the bonding layer, such as nickel or a nickel-chromium alloy, can cause signal loss.

[0041] Taking these points into consideration, the inventors of the present invention propose a copper-clad laminate film and components and devices including the same.

[0042] Fig. 1 is a cross-sectional schematic diagram of a copper-clad laminate film according to one embodiment. Fig. 2 is a cross-sectional schematic diagram of a copper-clad laminate film according to another embodiment.

[0043] Referring to FIGS. 1 and 2, the copper-clad laminate film (10, 20) has a ternary alloy tie layer (2, 12, 12'), a copper layer (5, 15, 15'), and a copper plating layer (4, 14, 14') sequentially arranged on one or both sides of the substrate (1, 11). The copper layer (5, 15, 15') is composed of a copper seed layer (3, 13, 13') and a copper plating layer (4, 14, 14').

[0044]

[0045] Hereinafter, the non-conductive polymer substrate (1, 11), ternary alloy tie layer (2, 12, 12'), copper layer (5, 15, 15'), copper laminate film (10, 20), components, and devices constituting the above copper laminate film will be described in detail.

[0046]

[0047] [Non-conductive polymer substrate (1, 11)]

[0048] The non-conductive polymer substrate (1, 11) according to one embodiment may be a film or a sheet. For example, the non-conductive polymer substrate (1, 11) may be a film. The non-conductive polymer substrate (1, 11) may be a film with excellent heat resistance that can withstand high temperatures during the manufacture of printed circuit boards.

[0049] The non-conductive polymer substrate (1, 11) may include a polyimide-based film.

[0050] The polyimide-based film used in the non-conductive polymer substrate (1, 11) can be manufactured by extruding polyamic acid, a polyimide precursor, into a film, and heat-treating and drying the film to imidize the polyamic acid. Moisture and residual gases can be removed through a drying process commonly used in the art. For example, drying can be performed through a roll-to-roll type heat treatment under atmospheric pressure or using an infrared (IR) heater in a vacuum atmosphere.

[0051] The non-conductive polymer substrate (1, 11) may include polyimide, a modified polyimide having a low dielectric constant, polyamide, polyetherimide, polyamideimide, or a combination thereof. For example, the non-conductive polymer substrate (1, 11) may use a polyimide or a modified polyimide film having a low dielectric constant. For example, the non-conductive polymer substrate (1, 11) may use a modified polyimide film having a low dielectric constant.

[0052] Modified polyimide substrates are resin substrates with reduced polarity substituents. When a wireless signal is applied to a circuit, the electric field surrounding the circuit changes. This change in electric field causes a delay in electrical displacement when it approaches the relaxation time of the internal polarization of the resin substrate. This causes molecular friction within the resin substrate, generating heat that affects dielectric properties. Therefore, modified polyimide substrates with reduced polarity substituents and a low dielectric constant are used as non-conductive polymer substrates.

[0053] The non-conductive polymer substrate (110) has a dielectric constant (D) of 3.5 or less at a frequency of 28 GHz. k ) and dielectric loss (D) of 0.005 or less f ) can have.

[0054] Meanwhile, moisture absorption is a ratio representing the amount of moisture a material absorbs. Generally, higher moisture absorption is known to increase dielectric constant and dielectric loss.

[0055] Water, present in a vapor state outside of the substrate, has no significant effect on the substrate's permittivity and dielectric loss. However, when water vapor or other substances are absorbed by the substrate, the water exists in a liquid state. In such cases, the substrate's permittivity and dielectric loss can increase dramatically. Therefore, reducing the substrate's moisture absorption rate is a critical factor for non-conductive polymer films.

[0056] The moisture absorption of the non-conductive polymer substrate (1, 11) may be less than 5 wt%. For example, the moisture absorption of the non-conductive polymer substrate (1, 11) may be 4 wt% or less, 3 wt% or less, or 2 wt% or less. If the moisture absorption of the non-conductive polymer substrate (1, 11) is 5 wt% or more, signal loss may increase in a high-frequency circuit.

[0057] Glass transition temperature (T) of non-conductive polymer substrate (1, 11) g ) can be 200 ℃ or higher. The non-conductive polymer substrate (1, 11) can have sufficient heat resistance, so that no physical-chemical changes may occur within a high temperature range and for a long time. The glass transition temperature (T of the non-conductive polymer substrate (1, 11) g ) is below 200℃, the substrate may melt during the printed circuit board manufacturing process or the substrate may change in size after the high-temperature process, causing the circuit board to warp.

[0058] The thickness of the non-conductive polymer substrate (1, 11) may be 7.5 ㎛ to 100 ㎛. For example, the thickness of the non-conductive polymer substrate (1, 11) may be 7.5 ㎛ to 90 ㎛, 7.5 ㎛ to 80 ㎛, 7.5 ㎛ to 70 ㎛, 7.5 ㎛ to 60 ㎛, or 7.5 ㎛ to 50 ㎛. If the thickness of the non-conductive polymer substrate (1, 11) is less than 7.5 ㎛, productivity may be reduced when manufacturing the copper-clad laminate film (10, 20), and if it exceeds 100 ㎛, thin film formation may not be achieved.

[0059] The non-conductive polymer substrate (1, 11) can be subjected to plasma treatment on its surface. The plasma treatment can be performed on one or both sides of the non-conductive polymer substrate (1, 11). The plasma treatment can use RF plasma or an ion beam. The RF plasma treatment can be performed by injecting an inert gas and oxygen gas at a volume ratio of 1:1 to 4:1 and using a power of about 500 W or more. The plasma-treated non-conductive polymer substrate (110) can not only enhance the chemical activity of its surface but also improve the surface roughness, thereby further enhancing the adhesion between the non-conductive polymer substrate (1, 11) and the copper layer (5, 15, 15').

[0060] If necessary, the non-conductive polymer substrate (1, 11) may be subjected to primer treatment on its surface. For example, the primer treatment may use a silane coupling agent. The silane coupling agent may include an amino silane compound and / or a vinyl silane compound. The silane coupling agent may be included in an amount of 0.01 to less than 10 wt% based on the total weight of the primer treatment layer. The primer treatment layer may be formed by applying and drying a primer treatment composition on the surface of the non-conductive polymer substrate (1, 11) using a solution application method. The solvent used in the primer treatment composition is not limited, but may be, for example, one or more solvents selected from water, acetone, methanol, ethanol, and isopropanol. The solvents may be used alone or in combination. The thickness of the primer treatment layer may be 20 nm or less. For example, the thickness of the primer treatment layer may be 18 nm or less, 16 nm or less, or 15 nm or less. Even when the thickness of the primer treatment layer is a thin film thickness as described above, the room temperature adhesion, heat resistance, and chemical resistance between the non-conductive polymer substrate (1, 11) and the copper layer (5, 15, 15') can be improved.

[0061]

[0062] [Ternary alloy tie layer (2, 12, 12')]

[0063] A ternary alloy tie layer (2, 12, 12') composed of Cu, Ni, and Ti is positioned on a non-conductive polymer substrate (1, 11).

[0064] The ternary alloy tie layer (2, 12, 12') can maintain the surface roughness of the non-conductive polymer substrate (1, 11) itself, so that the surface roughness (R) is low. z) can reduce transmission loss. The ternary alloy tie layer (2, 12, 12') has low resistivity and permeability, and thus has low surface resistance. In addition, the copper-clad laminate film (10, 20) including the ternary alloy tie layer (2, 12, 12') has a reduced surface resistance as the transmission line becomes shorter when current flows.

[0065] The Ti content may be 1 wt% to 10 wt% based on the total weight of the ternary alloy tie layer (2, 12, 12'). The weight ratio of Cu, Ni, and Ti in the ternary alloy tie layer (2, 12, 12') may be 70:20:10 to 70:25:1. If the Ni content is less than 20 wt% in the weight ratio between the metal elements of the ternary alloy tie layer (2, 12, 12'), the copper-clad laminate film (10, 20) including it may experience pattern peeling during etching due to chemical resistance issues. If the Ti content exceeds 10 wt%, etching residue may remain when a user uses the copper-clad laminate film (10, 20) in a product process.

[0066] The ternary alloy tie layer (2, 12, 12') may be a sputtered layer. The sputtering method may include physical vapor deposition (PVD), chemical vapor deposition (CVD), low-pressure chemical vapor deposition (LPCVD), or vacuum deposition. For example, the physical vapor deposition (PVD) method may be used as the sputtering method.

[0067] The thickness of the ternary alloy tie layer (2, 12, 12') may be 60 Å to 3500 Å. For example, the thickness of the ternary alloy tie layer (2, 12, 12') may be 70 Å to 3000 Å, or 80 Å to 2500 Å, or 90 Å to 2000 Å, or 90 Å to 1500 Å. If the thickness of the ternary alloy tie layer (2, 12, 12') is within the above range, conductivity can be secured during film formation and low surface roughness (R z) and can provide a copper-clad laminate film (10, 20) having low transmission loss.

[0068]

[0069] [Copper layer (5, 15, 15')]

[0070] According to one embodiment, the copper layer (5, 15, 15') includes a copper seed layer (3, 13, 13') and a copper plating layer (4, 14, 14').

[0071] The copper seed layer (3, 13, 13') may be a sputtered layer. For example, the copper seed layer (3, 13, 13') may be 10 on one side of the ternary alloy tie layer (2, 12, 12'). -4 torr to 10 -2 It can be deposited by sputtering in a vacuum tank under reduced pressure of 10 torr. Any deposition method available in the relevant technical field can be used for deposition, but for example, physical vapor deposition (PVD), chemical vapor deposition (CVD), low-pressure chemical vapor deposition (LPCVD), or vacuum deposition can be used.

[0072] The thickness of the copper seed layer (3, 13, 13') may be 50 Å to 4000 Å. For example, the thickness of the copper seed layer (3, 13, 13') may be 50 Å to 3500 Å, or 50 Å to 3000 Å, or 50 Å to 2500 Å, or 50 Å to 2000 Å, or 50 Å to 1500 Å. If the copper seed layer (3, 13, 13') is within the above thickness range, conductivity can be secured during film formation, and low surface roughness (R z ) can provide a copper-clad laminate film (10, 20).

[0073] A copper plating layer (4, 14, 14') is positioned on the copper seed layer (3, 13, 13'). The copper plating layer (4, 14, 14') can be formed using an electroless plating method or an electrolytic plating method. For example, the copper plating layer (4, 14, 14') can be formed using an electrolytic plating method.

[0074] Any electroplating method available in the relevant technical field can be used as a method for forming a copper electroplating layer. For example, a copper electroplating layer can be formed on one surface of a copper seed layer (3, 13, 13') by performing electroplating using an electroplating solution containing copper sulfate and sulfuric acid as basic substances.

[0075] Electrolytic plating can be performed using a plating solution containing copper at a concentration of 15 g / L to 40 g / L, for example, 15 g / L to 38 g / L, for example, 17 g / L to 36 g / L. Electrolytic plating can be performed while the temperature of the plating solution is maintained at 22°C to 37°C, for example, 25°C to 35°C, for example, 27°C to 34°C. Within the temperature range of the plating solution, the plating layer can be easily formed and excellent productivity can be achieved.

[0076] The pH of the plating solution may be greater than 7. Optionally, one or more pH adjusters may be included in the plating solution to adjust the pH of the plating solution to an alkaline pH. The pH adjuster may include an organic acid, an inorganic acid, an organic base, an inorganic base, or a mixture thereof. For example, the inorganic acid may include phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, or a combination thereof. For example, the inorganic base may include ammonium hydroxide, sodium hydroxide, potassium hydroxide, or a combination thereof.

[0077] Known additives such as brighteners, levelers, correctors, softeners, etc. may be added to the plating solution to improve productivity and surface uniformity.

[0078] Electroplating can be performed under conditions of a current density of 0.1 A / m² to 20 A / m², for example, 0.1 A / m² to 17 A / m², for example, 0.3 A / m² to 15 A / m². Within the above range of current density, formation of a metal plating layer can be easily achieved and excellent productivity can be achieved.

[0079] The thickness of the copper plating layer (4, 14, 14') may be 12 ㎛ or less. For example, the thickness of the copper plating layer (4, 14, 14') may be 0.1 ㎛ to 12 ㎛, or 1.0 ㎛ to 12 ㎛, or 2.0 ㎛ to 12 ㎛, or 3.0 ㎛ to 12 ㎛. When the thickness of the copper plating layer (4, 14, 14') is within the above range, the formation of the copper plating layer (4, 14, 14') is easy and the productivity is excellent, and the room temperature adhesive strength and heat-resistant adhesive strength between the non-conductive polymer substrate (1, 11) and the copper layer (5, 15, 15') can be improved.

[0080]

[0081] [Copper Clad Laminate Film (10, 20), Parts, Devices]

[0082] The adhesion of the copper layer (5, 15, 15') to the non-conductive polymer substrate (1, 11) of the copper-clad laminate film (10, 20) at room temperature can be 0.9 kgf / cm to 1.5 kgf / cm.

[0083] The adhesion of the copper layer (5, 15, 15') to the non-conductive polymer substrate (1, 11) after the copper-clad laminate film (10, 20) is heat-treated twice at 150°C for 2 hours and additionally heat-treated at 240°C for 10 minutes can be 0.9 kgf / cm to 1.5 kgf / cm.

[0084]

[0085] A component according to another embodiment may include a copper foil laminate film (10, 20). Examples of the component may include an antenna, an antenna cable, or a circuit board.

[0086] A device according to another embodiment may include a copper foil laminate film (10, 20). Examples of the device may include a network server, an IOT (Internet of Things) home appliance for 5G, or a radar.

[0087]

[0088] Hereinafter, the composition and resulting effects of the present invention will be described in more detail through examples and comparative examples. However, it should be clear that these examples are intended to illustrate the present invention more specifically, and that the scope of the present invention is not limited to these examples.

[0089]

[0090] [Example]

[0091]

[0092] Example 1: Copper-clad laminate film

[0093] As a substrate, a modified polyimide film with a thickness of about 50 ㎛ (m-PI, FN 200 A, PI Advanced Materials Co., Ltd., D k : 3.5, D f : 0.0035 @ 28 GHz) were prepared. RF plasma treatment was performed on both surfaces of the modified-polyimide base film. The RF plasma treatment was performed at a power of approximately 1000 W by injecting argon gas and oxygen gas at a volume ratio of 4:1. Then, a Cu-Ni-Ti alloy tie layer and a copper seed layer were sequentially formed on both surfaces of the RF plasma-treated modified-polyimide base film by physical vapor deposition (PVD) using a roll-to-roll type sputtering device. At this time, the Cu-Ni-Ti alloy tie layer was formed to a thickness of approximately 200 Å with a weight ratio of Cu, Ni, and Ti of 70:20:10 (purity: 99.9% or higher), and the copper seed layer was formed to a thickness of approximately 1000 Å using copper having a purity of 99.995%. A copper plating layer of about 12 ㎛ thickness was formed on the copper seed layer using an electrolytic copper plating method to manufacture a double-sided copper-clad laminate film as shown in Fig. 2.

[0094] The electrolytic copper plating solution used was Cu 2+ A solution containing 30 g / L of sulfuric acid and 150 g / L of sulfuric acid was used, which additionally contained 2.0 g / L of 3-N,N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid as a brightener and a corrector (Atotech). Electroplating was performed in a bath at a temperature of 30°C, and the plating was produced by applying a current at a current density of 2 A / m².

[0095]

[0096] Example 2: Copper-clad laminate film

[0097] A copper-clad laminate film was manufactured in the same manner as in Example 1, except that the Cu-Ni-Ti alloy tie layer was formed to a thickness of approximately 200 Å with a weight ratio of Cu, Ni, and Ti of 70:25:5 (purity: 99.9% or more).

[0098]

[0099] Example 3: Copper-clad laminate film

[0100] A copper-clad laminate film was manufactured in the same manner as in Example 1, except that the Cu-Ni-Ti alloy tie layer was formed to a thickness of approximately 200 Å with a weight ratio of Cu, Ni, and Ti of 70:29:1 (purity: 99.9% or more).

[0101]

[0102] Comparative Example 1: Manufacturing of copper-clad laminate film

[0103] A copper-clad laminate film was manufactured in the same manner as in Example 1, except that a Cu-Ni alloy tie layer was formed with a weight ratio of 70:30 (purity: 99.9% or more) and a thickness of about 200 Å using physical vapor deposition (PVD).

[0104]

[0105] Comparative Example 2: Manufacturing of copper-clad laminate film

[0106] A copper-clad laminate film was manufactured in the same manner as in Example 1, except that a Ni-Cr alloy tie layer was formed with a weight ratio of 80:20 (purity: 99.9% or more) and a thickness of about 200 Å using physical vapor deposition (PVD).

[0107]

[0108] Comparative Example 3: Manufacturing of copper-clad laminate film

[0109] A copper-clad laminate film was manufactured in the same manner as in Example 1, except that a 100% Cu layer (purity: 99.9% or more) was formed with a thickness of approximately 200 Å by physical vapor deposition (PVD).

[0110]

[0111] Comparative Example 4: Copper-clad laminate film

[0112] A copper-clad laminate film was manufactured in the same manner as in Example 1, except that a Cu-Ni-W alloy tie layer was formed with a weight ratio of 70:25:5 (purity: 99.9% or more) and a thickness of about 200 Å using physical vapor deposition (PVD).

[0113]

[0114] Comparative Example 5: Copper-clad laminate film

[0115] A copper-clad laminate film was manufactured in the same manner as in Example 1, except that a Cu-Ni-Mo alloy tie layer was formed with a weight ratio of 70:25:5 (purity: 99.9% or more) and a thickness of about 200 Å using physical vapor deposition (PVD).

[0116]

[0117] Evaluation Example 1: Physical Property Evaluation

[0118] The physical properties of each copper-clad laminate film manufactured in Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated as follows. The results are shown in Table 1, Figs. 3a, 3b, 4a, and 4b.

[0119]

[0120] (1) Permittivity (D) k) and dielectric loss (D f )

[0121] For each copper-clad laminate film, a sample of 4 cm x 4 cm in size was made and the permittivity (D) was measured using a network analyzer (manufactured by Anritsu) and a 28 GHz cavity resonator (manufactured by AET). k ) and dielectric loss (D f ) was measured.

[0122]

[0123] (2) Adhesion of copper layer to substrate (kgf / cm)

[0124] For each copper-clad laminate film, a sample with a circuit pattern approximately 4 mm wide was prepared. For each sample, the peel strength when separating the copper layer from the substrate was measured using an adhesion tester (TA.XT.plus, manufactured by Texture Analyser) at a speed of 50 mm / min at 25°C ('room temperature adhesion') and after two heat treatments at 150°C for 2 hours and an additional heat treatment at 240°C for 10 minutes ('heat-resistant adhesion').

[0125]

[0126] (3) Confirmation of peeling of circuit pattern after hydrochloric acid treatment (chemical resistance evaluation)

[0127] For each copper clad laminate film, a circuit pattern of about 3 mm in width was formed on the surface, and the entire reverse side of the copper clad laminate film on which the circuit pattern was formed was completely etched. Then, the copper clad laminate film on which the circuit pattern was formed was heat-treated in an oven at a temperature of 150°C for 12 hours. Then, the heat-treated copper clad laminate film was immersed in a 10% hydrochloric acid (HCl) solution for 3 minutes and the presence or absence of pattern peeling was checked. Among these, the presence or absence of circuit pattern peeling of the copper clad laminate films manufactured by Example 1 and Comparative Example 3 was photographed and shown in FIG. 3a and FIG. 3b, respectively.

[0128]

[0129] (4) Evaluation of etching properties of the substrate

[0130] For each copper-clad laminate film, a sample measuring 5 cm x 5 cm was prepared. Each sample was placed in an etcher (manufactured by TAK) to perform full-scale etching, and then observed with a tool microscope (OLYMPUS, STM6-LM) to check for residue. Among these, the etchability of the substrate of the copper-clad laminate film manufactured by Example 1 and Comparative Example 2 was examined by taking photographs and shown in FIG. 4a and FIG. 4b, respectively.

[0131]

[0132] Referring to Table 1 above, the copper-clad laminate films manufactured by Examples 1 to 3 had excellent room-temperature and heat-resistant adhesion, and no pattern peeling occurred in the chemical resistance evaluation. In addition, no residue remained in the etching evaluation. In comparison, the copper-clad laminate films manufactured by Comparative Examples 1 to 5 had low room-temperature and heat-resistant adhesion, and in the case of Comparative Example 2, residue was observed after etching, and in the case of Comparative Example 3, pattern peeling occurred in the chemical resistance evaluation. [Explanation of symbols]

[0133] 1, 11: Non-conductive polymer substrate, 2, 12, 12': Ternary alloy tie layer,

[0134] 3, 13, 13': copper seed layer, 4, 14, 14': copper plating layer,

[0135] 5, 15, 15': Copper layer 10, 20: Copper clad laminate film

Claims

Non-conductive polymer substrate; A ternary alloy tie layer composed of Cu, Ni, and Ti positioned on the non-conductive polymer substrate; and A copper layer positioned on the ternary alloy tie layer; A copper-clad laminate film having a Ti content of 1 wt% to 10 wt% based on the total weight of the ternary alloy. In the first paragraph, A copper-clad laminate film, wherein the non-conductive polymer substrate includes a polyimide-based polymer substrate. In the first paragraph, The above non-conductive polymer substrate has a dielectric constant (D) of 3.5 or less at a frequency of 28 GHz. k ) and dielectric loss (D) of 0.005 or less f ), copper foil laminated film. In the first paragraph, A copper-clad laminate film having a thickness of the non-conductive polymer substrate of 7.5 ㎛ to 100 ㎛. In the first paragraph, A copper-clad laminate film having a weight ratio of Cu, Ni, and Ti in the ternary alloy tie layer of 70:20:10 to 70:29:

1. In the first paragraph, A copper-clad laminate film having a thickness of the ternary alloy tie layer of 60 Å to 3500 Å. In the first paragraph, A copper-clad laminate film, wherein the copper layer includes a copper seed layer and a copper plating layer. In paragraph 7, A copper-clad laminate film having a thickness of the copper plating layer of 12 ㎛ or less. In the first paragraph, A copper-clad laminate film having an adhesion strength of the copper layer to the substrate of 0.9 kgf / cm to 1.5 kgf / cm at room temperature. In the first paragraph, A copper-clad laminate film having an adhesion strength of the copper layer to the substrate of 0.9 kgf / cm to 1.5 kgf / cm after two heat treatments at 150°C for 2 hours and an additional heat treatment at 240°C for 10 minutes. A component comprising a copper-clad laminate film according to any one of claims 1 to 10. A device comprising a copper foil laminate film according to any one of claims 1 to 10.

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