Copper-clad laminate film, electronic component and device comprising same, and method for manufacturing copper-clad laminate film

Abstract

Disclosed are a copper-clad laminate film, an electronic component and a device comprising same, and a method for manufacturing the copper-clad laminate film. The copper-clad laminate film comprises: a polyimide-containing substrate; a nickel tie layer disposed on one surface of the polyimide-containing substrate; and a copper layer disposed on the nickel tie layer, wherein the polyimide-containing substrate has a thickness of 3-10 µm, and the copper-clad laminate film has a fatigue life of 5,000 or more cycles when the flexibility thereof is measured using an MIT folding endurance tester according to JIS C 6471. A copper-clad laminate film according to an aspect has improved folding endurance, and has improved room-temperature adhesion and heat-resistant adhesion between a copper layer and a substrate having a relatively small thickness. In addition, the copper-clad laminate film has a sufficient level of room-temperature adhesion and heat-resistant adhesion even when including a polyimide-containing substrate having a relatively small thickness, and thus can be made thin. In addition, a method for manufacturing the copper-clad laminate film according to an embodiment can reduce wrinkle formation and improve runnability during general CCL manufacturing, and thus enables stable production of ultra-thin CCL.

Description

Copper clad laminate film, electronic component including the same, device, and method for manufacturing the copper clad laminate film

[0001] The invention relates to a copper clad laminate film, an electronic component including the same, a device, and a method for manufacturing the copper clad laminate film.

[0002] With the advancement of semiconductor integrated circuits, the trend toward miniaturization, lightweighting, thinning, high density, and high flexibility in electronic components and devices is accelerating. Materials capable of realizing high integration applicable to various electronic devices are being developed.

[0003] In the case of copper clad films used in such electronic devices, fine patterning, thinning, and durability are required. Accordingly, copper clad films manufactured using adhesives or polyimide resins used in printed circuit boards and camera coils are changing to the use of two-layer copper clad films using sputtering and plating processes.

[0004] In addition, thin film substrates with excellent flexibility are used for applications such as printed circuit boards (PCBs) and camera coils, and a method of sputtering one side of the thin film substrate followed by electroplating can be used. However, according to this method, when using a polyimide-containing substrate with a thin thickness of less than 10 μm, curls and wrinkles occur during sputtering and plating processes to form a nickel tie layer and a copper layer on the substrate, making processing difficult and failing to reach a high level of flexibility desired by the user.

[0005] One aspect is to provide a copper clad laminate film with improved flexibility and improved room-temperature adhesion and heat-resistant adhesion.

[0006] Another aspect is to provide an electronic component comprising the copper clad laminate film described above.

[0007] Another aspect is to provide a device including the copper clad laminate film described above.

[0008] Another aspect is to provide a method for manufacturing the copper clad laminated film described above.

[0009] According to one aspect, a polyimide-containing substrate;

[0010] A nickel tie layer located on one side of the above-mentioned polyimide-containing substrate;

[0011] A copper layer located on the nickel tie layer; comprising

[0012] The above-mentioned polyimide-containing substrate is a copper clad laminate film having a thickness of 3 to 10 μm, and

[0013] A copper clad laminate is provided having a fatigue life of 5,000 or more when the flexibility of the copper clad laminate is measured using an MIT bending tester according to JIS C 6471.

[0014] The difference between the room temperature adhesive strength (P1) and the heat-resistant adhesive strength (P2) of the copper clad laminate above is represented by the following Equation 1.

[0015] <Equation 1>

[0016] 0.1 ≤ P1-P2 ≤ 0.3

[0017] In Formula 1, P1 and P2 are evaluated in accordance with JIS C 6471.

[0018] The thickness of the above polyimide-containing substrate is 6 to 9 μm.

[0019] The nickel tie layer comprises nickel (Ni); a nickel alloy comprising one or more metals selected from nickel (Ni) and molybdenum (Mo), niobium (Nb), and iron (Fe); or a combination thereof.

[0020] The heat-resistant adhesive strength of the above copper clad laminate is 0.3 kgf / cm or higher.

[0021] The copper layer above includes a copper seed layer and a copper plating layer.

[0022] The thickness of the copper seed layer is 0.01 to 1.5 μm (10 nm to 1500 nm), and the thickness of the copper plating layer is 0.5 μm to 10 μm. The thickness of the nickel tie layer is 10 to 100 nm, and it does not contain chromium.

[0023] It may include a second protective film located on the upper part of the copper layer.

[0024] The copper clad laminate above is manufactured by comprising the steps of: providing a first protective film having a thickness of 30 μm or more on one side of a polyimide-containing substrate having a thickness of 3 to 10 μm; forming a nickel tie layer on the other side of the polyimide-containing substrate; forming a copper layer on the nickel tie layer; peeling off the first protective film from a structure obtained according to the steps above and placing a second protective film on the copper layer; and peeling off the second protective film and then applying oscillation to the film in the machine direction (MD) relative to the film's direction of travel, thereby causing the film to move, and then transferring and winding the film in the direction of travel.

[0025] An electronic component comprising the copper clad laminate film described above is provided according to another aspect.

[0026] According to another aspect, an apparatus including the copper clad laminate film described above is provided.

[0027] According to another aspect, a step of providing a first protective film having a thickness of 30 μm or more on one surface of a polyimide-containing substrate having a thickness of 3 to 10 μm;

[0028] A step of forming a nickel tie layer on the other side of the polyimide-containing substrate; and

[0029] A method for manufacturing a copper clad laminate film is provided, comprising the step of manufacturing the copper clad laminate film described above by performing the step of forming a copper layer on the nickel tie layer.

[0030] The method may include the step of peeling off a first protective film from the copper clad laminate and placing a second protective film on top of the copper layer.

[0031] After peeling off the second protective film, the method may include the step of applying oscillation to the film in the MD (Machine Direction) direction relative to the film's direction of travel, thereby moving the film and transporting and winding it in the direction of travel.

[0032] The above oscillation can be performed by reciprocating a guide roller installed in the MD direction relative to the film travel direction, with the reciprocating width being 1 mm to 100 mm to the left and right, and the reciprocating speed being 5 mpm (meters per minute) to 15 mpm.

[0033] According to another aspect, an electronic component comprising the copper clad laminate film described above is provided.

[0034] According to one aspect, the copper clad laminate film has improved flexibility and improved room temperature adhesion and heat-resistant adhesion between the copper layer and a substrate having a relatively thin thickness. In addition, since the copper clad laminate film has a sufficient level of room temperature adhesion and heat-resistant adhesion even when including a polyimide-containing substrate having a relatively thin thickness, thin film formation can be achieved.

[0035] Furthermore, according to the method for manufacturing a copper clad laminate film according to one embodiment, it is possible to improve the occurrence of wrinkles and runnability that occur during the manufacturing of general CCL (Copper Clad Laminate), thereby enabling stable production of ultra-thin CCL.

[0036] FIG. 1 is a schematic cross-sectional view of a copper clad laminate film according to one embodiment.

[0037] FIGS. 2a to 2c are drawings for explaining the manufacturing process of a copper clad laminate film according to one embodiment.

[0038] Figure 3a is a photograph of a copper clad laminate film manufactured according to Example 1.

[0039] Figure 3b is a photograph of a copper clad laminate film manufactured according to Comparative Example 1.

[0040] FIG. 4 is a schematic diagram of a sample used to measure the flexibility of copper clad laminates prepared by Examples 1 to 4 and Comparative Examples 1 to 9 using an MIT bending tester.

[0041] FIG. 5 illustrates a method for measuring flexibility using an MIT bending tester for copper clad laminate films prepared according to Examples 1 to 4 and Comparative Examples 1 to 9.

[0042] <Explanation of Symbols>

[0043] 11: First protective film 21: Polyimide-containing substrate,

[0044] 31: Nickel tie layer 41: Copper layer

[0045] 51: Second protective film 100: Copper clad laminate film

[0046] Hereinafter, a copper clad laminate film, an electronic component and device including the same, and a method for manufacturing the copper clad laminate film will be described in detail with reference to the embodiments and drawings of the present invention. These embodiments are presented merely as examples to explain the present invention more specifically, and it will be obvious to those skilled in the art that the scope of the present invention is not limited by these embodiments.

[0047] In this specification, expressions such as “at least one,” “more than one,” or “one or more” preceding components are to supplement the list of all components and do not mean that they are to supplement the individual components described above. In this specification, the term “include” means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. In this specification, the term “combination of these” means a mixture or combination with one or more of the described components. In this specification, the term “and / or” means to include any combination and all combinations of one or more items related to the description. In this specification, the term “or” means “and / or.” Where in this specification it is stated that one component is placed “on” or “above” another component, the one component may be placed directly on the other component, or there may be components interposed between the components. On the other hand, where it is stated that one component is placed “directly” or “directly on” another component, there may be no interposed components.

[0048] Throughout this specification, terms such as “one embodiment,” “an embodiment,” etc., mean that specific elements described in relation to an embodiment are included in at least one embodiment described herein and may or may not be present in other embodiments. Furthermore, it should be understood that the described elements may be combined in any appropriate manner in various embodiments.

[0049] Unless otherwise stated, all percentages, parts, ratios, etc. are based on weight. Furthermore, if a quantity, concentration, or other value or parameter is given as a range, a preferred range, or a list of preferred upper and lower limits, it should be understood that this specifically discloses any range formed from any pair of any upper limit or preferred value and any lower limit or preferred value, regardless of whether the range is disclosed separately. Where a range of numerical values ​​is mentioned herein, unless otherwise stated, the range is intended to include its endpoint and all integers and fractions within that range. The scope of the invention is not intended to be limited to the specific value mentioned when defining the range. As used herein, "about" means within an acceptable range of deviation from a specific value determined by a person skilled in the art, taking into account errors related to the measurement and the measurement of a specific quantity, including the mentioned value (i.e., the limits of the measurement system). For example, "about" may mean within one or more standard deviations, or within ± 30%, 20%, 10%, or 5% of the specified value.

[0050] In this specification, "polyimide" refers to a polymer containing repeating structural units that include an imide group. "Polyimide-containing" is a concept that includes both polyimide and polymers containing repeating structural units that include an amide group in addition to an imide group. Examples of polymers containing repeating structural units that include both an imide group and an amide group include polyamideimide.

[0051] The numerical values ​​described in this specification may be understood to include the meaning of "approximately" even if not explicitly stated.

[0052] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains. In the event of a conflict, the present specification, including definitions, shall prevail. Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described herein.

[0053] A method for manufacturing a printed circuit board (PCB) can be used in which sputtering is performed on one side of a substrate followed by electroplating. However, when using a polyimide-containing substrate with a thin thickness of 3 to 10 μm, the above method is difficult to process because curls and wrinkles occur during the sputtering and plating processes for forming a nickel tie layer and a copper layer on the substrate, and it fails to achieve a high level of flexibility desired by the user, thus requiring improvement.

[0054] According to one embodiment, in order to solve the aforementioned problem, the polyimide-containing substrate; a nickel tie layer located on one surface of the polyimide-containing substrate; and a copper layer located on the nickel tie layer are included.

[0055] A copper clad laminate film is provided, wherein the thickness of the polyimide-containing substrate is 3 to 10 μm, and when the flexibility of the copper clad laminate film is measured using an MIT bending tester according to JIS C 6471, the fatigue life is 5,000 or more.

[0056] When the flexibility of the copper clad laminated film is measured using an MIT bending tester according to JIS C 6471, the fatigue life may be, for example, 5,000 to 8,000 cycles or 5,000 to 7,000 cycles.

[0057] The difference between the room temperature adhesive strength (P1) and the heat-resistant adhesive strength (P2) of the copper clad laminate above is shown by the following Equation 1.

[0058] <Equation 1>

[0059] 0.1 ≤ P1-P2 ≤ 0.3

[0060] In Formula 1, the room temperature adhesion strength (P1) and heat-resistant adhesion strength (P2) are evaluated according to JIS C 6471

[0061] It is.

[0062] In Equation 1, P1-P2 is, for example, 0.12 to 0.28, 0.13 to 0.27, 0.14 to 0.26, 0.15 to 0.26, 0.18 to 0.26, 0.2 to 0.26, 0.22 to 0.25, or 0.23 to 0.25.

[0063] If the difference between the room temperature adhesive strength (P1) and the heat-resistant adhesive strength (P2) of the copper clad laminate film satisfies the above Equation 1, the running ability of the film can be secured when manufacturing the copper clad laminate film, and the bendability is improved as curl, wrinkles, etc. do not occur.

[0064] The heat-resistant adhesive strength of the copper clad laminate film according to JIS C 6471 is 0.3 kgf / cm or more, for example, 0.3 to 0.8 kgf / cm. Using a copper clad laminate film having such heat-resistant adhesive strength improves room temperature adhesion and heat-resistant adhesive strength.

[0065] Referring to the attached drawings, a copper clad laminate film according to one embodiment, an electronic component including the same, an apparatus, and a method for manufacturing the copper clad laminate film are described as follows.

[0066] FIG. 1 is a schematic cross-sectional view of a copper clad laminate film according to one embodiment, and FIGS. 2a to 2c are intended to explain a method for manufacturing a copper clad laminate film according to one embodiment.

[0067] Referring to FIG. 1, a copper clad laminate film (100) according to one embodiment has a structure in which a nickel tie layer (31) and a copper layer (41) are sequentially arranged on one side of a polyimide-containing substrate (21) having a thin thickness of 3 to 10 μm. On the other side of the polyimide-containing substrate (21), a first protective film (11) having a thickness of 30 μm or more is arranged.

[0068] The first protective film (11) may contain polyethylene terephthalate, etc. The thickness of the first protective film is 30 μm to 100 μm, 35 μm to 90 μm, 40 μm to 80 μm, or 50 μm to 70 μm. When using the first protective film having such thickness, a copper clad laminate film having excellent processability and flexibility can be manufactured even when using a polyimide-containing substrate having a thin thickness.

[0069] The copper layer (41) includes a copper seed layer and a copper plating layer, and has a structure in which they are sequentially stacked.

[0070] A first protective film (11) is placed on the other side of the polyimide-containing substrate (21).

[0071] On the other side of the polyimide-containing substrate (21) on which the first protective film (11) is disposed, the polyimide-containing substrate may be surface-treated prior to the first protective film (11) being disposed. According to one embodiment, the surface treatment may be, for example, corona treatment. Through this surface treatment, contaminants present on the surface of the polyimide-containing substrate are removed to achieve surface modification, and the adhesion to the first protective film (11) and / or nickel tie layer (31) to be formed in a subsequent process may be improved. For example, 10 to 50 W / cm² under an inert gas (e.g., Ar) or oxygen / nitrogen atmosphere of 0.5 to 20 Pa, 1 to 10 Pa, or 1.5 to 6 Pa. 2 , or 15 to 30 W / cm 2Surface treatment of the polyimide-containing substrate (21) can be performed using plasma generated by an RF voltage of power density.

[0072] An adhesive layer may be positioned between the first protective film (11) and the polyimide-containing substrate (21). The adhesive layer may contain, for example, an acrylic adhesive. The adhesive layer may have a thickness of, for example, 1 to 20 μm. The acrylic adhesive contains an acrylic resin obtained by copolymerization reaction of an acrylic monomer.

[0073] The first protective film (11) has a thickness of 30 μm or more. When using the first protective film having such a thickness, when manufacturing a copper clad laminate containing a polyimide-containing substrate having a thin thickness of 3 to 10 μm, it is possible to ensure the runability of the copper clad laminate and prevent wrinkles, thereby improving processability so that a nickel tie layer and a copper layer can be easily formed on the polyimide-containing substrate and the flexibility is improved. If the first protective film (11) is not included on one side of the polyimide-containing substrate, it is difficult to ensure the runability of the film during sputtering and electroplating to form a tie layer and a copper layer on one side of the polyimide-containing substrate (11), and wrinkles are formed on the film, making it difficult to perform the desired processing operation. Also, if the thickness of the first protective film is less than 30 μm, when manufacturing a copper clad laminate using the aforementioned thin-thickness polyimide-containing substrate, curls occur and wrinkles occur, making normal processing impossible and making it difficult to manufacture an ultra-thin copper clad laminate.

[0074] When manufacturing a copper clad laminate film according to one embodiment, a process of peeling and winding a first protective film is performed. During this process, wrinkles in the MD (Machine Direction) direction and curling of the film may occur. To prevent such phenomena, oscillation may be performed when winding the copper clad laminate film.

[0075] Referring to FIG. 2a, the copper clad laminate film (100) has a structure in which the first protective film (11) is peeled off and separated from the copper clad laminate film of FIG. 1.

[0076] Specifically, the copper clad laminate (100) comprises a polyimide-containing substrate (21), a nickel tie layer (31) located on one side of the polyimide-containing substrate (21), and a copper layer (41) located on the nickel tie layer (31).

[0077] As shown in FIG. 2a, when the first protective film (11) is removed, curling may occur in the copper clad laminate film. To prevent this phenomenon, a second protective film (51) is laminated on top of the copper layer (41) as shown in FIG. 2b.

[0078] The second protective film (51) can be formed with the same material and thickness as the first protective film (11).

[0079] A bonding sheet can be manufactured as shown in FIG. 2c by positioning a substrate (61) on the side of the polyimide-containing substrate (21) where the nickel tie layer (31) is not formed. Before attaching the substrate (61) to the polyimide-containing substrate (21), surface treatment can be performed on the polyimide-containing substrate (21) to improve the adhesion between the polyimide-containing substrate (21) and the substrate (61).

[0080] The polyimide-containing substrate (11) according to one embodiment may use a polyimide film or a polyimide film or sheet having a low dielectric constant (modified polyimide). For example, the polyimide film or sheet may be manufactured by extruding polyamic acid, which is a polyimide precursor, to form a film or sheet, and then heat-treating and drying the film or sheet to imidize the polyamic acid. The drying process may remove moisture and residual gas through a drying process commonly used in the art. For example, the drying may be performed by roll-to-roll type heat treatment under atmospheric pressure or by using an infrared (IR) heater under a vacuum atmosphere.

[0081] The polyimide-containing substrate (21) according to one embodiment may have a glass transition temperature (Tg) of 200°C or higher. Since the polyimide-containing substrate (21) has sufficient heat resistance, no physical or chemical changes occur within a high temperature range and for a long time. The glass transition temperature (Tg) of the polyimide-containing substrate (21) g If the temperature is 200°C or lower, the polyimide-containing substrate (21) may melt during the manufacturing process of electronic components such as printed circuit boards, or the polyimide-containing substrate (21) may undergo dimensional changes after the high-temperature process, causing the electronic components such as printed circuit boards to bend.

[0082] According to one embodiment, the thickness of the polyimide-containing substrate (21) may be 3 μm to 10 μm, 6 μm to 9 μm, 7 μm to 8.5 μm, 7.2 μm to 8 μm, or 7.5 μm. A copper clad laminate film (100) comprising a polyimide-containing substrate (21) of such thickness can achieve sufficient adhesion with a nickel tie layer and can improve flexibility. Accordingly, the copper clad laminate film (100) can be used in electronic devices requiring fine patterns, such as flexible printed circuit boards (FPCB) and / or camera coils.

[0083] If necessary, the polyimide-containing substrate (21) may be plasma-treated on its surface. Plasma treatment may be performed using RF plasma or an ion beam. Plasma treatment or an ion beam may be performed on one or both sides of the polyimide-containing substrate (21). Plasma treatment or an ion beam can not only enhance the chemical activity of the surface of the polyimide-containing substrate (21) but also improve surface roughness, thereby further enhancing the peel strength between the polyimide-containing substrate (11) and the nickel tie layer (31).

[0084] The nickel tie layer (31) is intended to increase the adhesion of the copper layer (41) to be formed in a subsequent process and may include nickel (Ni); a nickel alloy comprising one or more metals selected from nickel (Ni), molybdenum (Mo), niobium (Nb), and iron (Fe); or a combination thereof.

[0085] Nickel alloys are nickel alloys such as, for example, Ni-Mo alloy, Ni-Mo-Nb alloy, Ni-Mo-Co alloy, Ni-Mo-Fe alloy, etc.

[0086] The nickel tie layer does not contain chromium. When a tie layer is formed from a material that does not contain chromium in this way, the etchability is excellent, so the manufacturing process of the nickel tie layer can be easily performed. For example, the nickel tie layer (31) may contain a nickel alloy. In this case, the nickel content may be 70% to 99% by weight, 73% to 97% by weight, 75% to 95% by weight, or 75% to 85% by weight based on the total weight of the tie layer (31). A tie layer (31) having a nickel content within the above range may have excellent adhesion to the polyimide-containing substrate (11) and excellent flexural resistance.

[0087] According to an exemplary embodiment, the thickness of the nickel tie layer (31) may be 10 nm to 100 nm. For example, the thickness of the nickel tie layer (31) may be 10 nm to 80 nm, 10 nm to 30 nm, 10 nm to 20 nm, or 10 nm to 15 nm. A nickel tie layer (31) having a thickness within the above range may have excellent adhesion to the polyimide-containing substrate (21) and excellent flexibility. If the thickness of the nickel tie layer (31) is smaller than the above-described range, the adhesion between the polyimide-containing substrate (21) and the copper layer (41) may be reduced. If the thickness of the nickel tie layer (31) is larger than the above-described range, sufficient thinning of the copper clad laminate may not be achieved, and when an etching process for forming a circuit pattern is performed, a portion of the nickel tie layer that needs to be removed may remain, causing a short circuit in the circuit.

[0088] The thickness ratio of the polyimide-containing substrate to the nickel tie layer is 30:1 to 1,000:1, 30:1 to 800:1, 30:1 to 600:1, 50:1 to 600:1, 100:1 to 600:1, 150:1 to 600:1, or 375 to 600:1. When the thickness ratio of the polyimide-containing substrate to the nickel tie layer is within the above range, an ultra-thin copper clad laminate with excellent flexibility can be manufactured.

[0089] The copper foil laminated film according to the first embodiment may have almost no curling.

[0090] According to another embodiment, the copper clad laminate film may have a curl height of less than 30 mm. The curl height may be, for example, less than 30 mm, or less than 25 mm, or less than 20 mm, or less than 15 mm, or less than 10 mm, or less than 5 mm, or less than 3 mm, 0.01 to 2.99 mm, or 0.1 to 2.95 mm.

[0091] The copper layer (41) according to the first embodiment includes a copper seed layer and a copper plating layer.

[0092] The copper seed layer of the copper layer (41) may be a copper sputtered layer. The copper sputtered layer is 10 on the nickel tie layer (31). -4 to 10 -2 The layer may be deposited by sputtering in a vacuum tank under reduced pressure of torr. Any sputtering method available in the relevant technical field may be used. Examples of sputtering methods include physical vapor deposition (PVD), chemical vapor deposition (CVD), low-pressure chemical vapor deposition (LPCVD), or vacuum deposition.

[0093] A copper layer (41) can be placed on a nickel tie layer (31). The copper layer (41) can be in direct contact with the nickel tie layer (31). Since the nickel tie layer (31) is conductive, the copper layer (41) can be easily formed. The copper layer (41) may include a copper seed layer placed on the nickel tie layer (31) and a copper plating layer placed on the copper seed layer.

[0094] The copper seed layer may be a sputtered layer. Any deposition method available in the relevant technical field may be used as the sputtering method; however, examples of sputtering methods include physical vapor deposition (PVD), chemical vapor deposition (CVD), low-pressure chemical vapor deposition (LPCVD), or vacuum deposition. For example, the copper seed layer is 10 on the tie layer -4 torr to 10 -2 It can be deposited by sputtering in a vacuum tank under reduced pressure of torr.

[0095] The thickness of the copper seed layer may be 10 nm to 1500 nm. For example, the thickness of the copper seed layer may be 50 nm to 500 nm, 70 nm to 300 nm, 80 nm to 150 nm, or 100 nm to 140 nm. If the thickness of the copper seed layer is smaller than the above-described range, the signal transmission speed by the copper clad laminate film (100) may be reduced. If the thickness of the copper seed layer is larger than the above-described range, sufficient thinning of the copper clad laminate film (100) may not be achieved.

[0096] The copper plating layer may be placed on a copper seed layer. The copper plating layer may come into direct contact with the copper seed layer. As a method for forming the copper plating layer, any plating method available in the relevant technical field may be used, but for example, electroless plating or electrolytic plating may be used as the plating method.

[0097] A copper plating layer can be formed on a copper seed layer by performing electroplating with an electroplating solution based on copper sulfate and sulfuric acid. Electroplating can be performed using a plating solution containing copper at a concentration of 15 g / L to 40 g / L, 15 g / L to 38 g / L, or 17 g / L to 36 g / L.

[0098] In electrolytic plating, the temperature of the plating solution can be maintained at 22°C to 37°C, 25°C to 35°C, or 27°C to 34°C. Within the temperature range of the plating solution, the formation of a copper plating layer is easy and excellent productivity can be achieved.

[0099] 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 adjusters may include organic acids, inorganic acids, organic bases, inorganic bases, or any combination thereof. Examples of the inorganic acids include phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, or any combination thereof. Examples of the inorganic bases include ammonium hydroxide, sodium hydroxide, potassium hydroxide, or any combination thereof.

[0100] The above plating solution may include additives such as brighteners, levelers, correctors, and emollients to improve productivity and surface uniformity.

[0101] Electroplating has a current density of 0.1 A / m² 2 up to 20A / m 2 , 0.1A / m 2 Up to 17 A / m 2 , or 0.3A / m 2 Up to 15 A / m 2 It can be performed under the conditions of the above. Within the range of current densities, the formation of a copper plating layer is easy and can have excellent productivity.

[0102] The thickness of the copper plating layer may be 0.1 μm to 10 μm. For example, the thickness of the copper plating layer may be 0.5 μm to 8 μm, 1 μm to 5 μm, or about 2 μm. If the thickness of the copper plating layer is smaller than the above-described range, the signal transmission speed by the copper clad laminate film (100) may be reduced. If the thickness of the copper plating layer is larger than the above-described range, sufficient thinning of the copper clad laminate film may not be achieved. If the thickness of the copper plating layer is within the above-described range, the flexibility may be further improved.

[0103] According to one embodiment, the copper clad laminate film (100) has a fatigue life of 5,000 cycles or more when its flexibility is measured by an MIT bending tester according to JIS C 6471. By using such a copper clad laminate film, it is possible to meet the physical properties required by the user and develop electronic components that achieve high integration.

[0104] According to another aspect, an electronic component including the copper clad laminate film described above is provided.

[0105] Examples of electronic components include antenna elements and circuit boards. For example, an electronic component may be a (flexible) printed circuit board.

[0106] According to another aspect, a device including the copper clad laminate film described above is provided.

[0107] Examples of devices include components such as antenna elements or circuit boards, network servers, IoT (Internet of Things) for 5G, home appliances, USBs, or radar.

[0108] A method for manufacturing a copper clad laminate film according to one embodiment is described as follows.

[0109] A method for manufacturing a copper clad laminate includes the steps of providing a first protective film having a thickness of 30 μm or more on one side of a polyimide-containing substrate having a thickness of 3 to 10 μm, forming a nickel tie layer on the other side of the polyimide-containing substrate, and forming a copper layer on the nickel tie layer.

[0110] The method may further include the step of peeling off the first protective film from the copper clad laminate and placing a second protective film on the copper layer.

[0111] After peeling off the second protective film, the method may include the step of applying oscillation to the film in the MD (Machine Direction) direction relative to the film's direction of travel, thereby moving the film and transporting and winding it in the direction of travel.

[0112] The above oscillation reciprocates a guide roller installed in the machine direction (MD) relative to the film travel direction by a certain width or a certain angle, and the reciprocating width is 1 mm to 100 mm, 1 mm to 80 mm, 1 mm to 50 mm, 1 mm to 30 mm, 1 mm to 20 mm, 1 mm to 10 mm, or 5 mm to the left and right.

[0113] According to another embodiment, the reciprocating width is 1 mm to 30 mm, 1 mm to 15 mm, for example 3 to 10 mm, for example 5 mm. The reciprocating speed can be 5 mpm (meters per minute) to 15 mpm, 5 mpm (meters per minute) to 12 mpm, 5 to 10 mpm, or 5 mpm.

[0114] When oscillation is applied in the MD direction relative to the direction of travel of the film, a copper clad laminate containing a thin-thickness polyimide-containing substrate has improved flexural strength, and the room temperature adhesion and heat-resistant adhesion between the copper layer and the relatively thin-thickness substrate are improved.

[0115] According to the method for manufacturing a copper clad laminate film according to one embodiment, it is possible to improve the occurrence of wrinkles and runnability that occur during the manufacturing of general CCL (Copper Clad Laminate), thereby enabling stable production of ultra-thin CCL.

[0116] The copper clad laminate obtained according to the manufacturing method described above has improved flexibility and enhanced room-temperature adhesion and heat-resistant adhesion between the copper layer and a substrate having a relatively thin thickness. Furthermore, since the copper clad laminate possesses sufficient room-temperature adhesion and heat-resistant adhesion even when including a polyimide-containing substrate having a relatively thin thickness, thin film formation is possible. Such a copper clad laminate can meet the physical properties required by the user and enable the development of electronic components with high integration density.

[0117] Hereinafter, the structure of the present invention and the resulting effects are to be explained in more detail through examples and comparative examples. However, it will be obvious that these examples are intended to explain the present invention more specifically and that the scope of the present invention is not limited to these examples.

[0118] [Example]

[0119] Example 1: Copper clad laminate film

[0120] As shown in Figure 1, a copper clad laminate film was manufactured.

[0121] As a substrate, a polyimide (PI) film with a thickness of about 7.5 μm (7500 nm) (GL030A, manufactured by PI Advanced Materials) was prepared.

[0122] After performing corona treatment on one side of a polyimide film, a first protective film (thickness: about 60 μm) composed of an acrylic adhesive layer (thickness: about 10 μm) and a first protective film, a polyethylene terephthalate (PET) film (thickness: about 50 μm), is placed on one side of the corona-treated polyimide film to form a polyimide film having the first protective film placed on one side of a polyimide-containing substrate.

[0123] A nickel tie layer approximately 15 nm thick and a copper seed layer approximately 100 nm thick were sequentially formed on the other side of the polyimide film using physical vapor deposition (PVD) with a roll-to-roll sputtering apparatus. At this time, nickel with a purity of over 99.9% and copper with a purity of 99.995% were used for the nickel tie layer and the copper seed layer, respectively. A copper plating layer approximately 8.7 μm thick was formed on the copper seed layer by electroplating. The electroplating solution used was Cu 2+ A copper sulfate plating solution containing 180 g / L of sulfuric acid at a concentration of 28 g / L was used, and additionally, a solution containing 0.8 g / L of 3-N,N-dimethylaminodithiocarbamoyl-1-propanesulfonic acid as a brightener and a correction agent (product of Atotech) was used. Electroplating was performed at approximately 30°C and formed by applying a current at a current density of 2.3 A / m². Subsequently, the copper clad laminate film with the copper plating layer formed was subjected to oscillation at a speed of 5 m / min with a width of 5 mm to the left and right in the machine direction (MD) relative to the film's direction of travel, and wound to produce a copper clad laminate film with the first protective film removed. In the copper clad laminate film, the thickness ratio of the polyimide-containing substrate to the nickel tie layer is 500:1.

[0124] Example 2: Copper clad laminate film

[0125] A copper clad laminate film was manufactured in the same manner as in Example 1, except that the thickness of the polyimide substrate was changed to 6 μm. In the copper clad laminate film, the thickness ratio of the polyimide-containing substrate to the nickel tie layer is 400:1.

[0126] Example 3: Copper clad laminate film

[0127] A copper clad laminate film was manufactured in the same manner as in Example 1, except that the thickness of the polyimide substrate was changed to 9 μm. In the copper clad laminate film, the thickness ratio of the polyimide-containing substrate to the nickel tie layer is 600:1.

[0128] Example 4: Copper clad laminate film

[0129] A copper clad laminate film was prepared in the same manner as in Example 1, except that a polyimide film (GL030A, manufactured by PI Advanced Materials) with a thickness of approximately 7.5 μm was used as the substrate and the thickness of the nickel tie layer was changed to 20 nm. In the copper clad laminate film, the thickness ratio of the polyimide-containing substrate to the nickel tie layer is 375:1.

[0130] Comparative Example 1: Copper clad laminate film

[0131] A copper clad laminate film was manufactured in the same manner as in Example 1, except that a polyimide film with a thickness of about 7.5 μm (GL030A, manufactured by PI Advanced Materials) was used as the substrate instead of a polyimide film having a PET film disposed on one side, and a nickel-chromium alloy layer formed according to the following process was used as the tie layer instead of a Ni layer.

[0132] A nickel-chromium alloy tie layer (Ni:Cr weight ratio = 70:30) with a thickness of approximately 25 nm was formed on a polyimide film. At this time, nickel with a purity of 99.9% or higher and chromium with a purity of 99.995% were used for the nickel-chromium alloy tie layer.

[0133] Comparative Example 2: Copper clad laminate film

[0134] A copper clad laminate film was manufactured in the same manner as in Example 1, except that a polyimide film with a thickness of about 7.5 μm (GL030A, manufactured by PI Advanced Materials) was used as the substrate instead of a polyimide film having a PET film disposed on one side, and a nickel-copper alloy tie layer formed according to the following process was used as the tie layer instead of a Ni layer.

[0135] A nickel-copper alloy tie layer (Ni:Cu weight ratio = 80:20) with a thickness of about 10 nm was formed on a polyimide film. At this time, nickel with a purity of 99.9% or higher and copper with a purity of 99.995% were used for the nickel-copper alloy tie layer.

[0136] Comparative Example 3: Copper clad laminate film

[0137] A copper clad laminate film was manufactured in the same manner as in Example 1, except that a polyimide film with a thickness of about 7.5 μm (GL030A, manufactured by PI Advanced Materials) was used instead of a polyimide film having a PET film disposed on one side as a substrate, and a nickel tie layer was not formed.

[0138] Comparative Example 4: Copper clad laminate film

[0139] A copper clad laminate film was prepared by following the same method as in Example 1, except that a polyimide film with a thickness of about 7.5 μm (GL030A, manufactured by PI Advanced Materials) was used instead of a polyimide film having a PET film disposed on one side as a substrate.

[0140] Comparative Example 5: Copper clad laminate film

[0141] A copper clad laminate film was manufactured by following the same method as in Example 1, except that the thickness of the polyimide film used as the substrate was 12.5 μm.

[0142] Comparative Example 6: Copper clad laminate film

[0143] A copper clad laminate film was manufactured by following the same method as in Example 1, except that the thickness of the polyimide film used as the substrate was 25 μm.

[0144] Comparative Example 7: Copper clad laminate film

[0145] A copper clad laminate film was manufactured by following the same method as in Example 1, except that the thickness of the polyimide film used as the substrate was 35 μm.

[0146] Comparative Example 8: Copper clad laminate film

[0147] A copper clad laminate film was manufactured in the same manner as in Example 1, except that a film with the first protective film removed was manufactured by applying oscillation in the cross direction (CD) to a copper clad laminate film having a copper plating layer formed thereon and winding it.

[0148]

[0149] Evaluation Example 1: MIT Measurement - Fatigue Life Evaluation

[0150] The fatigue life of each copper clad laminate prepared in Examples 1 to 4 and Comparative Examples 1 to 8 was evaluated. The results are shown in Table 1 below.

[0151] Fatigue life evaluation was performed by measuring with an MIT bending tester (SFT-9250, manufactured by TOYO SEIKI Co., Ltd.) according to JIS C 6471.

[0152] Each copper clad laminate was cut to a size of 235 mm x 295 mm and stored in a constant temperature and humidity chamber (temperature: 23±2℃, humidity: 60±5%) for 72 hours, then a pattern (width: 1000 μm) was formed and etched with an acid solution. Subsequently, each patterned copper clad laminate was stored in a dimensional chamber for 24 hours and in an 80 ℃ oven for 1 hour to prepare the sample. One end of the sample in the longitudinal direction was fixed to the nip jig of the MIT bending tester, and the other end was fixed with a weight (500 g load). As shown in Fig. 4, (+) and (-) electrodes were attached to both ends of the sample, and as shown in Fig. 5, the sample was bent to a radius of curvature of 0.38 mm while rotating it alternately left and right at an angle of 135±5° around the nip portion, and the number of times the sample was short-circuited was determined.

[0153] Classification Use of First Protective Film Thickness of PI Substrate (㎛) Thickness of First Protective Film (㎛) Fatigue Life (cycles) Example 1 ○7.5305,411 Example 2 ○6307,312 Example 3 ○9305,742 Example 4 ○7.5305,314 Comparative Example 1 X--3,752 Comparative Example 2 X--4,752 Comparative Example 3 X--4,212 Comparative Example 4 X--4,117 Comparative Example 5 ○12.57.51,240 Comparative Example 6 ○257.5547 Comparative Example 7 ○357.5124 Comparative Example 8 ○7.5303,412

[0154] As shown in Table 1, the fatigue life of the copper clad laminates prepared in Examples 1 to 4 is 5,000 cycles or more, showing improved results compared to the fatigue life of the copper clad laminates prepared in Comparative Examples 1 to 8. From this, it was confirmed that the copper clad laminates prepared in Examples 1 to 4 have improved flexibility. Such copper clad laminates can meet the physical properties required by users and enable the development of electronic components with high integration density.

[0155] In addition, Comparative Examples 5 to 7 are cases where the thickness of the polyimide film used as the substrate exceeds 9 μm compared to Example 1, and it was found that in such cases, the flexural strength was significantly reduced.

[0156] The copper clad laminate of Comparative Example 8 is a case in which oscillation is applied to the film in the CD direction compared to the copper clad laminate of Example 1. According to Comparative Example 8, the internal grain structure of the film is refined and the stress increases, resulting in a decrease in the film's flexibility. Additionally, since the film is driven and wound in the MD direction, applying force in the CD direction causes curling, which reduces the processability of the copper clad laminate.

[0157] Evaluation Example 2: Adhesion Analysis

[0158] The copper clad laminate films prepared according to Examples 1 to 4 and Comparative Examples 1 to 8 were further plated with a Cu thickness of 7.5 μm, which is used in the process of making a Flexible Printed Circuit Board (FPCB), and room temperature adhesion and heat-resistant adhesion were measured according to the JISC 6471 evaluation method as follows, and the adhesion results of the measured values ​​are shown in Table 2 below.

[0159] (1) Room temperature adhesive strength (P1) (kgf / cm)

[0160] In accordance with JIS C 6471, patterned to a width of 3.0 mm, and at room temperature (23℃±2℃)

[0161] After leaving it for 24 hours, the 180° peel strength (test speed 50 mm / min) is measured and evaluated using a Texture Analyzer (TAXplus / 50, SMS).

[0162] (2) Heat-resistant adhesive strength (P2) (kgf / cm)

[0163] In accordance with JIS C 6471, after treatment at a high temperature of 150°C for 167 hours, to a width of 3.0 mm

[0164] Heat-resistant adhesive strength is evaluated by patterning and measuring the 180° peel strength (test speed 50 mm / min, load 5 N) using a Texture Analyzer (TAXplus / 50, SMS).

[0165] Classification Room Temperature Adhesion (P1) (kgf / cm) Heat Resistance Adhesion (P2) (kgf / cm) Adhesion Strength Difference (P1-P2) (kgf / cm) Example 1 0.5 6 0.3 1 0.25 Example 2 0.5 8 0.3 3 0.25 Example 3 0.5 9 0.3 1 0.28 Example 4 0.5 7 0.3 2 0.25 Comparative Example 10.6 1 0.2 7 0.34 Comparative Example 20.5 6 0.1 3 0.43 Comparative Example 30.4 7 0.1 3 0.34 Comparative Example 40.6 4 0.1 4 0.40 Comparative Example 50.6 3 0.1 9 0.44 Comparative Example 60.5 9 0.2 2 0.37 Comparative Example 70.6 1 0.2 4 0.37 Comparative Example 80.540.220.32

[0166] As shown in Table 2, the copper clad laminates of Examples 1 to 4 demonstrated improved heat-resistant adhesion with a heat-resistant adhesion of 0.3 kgf / cm or higher compared to the copper clad laminates of Comparative Examples 1 to 8. Furthermore, the copper clad laminates of Examples 1 to 4 secured excellent room-temperature adhesion and heat-resistant adhesion, while maintaining an adhesion difference (P1-P2) within the range of 0.25 to 0.28. This resulted in excellent runability during copper clad laminate manufacturing and exhibited improved flexibility. It was confirmed that using such copper clad laminates significantly improves circuit stability after patterning while maintaining excellent surface quality. In contrast, as shown in Table 2, the copper clad laminates of Comparative Examples 1 to 8 exhibited excellent room-temperature adhesion but showed a heat-resistant adhesion of less than 0.3 kgf / cm, indicating a decrease in heat-resistant adhesion compared to the copper clad laminates of Examples 1 to 4.

[0167] In addition, unlike the cases of Examples 1 to 4, the copper clad laminate films of Comparative Examples 1 to 8 had an adhesion difference (P1-P2) exceeding 0.3, and due to this difference, the running performance was poor when manufacturing the copper clad laminate film, and as can be confirmed in Evaluation Example 3 below, curls of 30 mm or more in height and wrinkles occurred, resulting in reduced flexibility.

[0168] Evaluation Example 3: Photo Analysis

[0169] The appearance of the copper clad laminate films of Examples 1 to 4 and Comparative Examples 1 to 8 was analyzed by photograph, and the results are shown in Table 3 below. As a result of the appearance analysis of each copper clad laminate film, cases where almost no curl occurred were marked with ○, and cases where curl of 30 mm or more occurred were marked with X.

[0170] Classification Curl Occurrence Example 1X Example 2X Example 3X Example 4X Comparative Example 1○ Comparative Example 2○ Comparative Example 3○ Comparative Example 4○ Comparative Example 5○ Comparative Example 6○ Comparative Example 7○ Comparative Example 8○

[0171] As shown in Table 3, unlike Comparative Examples 1 to 8, almost no curl occurred in the copper clad laminate films of Examples 1 to 4. In contrast, it was confirmed that the copper clad laminate films of Comparative Examples 1 to 8 had curls of 30 mm or more in height, and that many wrinkles were formed in addition to the curls.

[0172] In addition, the results of photographic analysis of the appearance of the copper clad laminate film (Width 500mm x Length 500mm) according to Example 1 and Comparative Example 1 are shown in FIG. 2a and FIG. 2b, respectively.

[0173] Referring to FIG. 2a, the copper clad laminate according to Example 1 had almost no curl or wrinkles.

[0174] In contrast, as shown in FIG. 2b, the copper clad laminate according to Comparative Example 1 is rolled to the extent that the height of the curl cannot be measured and wrinkles can be observed.

Claims

1. Polyimide-containing substrate; A nickel tie layer located on one side of the above-mentioned polyimide-containing substrate; A copper layer located on the nickel tie layer; comprising The above-mentioned polyimide-containing substrate is a copper clad laminate film having a thickness of 3 μm to 10 μm, and A copper clad laminate having a fatigue life of 5,000 cycles or more when the flexibility of the above copper clad laminate is measured using an MIT bending tester according to JIS C 6471.

2. In Paragraph 1, A copper clad laminate, wherein the difference between the room temperature adhesive strength (P1) and the heat-resistant adhesive strength (P2) of the above copper clad laminate is represented by the following Equation 1: <Equation 1> 0.1 ≤ P1 - P2 ≤ 0.3 In Formula 1, P1 and P2 are evaluated in accordance with JIS C 6471.

3. In Paragraph 1, A copper clad laminate film having a thickness of 6 μm to 9 μm of the polyimide-containing substrate.

4. In Paragraph 1, A copper clad laminate film comprising the nickel tie layer comprising nickel (Ni); a nickel alloy comprising one or more metals selected from nickel (Ni), molybdenum (Mo), niobium (Nb), and iron (Fe); or a combination thereof.

5. In Paragraph 1, A copper clad laminate film having a heat-resistant adhesive strength of 0.3 kgf / cm or more according to JIS C 6471.

6. In Paragraph 1, A copper clad laminate film having a thickness ratio of the polyimide-containing substrate and the nickel tie layer of 30:1 to 1000:

1.

7. In Paragraph 1, The copper layer above comprises a copper seed layer and a copper plating layer, forming a copper clad laminate film.

8. In Paragraph 7, A copper clad laminate film having a copper seed layer thickness of 10 nm to 1500 nm.

9. In Paragraph 7, A copper clad laminate film having a copper plating layer thickness of 0.5 μm to 10 μm.

10. In Paragraph 1, The thickness of the nickel tie layer is 10 nm to 100 nm, and The above nickel tie layer is a copper clad laminate film that does not contain chromium.

11. In claim 1, the copper clad laminate film is, A step of providing a first protective film having a thickness of 30 μm or more on one surface of a polyimide-containing substrate having a thickness of 3 to 10 μm; A step of forming a nickel tie layer on the other side of the polyimide-containing substrate; A step of forming a copper layer on the nickel tie layer; A step of peeling off a first protective film from a structure obtained according to the above steps and placing a second protective film on top of a copper layer; and A copper clad laminate film manufactured by including the step of peeling off the second protective film, then applying oscillation to the film in the MD (Machine Direction) direction relative to the film's direction of travel, thereby causing the film to move, and then transporting and winding the film in the direction of travel.

12. An electronic component comprising a copper foil laminated film according to any one of claims 1 to 11.

13. An apparatus comprising a copper clad laminate film according to any one of claims 1 to 11.

14. A step of providing a first protective film having a thickness of 30 μm or more on one surface of a polyimide-containing substrate having a thickness of 3 to 10 μm; A step of forming a nickel tie layer on the other side of the polyimide-containing substrate; and A method for manufacturing a copper clad laminate film, comprising the step of forming a copper layer on the nickel tie layer above; and the step of manufacturing a copper clad laminate film according to claim 1 by carrying out the step of forming a copper layer on the nickel tie layer above.

15. In Paragraph 14, A method for manufacturing a copper clad laminate, further comprising the step of peeling off a first protective film from the copper clad laminate and placing a second protective film on top of the copper layer.

16. In Paragraph 14, A method for manufacturing a copper clad laminate film comprising the step of peeling off the second protective film, then applying oscillation to the film in the MD (Machine Direction) direction relative to the film's direction of travel, thereby moving the film while transferring and winding it in the direction of travel.

17. In Paragraph 16, A method for manufacturing a copper clad laminate film, wherein the above oscillation is performed by reciprocating a guide roller installed in the MD direction relative to the film travel direction, wherein the reciprocating width is within 1 mm to 100 mm to the left and right, and the reciprocating speed is 5 mpm to 15 mpm.

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