TW201942422A - Surface-treated copper foil, copper-cladded laminate, and manufacturing method for printed wiring board - Google Patents

Abstract

Provided is a surface-treated copper foil which exhibits excellent adhesion to resin, chemical resistance, and heat resistance, is less likely to produce etching residue, and is thus capable of achieving improved reliability of adhesion between copper foil and substrate and between substrate and substrate during manufacture of a printed wiring board. This surface-treated copper foil comprises: a copper foil; and a Zn-Ni-Mo layer disposed at least on one surface of the copper foil, said Zn-Ni-Mo layer having a Zn coating weight of 3 mg/m2 to 100 mg/m2, an Ni coating weight of 5 mg/m2 to 60 mg/m2, and an Mo coating weight of 2.0 mg/m2 to 40 mg/m2, wherein Ni/(Zn + Ni + Mo), that is, the ratio of the Ni coating weight to the total amount of the Zn coating weight, the Ni coating weight, and the Mo coating weight, is 0.40 to 0.80.

Description

Method for manufacturing surface-treated copper foil, copper-clad laminated board, and printed wiring board

The present invention relates to a method for manufacturing a surface-treated copper foil, a copper-clad laminate, and a printed wiring board.

In the manufacturing process of a printed wiring board, the form of a copper-clad laminated board in which a copper foil and an insulating resin base material are bonded is widely used. In this regard, in order to prevent peeling of the wiring during the production of the printed wiring board, it is desirable that the copper foil and the insulating resin substrate have high adhesion. Among them, in general copper foils for the manufacture of printed wiring boards, roughening treatment is performed on the bonding surfaces of the copper foils to form irregularities made of fine copper particles, and the irregularities are caused to fall into the insulating resin substrate by press working. The anchoring effect of the inside of the to enhance adhesion.

In addition, for the purpose of preventing deterioration of copper foil due to an oxide film (rust) that may occur on the surface of the copper foil during storage, etc., a rust prevention treatment is usually applied to the surface of the copper foil, and it is known as a rust prevention treatment layer Various alloy layers. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2008-285751) discloses a surface-treated copper foil having a total amount of Zn and Ni of 40 mg / m ² or more on an adhesive surface bonded to an insulating resin substrate, because By this copper foil, the surface of a copper foil can be fully covered with a Zn-Ni alloy, and the adhesiveness and chemical resistance with an insulating resin base material can be improved. In addition, Patent Document 2 (Japanese Patent Application Laid-Open No. 62-142389) discloses that a copper foil for a printed circuit having a Ni-Mo layer is excellent in chemical resistance and heat resistance after the copper foil circuit is formed.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] JP 2008-285751
[Patent Document 2] Japanese Unexamined Patent Publication No. 62-142389

In addition, in recent years, with the increase in the performance of portable electronic devices and the like, in order to perform high-speed processing of a large amount of information, no matter whether it is digital or analog, high-frequency signals are being performed, and printed wiring boards suitable for high-frequency applications are required. In such a high-frequency printed wiring board, in order to transmit without degrading the quality of high-frequency signals, it is desirable to reduce transmission loss. Although a printed wiring board includes a copper foil and an insulating base material processed in a wiring pattern, the transmission loss is mainly a conductor loss caused by the copper foil and a dielectric loss caused by the insulating base material. Therefore, in order to reduce the conductor loss caused by the copper foil and the dielectric loss caused by the insulating base material, it is good to use a copper foil with small unevenness and an insulating base material having a low loss factor. However, when the copper foil with small unevenness is used, the anchoring effect is weakened, and the physical adhesion between the copper foil and the substrate is reduced. In particular, a decrease in peel strength (peel strength) after immersion of a drug or after a welding process becomes a problem. . In addition, an insulating base material having a low loss factor generally has a low activity of a functional group and a low chemical adhesion with a copper foil. Therefore, when the unevenness of the copper foil is small, the surface of the insulating base material that comes into contact with the copper foil becomes flat when the copper foil is etched away, not only between the copper foil and the base material, but also on the surface of the insulating base material. The substrate-to-substrate adhesion between other insulating substrates is also reduced. In this regard, when the Ni-Mo layer disclosed in Patent Document 2 is used as a rust-preventive treatment layer for copper foil, residues due to the Ni-Mo layer after copper foil etching will remain on the surface of the insulating base material, preventing it. There is a problem that the resin adheres to other insulating substrates laminated on the surface of the insulating substrate, and the adhesion force is further reduced.

The present inventors have now obtained a surface-treated copper foil capable of providing a Zn-Ni-Mo layer of a predetermined composition as a rust-preventive treatment layer, which is excellent in adhesion, chemical resistance, and heat resistance to a resin, and is etched Residues are not easily left. Therefore, when used for the production of a printed wiring board, it is possible to improve the insight of the close reliability between the copper foil and the substrate and between the substrate and the substrate.

Therefore, the object of the present invention is to provide a surface-treated copper foil that has excellent adhesion, resin resistance, and heat resistance to the resin, and that etching residues are not easily left. Therefore, the copper foil can be improved when used in the manufacture of printed wiring boards- Adhesion reliability between substrates and substrate-to-substrate.

According to one aspect of the present invention, a surface-treated copper foil is provided, including: a copper foil and a Zn-Ni-Mo layer;
The Zn-Ni-Mo layer is provided on at least one side of the copper foil. The Zn adhesion amount is 3 mg / m ² or more and 100 mg / m ² or less, the Ni adhesion amount is 5 mg / m ² or more and 60 mg / m ² or less, and the Mo adhesion amount. It is 2.0 mg / m ² or more and 40 mg / m ² or less, and Ni / (Zn + Ni + Mo) is a ratio of the Ni adhesion amount to the total amount of the Zn adhesion amount, the Ni adhesion amount, and the Mo adhesion amount, that is, Ni / (Zn + Ni + Mo) is 0.40 or more and 0.80 or less.

According to one aspect of the present invention, a copper-clad laminate is provided, comprising: the aforementioned surface-treated copper foil;
An insulating base material provided on the at least one side of the surface-treated copper foil.

According to another aspect of the present invention, a method for manufacturing a printed wiring board is provided. The printed wiring board is manufactured by using the surface-treated copper foil or the copper-clad laminate.

The definitions of terms and parameters used to specify the present invention are as follows.

In this specification, the "maximum height Sz" refers to a parameter that indicates the distance from the highest point to the lowest point of the surface, measured based on ISO25178. The maximum height Sz can be calculated by measuring a surface profile of a predetermined measurement area (for example, an area of 22500 μm ² ) on the copper foil surface with a commercially available laser microscope.

In this specification, the "M adhesion amount (M is Zn, Ni, or Mo)" refers to the weight per unit area of the M (mg / mg) present in the rust-preventive treatment layer (typically a Zn-Ni-Mo layer). m ² ). The amount of M deposited can be calculated by dissolving a predetermined area of the surface of the copper foil on the side having the anti-rust treatment layer with an acid, and analyzing the concentration of M in the obtained dissolved solution based on ICP emission analysis.

In this specification, the "electrode surface" of an electrolytic copper foil refers to the surface on the side connected to a cathode at the time of manufacture of an electrolytic copper foil.

In the present specification, the "precipitation surface" of the electrolytic copper foil is the surface on the side where the electrolytic copper is deposited during the production of the electrolytic copper foil, that is, the side on the side not connected to the cathode.

Surface-treated copper foil The surface-treated copper foil of the present invention includes a copper foil and a Zn-Ni-Mo layer provided on at least one side of the copper foil. If necessary, Zn-Ni-Mo layers may be provided on both sides of the copper foil. The Zn-Ni-Mo layer has a Zn adhesion amount of 3 mg / m ² or more and 100 mg / m ² or less, a Ni adhesion amount of 5 mg / m ² or more and 60 mg / m ² or less, and a Mo adhesion amount of 2.0 mg / m ² or more and 40 mg / m ^{2. 2} or less. Next, Ni / (Zn + Ni + Mo), which is a ratio of the total amount of Ni deposition to the total amount of Zn deposition, Ni deposition, and Mo deposition, is 0.40 or more and 0.80 or less. By using a Zn-Ni-Mo layer with a predetermined composition as the rust-preventive treatment layer, it has excellent adhesion to the resin, chemical resistance, and heat resistance, and it is not easy to leave etching residues. Therefore, it can be used in the manufacture of printed wiring boards. Improves the adhesion reliability between copper foil-to-substrate and substrate-to-substrate.

In this regard, when the conventional surface-treated copper foil subjected to the rust prevention treatment is used for a printed wiring board, the adhesion reliability between the copper foil and the substrate and between the substrate and the substrate is not necessarily good. For example, the surface-treated copper foil provided with a Zn-Ni layer disclosed in Patent Document 1 is one having poor heat resistance, and the peel strength after welding process and the like is reduced. Also, as described above, when a printed wiring board is manufactured using a surface-treated copper foil provided with a Ni-Mo layer as disclosed in Patent Document 2, residues due to the Ni-Mo layer after copper foil etching remain on the surface of the insulating substrate , The substrate-to-substrate resin adhesion will be reduced. On the other hand, the surface-treated copper foil of the present invention is excellent in chemical resistance and heat resistance by including a Zn-Ni-Mo layer containing Zn, Ni, and Mo in a predetermined adhesion amount and adhesion ratio as a rust-preventive treatment layer. In addition, a copper etchant (for example, a second chlorinated copper etchant) rapidly dissolves and it is difficult to generate residues due to the rust-preventive treatment layer. As a result, the surface-treated copper foil of the present invention has excellent adhesion between the copper foil and the substrate, not only in the normal state, but also after the welding process and after the acid treatment. Shows stable high adhesion. Furthermore, in the manufacturing process of the printed wiring board, the residue on the surface of the insulating base material after the copper foil is removed by etching is not easy to remain, and it does not prevent the resin from adhering to other insulating base materials laminated on the surface of the insulating base material. However, full use can ensure high adhesion between the substrate and the substrate. Therefore, the surface-treated copper foil of the present invention is highly suitable for copper foil-to-substrate and substrate substrates because it can improve the reliability of both the copper-to-substrate and substrate-to-substrate substrates when used in printed wiring boards. -Use of a high-frequency printed wiring board in which the adhesion between substrates is easily reduced.

Zn is a basic component that brings rust prevention performance. Although it has good solubility in copper etchant, it is a metal with poor heat resistance. From the above viewpoint, the Zn adhesion amount in the Zn-Ni-Mo layer is 3 mg / m ² or more and 100 mg / m ² or less, preferably 3 mg / m ² or more and 80 mg / m ² or less, and more preferably 4 mg / m ^2. It is 50 mg / m ² or less, more preferably 5 mg / m ² or more and 30 mg / m ² or less. Within this range, desired heat resistance is ensured, and the solubility of the Zn-Ni-Mo layer with respect to the copper etching solution is improved, which can effectively prevent the generation of residues.

Although Ni is excellent in chemical resistance and heat resistance, it is a metal that is difficult to dissolve in a copper etchant. From the viewpoint described above, the Ni adhesion amount in the Zn-Ni-Mo layer is 5 mg / m ² or more and 60 mg / m ² or less, preferably 10 mg / m ² or more and 50 mg / m ² or less, and more preferably 15 mg / m ^2. Above 30 mg / m ² or less. Within this range, the excellent solubility of the Zn-Ni-Mo layer during copper foil etching is ensured, and the chemical resistance and heat resistance of the copper foil can be improved, which can effectively prevent chemical impregnation and soldering processes. The adhesion to the insulating substrate is reduced.

Mo is a metal that contributes to the prevention of the diffusion of Cu, but if it is present in a large amount, residue is liable to be generated during copper foil etching. From the above viewpoint, the Mo adhesion amount in the Zn-Ni-Mo layer is 2.0 mg / m ² or more and 40 mg / m ² or less, preferably 2.0 mg / m ² or more and 20 mg / m ² or less, and more preferably 2.2 mg. / m ² or more and 10 mg / m ² or less. Within this range, excellent solubility of the Zn-Ni-Mo layer during copper foil etching is ensured, and Cu diffusion can be effectively prevented. As a result, the chemical resistance of the copper foil is improved, and it is possible to effectively prevent a decrease in adhesion with the insulating base material after the welding process and the like.

The ratio of the Ni adhesion amount to the total amount of the Zn adhesion amount, the Ni adhesion amount, and the Mo adhesion amount, that is, Ni / (Zn + Ni + Mo) is 0.40 or more and 0.80 or less, preferably 0.45 or more and 0.75 or less, and more preferably 0.50 or more. 0.65 or less. The good chemical resistance and heat resistance of the copper foil are ensured within this range, and the good solubility of the Zn-Ni-Mo layer with respect to the copper etchant is also ensured, and the occurrence of residues can be effectively prevented during copper foil etching.

The Zn-Ni-Mo layer may be a layer (preferably an alloy layer) containing Zn, Ni, and Mo. The amount of Zn deposited in the Zn-Ni-Mo layer may be appropriately adjusted by providing a Zn layer on the surface of the Zn-Ni-Mo layer.

From the viewpoint of improving the adhesion with the insulating substrate, it is preferable that the surface-treated copper foil further includes a roughened layer composed of a plurality of roughened particles between the copper foil and the Zn-Ni-Mo layer. The thickness of the roughened layer is preferably 0.01 μm or more and 0.50 μm or less, and more preferably 0.05 μm or more and 0.30 μm or less.

The maximum height Sz of the surface-treated copper foil, the surface of the Zn-Ni-Mo layer side (that is, the outermost surface away from the copper foil side) is preferably 7.0 μm or less, and more preferably 1.0 μm or more and 7.0 μm or less. If it is within this range, it is more suitable to use a macro circuit formation and high-frequency applications. In particular, such a low thickness reduces the skin effect of the copper foil that is a problem in the transmission of high-frequency signals, and reduces the conductor loss caused by the copper foil, thereby making it possible to intentionally reduce the transmission loss of high-frequency signals.

The surface-treated copper foil preferably has a chromate layer or a silane coupling agent layer on the surface of the Zn-Ni-Mo layer, and more preferably has both a chromate layer and a silane coupling agent layer. With the addition of a chromate layer and / or a silane coupling agent layer, in addition to the improvement of rust prevention, moisture resistance, and chemical resistance, the combination with the Zn-Ni-Mo layer can also improve and insulate the substrate. Of adhesion.

Although the thickness of the surface-treated copper foil is not particularly limited, it is preferably 0.1 μm or more and 105 μm or less, and more preferably 0.5 μm or more and 70 μm or less. The surface-treated copper foil is not limited to those having a Zn-Ni-Mo layer on the surface of a normal copper foil, and those having a Zn-Ni-Mo layer on the surface of a copper foil with a carrier copper foil may be used.

The manufacturing method of the surface-treated copper foil is an example of the preferable manufacturing method of the surface-treated copper foil of this invention. The preferred manufacturing method includes preparing a copper foil, and subjecting the copper foil to a surface treatment with a solution containing Zn, Ni, and Mo. The surface-treated copper foil of the present invention is not limited to the method described below, and may be produced by any method.

(1) Preparation of copper foil As a copper foil used for the manufacture of a surface-treated copper foil, both electrolytic copper foil and rolled copper foil can be used, and electrolytic copper foil is preferred. In addition, the copper foil may be a copper foil without roughening, or it may be provided by a preliminary roughening. Although the thickness of the copper foil is not particularly limited, it is preferably from 0.1 μm to 105 μm, and more preferably from 0.5 μm to 70 μm. When the copper foil is prepared in the form of a copper foil with a carrier, the copper foil is formed by a wet film formation method such as electroless copper plating method and electrolytic copper plating method, a dry film formation method such as sputtering and chemical vapor deposition, or a combination thereof. Only those who are formed by the method can be used.

When the copper foil is roughened, the maximum height Sz of the surface of the copper foil obtained by the roughening treatment based on ISO25178 is preferably 2.0 μm or less, more preferably 1.5 μm or less, and even more preferably 1.0. μm or less. Within the above range, it is easy to achieve a desired low surface profile on the surface Sz of the surface-treated copper foil. The lower limit value of Sz is not particularly limited, but is typically 0.1 μm or more.

(2) Roughening treatment It is preferable to apply a roughening treatment to the surface of the copper foil provided with the low Sz as described above. The surface of the copper foil subjected to the roughening treatment may be any one of an electrode surface and a precipitation surface, and is not particularly limited. The roughening treatment is performed in a copper sulfate solution containing a copper concentration of 4 g / L or more and 25 g / L or less and a sulfuric acid concentration of 50 g / L or more and 300 g / L or less, at a temperature of 20 ° C or higher and 60 ° C or lower, and at 10A / dm ² or higher. 100 A / dm ² or less is preferably performed by electrolysis, and the electrolysis is preferably performed at 1 second or more and 20 seconds or less. The roughening treatment is performed according to a known coating method including at least two types of coating processes including a firing coating process for depositing and depositing fine copper particles on a copper foil and a covering coating process for preventing the fine copper particles from falling off. can. At this time, it is preferable that the firing coating process is performed by electrolytic analysis under the above roughening treatment conditions. In addition, the coating process is performed at a temperature of 40 ° C. to 60 ° C. and 1 A / dm in a copper sulfate solution containing a copper concentration of 6 g / L to 80 g / L and a sulfuric acid concentration of 100 g / L to 300 g / L. ^{2 to} 70 A / dm ² or less is preferred for electrical resolution, and the electrical resolution is preferably 1 to 20 seconds.

(3) Anti-rust treatment The copper foil is subjected to an anti-rust treatment to form a Zn-Ni-Mo layer. When the copper foil is roughened, it is preferable to perform rust prevention treatment on at least the surface of the copper foil on the side where the roughened layer exists, and more preferably to perform rust prevention treatment on both sides of the copper foil. The rust prevention treatment preferably includes a plating treatment using Zn, Ni, and Mo. This coating process can be performed using a coating solution containing Zn, Ni, and Mo. The coating treatment is preferably performed using a pyrroline acid bath, and can be performed using, for example, potassium pyrroline acid having a concentration of 50 g / L or more and 150 g / L or less. As the Zn source of the coating solution, zinc pyrrolinate, zinc sulfate, etc. are preferably used. The Zn concentration in the coating solution is preferably 0.1 g / L or more and 10 g / L or less, and more preferably 1 g / L or more and 5 g / L or less as the coating film. As the Ni source of the liquid, nickel sulfate, nickel chloride, nickel acetate, etc. are preferably used. The Ni concentration in the coating solution is preferably 0.1 g / L or more and 10 g / L or less, and more preferably 1 g / L or more and 5 g / L or less as the coating film. The Mo source of the liquid is preferably sodium molybdate, potassium molybdate, ammonia molybdate, etc. The Mo concentration in the coating solution is preferably 0.1 g / L or more and 10 g / L or less, and more preferably 0.5 g / L or more and 5 g / L or more. using the following plating liquid at a temperature within the above range above 20 ℃ or less 50 ℃, to 0.1A / dm ² or more 5.0A / dm ² or less preferred electrolysis, the electrolysis is preferably 1 second or more to 30 seconds or less.

(4) Chromate treatment It is preferable to perform a chromate treatment on the copper foil subjected to the rust prevention treatment to form a chromate layer. The chromate treatment is preferably performed at a chromic acid concentration of 0.5 g / L or more and 8 g / L or less, pH 1 or more and 13 or less, and a current density of 0.1 A / dm ² or more and 10 A / dm ² or less. The electrolysis is performed for 1 second or more and 30 seconds or less. The following is preferred.

(5) Silane coupling agent treatment It is preferable to apply a silane coupling agent treatment to copper foil to form a silane coupling agent layer. The silane coupling agent layer can be formed by appropriately diluting and coating the silane coupling agent and drying it. Examples of the silane coupling agent include epoxy-functional silane coupling agents such as 4-glycidyl ether trimethyl, 3-glycidoxypropyltrimethoxysilane, or 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltriethoxy Ammonia-functional silane coupling agents such as silane, N-phenyl-3-aminopropyltriethoxysilane, or mercapto-functional silane coupling agents such as 3-aminopropyltriethoxysilane, or vinyltrimethoxy Olefin-functional silane coupling agents such as silanes and vinylphenyltrimethoxysilane; acrylic functional silane coupling agents such as 3-methacryloxypropyltrimethoxysilane; or imidazoles such as imidazole silane A functional silane coupling agent, or a triazine functional silane coupling agent such as a triazine silane.

Copper-clad laminate The surface-treated copper foil of the present invention is preferably used for producing a copper-clad laminate for a printed wiring board. That is, according to a preferred aspect of the present invention, a copper-clad laminate is provided, including the above-mentioned surface-treated copper foil and an insulating substrate provided on at least one side of the surface-treated copper foil. The surface-treated copper foil may be provided on one side or both sides of the insulating substrate. The loss factor of the insulating base material is preferably 0.004 or less and more preferably 0.003 or less at a frequency of 10 GHz. Accordingly, when used for a printed wiring board, the dielectric loss caused by the insulating substrate can be reduced, so that a printed wiring board suitable for high-frequency applications can be produced. The insulating substrate preferably contains an insulating resin. The insulating substrate is preferably a prepreg and / or a resin sheet. The prepreg is a general term for a composite material in which a substrate such as a synthetic resin plate, a glass plate, a glass woven fabric, a glass non-woven fabric, and paper is impregnated with a synthetic resin. Preferred examples of the insulating resin impregnated with the prepreg include epoxy resin, cyanate resin, bismaleimide triazine resin (BT resin), polyphenylene ether resin, and phenol resin. Examples of the insulating resin constituting the resin sheet include epoxy resin, polyimide resin, and polyester fiber resin. In addition, the insulating substrate may contain filler particles composed of various inorganic particles such as silicon dioxide and alumina from the viewpoint of improving insulation properties and the like. The thickness of the insulating substrate is not particularly limited, but it is preferably 1 μm or more and 1000 μm or less, more preferably 2 μm or more and 400 μm or less, and even more preferably 3 μm or more and 200 μm or less. The insulating substrate may be composed of a plurality of layers. An insulating base material such as a prepreg and / or a resin sheet may be provided on the surface-treated copper foil by an undercoat resin layer applied on the surface of the copper foil in advance.

The surface-treated copper foil or copper-clad laminated board of the present invention is preferably used for manufacturing a printed wiring board. That is, according to a preferred aspect of the present invention, there is provided a method for manufacturing a printed wiring board using the aforementioned surface-treated copper foil or the aforementioned copper-clad laminate to produce a printed wiring board, or using the aforementioned surface-treated copper foil or the aforementioned copper-clad A printed wiring board obtained by laminating a board. By using the surface-treated copper foil or the copper-clad laminated board of the present invention, it is possible to provide a printed wiring board having excellent adhesion and reliability between the copper foil-to-base material and the substrate-to-base material as described above. The printed wiring board of this aspect includes a layer structure in which an insulating base material and a copper layer are sequentially laminated. In addition, regarding the insulating base material, the copper-clad laminate is the same as described above. In any case, the printed wiring board can be constructed using a known layer. As a specific example of the printed wiring board, there is a single-sided or double-sided printed wiring board that forms a circuit after the surface-treated copper foil of the present invention is adhered and cured on one or both sides of a prepreg, or the Such multilayer printed wiring boards and the like. In addition, as another specific example, a flexible printed circuit wiring board, a COF, a TAB tape, or the like, in which the surface-treated copper foil of the present invention is formed on a resin film to form a circuit, may also be used. As another specific example, a resin-coated copper foil (RCC) coated with the insulating resin is formed on the surface-treated copper foil of the present invention, and the insulating resin is laminated on the printed wiring board as an insulating adhesive. The surface-treated copper foil is used as the whole or a part of the wiring layer to form a laminated wiring board of a circuit by a method such as modified semi-additive (MSAP) method or subtractive process method, or the surface-treated copper foil is removed and formed by the semi-additive (SAP) method Laminated wiring boards for circuits, lamination with resin copper foil alternately on semiconductor integrated circuits, and direct lamination on wafers to form circuits.

[Example]

Hereinafter, the present invention will be further described using examples.

Examples 1-9
The preparation and evaluation of the surface-treated copper foil of this invention were performed as follows.

(1) Production of electrolytic copper foil As a copper electrolyte, a sulfuric acidic copper sulfate solution having the composition shown below was used, a rotating electrode made of titanium was used for the cathode, and a DSA (dimensional stability anode) was used for the anode. Electrolysis was performed at a current density of 55 A / dm ^{2 to} obtain an electrolytic copper foil having a thickness of 18 μm. The maximum height Sz of the precipitation surface and the electrode surface of this electrolytic copper foil was measured with a laser microscope (VK-X100, manufactured by Keynes Corporation) based on ISO25178. The Sz of the precipitation surface was 0.5 μm, and the Sz of the electrode surface was 1.2. μm. This measurement was performed by measuring the surface profile of a region (150 μm × 150 μm) with an area of 22,500 μm ² for the precipitation surface and the electrode surface of the electrolytic copper foil, and a measurement area filter was not used.

<Composition of Acidic Copper Sulfate Solution>
‐ Copper concentration: 80g / L
‐ Sulfuric acid concentration: 260g / L
‐ Bis (3-sulfopropyl) disulfide concentration: 30mg / L
‐ Diallyl dimethyl ammonium chloride polymer concentration: 50mg / L
‐ Chlorine concentration: 40mg / L

(2) Roughening treatment On the deposition surface side of the electrolytic copper foil obtained as described above, the condition A (first-stage coating, Examples 1 to 3 and 5-9) or condition B (two-stage coating, Example 4) shown below was performed. Roughening caused by.

<Condition A (1-stage coating)>
The electrolytic copper foil was immersed in a copper sulfate solution having a copper concentration of 10 g / L and a sulfuric acid concentration of 100 g / L, and roughened under the conditions of a liquid temperature of 30 ° C and a current density of 40 A / dm ² to form a rough surface on the precipitation surface side of the electrolytic copper foil.化 层。 The layer.

<Condition B (two-stage coating)>
The electrolytic copper foil was immersed in a copper sulfate solution having a copper concentration of 4 g / L and a sulfuric acid concentration of 200 g / L, and the first-stage roughening treatment was performed under the conditions of a liquid temperature of 30 ° C and a current density of 30 A / dm ² . After that, as the second-stage roughening treatment, the copper sulfate solution was immersed in a copper sulfate solution having a copper concentration of 69 g / L and a sulfuric acid concentration of 240 g / L, and the coating was performed under the conditions of a liquid temperature of 50 ° C and a current density of 10 A / dm ² . A roughened layer is formed on the precipitation surface side of the electrolytic copper foil.

(3) Rust prevention treatment The electrolytic copper foil after the roughening treatment is subjected to a one-stage (examples 1 to 7) or two-stage (examples 8 and 9) rust prevention treatment, and the surface of the roughened layer of the electrolytic copper foil is formed. A Zn-Ni-Mo layer is formed. Specifically, in the first stage of the treatment, the concentration of Zn, Ni, and Mo shown in Table 1 includes zinc pyrrolinate (Zn source), nickel sulfate (Ni source), and sodium molybdate (Mo source). An electrolytic copper foil was immersed in a pyrroline acid bath having a potassium pyrroline acid concentration of 100 g / L, and Zn-Ni-Mo was electrodeposited at a liquid temperature of 40 ° C, a current density shown in Table 1, and a treatment time. In the second-stage treatment, electrolysis through the first-stage treatment was performed in a pyrroline acid bath having a potassium pyrroline acid concentration of 145 g / L containing zinc pyrroline acid (Zn source) at a Zn concentration shown in Table 1. The copper foil was immersed, and Zn was electrodeposited at a liquid temperature of 30 ° C, a current density shown in Table 1, and a treatment time. At this time, by appropriately changing the Zn concentration, Ni concentration, Mo concentration, current density, and processing time as shown in Table 1, a Zn-Ni-Mo layer, a Ni-layer, a Mo-layer, and a Ni-layer in the Zn-Ni-Mo layer were produced. / (Zn + Ni + Mo) different samples.

(4) Chromate treatment A chromate treatment is performed on both sides of the electrolytic copper foil subjected to the rust prevention treatment to form a chromate layer on the Zn-Ni-Mo layer. This chromate treatment was performed under conditions of a chromic acid concentration of 1 g / L, a pH of 11, a liquid temperature of 25 ° C, and a current density of 1 A / dm ² .

(5) Silane coupling agent treatment The copper foil forming the chromate layer was washed with water, and immediately after the silane coupling agent treatment, a silane coupling agent layer was formed on the chromate layer on the roughened surface. This silane coupling agent treatment is performed by using pure water as a solvent and using a solution of 3-aminopropyltriethoxysilane concentration of 3 g / L, and blowing the solution to a roughened surface through a spray ring, followed by adsorption treatment. . After adsorption of the silane coupling agent, water was finally evaporated by an electric heater to obtain a surface-treated copper foil having a thickness of 18 μm.

(6) Evaluation About the produced surface-treated copper foil, the measurement and evaluation shown below were performed.

(a) Measurement of the maximum height Sz The surface of the Zn-Ni-Mo layer side of the surface-treated copper foil (that is, the Surface) maximum height Sz. The Sz on the surface of the Zn-Ni-Mo layer side is the one that roughly reflects the Sz on the surface of the roughened layer. This measurement was performed using the surface profile of a region (150 μm × 150 μm) of the surface area of the surface-treated copper foil of 22,500 μm ² , and a measurement area filter was not used. The results are shown in Table 2.

(b) Measurement of adhesion amount of each element in the Zn-Ni-Mo layer An area having a surface area of 25 cm ² (5 cm × 5 cm) on the Zn-Ni-Mo layer side of the surface-treated copper foil was dissolved with an acid, and the obtained Each concentration of Zn, Ni, and Mo in the dissolved solution was analyzed by ICP emission analysis, and the amount of Zn, Ni, and Mo were measured. From the obtained measurement results, Ni / (Zn + Ni + Mo) was calculated as a ratio of the Ni deposition amount to the total amount of the Zn deposition amount, the Ni deposition amount, and the Mo deposition amount. The results are shown in Table 2.

(c) Evaluation of adhesion reliability between copper foil and substrate The surface treated copper foil in various states (for example, normal state, after heat load, and after chemical impregnation) was evaluated as follows for the adhesion to the insulating substrate. Measurement of normal peeling strength, peeling strength after welding process, and peeling strength (resistance to hydrochloric acid deterioration) after acid treatment. The results are shown in Table 2.

(c-1) Prepare two pieces of prepreg (thickness: 100 μm) with polyphenylene ether, triallyl isocyanurate, and bismaleimide resin as main components as the insulating base material. accumulation. The deposited prepreg was laminated with the prepared surface-treated copper foil such that the roughened surface abuts the prepreg, and was pressed at 32 kgf / cm ² at 205 ° C for 120 minutes to produce a copper-clad layer. Product board. Next, a circuit board was formed on the copper-clad laminate by an etching method, and a test substrate having a linear circuit having a width of 3 mm was produced. The linear circuit thus obtained was peeled from the insulating substrate in accordance with A method (90 ° peeling) of JIS C 5016-1994 to measure the normal peel strength (kgf / cm). The results are shown in Table 2.

(c-2) Peel strength after soldering process Before the peel strength is measured, the test substrate with a linear circuit is floated in a solder bath at 288 ° C for 300 seconds, and measured in the same procedure as the above-mentioned normal peel strength. Peel strength (kgf / cm) after welding process. The results are shown in Table 2.

(c-3) Peel strength after acid treatment (resistance to hydrochloric acid)
Using a circuit width other than 0.4 mm, the peel strength (kgf / cm) before acid treatment was measured in the same procedure as the normal peel strength. In addition, before (i) setting the circuit width to 0.4 mm and (ii) measuring the peel strength, a test substrate provided with a linear circuit was immersed in 4 mol / L hydrochloric acid at 60 ° C for 90 minutes by using In the same procedure as the above-mentioned normal peel strength, the peel strength (kgf / cm) after the acid treatment was measured. From the peel strength before and after the acid treatment thus obtained, the degradation rate (%) of hydrochloric acid resistance was calculated.

(c) Evaluation of adhesion reliability between the substrate and the substrate The adhesion between the substrate and the substrate in the multilayer laminate produced by etching removal of the copper foil was evaluated as follows. First, two surfaces of two stacked insulating substrates 110 were prepared on a prepreg (thickness: 100 μm) containing polyphenylene ether, triallyl isocyanurate, and bismaleimide resin as main components, and the surfaces were The processed copper foil 112 is laminated so that the roughened surface thereof comes into contact with the insulating substrate 110, and is pressed at 32 kgf / cm ² at 205 ° C for 120 minutes to obtain a first copper-clad laminate 114 (Fig. 1 (a) ). The two surfaces of the first copper-clad laminate 114 were etched with a second copper etchant with an acid concentration of 3 mol / L at a bath temperature of 50 ° C, and the surface-treated copper foil 112 existing on both sides was dissolved and removed to obtain a surface. The shape of the roughened surface of the processed copper foil 112 is transferred to the surface of the insulating substrate 110 '(FIG. 1 (b)). This etching was performed by performing a total of 2 operations (speed 1.3 m / min) passing the first copper-clad laminate 114 in an etching tank having a length of about 50 cm for 23 seconds (speed 1.3 m / min). Next, the insulating base material 110 'after the etching treatment is sequentially washed with pure water, diluted with hydrochloric acid (concentration: 10% by volume), and washed with pure water. The washed insulating substrate 110 'was dried in a cleaning oven at 80 ° C for 20 minutes. The prepreg 116 and the surface-treated copper foil 112 having a thickness of 100 μm were sequentially laminated on both sides of the dried insulating substrate 110 ′, and pressed at 32 kgf / cm ² at 205 ° C. for 120 minutes to form a second copper-clad laminate. 118 (Figure 1 (c)). The two surfaces of the second copper-clad laminate 118 were etched with a second copper etchant of chloride with an acid concentration of 3 mol / L at a bath temperature of 50 ° C., and the surface-treated copper foil 112 existing on both sides was dissolved and removed to obtain an evaluation. Sample 120 is used (Fig. 1 (d)). Two test pieces having a size of 5 cm × 10 cm were cut out from the sample 120 for evaluation. These test pieces were put into a PCT (Pressure Cooker Test) tester, and moisture absorption was performed for 50 minutes under the conditions of 2 atmospheres, 121 ° C, and 100% RH. The moisture-absorbing test piece was taken out by a PCT tester, and after the water was wiped off, it was welded and immersed within 10 minutes after taking out. This welding immersion was performed by performing a total of 20 operations of immersing a test piece in a welding bath at 288 ° C. for 20 seconds. After welding and dipping, the presence or absence of bulges in the test piece (that is, bubble-like gaps caused by peeling between substrates in the laminate) was visually confirmed. It was determined when bulges occurred in at least one of the two test pieces. Has bulging. The bulging should be caused by the residue of the rust-preventive treatment layer remaining after the etching of the copper foil. The results are shown in Table 2.

110‧‧‧ insulating substrate

112‧‧‧Surface-treated copper foil

114‧‧‧The first copper-clad laminate

116‧‧‧ Prepreg

118‧‧‧The second copper-clad laminate

120‧‧‧ Evaluation Sample

[Fig. 1] A process flow of a production process (processes (a) to (d)) for preparing a sample for evaluation in the substrate-to-substrate adhesion evaluation in Table Examples 1 to 9.

Claims (8)

A surface-treated copper foil comprising: a copper foil and a Zn-Ni-Mo layer; the Zn-Ni-Mo layer is provided on at least one side of the copper foil, and an Zn adhesion amount is 3 mg / m ² or more and 100 mg / m ² or less, The Ni adhesion amount is 5 mg / m ² or more and 60 mg / m ² or less, and the Mo adhesion amount is 2.0 mg / m ² or more and 40 mg / m ² or less, and the Ni adhesion amount is relative to the Zn adhesion amount, the Ni adhesion amount, and the Mo. Ni / (Zn + Ni + Mo), which is the total ratio of the adhesion amount, is 0.40 or more and 0.80 or less. The surface-treated copper foil according to claim 1, further comprising a roughened layer composed of a plurality of roughened particles between the copper foil and the Zn-Ni-Mo layer. The surface-treated copper foil according to claim 1, wherein the maximum height Sz of the surface on the Zn-Ni-Mo layer side of the surface-treated copper foil measured based on ISO25178 is 7.0 μm or less. The surface-treated copper foil according to claim 1, further comprising a chromate layer and / or a silane coupling agent layer on the surface of the Zn-Ni-Mo layer. A copper-clad laminated board comprising: the surface-treated copper foil according to any one of claims 1 to 4; An insulating base material provided on the at least one side of the surface-treated copper foil. The copper-clad laminate according to claim 5, wherein the loss factor of the insulating base material is 0.004 or less at a frequency of 10 GHz. A method for manufacturing a printed wiring board, which uses a surface-treated copper foil according to any one of claims 1 to 4 to manufacture a printed wiring board. A method for manufacturing a printed wiring board, which uses the copper-clad laminate according to claim 5 or 6 to manufacture the printed wiring board.