JP2018141228A - Electrolytic copper foil having villus-like copper particles and production method of circuit board component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolytic copper foil having villus-like copper particles and a production method thereof.SOLUTION: A production method of an electrolytic copper foil having villus-like copper particles includes: a step of forming a copper foil layer having a predetermined surface by an electrolytic method; and, then a step of forming a surface treatment layer on a predetermined surface of the copper foil layer such that an electrolytic copper foil having a villus structure on a superficial layer is formed. The surface treatment layer contains a plurality of villus-like copper particles and forms a villus-like housing space between each two adjacent villus-like copper particles. The step of forming the surface treatment layer further includes a step of executing a first time plating roughening treatment and a step of executing a first time plating hardening treatment. In a first plating liquid used in the first time plating roughening treatment, 3 to 40 g/L of copper, 100 to 120 g/L of sulfuric acid, 20 ppm or lower of arsenic oxide, and 5 to 20 ppm of tungstate ions are contained.SELECTED DRAWING: Figure 2

Description

  The present invention relates to an electrolytic copper foil and a method for manufacturing a circuit board component, and more particularly, a method for manufacturing an electrolytic copper foil having a villi structure on a surface layer, and a manufacturing of a circuit board component using the electrolytic copper foil having a villi structure on a surface layer. Regarding the method.

  A conventional copper foil applied to a printed circuit board is formed as a final product through a subsequent processing process after an original foil is formed on a cathode drum by plating. In subsequent processing, the roughening treatment is performed on the rough surface of the original foil, thereby forming a plurality of copper particles on the rough surface of the original foil, thereby improving the adhesive strength between the copper foil and the circuit board. Let That is, the subsequent process includes a step of improving the peel strength of the copper foil.

  However, in recent years, electronic products tend to have higher frequencies and higher speeds, and a so-called skin effect occurs during high-frequency signal transmission. In patent document 1 (patent No. 5116943), the copper foil for high frequency circuits and its manufacturing method are disclosed. Patent Document 1 explains that the copper foil surface shape greatly affects transmission loss, and that a copper foil having a large roughness increases the signal propagation distance and causes signal attenuation and delay problems. . In other words, the smoother the surface of the copper foil, the smaller the transmission loss in the signal conductor. Therefore, the smoothness of the copper foil surface plays a very important role. The higher the roughness of the copper foil surface, the easier it is to lose during high frequency signal transmission.

  FIG. 1 is a local sectional view of a copper foil in the prior art. As shown in FIG. 1, in the prior art, the plurality of copper particles F10 formed on the surface of the copper foil F1 are substantially spherical, and most of the spherical copper particles F10 have a maximum horizontal dimension that is the maximum in the vertical direction. Greater than dimensions. Therefore, although the roughness of the copper foil can be maintained at a predetermined value, there arises a problem that the peel strength of the copper foil is insufficient when the copper foil is bonded to the high-frequency substrate.

  However, if it is attempted to reduce the transmission loss of the high-frequency signal by reducing the roughness of the copper foil surface, the peel strength of the crimping between the copper foil and the circuit board is lowered. Therefore, how to improve the peel strength of the copper foil and maintain the smoothness of the copper foil surface is now an important issue in this field.

Japanese Patent No. 5116943

  The technical problem to be solved by the present invention is to provide an electrolytic copper foil having villi-like copper particles and a method for producing a circuit board component, which can eliminate the drawbacks in the prior art.

  In order to solve the above-mentioned subject, the manufacturing method of the electrolytic copper foil which has the villi-like copper particle concerning the present invention includes the following processes. A copper foil layer having a predetermined surface is formed by an electrolysis method. Next, a surface treatment layer is formed on a predetermined surface of the copper foil layer so as to form an electrolytic copper foil having a villi-like structure on the surface layer. The surface treatment layer includes a plurality of villi-like copper particles, and forms a villi-like accommodation space between each two adjacent villi-like copper particles. The step of forming the surface treatment layer further includes a step of executing the first plating roughening treatment and a step of executing the first plating hardening treatment. The first plating solution used for the first plating roughening treatment contains 3 to 40 g / L of copper, 100 to 120 g / L of sulfuric acid, 20 ppm or less of arsenic oxide and 5 to 20 ppm of tungstate ion. It is.

  The method for manufacturing a circuit board component according to the present invention includes the following steps. First, the electrolytic copper foil which has the villi-like copper particle formed by the manufacturing method of the electrolytic copper foil which has the above-mentioned villi-like copper particle is provided. Next, the electrolytic copper foil having the above-mentioned villi-like copper particles is pressure-bonded to the resin substrate so as to form a circuit board component. In the electrolytic copper foil having the villi-like copper particles, the surface treatment layer faces the resin substrate.

  The effect of the present invention is that the surface treatment layer of the electrolytic copper foil has a plurality of villi-like copper particles or villi-like copper particles by the above-described method for producing an electrolytic copper foil having villi-like copper particles. There is in point that can. That is, the width of the villi-like copper particles or villi-like copper particles is smaller than the width of the spherical copper particles in the prior art. Therefore, when the electrolytic copper foil having a villi-like structure on the surface layer and the resin substrate are bonded, the electrolytic copper foil having the villi-like structure on the surface layer is compared with the resin substrate in comparison with the electrolytic copper foil having the spherical copper particles in the prior art. Since it has a larger contact area between the two, it can have a higher peel strength.

It is local sectional drawing of the electrolytic copper foil in a prior art. It is a flowchart of the manufacturing method of the electrolytic copper foil which has a villi-like copper particle based on the Example of this invention. It is a figure which shows the system for performing the manufacturing method of the electrolytic copper foil which has a villi-like copper particle of FIG. It is local sectional drawing of the electrolytic copper foil which has a villi-like copper particle which concerns on the Example of this invention. It is a local enlarged view which shows the area | region V in the electrolytic copper foil which has a villi-like copper particle of FIG. It is a photograph by the scanning electron microscope (SEM) of the electrolytic copper foil which has a villi-like copper particle which concerns on the Example of this invention. It is a photograph by the scanning electron microscope (SEM) of the electrolytic copper foil of a comparative example. It is a focused ion beam (FIB) photograph of the electrolytic copper foil which has a villi-like copper particle based on the Example of this invention. It is sectional drawing which shows the circuit board component which concerns on the Example of this invention. FIG. 10 is a locally enlarged view showing a region X of the circuit board component of FIG. 9. It is sectional drawing which shows the circuit board component which concerns on the other Example of this invention.

  Hereinafter, the present invention will be described in detail with reference to the drawings so that the features and technical contents of the present invention can be further understood. However, the drawings are merely presented for reference and convenience of description, and do not limit the present invention.

  Hereinafter, an embodiment of an electrolytic copper foil having a villi-like copper particle and a method for manufacturing a circuit board component according to the present invention will be described by specific examples. By the manufacturing method according to the embodiment of the present invention, an electrolytic copper foil having villi-like copper particles having low roughness and high peel strength can be obtained. Further, the circuit board component formed by bonding the electrolytic copper foil having the villi-like copper particles and the resin substrate manufactured by the manufacturing method can be applied to transmission of a high frequency signal.

  This will be described with reference to FIGS. FIG. 2 is a flowchart of a method for producing an electrolytic copper foil having chilli-like copper particles according to an embodiment of the present invention. FIG. 3 is a view showing an apparatus for carrying out the method for producing an electrolytic copper foil having the villi-like copper particles of FIG.

  First, as shown in FIG. 2, in step S100, a copper foil layer is formed by an electrolysis method. The copper foil layer has a predetermined surface.

  As shown in FIG. 3, the step of forming the copper foil layer by the electrolysis method includes a step of providing the foil making apparatus 1. The foil making apparatus 1 includes at least an electrolytic cell 10, an anode plate 11, a cathode drum 12, and a roller 13.

  Furthermore, the electrolytic cell 10 is used to fill the electrolytic solution L0. The anode plate 11 is provided in the electrolytic cell 10 and is electrically connected to the positive electrode output terminal of the power supply device E1. The anode plate 11 is formed by coating a titanium plate with an iridium element or an oxide thereof. The cathode drum 12 is provided corresponding to the electrolytic cell 10 and is located above the anode plate 11. The cathode drum 12 is electrically connected to the negative output terminal of the power supply device E1. In this embodiment, the cathode drum 12 is a titanium roller.

  In the present embodiment, the foil making apparatus 1 further includes a liquid supply pipe 14 that communicates with the fluid in the electrolytic cell 10. The above-described electrolytic solution L0 is injected into the electrolytic cell 10 through the liquid supply pipe 14, and the anode plate 11 is completely immersed, and a part of the cathode drum 12 is immersed in the electrolytic solution L0.

  Next, as shown in FIG. 3, the power supply device E1 outputs a direct current to the anode plate 11 and the cathode drum 12 and applies a current to the electrolyte L0, thereby converting the copper ions in the electrolyte L0 into the cathode drum. The copper foil layer 30 is deposited on the surface of 12.

  Further, when the electrolytic solution L0 is electrolyzed to form the copper foil layer 30, the electrolytic solution L0 is continuously supplied into the electrolytic cell 10. Specifically, the electrolytic solution L0 can be caused to flow into the electrolytic cell 10 via the liquid supply pipe 14 so as to maintain the copper ion concentration of the electrolytic solution L0 in the electrolytic cell 10. As shown in FIG. 3, the copper foil layer 30 formed on the surface of the cathode drum 12 is peeled off from the surface of the cathode drum 12 and passes through a roller 13 to perform subsequent processes.

  Furthermore, the copper foil layer 30 has a rough surface 30a and a smooth surface 30b facing the rough surface 30a. In the electrolysis process, since the smooth surface 30b is a surface in contact with the cathode drum 12 in the copper foil layer 30, the roughness of the smooth surface 30b is relatively constant. The rough surface 30a is a surface in contact with the electrolytic solution L0. The rough surface 30a or the smooth surface 30b of the copper foil layer 30 usually has a plurality of granular protrusions. In one Example, the ten-point average roughness of the rough surface 30a of the copper foil layer 30 is 2 micrometers or less, for example, 0.9 micrometer-1.9 micrometers.

  Next, as shown in FIG. 2, in step S200, the surface treatment layer is formed on a predetermined surface of the copper foil layer, thereby forming an electrolytic copper foil having a villi-like structure on the surface layer. The surface treatment layer includes a plurality of villi-like copper particles, and forms a villi-like accommodation space between each two adjacent copper particles.

  Furthermore, step S200 of forming the surface treatment layer further includes a step of executing at least one plating roughening treatment and at least one plating hardening treatment. In a present Example, a surface treatment layer is formed in the predetermined surface in a copper foil layer because a copper foil layer passes through the plating roughening process twice and the plating hardening process twice. The predetermined surface may be at least one of a rough surface and a smooth surface.

  More specifically, as shown in FIG. 2, in one embodiment, after step S100, the first plating roughening process (step S201), the first plating hardening process (step S203), and the second time The plating roughening process (step S202) and the second plating hardening process (step S204) are sequentially executed.

  In another embodiment, after step S100, the first plating roughening process (step S201), the second plating roughening process (step S202), the first plating hardening process (step S203), and the first The second plating hardening process (step S204) is sequentially executed.

  Furthermore, the greater the number of plating roughening treatments and plating hardening treatments, the higher the adhesion strength between the electrolytic copper foil and the resin substrate, but at the same time the surface roughness of the electrolytic copper foil increases, Disadvantageous for transmission applications. Therefore, according to the necessity of an actual manufacturing process, the number of times of plating roughening treatment and plating hardening treatment can be increased or decreased to adjust the order.

  With reference to FIG. 3, an example will be described in which a first plating roughening process, a first plating hardening process, a second plating roughening process, and a second plating hardening process are sequentially performed. .

  As shown in FIG. 3, the surface treatment apparatus 2 used when executing steps S201 to S204 includes a plurality of transmission units 20 arranged on the production line, at least one roughening unit 21 (2 in FIG. 3). 1), at least one curing unit 22 (two are shown in FIG. 3), and a plurality of cleaning baths 23. The number of the roughening unit 21, the curing unit 22, and the cleaning tank 23 can be determined as necessary. The plurality of transmission units 20 transmit the copper foil layer 30 to the roughening unit 21, the cleaning tank 23, and the curing unit 22 based on a predetermined process flow so that each processing can be performed.

The roughening unit 21 includes a roughening tank 210 for containing the first plating solution L1 and a set of roughening anode plates 211 provided in the roughening tank 210. As shown in FIG. 3, when the first plating roughening process is performed, the copper foil layer 30 is put into a roughening tank 210 in which the first plating solution L1 has already been placed. The first plating solution L1 used in this example is 3 to 40 g / L copper, 100 to 120 g / L sulfuric acid, 20 ppm or less arsenic oxide (As ₂ O ₃ ), and 5 to 20 ppm tungstate ion. (WO ₄ ²⁻ ) is included.

  When the first plating roughening process is performed, a positive voltage and a negative voltage are applied to the roughened anode plate 211 and the copper foil layer 30, respectively, to reduce the copper ions in the first plating solution L1. A plurality of bump-shaped copper particles are formed on the rough surface 30 a of the copper foil layer 30.

  The first plating solution L1 used in this embodiment has a special composition. That is, it contains a low concentration of copper and can limit the crystal growth direction of the bumpy copper particles. The concentration of arsenic oxide and the concentration of tungstate ions are 20 ppm or less. If the concentration of arsenic oxide is too high, spherical copper particles with large dimensions may be formed, making it difficult to form villi-like or villi-like copper particles.

  Furthermore, when the first plating roughening process is executed, the copper concentration in the first plating solution L1 is low, so that the copper atoms are stacked only in the deviated crystal direction (ie, the vertical direction). Limited. In other words, the bumpy copper particles grow in a direction that is substantially perpendicular to the rough surface 30a of the copper foil layer 30, and are biased in a direction that is substantially parallel to the rough surface 30a of the copper foil layer 30 to form a bumpy copper particle. It can be said that it is not easy to grow. Therefore, after the first plating roughening treatment, the horizontal dimension of most of the bump-shaped copper particles formed on the rough surface 30a of the copper foil layer 30 is smaller than the vertical dimension, and 2 The spacing between two adjacent bumpy copper particles is also increased.

Moreover, in one Example, when the 1st plating roughening process was performed, the current density of the copper foil layer 30 is 15-40 A / dm < ² >, and it can form a bump-shaped copper particle with a small dimension. it can. If the current density is further reduced by 15 A / dm ² , the peel strength of the electrolytic copper foil becomes insufficient, and if the current density is higher than 40 A / dm ² , copper powder may be dropped. Further, when the first plating roughening process is executed, the temperature of the first plating solution is maintained at about 20 to 40 degrees Celsius.

  After the first plating roughening treatment is completed, the first plating hardening treatment is performed to form a copper protective layer that covers the bumpy copper particles, thereby forming the copper foil layers into the copper foil layer. Thirty rough surfaces 30a or smooth surface 30b are fixed tightly to prevent the “powder falling” phenomenon.

  As shown in FIG. 3, the first plating curing process is performed by the curing unit 22. The curing unit 22 includes a curing tank 220 for containing the second plating solution L2 and a set of cured anode plates 221 provided in the curing tank 220.

  In the present embodiment, the copper foil layer 30 that has been subjected to the first plating roughening process in the roughening tank 210 is first transmitted to the cleaning tank 23 by the transmission unit 20 and cleaned, and then the first plating hardening process. Is transmitted to the curing tank 220 in order to execute.

  When the first plating hardening process is executed, a positive voltage and a negative voltage are applied to the hardening anode plate 221 and the copper foil layer 30 to reduce the copper ions in the second plating solution L2, respectively. A copper protective layer that covers the bump-shaped copper particles is formed on the foil layer 30.

  The second plating solution L2 used when performing the first plating hardening treatment contains 50 to 70 g / L copper, 70 to 100 g / L sulfuric acid, and arsenic oxide lower than 30 ppm, and The temperature of the second plating solution L2 is maintained at about 50 to 70 degrees Celsius.

The height of the bump-shaped copper particles formed in the first plating roughening treatment is not high. If a thick copper protective layer is formed during the first plating hardening process, the probability of occurrence of powder falling phenomenon can be reduced and the roughness of the electrolytic copper foil surface can be reduced. The surface area where the copper foil is bonded to the resin substrate is reduced, and the peel strength may be reduced. Therefore, when the first plating hardening process is executed, the current density is made lower than the current density used conventionally, thereby forming a thin copper protective layer having a favorable covering effect. Thereby, it is possible to prevent the surface area where the electrolytic copper foil is bonded to the resin substrate from being reduced while preventing powder falling. In one embodiment, when the first plating hardening process is executed, the current density is ² to 9 A / dm2.

  In one Example, after performing the 1st plating roughening process and the 1st plating hardening process, the electrolytic copper foil which has a villi-like structure in a surface layer can be formed. The detailed structure of the surface treatment layer will be described later.

  Next, the copper foil layer 30 that has been subjected to the first plating hardening process is first transferred from the hardening tank 220 to the cleaning tank 23 and cleaned by the transmission unit 20, and then the second plating roughening process is performed. To the next roughening tank 210.

  In the present embodiment, the parameters of the second plating roughening process are substantially the same as the parameters of the first plating roughening process. In the second plating roughening treatment, a plurality of bump-shaped copper particles already formed on the rough surface 30a of the copper foil layer 30 can be continuously grown. Further, in the second plating roughening treatment, the same first plating solution L1 as that in the first plating roughening treatment is used. Therefore, the growth direction of the bump-shaped copper particles is still limited to a direction that is substantially perpendicular to the rough surface 30 a of the copper foil layer 30. Thereby, the adhesion area of the final electrolytic copper foil and the resin substrate can be further increased.

Thereafter, the copper foil layer 30 that has been subjected to the second plating roughening treatment is transferred from the roughening vessel 210 to the other washing vessel 23 and washed by the transmission unit 20, and then the second plating hardening treatment is performed. Transmit to another curing tank 220 to do. The composition of the second plating solution L2 in the second plating hardening treatment may be the same as the composition of the second plating solution L2 in the first plating hardening treatment. Further, the current density at which the second plating curing process is executed may be about ² to 9 A / dm ² , similar to the current density in the first plating curing process. By performing the second plating curing treatment, a copper protective layer can be further provided so that powder does not fall off.

  This will be described with reference to FIGS. FIG. 4 is a partial cross-sectional view of the electrolytic copper foil according to the embodiment of the present invention. FIG. 5 is a local enlarged view showing a region V in the electrolytic copper foil of FIG. 4.

  The electrolytic copper foil 3 produced by the method for producing an electrolytic copper foil having the villi-like copper particles described above has a villi-like structure on the surface layer, and the area bonded to the resin substrate is increased. More specifically, the electrolytic copper foil 3 according to the embodiment of the present invention includes a copper foil layer 30 and a surface treatment layer 31 located on the copper foil layer 30.

  The surface treatment layer 31 is located on the rough surface 30a or the smooth surface 30b of the copper foil layer 30. In one Example, the total thickness T of the electrolytic copper foil 3 is 6-400 micrometers, and can be determined as needed.

  As shown in FIG. 5, in this embodiment, the surface treatment layer 31 includes a plurality of villi-like or villi-like copper particles 310, and each villi-like or villi-like copper particle 310 has a rough surface 30a. Or it extends along the long axis direction which is not parallel to the smooth surface 30b.

  Each villi-like or villi-like copper particle 310 has a long axis maximum diameter D1 and a short axis maximum diameter D2. In one embodiment, the long axis has a maximum diameter D1 of 0.5 μm to 1.5 μm, and the short axis has a maximum diameter D2 of 0.1 μm to 1.0 μm. In addition, a villi-like accommodation space S1 is formed between each two adjacent copper particles 310.

  As can be seen by comparing FIG. 1 and FIG. 5, the dimension in the minor axis direction of the spherical copper particles in the prior art is larger than the dimension in the major axis direction and is densely distributed. In comparison, the plurality of villi-like or villi-like copper particles 310 of the electrolytic copper foil 3 according to the present invention is in the short axis direction (that is, the direction parallel to the rough surface 30a or the smooth surface 30b of the copper foil layer 30). The diameter is smaller than the diameter in the major axis direction. In a preferred embodiment, the ratio of the short axis maximum diameter D2 to the long axis maximum diameter D1 of the chorionic copper particles 310 is 0.2 to 0.7.

In this example, the maximum diameter D1 of the major axis of the villi-like or villi-like copper particles 310 is not larger than the diameter of the conventional spherical copper particles. Therefore, the surface roughness of the electrolytic copper foil 3 in the present embodiment is not significantly increased by changing the shape of the copper particles. In one embodiment, the thickness t of the surface treatment layer 31 is approximately 0.1 to 4 μm, and the ten-point average surface roughness (R _z ) of the surface treatment layer 31 is approximately 1 to 4 μm. Thereby, the electrolytic copper foil 3 of a present Example can be applied to transmit a high frequency signal still combining with a high frequency board | substrate.

  Moreover, in the electrolytic copper foil 3 of the present embodiment, the interval P1 between each two adjacent villi-like or villi-like copper particles 310 is also wide. In other words, the villi-like or villi-like copper particles 310 of this embodiment also have a low density. In one embodiment, the spacing P1 between each two adjacent villi-like or villi-like copper particles 310 is 0.1 to 0.4 μm, and these villi-like or villi-like copper particles 310. The distribution density is 2 to 5 per square micrometer.

  This will be described with reference to FIGS. FIG. 6 is a scanning electron microscope (SEM) photograph obtained by photographing an electrolytic copper foil according to an example of the present invention, and FIG. 7 is a scanning electron microscope photograph obtained by photographing an electrolytic copper foil of a comparative example.

  When manufacturing the electrolytic copper foil of the comparative example, the parameters for executing the plating roughening treatment are substantially the same as those of the example of the present invention. However, the plating solution composition used when performing the plating roughening treatment contains copper having a concentration higher than 40 g / L.

  6 and 7, the copper particles of the electrolytic copper foil produced by adjusting the composition of the first plating solution in the examples of the present invention have small dimensions and long and narrow shapes. . In contrast, the copper particles of the electrolytic copper foil of the comparative example of FIG. 7 are spherical and large in shape.

  FIG. 8 is a photograph of a focused ion beam (FIB) of an electrolytic copper foil according to an embodiment of the present invention, taken by a focused ion beam and electron beam microscope system. FIG. 8 shows a cross section of the electrolytic copper foil of this example.

  As can be proved from the photographs of FIG. 6 and FIG. 8, when the surface treatment is performed on the electrolytic copper foil of the embodiment of the present invention, a plurality of villi-like copper particles are formed, and spherical copper particles are formed. Not. Further, when the electrolytic copper foil 3 of this example is analyzed by a focused ion beam and electron beam microscope system, the copper crystal grains of the electrolytic copper foil have a major axis dimension of 2.5 to 6.0 μm and a short axis. The direction dimension is 0.2 to 2.0 μm.

  Next, as shown in FIG. 2, in the present embodiment, surface treatment is performed in step S <b> 300. The surface treatment may be at least one of a heat treatment, an antioxidant treatment, and a silane coupling agent treatment.

When the surface treatment is a heat treatment, a zinc alloy heat resistant layer is formed on the surface treatment layer by an electrolysis method, and the heat resistance of the electrolytic copper foil is increased. In one embodiment, the composition of the electrolytic solution used when performing the heat treatment includes 1 to 4 g / L zinc and 0.3 to 2.0 g / L nickel, and when performing the heat treatment. the current density used was 0.4~2.5A / dm ^2.

When the surface treatment is an antioxidant treatment, the antioxidant property of the electrolytic copper foil is enhanced by forming an antioxidant layer on the surface treatment layer by an electrolysis method. The composition of the electrolyte used when performing the antioxidant treatment includes 1-4 g / L chromium oxide and 5-20 g / L sodium hydroxide, and the current density used when performing the antioxidant treatment is it is a 0.3~3.0A / dm ^2.

  When the surface treatment is a silane coupling treatment, a silane coupling agent treatment layer is formed on the surface treatment layer. When the silane coupling treatment is performed, 0.3 to 1.5% by weight of a silane coupling agent is used.

  This will be described with reference to FIGS. FIG. 9 is a cross-sectional view showing the circuit board component of the present embodiment. 10 is a local enlarged view showing a region X in the circuit board component of FIG. The electrolytic copper foil of the present embodiment can be applied to different circuit board components such as a rigid printed circuit board (PCB), a flexible printed circuit board (FPC), and the like.

  9, the circuit board component M1 is formed by pressing the resin substrate 4 and the above-described electrolytic copper foil 3 face-to-face, and the surface treatment layer 31 of the electrolytic copper foil 3 faces the resin substrate 4. doing.

  The resin substrate 4 is a high frequency substrate such as an epoxy resin substrate, a polyphenylene oxide resin substrate (PPO) or a fluorine resin substrate, or a substrate made of a material such as polyimide, ethylene terephthalate, polycarbonate, liquid crystal polymer, or polytetrafluoroethylene. May be.

  9 and 10, the resin substrate 4 is a prepreg substrate or a liquid crystal polymer substrate. As can be seen from FIG. 10, since the space between the villi-shaped copper particles 310 of the present embodiment is wide, when the electrolytic copper foil 3 and the resin substrate 4 are pressure-bonded, the resin substrate 4 has a contact villi shape or villi shape. The surface of most of the copper particles 310 is covered and in contact with the copper particles 310, and can penetrate deeply into the villi-like accommodation space S1. Thereby, the adhesive strength between the electrolytic copper foil 3 and the resin substrate 4 can be enhanced.

  FIG. 11 is a sectional view showing a circuit board component according to another embodiment of the present invention. In the present embodiment, the resin substrate 4 and the electrolytic copper foil 3 are bonded by the adhesive 5 and a part of the adhesive 5 is filled in the villi-like accommodation space.

  As a result of measuring after pressure-bonding the electrolytic copper foil 3 and the resin substrate 4 of the present example, the peel strength was higher than 3 lb / in. Specifically, in the experimental example, the resin substrate 4 was a glass fiber plate (FR4), and the glass fiber plate (FR4) was pressure-bonded to the electrolytic copper foil of this example to form a laminate test piece. Subsequently, it measured using the peeling strength tensile tester. According to the test results, the peel strength of the electrolytic copper foil was at least greater than 3.5 lb / in.

  The circuit board component manufacturing method of the present embodiment may further include a step of forming a circuit layer by patterning the electrolytic copper foil 3 by etching after the electrolytic copper foil 3 is pressure-bonded to the resin substrate 4. .

  As described above, the beneficial effect of the present invention is that the copper concentration is adjusted by adjusting the composition of the first plating solution L1 in the plating roughening treatment by using the method for producing the electrolytic copper foil of the present embodiment. Since the content of arsenic oxide and tungstate ion can be reduced to 20 ppm or less, the crystal direction and growth direction of the copper particles can be restricted, and the villi-like or villi-like copper particles 310 are formed. There is a point that can be.

  Compared to the spherical copper particles F10 in the prior art, the villi-like or villi-like copper particles 310 have a small size in the lateral direction (horizontal direction) and increase the adhesion area between the electrolytic copper foil 3 and the resin substrate 4. be able to. In addition, since a wide distance is provided between two adjacent villi-like or villi-like copper particles 310, when the resin substrate 4 and the electrolytic copper foil 3 are bonded, the resin substrate 4 has the entire surface of the copper particles. And can penetrate deeply into the space between the two villi-like or villi-like copper particles 310, between the electrolytic copper foil 3 and the resin substrate 4 or the adhesive 5. Increases adhesion.

  Since the villi-like or villi-like copper particles 310 of the electrolytic copper foil 3 of the present embodiment have a vertical dimension that is not larger than the vertical dimension of the spherical copper particles F10 in the prior art, the surface roughness of the electrolytic copper foil 3 is The thickness is even lower than the surface roughness of the conventional copper foil. However, the peel strength of the electrolytic copper foil 3 of the present embodiment is not greatly reduced due to the reduction in surface roughness, and satisfies the actual application demand.

  Table 1 shows the surface roughness (Roughness), the peel strength (Peel Strength), and the ratio of the peel strength to the surface roughness (P / R ratio) of Examples and Comparative Examples of the present invention. The surface roughness is a ten-point average roughness (Rz). An example of the present invention is an electrolytic copper foil having villi-like or villi-like copper particles, and a comparative example is an electrolytic copper foil having spherical copper particles.

  As can be seen from Table 1, the surface roughness of the electrolytic copper foil according to the example of the present invention is even lower than the surface roughness of the comparative example (having spherical copper particles with large dimensions). Therefore, the electrolytic copper foil according to the embodiment of the present invention can further reduce the signal loss when applied to high frequency transmission.

  Moreover, the larger the ratio between the peel strength and the surface roughness, the smaller the influence of the surface roughness on the peel strength of the copper foil, and the better the peel strength characteristics. As can be seen from Table 1, the ratio of the peel strength and the surface roughness of the electrolytic copper foil according to the example of the present invention is larger than that of the comparative example. Accordingly, the peel strength of the electrolytic copper foil according to the example of the present invention does not cause excessive loss due to the low surface roughness.

  The foregoing descriptions are merely preferred embodiments of the present invention, and do not limit the scope of the claims of the present invention. Accordingly, any equivalent technical changes made by operating the contents of this specification and the drawings are included in the claims of the present invention.

F1 Conventional copper foil F10 Spherical copper particle 1 Foil making device 10 Electrolytic tank 11 Anode plate 12 Cathode drum 13 Roller L0 Electrolytic solution 14 Supply pipe E1 Power supply device 2 Surface treatment device 20 Transmission unit 21 Roughening unit L1 First Plating solution 210 Roughening tank 211 Roughening anode plate 22 Curing unit L2 Second plating solution 220 Curing tank 221 Curing anode plate 23 Cleaning tank 3 Electrolytic copper foil T Total thickness 30 Copper foil layer 30a Rough surface 30b Smooth surface 31 Surface treatment Layer 310 Copper particle D1 Maximum diameter of major axis D2 Maximum diameter of minor axis S1 Villiform accommodation space t Surface treatment layer thickness P1 Interval M1, M1 ′ Circuit board component 4 Resin substrate 5 Adhesive S100, S200 to 204, S300 Process steps

Claims (15)

Forming a copper foil layer having a predetermined surface by an electrolysis method;
A surface treatment layer containing a plurality of villi-like copper particles on the predetermined surface of the copper foil layer and forming a villi-like accommodation space between each two adjacent villi-like copper particles; Forming an electrolytic copper foil having a villi-like structure on the surface layer by forming,
Including
The step of forming the surface treatment layer further includes a step of executing a first plating roughening treatment and a step of executing a first plating hardening treatment,
The first plating solution used for the first plating roughening treatment includes 3 to 40 g / L copper, 100 to 120 g / L sulfuric acid, 20 ppm or less arsenic oxide, and 5 to 20 ppm tungstate ion. A method for producing an electrolytic copper foil having chilli-like copper particles, characterized in that it is contained. The current density used when performing the first plating roughening treatment is 15 to 40 A / dm ² ,
The method for producing an electrolytic copper foil having chilli-like copper particles according to claim 1, wherein the predetermined surface is a rough surface or a smooth surface. The step of forming the surface treatment layer further includes a step of executing a second plating roughening treatment and a step of executing a second plating hardening treatment,
The parameters of the second plating roughening treatment are the same as the parameters of the first plating roughening treatment, and the parameters of the second plating hardening treatment are the same as the parameters of the first plating hardening treatment. The method for producing an electrolytic copper foil having chilli-like copper particles according to claim 2, which is the same.   In the step of forming the surface treatment layer, the first plating roughening treatment, the first plating hardening treatment, the second plating roughening treatment, and the second plating hardening treatment are sequentially executed. The method for producing an electrolytic copper foil having chilli-like copper particles according to claim 3.   In the step of forming the surface treatment layer, the first plating roughening treatment, the second plating roughening treatment, the first plating hardening treatment, and the second plating hardening treatment are sequentially executed. The method for producing an electrolytic copper foil having chilli-like copper particles according to claim 3. The second plating solution used when performing the first plating curing treatment includes 50 to 70 g / L copper, 70 to 100 g / L sulfuric acid, and arsenic oxide lower than 30 ppm,
^{2. The} method for producing an electrolytic copper foil having chilli-like copper particles according to claim 1, wherein a current density used when performing the first plating hardening treatment is ² to 9 A / dm ^2. . A step of performing a heat treatment so as to form a zinc alloy heat-resistant layer on the surface treatment layer;
The composition of the electrolytic solution used when performing the heat treatment includes 1 to 4 g / L zinc and 0.3 to 2.0 g / L nickel.
^{2. The} method for producing an electrolytic copper foil having chilli-like copper particles according to claim 1, wherein a current density used when performing the heat-resistant treatment is 0.4 to 2.5 A / dm ² . Further comprising performing an antioxidant treatment to form an antioxidant layer on the surface treatment layer,
The composition of the electrolytic solution used when performing the antioxidant treatment includes 1 to 4 g / L of chromium oxide and 5 to 20 g / L of sodium hydroxide.
^{2. The} method for producing an electrolytic copper foil having chilli-like copper particles according to claim 1, wherein a current density used when performing the antioxidant treatment is 0.3 to 3.0 A / dm ^2. . A step of performing a silane coupling treatment so as to form a silane coupling agent treatment layer on the surface treatment layer;
The production of an electrolytic copper foil having chilli-like copper particles according to claim 1, wherein 0.3 to 1.5 wt% of a silane coupling agent is used when the silane coupling treatment is performed. Method. The plurality of villi-like copper particles have a maximum diameter of a major axis and a maximum diameter of a minor axis,
The long axis has a maximum diameter of 0.5 μm to 1.5 μm, the short axis has a maximum diameter of 0.1 μm to 1.0 μm,
2. The electrolytic copper foil having chilli-like copper particles according to claim 1, wherein a ratio between a maximum diameter of the short axis and a maximum diameter of the long axis is 0.2 to 0.7. Production method. The distribution density of the plurality of villi-like copper particles is 2 to 5 per square micrometer,
2. The method for producing an electrolytic copper foil having chilli-like copper particles according to claim 1, wherein a distance between each two adjacent chilli-like copper particles is 0.1 to 0.4 μm. . The process of providing the electrolytic copper foil which has the villi-like copper particle formed by the manufacturing method of the electrolytic copper foil of any one of Claims 1-11,
Forming a circuit board component by pressing the electrolytic copper foil having the villi-like copper particles face-to-face with the resin substrate so that the surface treatment layer of the electrolytic copper foil faces the resin substrate; A method of manufacturing a circuit board component comprising:   The method of manufacturing a circuit board component according to claim 12, wherein the peel strength of the electrolytic copper foil having the villi-like copper particles is at least greater than 3 lb / in. Bonding the electrolytic copper foil having the villi-like copper particles and the resin substrate with an adhesive,
13. The circuit board component manufacturing method according to claim 12, wherein a part of the adhesive is filled in the villi-like accommodation space. The resin substrate is a prepreg substrate or a liquid crystal polymer substrate,
The said viscose-like accommodation space is filled with a part of said resin board | substrate when the said electrolytic copper foil which has the said villi-like copper particle is crimped | bonded to the said resin board | substrate. Circuit board component manufacturing method.