JP2020132958A - Copper-clad laminate and manufacturing method of copper-clad laminate - Google Patents

Abstract

To provide a manufacturing method of a copper-clad laminate having a copper plating film in which progress of recrystallization is slow, and a manufacturing method of the copper-clad laminate.SOLUTION: A copper-clad laminate 1 includes a substrate 10 and a copper plating film 20 deposited on a surface of the substrate 10. After making a brightener solution including a brightener component contact with a surface of the substrate 10 in a non-conducting state, the copper plating film 20 is deposited through electrolytic plating using the copper plating solution. A method is for obtaining a copper-clad laminate 1 through depositing a copper plating film 20 on a surface of a substrate 10. After making a brightener solution including a brightener component contact with a surface of the substrate 10 in a non-conducting state, electrolytic plating using the copper plating solution is carried out to deposit the copper plating film 20.SELECTED DRAWING: Figure 1

Description

The present invention relates to a copper-clad laminate and a method for manufacturing a copper-clad laminate. More specifically, the present invention relates to a copper-clad laminate used for manufacturing a flexible printed wiring board (FPC) and the like, and a method for manufacturing the copper-clad laminate.

Flexible printed wiring boards having a wiring pattern formed on the surface of a resin film are used for liquid crystal panels, notebook computers, digital cameras, mobile phones, and the like. The flexible printed wiring board is manufactured from, for example, a copper-clad laminate.

The metallizing method is known as a method for manufacturing a copper-clad laminate. The production of the copper-clad laminate by the metallizing method is performed, for example, by the following procedure. First, a base metal layer made of a nickel-chromium alloy is formed on the surface of the resin film. Next, a copper thin film layer is formed on the base metal layer. Next, a copper plating film is formed on the copper thin film layer. By copper plating, the conductor layer is thickened until the film thickness is suitable for forming the wiring pattern. By the metallizing method, a copper-clad laminate of a type called a so-called two-layer substrate in which a conductor layer is directly formed on a resin film can be obtained.

A semi-additive method is known as a method for manufacturing a flexible printed wiring board using this type of copper-clad laminate. The flexible printed wiring board is manufactured by the semi-additive method according to the following procedure (see Patent Document 1). First, a resist layer is formed on the surface of the copper plating film of the copper-clad laminate. Next, an opening is formed in the portion of the resist layer that forms the wiring pattern. Next, electrolytic plating is performed using the copper plating film exposed from the opening of the resist layer as a cathode to form a wiring portion. Next, the resist layer is removed, and the conductor layer other than the wiring portion is removed by flash etching or the like. As a result, a flexible printed wiring board can be obtained.

In the semi-additive method, a dry film resist may be used to form a resist layer on the surface of the copper plating film. In this case, after the surface of the copper plating film is chemically polished, a dry film resist is attached. By making fine irregularities on the surface of the copper plating film by chemical polishing, the adhesion of the dry film resist is improved by the anchor effect. However, if the surface of the copper plating film is excessively uneven, the adhesion of the dry film resist may be deteriorated.

Japanese Unexamined Patent Publication No. 2006-278950

The surface roughness of the copper plating film after chemical polishing is affected by the size of the crystal grains of the copper plating film. The smaller the crystal grains, the smoother the surface of the copper plating film after chemical polishing, and the larger the crystal grains, the rougher the surface of the copper plating film after chemical polishing.

The crystal grains of the copper plating film gradually increase in size as the recrystallization progresses after the plating treatment. When the copper plating film in which recrystallization is in progress is chemically polished, the surface roughness of the copper plating film after the chemical polishing changes depending on the elapsed time from the plating treatment at the time of the chemical polishing. Therefore, process control in wiring processing becomes difficult. Further, since the crystal grains of the copper-plated coating that has been recrystallized are large, the surface roughness after chemical polishing may be excessive. Therefore, the copper-plated coating of the copper-clad laminate may be required to have a slow progress of recrystallization.

In view of the above circumstances, an object of the present invention is to provide a copper-clad laminate having a copper-plated coating in which recrystallization proceeds slowly, and a method for producing the copper-clad laminate.

The copper-clad laminate of the first invention comprises a base material and a copper plating film formed on the surface of the base material, and the copper plating film is a brightener on the surface of the base material in a non-energized state. It is characterized in that the film is formed by electrolytic plating using a copper plating solution after contacting the Brightener solution containing the components.
In the method for producing a copper-clad laminate of the second invention, when a copper-plated coating is formed on the surface of a base material to obtain a copper-clad laminate, a bright containing a brightener component on the surface of the base material in a non-energized state It is characterized in that the copper plating film is formed by performing electrolytic plating with a copper plating solution after contacting the ner liquid.
The method for producing a copper-clad laminate according to the third invention is to obtain a copper-clad laminate by forming a copper plating film on the surface of the substrate while transporting the substrate by roll-to-roll. A pretreatment tank in which a Brightener liquid containing a Brightener component is stored and a plating tank for electrolytic plating using a copper plating liquid are arranged in this order from upstream to downstream in a transport path. ..
The method for producing a copper-clad laminate according to the fourth invention is characterized in that, in the second or third invention, the concentration of the Brightner component in the Brightener solution is 5 mg / L or more.
The method for producing a copper-clad laminate of the fifth invention is characterized in that, in any one of the second to fourth inventions, the contact time of the base material with the Brightener liquid is 5 seconds or more.
The method for producing a copper-clad laminate of the sixth invention is characterized in that, in any one of the second to fifth inventions, the Brightener component contained in the Brightener solution is bis (3-sulfopropyl) disulfide. ..

According to the present invention, the sulfur concentration in the copper plating film near the interface with the base material is high. Since a large amount of sulfur that suppresses the progress of recrystallization is contained in the vicinity of the interface with the base material where recrystallization easily proceeds, the progress of recrystallization of the copper plating film can be slowed down.

It is sectional drawing of the copper-clad laminate which concerns on one Embodiment of this invention. It is a perspective view of a plating apparatus. It is a top view of the pretreatment tank.

Next, an embodiment of the present invention will be described with reference to the drawings.
As shown in FIG. 1, the copper-clad laminate 1 according to the embodiment of the present invention comprises a base material 10 and a copper plating film 20 formed on the surface of the base material 10. As shown in FIG. 1, the copper plating film 20 may be formed on only one side of the base material 10, or the copper plating film 20 may be formed on both sides of the base material 10.

The copper plating film 20 is formed by electrolytic plating. Therefore, the base material 10 may be a material having conductivity on the surface on the side where the copper plating film 20 is formed. For example, the base material 10 has a metal layer 12 formed on the surface of a base film 11 having an insulating property. A resin film such as a polyimide film can be used as the base film 11. The metal layer 12 is formed by, for example, a sputtering method. The metal layer 12 is composed of a base metal layer 13 and a copper thin film layer 14. The base metal layer 13 and the copper thin film layer 14 are laminated in this order on the surface of the base film 11. Generally, the base metal layer 13 is made of nickel, chromium, or a nickel-chromium alloy. Although not particularly limited, the thickness of the base metal layer 13 is generally 5 to 50 nm, and the thickness of the copper thin film layer 14 is generally 50 to 400 nm.

The copper plating film 20 is formed on the surface of the metal layer 12. Although not particularly limited, the thickness of the copper plating film 20 is generally 1 to 3 μm. The metal layer 12 and the copper plating film 20 are collectively referred to as a "conductor layer".

The copper plating film 20 is not particularly limited, but is formed by the plating apparatus 3 shown in FIG.
The plating device 3 is a device that performs electrolytic plating on the base material 10 while transporting the long strip-shaped base material 10 by roll-to-roll. The plating device 3 has a supply device 31 for feeding out the base material 10 wound in a roll shape, and a winding device 32 for winding up the base material 10 (copper-clad laminate 1) after plating in a roll shape.

Further, the plating apparatus 3 has a pair of upper and lower endless belts 33 (the lower endless belt 33 is not shown) that conveys the base material 10. Each endless belt 33 is provided with a plurality of clamps 34 for gripping the base material 10. The base material 10 unwound from the supply device 31 is in a suspended posture in the width direction along the vertical direction, and both edges are gripped by the upper and lower clamps 34. The base material 10 circulates in the plating device 3 by driving the endless belt 33, is released from the clamp 34, and is wound by the winding device 32.

In the transport path of the base material 10, a pretreatment tank 40, a plating tank 35, and a posttreatment tank 36 are arranged in this order from upstream to downstream. While the base material 10 is conveyed in the plating tank 35, a copper plating film 20 is formed on the surface thereof by electrolytic plating. As a result, a long strip-shaped copper-clad laminate 1 can be obtained.

As shown in FIG. 3, the pretreatment tank 40 is a horizontally long tank along the transport direction of the base material 10. The inside of the pretreatment tank 40 is divided into six sections 41 to 46. From upstream to downstream of the transport path of the base material 10, the alkali-treated section 41, the water-washed section 42, the acid-treated section 43, the water-washed section 44, the Brightner-treated section 45, and the water-washed section 46 are arranged in this order.

A degreasing solution using an alkali salt such as sodium hydroxide or sodium carbonate is stored in the alkali treatment section 41. The entire base material 10 transported through the alkali treatment section 41 is immersed in the degreasing liquid. The oil and fat adhering to the surface of the base material 10 is removed by this alkali treatment.

Water is stored in each of the flush sections 42, 44, and 46. The entire base material 10 transported through the water-washing sections 42, 44, and 46 is immersed in water and is washed with water.

Acids such as sulfuric acid and hydrochloric acid are stored in the acid treatment section 43. The entire base material 10 transported through the acid treatment section 43 is immersed in the acid. By this acid treatment, the oxide on the surface of the base material 10 (the surface of the copper thin film layer 14) is removed.

The Brightner liquid is stored in the Brightener treatment section 45. The Brightener liquid is a liquid containing a Brightner component. As the Brightener component, one generally added to the plating solution can be used. Although not particularly limited, as a brightener component, one type selected from bis (3-sulfopropyl) disulfide (abbreviated as SPS), 3-mercaptopropane-1-sulfonic acid (abbreviated as MPS), etc. may be used alone or in two types. It is preferable to use the above in combination.

The Brightener solution preferably contains sulfuric acid and copper. By doing so, it is possible to prevent algae from growing on the wall surface of the tank that stores the Brightener solution. Further, a copper plating solution stored in the plating tank 35 may be used as the Brightener solution. In this case, the copper plating solution may contain additives other than the Brightener component, that is, a leveler component, a polymer component, a chlorine component, and the like. If a copper plating solution is used as the brightener solution, it is not necessary to prepare a brightener solution separately from the copper plating solution.

The entire base material 10 transported through the Brightener treatment section 45 is immersed in the Brightener liquid. By this Brightener treatment, the Brightener liquid comes into contact with the surface of the base material 10 (the surface of the copper thin film layer 14), and the Brightener component is adsorbed.

The base material 10 is subjected to alkali treatment, acid treatment, and Brightener treatment while being conveyed in the pretreatment tank 40. It is preferable that the alkali treatment, the acid treatment, and the Brightener treatment are performed in this order. Then, the Brightener component can be adsorbed on a clean metal surface from which fats and oils and oxides have been removed. However, at least the Brightener treatment may be performed as the pretreatment. Other processing may be performed as needed.

The pretreatment is performed in a non-energized state, that is, in a state where no current is supplied to the base material 10. Even if the Brightener treatment is performed in a non-energized state, the Brightener component is adsorbed on the surface of the base material 10 (the surface of the copper thin film layer 14).

It is preferable to provide a nozzle for ejecting the treatment liquid (alkali, acid, Brightener liquid, washing water) toward the base material 10 inside each section 41 to 46.

As shown in FIG. 2, the plating tank 35 is a single horizontally long tank along the transport direction of the base material 10. A copper plating solution is stored in the plating tank 35. The entire base material 10 conveyed in the plating tank 35 is immersed in a copper plating solution.

The copper plating solution contains a water-soluble copper salt. Any water-soluble copper salt generally used in the copper plating solution is used without particular limitation. Examples of the water-soluble copper salt include an inorganic copper salt, an alkane sulfonic acid copper salt, an alkanol sulfonic acid copper salt, and an organic acid copper salt. Examples of the inorganic copper salt include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of the alkane sulfonic acid copper salt include copper methanesulfonate and copper propane sulfonate. Examples of the alkanol sulfonic acid copper salt include copper isethionic acid and copper propanol sulfonate. Examples of the organic acid copper salt include copper acetate, copper citrate, copper tartrate and the like.

As the water-soluble copper salt used in the copper plating solution, one type selected from inorganic copper salt, alkane sulfonic acid copper salt, alkanol sulfonic acid copper salt, organic acid copper salt and the like may be used alone, or two or more types may be used. May be used in combination. For example, as in the case of combining copper sulfate and copper chloride, two or more different types in one category selected from inorganic copper salt, alkane sulfonic acid copper salt, alkanol sulfonic acid copper salt, organic acid copper salt, etc. It may be used in combination. However, from the viewpoint of controlling the copper plating solution, it is preferable to use one kind of water-soluble copper salt alone.

The copper plating solution may contain sulfuric acid. By adjusting the amount of sulfuric acid added, the pH and sulfate ion concentration of the copper plating solution can be adjusted.

The copper plating solution may contain additives that are generally added to the plating solution. Examples of the additive include a Brightner component, a leveler component, a polymer component, a chlorine component and the like. The copper plating solution may contain one type selected from a Brightener component, a leveler component, a polymer component, a chlorine component, and the like, or may contain two or more types.

The Brightner component contains sulfur. The Brightener component is not particularly limited, but one type selected from bis (3-sulfopropyl) disulfide (abbreviated as SPS), 3-mercaptopropane-1-sulfonic acid (abbreviated as MPS), etc. may be used alone or as two types. It is preferable to use the above in combination. The leveler component is composed of nitrogen-containing amines and the like. The leveler component is not particularly limited, but it is preferable to use one selected from diallyldimethylammonium chloride, Janus Green B, etc. alone or in combination of two or more. The polymer component is not particularly limited, but it is preferable to use one selected from polyethylene glycol, polypropylene glycol, and polyethylene glycol-polypropylene glycol copolymer alone or in combination of two or more. The chlorine component is not particularly limited, but it is preferable to use one selected from hydrochloric acid, sodium chloride and the like alone or in combination of two or more.

The content of each component of the copper plating solution can be arbitrarily selected. However, the copper plating solution preferably contains 15 to 70 g / L of copper and 20 to 250 g / L of sulfuric acid. Then, the copper plating film 20 can be formed at a sufficient speed. The copper plating solution preferably contains 1 to 30 mg / L of the Brightener component. Then, the precipitated crystals can be made finer and the surface of the copper plating film 20 can be smoothed. The copper plating solution preferably contains a leveler component of 0.5 to 50 mg / L. Then, the protrusions can be suppressed and the flat copper plating film 20 can be formed. The copper plating solution preferably contains a polymer component of 10 to 1,500 mg / L. Then, the current concentration on the end of the base material 10 can be relaxed and a uniform copper plating film 20 can be formed. The copper plating solution preferably contains a chlorine component of 20 to 80 mg / L. Then, abnormal precipitation can be suppressed.

The temperature of the copper plating solution is preferably 23 to 38 ° C. Further, it is preferable to stir the copper plating solution in the plating tank 35. The means for stirring the copper plating solution is not particularly limited, but a means using a jet can be used. For example, the copper plating solution can be agitated by spraying the copper plating solution ejected from the nozzle onto the base material 10.

Inside the plating tank 35, a plurality of anodes are arranged along the transport direction of the base material 10. The material and structure of the anode are not particularly limited, but may be, for example, a mesh-like insoluble electrode obtained by coating titanium with iridium oxide. Further, an electric current is supplied to the base material 10 via a clamp 34 that grips the base material 10. When an electric current is passed between the base material 10 and the anode, electrolytic plating is performed using the base material 10 as a cathode. By performing electrolytic plating, a copper plating film 20 can be formed on the surface of the base material 10, and a long strip-shaped copper-clad laminate 1 can be obtained.

A rectifier is connected to each of the plurality of anodes arranged inside the plating tank 35. Therefore, the current density can be set to be different for each anode. The current density is preferably set to 0.3 to 10 A / dm ² . Further, it is preferable that the current density is set so as to gradually increase toward the downstream side in the transport direction of the base material 10.

As described above, after the Brightener solution is brought into contact with the surface of the base material 10 in a non-energized state, electrolytic plating using the copper plating solution is performed to form a copper plating film 20. The copper-plated coating 20 formed by such a method contains a large amount of sulfur as an impurity in the vicinity of the interface with the base material 10. That is, as shown in FIG. 1, the copper plating film 20 includes a high sulfur concentration layer 21 near the interface with the base material 10 and a low sulfur concentration layer 22 laminated on the high sulfur concentration layer 21. Here, the high sulfur concentration layer 21 is a layer having a relatively high sulfur concentration, and the low sulfur concentration layer 22 is a layer having a relatively low sulfur concentration.

The reason why the high sulfur concentration layer 21 and the low sulfur concentration layer 22 are formed in this way is considered to be as follows.
When the base material 10 comes into contact with the Brightener liquid in the pretreatment tank 40, the Brightener component is adsorbed on the surface of the base material 10, that is, the surface of the copper thin film layer 14. When the base material 10 in this state is electroplated, the copper plating film 20 is formed while incorporating the Brightener component adsorbed on the surface of the copper thin film layer 14 in the initial stage of electrolysis. Therefore, the vicinity of the interface between the copper plating film 20 and the base material 10 contains a large amount of sulfur derived from the Brightener component, and the high sulfur concentration layer 21 is formed.

When electrolytic plating is subsequently performed, since the Brightener component is only supplied from the copper plating solution, a layer having a sulfur concentration obtained by ordinary electrolysis is formed. This is the low sulfur concentration layer 22.

The copper-plated coating 20 having such a structure has a property that the progress of recrystallization is slow. The reason for this is unknown, but it is thought to be as follows.
Immediately after the electrolytic plating of the copper plating film 20 is completed, the portion containing a large amount of impurities tends to grow, and the portion containing a small amount of impurities tends to shrink. However, since the copper plating film 20 is in close contact with the base material 10, it cannot actually expand and contract, and therefore stress is generated in the copper plating film 20. In particular, the stress increases in the vicinity of the interface between the copper plating film 20 and the base material 10. Therefore, the recrystallization of the copper plating film 20 proceeds from the vicinity of the interface with the base material 10.

On the other hand, the sulfur concentration in the copper plating film 20 near the interface with the base material 10 is high. Sulfur in the copper plating film 20 has the effect of suppressing the progress of recrystallization. Since a large amount of sulfur that suppresses the progress of recrystallization is contained in the vicinity of the interface with the base material 10 where recrystallization easily proceeds, the progress of recrystallization of the copper plating film 20 can be slowed down.

In order to obtain the above effects, it is sufficient that a sufficient amount of the Brightener component is adsorbed on the surface of the base material 10 before the electrolytic plating is performed. Therefore, it is preferable that the concentration of the Brightner component in the Brightner solution (hereinafter, referred to as "Brightner concentration") is 5 mg / L or more. Further, it is preferable that the contact time of the base material 10 with the Brightner solution (hereinafter, referred to as "contact time") is 5 seconds or more. The contact time can be adjusted by the transport speed of the base material 10 and the length of the Brightener treatment section 45.

Since the Brightener component is adsorbed on copper, it is considered that the adsorption does not proceed when the surface of the copper thin film layer 14 is covered with the Brightner component. After the adsorption amount of the Brightener component is saturated, it is considered that the sulfur concentration in the high sulfur concentration layer 21 does not increase even if the Brightner concentration is increased or the contact time is lengthened. From this point of view, there is no upper limit to the Brightner concentration and contact time.

The copper plating film 20 may contain impurities other than sulfur, such as nitrogen, chlorine, carbon, and oxygen derived from additives in the copper plating solution.

Next, an embodiment will be described.
(Recrystallization time measurement test)
First, a recrystallization time measurement test was performed.
The substrate was prepared by the following procedure. As a base film, a polyimide film having a thickness of 35 μm (Upilex-35SGAV1 manufactured by Ube Industries, Ltd.) was prepared. The base film was set in the magnetron sputtering apparatus. A nickel-chromium alloy target and a copper target are installed in the magnetron sputtering apparatus. The composition of the nickel-chromium alloy target is 20% by mass of Cr and 80% by mass of Ni. Under a vacuum atmosphere, a base metal layer made of a nickel-chromium alloy having a thickness of 25 nm was formed on one side of the base film, and a copper thin film layer having a thickness of 150 nm was formed on the base metal layer.

Next, a Brightener solution was prepared. The Brightner solution contains a Brightner component. Bis (3-sulfopropyl) disulfide (reagent manufactured by RASCHIG GmbH, the same applies hereinafter) was used as the Brightener component. The Brightner solution contains 120 g / L of copper sulfate and 70 g / L of sulfuric acid.

Next, a copper plating solution was prepared. The copper plating solution contains 120 g / L of copper sulfate, 70 g / L of sulfuric acid, 16 mg / L of Brightener component, 50 mg / L of leveler component, 1,100 mg / L of polymer component, and 50 mg / L of chlorine component. Bis (3-sulfopropyl) disulfide was used as the Brightener component. A diallyldimethylammonium chloride-sulfur dioxide copolymer (PAS-A-5 manufactured by Nittobo Medical Co., Ltd.) was used as a leveler component. A polyethylene glycol-polypropylene glycol copolymer (Unilube 50MB-11 manufactured by NOF CORPORATION) was used as a polymer component. Hydrochloric acid (35% hydrochloric acid manufactured by Wako Pure Chemical Industries, Ltd.) was used as the chlorine component.

The base material was pretreated and electrolytically plated to form a 2.0 μm-thick copper plating film on one side of the base material. As pretreatment, alkali treatment, acid treatment, and Brightener treatment were performed in this order. The alkaline treatment was carried out by immersing the base material in a degreasing solution (Pakuna LF-612N2, 40 g / L manufactured by Yuken Kogyo Co., Ltd.). The acid treatment was carried out by immersing the base material in sulfuric acid (96% sulfuric acid manufactured by Kanto Chemical Co., Inc. adjusted to 100 g / L). The treatment time for the alkali treatment and the acid treatment is 20 seconds each.

The temperature of the copper plating solution was 31 ° C. In electrolytic plating, the current density from the start to the end of plating was changed to 0.4 A / dm ² for 40 seconds, 1.5 A / dm ² for 40 seconds, and 3.0 A / dm ² for 175 seconds.

In the above procedure, the contact time in the Brightener treatment was changed in three patterns of 5, 15, and 25 seconds. In addition, the Brightner concentration of the Brightner solution was changed in three patterns of 5, 15, and 25 mg / L. Furthermore, a sample not subjected to Brightener treatment was also prepared.

The 10 types of copper-clad laminates obtained by the above treatment are referred to as Samples 1 to 10, respectively. The recrystallization time of the copper plating film was measured for Samples 1 to 10. The recrystallization time was measured by observing the change in resistivity of the copper plating film by the four-probe method. As the recrystallization of the copper plating film progresses, the crystal grains become larger and the resistivity changes. When the resistivity becomes constant, it is judged that recrystallization is completed. The elapsed time from the plating treatment to the end of recrystallization was defined as the recrystallization time. As a resistivity measuring instrument, Lola TAX MCP-T370 manufactured by Mitsubishi Chemical Analytical Co., Ltd. was used.

The results are shown in Table 1.

From Table 1, it can be seen that when the Brightener treatment is performed (Samples 2 to 10), the progress of recrystallization of the copper plating film is slower than when it is not performed (Sample 1). In addition, the longer the contact time, the longer the recrystallization time. If the contact time is 5 seconds or more, the recrystallization time can be sufficiently lengthened. At least, the recrystallization time can be sufficiently long in the range of 5 to 25 seconds. In addition, the higher the Brightner concentration, the longer the recrystallization time. When the Brightner concentration is 5 mg / L or more, the recrystallization time can be sufficiently lengthened. At least, the recrystallization time can be sufficiently lengthened in the range of Brightener concentration of 5 to 25 mg / L.

(Gloss measurement test)
Next, a glossiness measurement test was performed on the samples 1 to 10.
The glossiness of the surface of the copper plating film immediately after plating was measured for each of Samples 1 to 10. In addition, each of the samples 1 to 10 one week after the plating treatment was chemically polished, and the glossiness of the surface of the copper plating film after the chemical polishing was measured. Further, each of the samples 1 to 10 2 weeks after the plating treatment was chemically polished, and the glossiness of the surface of the copper plating film after the chemical polishing was measured. As a glossiness measuring instrument, VSR400 manufactured by Nippon Denshoku Industries Co., Ltd. was used.

The results are shown in Table 2.

The glossiness can be used as an index of the surface roughness of the copper plating film. The higher the gloss, the smoother it is, and the lower the gloss, the coarser it is. From Table 2, if the contact time is 5 seconds or more and the Brightener concentration is 5 mg / L or more, the glossiness can be maintained at 0.9 or more even two weeks after the plating treatment, and the surface of the copper plating film after chemical polishing can be maintained. It was confirmed that it can be smoothed.

1 Copper-clad laminate 10 Base film 11 Base film 12 Metal layer 13 Base metal layer 14 Copper thin film layer 20 Copper plating film 21 High sulfur concentration layer 22 Low sulfur concentration layer

Claims (6)

With the base material
A copper-plated coating film formed on the surface of the base material is provided.
The copper plating film is characterized in that it is formed by electrolytic plating using a copper plating solution after contacting a brightener solution containing a Brightener component with the surface of the base material in a non-energized state. Copper-clad laminate. When forming a copper plating film on the surface of a base material to obtain a copper-clad laminate,
A copper clading characterized in that the surface of the base material is brought into contact with a Brightener solution containing a Brightener component in a non-energized state, and then electrolytic plating is performed using the copper plating solution to form the copper plating film. Method of manufacturing laminated plate. In obtaining a copper-clad laminate by forming a copper plating film on the surface of the base material while transporting the base material by roll-to-roll.
In the transport path of the base material, a pretreatment tank for storing a Brightener liquid containing a Brightener component and a plating tank for performing electrolytic plating with a copper plating liquid are arranged in this order from upstream to downstream. A method for manufacturing a copper-clad laminate characterized by. The method for producing a copper-clad laminate according to claim 2 or 3, wherein the concentration of the Brightner component in the Brightener solution is 5 mg / L or more. The method for producing a copper-clad laminate according to any one of claims 2 to 4, wherein the contact time of the base material with the Brightener liquid is 5 seconds or more. The method for producing a copper-clad laminate according to any one of claims 2 to 5, wherein the Brightner component contained in the Brightener solution is bis (3-sulfopropyl) disulfide.