KR101974687B1 - Surface-treated copper foil and laminate - Google Patents

Surface-treated copper foil and laminate Download PDF

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Publication number
KR101974687B1
KR101974687B1 KR1020150046805A KR20150046805A KR101974687B1 KR 101974687 B1 KR101974687 B1 KR 101974687B1 KR 1020150046805 A KR1020150046805 A KR 1020150046805A KR 20150046805 A KR20150046805 A KR 20150046805A KR 101974687 B1 KR101974687 B1 KR 101974687B1
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copper foil
plating layer
copper
base material
copper plating
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KR1020150046805A
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KR20150124388A (en
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다케미 무로가
지즈루 고토
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장 춘 페트로케미컬 컴퍼니 리미티드
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

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  • Electroplating Methods And Accessories (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Laminated Bodies (AREA)

Abstract

[PROBLEMS] To provide a technique for improving mounting workability when mounting an electronic component or the like on a flexible printed wiring board.
A surface-treated copper foil comprising a copper foil base material, a copper plating layer formed on the copper foil base material, and a copper-clad coating layer formed on the copper plating layer, characterized in that the surface-treated copper foil is opposed to the copper- When the surface-treated copper foil is removed on both major surfaces of the resin substrate after bonding the surface-treated copper foil so that the side of the resin substrate is in contact with the resin substrate, the resin substrate has a haze value of 80% or less and a transparency of 70% , And the fill strength between the surface-treated copper foil and the resin base material is 0.6 N / mm or more.

Description

[0001] SURFACE-TREATED COPPER FOIL AND LAMINATE [0002]

The present invention relates to a surface-treated copper foil (surface treated copper foil) and a laminated board (laminated board).

Background Art A flexible printed wiring board (FPC) conventionally used as a wiring board of an electronic device such as a cellular phone is a flexible printed wiring board (FPC), for example, a polyimide film provided on a main surface of at least one of a copper foil and a copper foil (Resin base material) of a resin substrate. A circuit pattern (copper wiring) is formed on the laminated board by removing the copper foil at a predetermined place by etching or the like. When an electronic part or the like is mounted on the FPC, the positioning mark is visually inspected (through the resin substrate where the copper foil is removed) from the place where the copper foil is removed, Position is determined. Therefore, the FPC is required to have high transparency (hereinafter, simply referred to as " transparency of the resin substrate ") of the resin substrate after the copper foil is bonded and removed. Therefore, the surface roughness of the copper foil is adjusted so that the light transmittance of the resin substrate is 30% or the haze value (haze value) of the resin substrate is 40% Of the surface roughness of the copper foil to 30% or less (see, for example, Patent Documents 1 to 3).

Japanese Patent Application Laid-Open No. 2013-147688 Japanese Patent No. 5035220 Japanese Patent Application Laid-Open No. 2004-98659

However, when electronic parts or the like are mounted on the FPC, the resin substrate and the positioning mark are not in close contact with each other and are spaced apart from each other by a predetermined distance. Therefore, even when the light transmittance of the resin base material and the haze value of the resin base material are adjusted, positioning marks can not be visually recognized or visually recognized when the electronic parts or the like are mounted on the FPC. As a result, the mounting workability is deteriorated.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and to provide a technique for improving mounting workability when mounting an electronic component or the like on a flexible printed wiring board.

According to one aspect of the present invention, there is provided a surface-treated copper foil comprising a copper foil substrate, a copper plating layer formed on the copper foil substrate, and a copper plating layer formed on the copper plating layer, Treated copper foil is peeled off on both main surfaces of the resin base material after bonding the surface-treated copper foil such that the side of the copper foil facing the side where the copper-clad coating layer is formed comes into contact with the resin base material, Treated copper foil and the resin base material has a value of 80% or less and a transparency of 70% or more and a peel strength between the surface-treated copper foil and the resin base material is 0.6 N / mm or more, and the copper coplanar plating layer has an average thickness of 0.05 to 0.30 Treated copper foil.

According to another aspect of the present invention, there is provided a copper-clad laminate comprising: a surface-treated copper foil having a copper foil base, a copper plated layer formed on the copper foil base, and a copper foil layer formed on the copper plated layer; Treating the surface-treated copper foil on both main surfaces of the resin base material after the surface-treated copper foil is opposed to the surface of the resin base material, , A haze value of the resin substrate is 80% or less, a transparency is 70% or more, and a peel strength between the surface-treated copper foil and the resin substrate is 0.6 N / mm or more.

According to the present invention, it is possible to improve the mounting workability when mounting electronic components or the like on the flexible printed wiring board.

1 is a schematic cross-sectional view of a laminated board having a surface-treated copper foil according to an embodiment of the present invention.
2 is a schematic view showing an apparatus for measuring the haze value of a resin substrate.
Fig. 3 (a) is a schematic view showing an apparatus for measuring transparency of a resin substrate, and Fig. 3 (b) is a schematic plan view of a sensor used in the apparatus shown in Fig. 3 (a).
Fig. 4 is a flowchart showing the steps of manufacturing a surface-treated copper foil and a laminated board according to an embodiment of the present invention.
Fig. 5 is a schematic view showing a state where an electronic part or the like is mounted on a flexible printed wiring board formed of a laminated board according to an embodiment of the present invention. Fig.

(Knowledge acquired by the inventors)

Prior to the description of the embodiments of the present invention, the knowledge acquired by the inventors will be described. A surface-treated copper foil having a copper plating layer (roughened copper plating layer) formed on a main surface of any one of a copper foil substrate and a copper foil substrate is provided on a wiring board such as an FPC, (Copper clad laminates)) having a high thermal conductivity is used. The laminated board is formed by bonding the resin base material to the surface of the surface-treated copper foil on which the copper plating layer is formed. For example, as shown in Fig. 5, alignment of mounting positions of electronic components or the like when mounting electronic components or the like in the FPC 100 is performed by irradiating light from a light source (light source) 101, for example, And the positioning mark 103 at the mounting position is visible beyond the resin substrate in the place where the surface-treated copper foil is removed in order to form the copper wiring. Therefore, it is required that the resin base material where the surface-treated copper foil is removed has high transparency. However, when the resin substrate and the surface-treated copper foil are bonded to each other at the time of forming the laminate, the unevenness formed on the surface of the surface-treated copper foil is transferred to the resin substrate by the copper plating layer, . Therefore, when the haze value (HAZE value) and the light transmittance (hereinafter also referred to as " haze value of resin substrate " or " light transmittance of resin substrate ") of the resin substrate after bonding and removing the surface- The surface roughness of the surface of the surface-treated copper foil to be bonded to the resin base material is adjusted so that the surface roughness of the surface-treated copper foil becomes uniform. The haze value of the resin base material is a ratio of the amount of diffused transmission light (amount of light diffused without straight advancing) to the amount of light of all the light rays (all rays) transmitted through the resin base material. The light transmittance of the resin base material is a value measured with parallel rays without considering reflection or scattering of light. When light reflection or scattering is large, the light transmittance of the resin base material is low. That is, the light transmittance of the resin base material is related to the ratio of the amount of linearly transmitted light (amount of light straightened without being diffused) to the amount of light of all the light rays transmitted through the resin base material. However, the absolute value of the numerical value of the light transmittance and the absolute value of the ratio of the amount of linearly transmitted light do not coincide with each other because the light transmittance and the amount of linearly transmitted light differ from each other. As described above, the haze value of the resin substrate and the transmittance of the resin substrate are indicative of the transparency (turbidity) of the resin substrate itself, respectively, and are in the relationship of the front and back sides. For example, when the haze value of the resin substrate becomes large, the light transmittance of the resin substrate becomes small, and when the haze value of the resin substrate becomes small, the light transmittance of the resin substrate becomes large.

The resin base material (FPC 100) is disposed at a position spaced apart from the positioning mark 103 (see Fig. 5) when actually mounting electronic parts or the like on the FPC 100. Fig. That is, in the actual mounting step, the resin base material and the positioning mark 103 are not in close contact with each other. Therefore, in the actual mounting process, when light is irradiated from the light source 101 to the resin substrate, a part of the light transmitted through the resin substrate is scattered. As a result, even if the surface-treated copper foil is adjusted so that the haze value and the light transmittance of the resin substrate are adjusted to a predetermined value, it is difficult to visually check the positioning marks 103 over the resin substrate in the actual mounting step, There is a case. That is, as an index for evaluating the transparency of the resin substrate itself, it is not possible to improve the mounting workability only by controlling the haze value and the light transmittance of the resin substrate, which is not taken into account for scattering of light transmitted through the resin substrate There is a case. The present invention is based on the above finding found by the inventor.

≪ One embodiment of the present invention &

(1) Composition of surface-treated copper foil and laminate

First, the configuration of a surface-treated copper foil according to an embodiment of the present invention will be described with reference to Fig. 1 is a schematic cross-sectional view of a laminate 10 having a surface-treated copper foil 1 according to the present embodiment.

(Surface treated copper foil)

1, the surface-treated copper foil 1 according to the present embodiment includes a copper foil base 2, a copper plating layer 3 formed on the copper foil base 2, and a copper plating layer 3 formed on the copper plating layer 3 And a copper plating layer (4). Further, the surface-treated copper foil 1 is subjected to a surface treatment such that the side of the copper plating layer 4 comes into contact with the resin substrate, for example, by opposing the surface-treated copper foil 1 on both main surfaces of a polyimide resin film, When the surface-treated copper foil 1 is removed from the resin substrate after bonding the copper foil 1, the resin substrate has a haze value of 80% or less and a transparency of 70% or more, And a peel strength of 0.6 N / mm or more.

The haze value (soaking) of the resin substrate is an index for evaluating the apparent transparency (apparent turbidity) of the resin substrate. That is, the haze value of the resin base material is a ratio of the amount of light (diffuse transmission light amount) of the diffusion light of the resin base material to the light amount of the total light ray (total light ray transmission light amount) transmitted through the resin base material. Treated copper foil 1 is brought into contact with the resin base material and the two surface-treated copper foils 1 are opposed to each other and bonded to each other on both main surfaces of the resin base material, The haze value of the resin base material from which the surface-treated copper foil 1 has been removed by etching or the like (hereinafter simply referred to as " resin base material after etching ") is measured to determine the resin base material after etching and the positioning mark Mark) can be evaluated, it is possible to evaluate whether or not the positioning mark can be visually recognized (through the resin substrate after etching) through the resin substrate after etching.

The measurement of the haze value is performed using, for example, the measuring device 20 shown in Fig. For example, the haze value is measured by a device including an integrating sphere 21, a light source 22 and a detector 23. [ The inner circumferential surface of the integrating sphere 21 is configured to uniformly diffuse (reflect) light emitted from the light source 22 and introduced into the integrating sphere 21 from the light oil inlet 21a. The integrating sphere 21 is provided with a light oil inlet 21a into which light from the light source 22 flows and a light outlet port 21b formed in a position opposite to the light oil inlet 21a and through which light is emitted Respectively. In the light outlet port 21b, a lid 24 for closing the light outlet port 21b is provided. The surface of the lid 24 located inside the integrating sphere 21 is configured to diffuse (reflect) the light introduced into the integrating sphere 21.

A light source 22 is disposed at a position facing the light oil inlet 21a as an outer side of the integrating sphere 21. The light source 22 is disposed, for example, so that the optical axis of the light source 22 and the center position of the light oil inlet 21a coincide with each other. The light source 22 may be arranged so that the distance L between the light output position and the center position of the light oil inlet 21a coincides with the mounting distance. However, the light source 22 may not be arranged so that the distance L and the mounting distance coincide with each other. The mounting distance is a distance between the resin base material 11 and the light source 22 when an electronic component or the like is mounted on the laminate 10 described later. The detector 23 is configured to measure the amount of light emitted from the light source 22 and introduced into the integrating sphere 21 from the light oil inlet 21a.

The haze value of the resin base material is measured as follows. First, the resin base material 25 to be measured is arranged in the light oil inlet 21a. For example, the resin base material 25 is arranged so as to cover the light oil inlet 21a from the outside of the integrating sphere 21. The amount of the light that has passed through the resin base material 25 and has flowed into the integrating sphere 21 by irradiating the light from the light source 22 in the state in which the light outlet port 21b is closed (closed) by the cover 24 The amount of transmitted light) is measured by the detector 23. The cover 24 is peeled off so that the light is emitted from the light source 22 in the state in which the light outlet port 21b is opened so that the light emitted from the light source 22 through the resin base 25, (Amount of diffusion transmitted light) is measured. Then, the haze value of the resin base material 25 to be measured is calculated from the following equation (1).

(Number 1)

Haze value (%) = (diffusion transmitted light amount / total transmitted light amount) × 100

CLARITY is an index for evaluating the directivity of light transmitted through a resin substrate. In particular, transparency is an index for evaluating the directivity of light transmitted through a resin substrate. In other words, transparency means that transparency of a resin substrate is evaluated by detecting scattered light (narrow angle scattered light) of light transmitted through the resin substrate. The degree of transparency of the resin substrate after the etching is measured. When the resin substrate after etching is disposed at a position spaced apart from the positioning mark (that is, when the resin substrate after etching is not closely adhered to the positioning mark) It is possible to evaluate whether or not the positioning mark can be visually recognized.

The transparency is measured by using the measuring device 30 shown in Fig. 3 (a), for example. The measuring device 30 shown in Fig. 3 is the same as the measuring device 20 for measuring the haze value shown in Fig. 2, except that the sensor 31 is provided at the light outlet port 21b. The sensor 31 of the measuring apparatus 30 is provided with a circular center sensor 31a and an annular ring sensor 31b. As shown in Fig. 3 (b), the ring sensor 31b is provided so as to surround the outer periphery of the center sensor 31a.

The transparency of the resin substrate is measured as follows. First, the resin base material 25 to be measured is arranged at the light emission position of the light source 22. Light emitted from the light source 22 is transmitted through the resin base material 25 and introduced into the integrating sphere 21 from the light oil inlet 21a without attaching the lid 24 to the center sensor 31a, And receives light by the sensor 31b. The transparency of the resin base material 25 to be measured is calculated from the following equation (2) using the light amount IC received by the center sensor 31a and the light amount IR received by the ring sensor 31b.

(Number 2)

Transparency (%) = {(IC-IR) / (IC + IR)} 100

The peel strength is an index for evaluating the adhesion between the resin substrate and the surface-treated copper foil. The higher the peel strength, the higher the adhesion.

(Based on copper foil)

As described above, the surface-treated copper foil 1 according to the present embodiment is provided with the copper foil base 2. [ As the copper foil base material 2, for example, a rolled copper foil or an electrolytic copper foil is used. It is preferable that the copper foil base material (2) is a rolled copper foil which is superior in bending resistance to an electrolytic copper foil and does not break even if bent repeatedly. As the material for forming the rolled copper foil, for example, oxygen-free copper (OFC) or pure copper (TPC: Tough-Pitch Copper) is used. Anoxic copper is a copper material having a purity of not less than 99.96% specified by JIS C1020 or JIS H3100. The oxygen-free copper may contain, for example, several ppm of oxygen. That is, the oxygen content of the oxygen free copper may not be zero. The tough pitch copper is, for example, a copper material having a purity of 99.9% or more specified by JIS C1100 or JIS H3100. The tough pitch copper may contain about 100 ppm to 600 ppm of oxygen, for example. As a material for forming the rolled copper foil, a lean copper alloy to which a small amount of a predetermined additive such as tin (Sn) or silver (Ag) is added to oxygen-free copper or toughpitch copper may be used. Accordingly, heat resistance and the like of the rolled copper foil can be improved.

(Copper plated layer)

On the main surface of any one of the copper foil base 2, a copper plating layer 3 is formed by, for example, electrolytic plating or the like. The copper plating layer 3 is a smooth copper plating layer and functions as a base layer of the copper plating layer 4. [ The copper plating layer 3 contains a predetermined amount of sulfur element (S). That is, the copper plating layer 3 is formed by using a copper plating solution to which an organic compound (organic sulfur compound) having a mercapto group is added. Hereinafter, the copper plating solution for forming the copper plating layer 3 is simply referred to as " copper plating solution ". As the organic compound having a mercapto group, for example, bis (3-sulfopropyl) disulfide (SPS) is used.

The addition amount of the organic sulfur compound may be, for example, 5 mg / L or more and 60 mg / L or less, more preferably 5 mg / L or more and 45 mg / L or less and more preferably 5 mg / L or more and 30 mg / L or less. When the addition amount of the organic sulfur compound is less than 5 mg / L, the effect of suppressing the deterioration of the adhesiveness can not be sufficiently obtained while increasing the transparency of the resin base material. This can be solved by setting the addition amount of the organic sulfur compound to 5 mg / L or more, and it is possible to suppress the deterioration of the adhesion while increasing the transparency of the resin substrate. Namely, transparency of a desired resin base material and desired adhesion can be obtained. However, if the addition amount of the organic sulfur compound exceeds 60 mg / L, the solubility of the organic sulfur compound in the copper plating solution lowers, and the effect of adding the organic sulfur compound may not be sufficiently obtained in some cases. Since the organic sulfur compound is an expensive raw material, if the addition amount exceeds 60 mg / L, the production cost of the surface-treated copper foil becomes high. These can be solved by reducing the addition amount of the organic sulfur compound to 60 mg / L or less. That is, it is possible to suppress deterioration of the solubility of the organic sulfur compound and to suppress an increase in the production cost. When the addition amount of the organic sulfur compound is 45 mg / L, the lowering of the solubility of the organic sulfur compound can be further suppressed and the increase of the production cost can be further suppressed. When the addition amount of the organic sulfur compound is 30 mg / L, the lowering of the solubility of the organic sulfur compound can be further suppressed, and the increase in the production cost can be further suppressed.

Surfactants, leveling agents, chloride ions and the like may be added to the copper plating solution.

As the surfactant, any one of polyethylene glycol, polypropylene glycol, polyoxyalkylene ether and the like is used. Specifically, a chemical solution containing any one of polyethylene glycol, polypropylene glycol and polyoxyalkylene ether as a surfactant is used as a surfactant. As the surfactant, for example, a surfactant chemical solution of CU-BRITE TH-RIII (registered trademark) series manufactured by EBARA-UDYLITE CO., LTD. Is used. The addition amount of the surfactant may be, for example, 1 ml / L or more and 4 ml / L or less.

As the leveling agent, diaryldialkylammonium alkylsulfate and the like are used. Specifically, as a leveling agent, a chemical liquid containing diaryldialkylammonium alkylsulfate or the like as a main component is used. As a leveling agent, for example, a leveling agent solution containing a polymeric hydrocarbon as a main component such as CU-BRITE TH-RIII series manufactured by Eva Yasei Light Co., Ltd. may be used. When the CU-BRITE TH-RIII series as a leveling agent is used, the leveling agent may be added in an amount of, for example, 3 ml / L or more and 10 ml / L or less.

As the chloride ion, for example, a chemical solution containing chloride ion (i.e., hydrochloric acid, HCl aqueous solution) is used. The amount of hydrochloric acid to be added may be, for example, 0.05 ml / L or more and 0.3 ml / L or less.

The copper plating layer 3 may be formed to have a thickness of 0.1 占 퐉 or more and 0.6 占 퐉 or less, for example. As a result, the haze value of the resin substrate after etching can be lowered and the transparency can be further increased. That is, the transparency of the resin substrate after etching can be further improved. If the thickness of the copper plating layer 3 is less than 0.1 탆, the effect of forming the copper plating layer 3 is not obtained and the transparency of the resin substrate after etching is lowered. When the thickness of the copper plating layer 3 exceeds 0.6 占 퐉, for example, when a rolled copper foil is used as the copper foil base material 2, the recrystallization of the copper foil base material 2 is disturbed, There may be a case where it is lowered.

(Coated copper plating layer)

On the copper plating layer 3, a copper plating layer 4 is formed. The anchor effect is obtained so that the adhesion between the surface treated copper foil 1 and the resin base material 11 in the laminated board 10 to be described later (hereinafter simply referred to as " adhesion property " Can be improved. The coarsened copper plating layer 4 is mainly composed of a plurality of coarse grains (roughened grains). The coarsely-grained copper plating layer 4 may be in a state in which blurring does not occur. For example, the copper plating layer 4 may be formed so that the copper plating layer 3 is not exposed when the copper plating layer 4 is viewed from above.

The coarse copper plating layer 4 is formed of, for example, copper (Cu) (that is, Cu single element). The harmonic rib is made of at least one metal of, for example, Cu and at least one of iron (Fe), molybdenum (Mo), nickel (Ni), cobalt (Co), chromium (Cr), zinc (Zn) or tungsten Or may be formed using a plating solution containing an element and.

The coarsened copper plating layer 4 may be formed so as to have an average thickness of 0.05 탆 or more and 0.30 탆 or less. The average thickness of the coarsened copper plating layer 4 is the thickness when the coarsened copper plating layer 4 is uniformly arranged. This makes it possible to maintain the adhesion while improving the transparency of the resin substrate. If the average thickness of the coarsened copper plating layer 4 is less than 0.05 탆, an anchor effect due to the formation of the coarsened copper plating layer 4 can not be obtained and the adhesion is lowered. If the average thickness of the coarsened copper plating layer 4 is more than 0.30 탆, the size of the projections and depressions transferred to the resin base material 11 at the time of forming the laminate board 10 to be described later (for example, The transparency of the resin substrate is deteriorated.

(Rust preventive layer)

A rust resisting layer (post-treatment plating layer) 5 having a predetermined thickness (for example, 1 nm or more and 70 nm or less) may be formed on the copper plating layer 4. The anticorrosive layer 5 is formed using a predetermined plating liquid. Thus, heat resistance and chemical resistance of the surface-treated copper foil 1 can be improved. The surface-treated copper foil 1 can be easily removed when forming a copper wiring by removing predetermined portions of the surface-treated copper foil 1 by etching after the laminate 10 is formed.

The anticorrosive layer 5 comprises a nickel (Ni) plated layer having a thickness of 10 nm or more and 50 nm or less, a zinc (Zn) plated layer having a thickness of 1 nm or more and 10 nm or less, A chromate treatment layer (trivalent chromation treatment layer) having a thickness of 10 nm or more and a silane coupling layer having a very thin thickness (extremely thin) may be provided. When the Ni plating layer is formed, the Cu of the surface-treated copper foil 1 can be prevented from diffusing toward the resin base material when the laminate 10 is formed, and the heat resistance and chemical resistance of the surface-treated copper foil 1 can be improved . The Zn plating layer functions as a base layer for forming a chromate treatment layer or a silane coupling layer. Further, when the Zn plating layer is formed, the heat resistance of the surface-treated copper foil 1 can be further improved. The chromate treatment layer and the silane coupling layer each also function as a chemical conversion treatment layer (chemical conversion coating). When the silane coupling layer is formed, the chemical adhesion between the surface-treated copper foil 1 and the resin base material 11 described later can be improved, so that the adhesion can be further improved.

(Laminates)

The CCL (Copper Clad Laminate) 10 according to the present embodiment is formed by bonding a resin base 11 to a surface of the surface-treated copper foil 1 on which the copper plating layer 4 is formed. The laminated board 10 may be formed using, for example, two surface-treated copper foils 1. Namely, in the laminated board 10, the side where the coarsened copper plating layer 4 of the two surface-treated copper foils 1 is formed is brought into contact with the resin substrate 11 on both main surfaces (both surfaces) of the resin substrate 11 And the two surface-treated copper foils 1 are opposed to each other and bonded to each other. As the resin substrate 11, for example, a polyimide (PI) resin film, a polyester film such as polyethylene terephthalate (PET), a liquid crystal polymer (LCP) and the like are used.

(2) Method for producing surface-treated copper foil and laminate

Next, a surface-treated copper foil 1 according to the present embodiment, a laminate 10, and a method for manufacturing a flexible printed wiring board (FPC) formed using the laminate 10 will be described with reference to Fig. Fig. 4 is a flowchart showing a manufacturing process of the surface-treated copper foil 1 and the laminate 10 according to the present embodiment.

[Surface-treated copper foil forming step (S10)]

First, a method of manufacturing the surface-treated copper foil 1 according to the present embodiment will be described.

(Copper foil base material forming step (S11))

As the copper foil base material 2, for example, a rolled copper foil or an electrolytic copper foil is formed. When a rolled copper foil is used, for example, as the copper foil base material 2, firstly, a copper ingot made of oxygen-free copper or toughpiped copper, a copper ingot made of oxygen-free copper or tough pitch copper, An ingot of a lean copper alloy to which a predetermined amount of additive such as Sn or Ag is added is cast. Then, the cast ingot is subjected to a predetermined hot rolling treatment, a predetermined cold rolling treatment, a predetermined annealing treatment (annealing treatment, etc.) 11 [micro] m) rolled copper foil. At this time, the heat resistance of the rolled copper foil may be adjusted according to the heating temperature at the time of recrystallizing the rolled copper foil.

(Copper plating layer forming step (S12))

After the copper foil base material forming step (S11) is completed, first, the surface of the copper foil base material 2 is cleaned. And a copper plating process for forming a copper plating layer 3 on the main surface of any one of the copper foil base material 2 is performed.

≪ Clean process (S121) >

After completion of the copper foil base forming step (S11), the surface of the copper foil base material 2 is cleaned. For example, electrolytic degreasing treatment (electrolytic degreasing treatment) and pickling treatment (pickling treatment) are performed on the surface of the copper foil base 2 as a clean treatment. As the electrolytic degreasing treatment, a negative electrolytic degreasing treatment using an alkali solution such as sodium hydroxide is performed. As the alkali solution, for example, an aqueous solution containing 20 g / L or more and 60 g / L or less of sodium hydroxide and containing 10 g / L or more and 30 g / L or less of sodium carbonate is used. As the pickling treatment, for example, the copper foil base material 2 is immersed in an acidic aqueous solution such as sulfuric acid to neutralize the alkali component remaining on the surface of the copper foil base 2 or to remove the copper oxide film. An aqueous solution containing sulfuric acid in an amount of 120 g / L or more and 180 g / L or less as an acidic aqueous solution, an aqueous solution containing citric acid or the like, and a copper etching solution for etching copper are used.

≪ Copper plating process (S122) >

Upon completion of the cleaning process (S121), a copper plating solution is prepared. As the copper plating solution, for example, an aqueous solution (an acidic copper plating bath (plating bath)) containing mainly copper sulfate and sulfuric acid is prepared. Then, a predetermined amount (for example, 5 mg / L or more and 60 mg / L or less) of, for example, SPS as an organic sulfur compound is added to the copper plating solution. If necessary, a surfactant, a leveling agent, and a chloride ion may be added to the copper plating solution. (For example, 1 ml / L or more and 4 ml / L or less) of the surfactant chemical solution of CU-BRITE TH-RIII series manufactured by Eva YASE LIGHT Co., Ltd. may be added as the surfactant in the copper plating solution. A leveling agent (for example, 3 ml / L or more and 10 ml / L or less) may be added to the copper plating solution as a leveling agent, for example, a leveling agent solution of CU-BRITE TH-RIII series manufactured by Eva Yasei Light Co., In addition, a predetermined amount of hydrochloric acid (for example, not less than 0.05 ml / L and not more than 0.3 ml / L) may be added as the chloride ion in the copper plating solution.

A copper plating layer 3 of a predetermined thickness (for example, 0.1 μm or more and 0.6 μm or less) is formed on the main surface of any one of the copper foil base material 2 by electrolytic plating treatment in the copper plating liquid as a copper plating treatment. The current density at the time of forming the copper plating layer 3 is made less than the critical current density in the plating condition. That is, the current density is set so as not to precipitate metal grains (so-called "burning plating") in the copper plating solution. As a result, a smooth copper plating layer can be formed as the copper plating layer 3. On the other hand, the higher the current density, the higher the productivity. Therefore, the current density may be set as high as possible within a range below the critical current density.

The processing conditions such as liquid composition, liquid temperature, current density, and processing time (plating time) of the copper plating solution in the copper plating process (S122) can be set as shown in Table 1 below. At this time, the copper plate as the anode and the copper foil base material 2 itself to be subjected to the copper plating treatment (S122) may be used as the cathode.

Figure 112015032418930-pat00001

It is more preferable that the addition amount of copper sulfate pentahydrate in the copper plating solution is 50 g / L or more and 300 g / L or less, and the addition amount of sulfuric acid is 30 g / L or more and 200 g / L or less. As shown in Table 1, the thickness of the copper plating layer 3 can be set to 0.1 μm or more and 0.6 μm or less by setting the treatment time to 1 second or more and 30 seconds or less.

(Coarsened copper plating layer forming step (S13))

After completion of the copper plating layer forming step S12, the copper foil base material 2 on which the copper plating layer 3 is formed is washed with water and then a predetermined thickness (for example, 0.05 탆 or more and 0.3 탆 or less) Thereby forming the coarsened copper plating layer 4. That is, the copper plating layer 4 is formed by electrolytic plating in the plating liquid (copper plating plating liquid) forming the copper plating layer 4. As the harmful copper plating solution, for example, an acidic copper plating bath containing copper sulfate and sulfuric acid as a main component is used. An aqueous solution containing a predetermined amount (for example, 10 g / L or more and 30 g / L or less) of iron sulfate heptahydrate may be added to the copper plating solution.

The current density at the time of forming the coarsened copper plating layer 4 is set to be not less than the critical current density in the plating condition. That is, the current density is set so that the metal lips are precipitated in the coarsened copper plating solution so that the coarsened lips are attached (called "burn-in plating") on the copper plating layer 3.

In the coarsened copper plating layer forming step (S13), the plating treatment conditions such as liquid composition, liquid temperature, current density, treatment time and the like of the coarsened copper plating solution can be set, for example, as shown in Table 2 below. At this time, a Cu plate is used as an anode, and the copper foil base 2 itself, which is a subject to be subjected to co-plating treatment, is used as a cathode.

Figure 112015032418930-pat00002

As shown in Table 2, the average thickness of the coarsened copper plating layer 4 can be set to 0.05 탆 or more and 0.3 탆 or less by setting the treatment time to 0.3 seconds or more and 2.5 seconds or less.

(Rust-preventive layer forming step (S14))

After the step of forming the coarsened copper plating layer (S13), the copper foil base material 2 on which the coarsened copper plating layer 4 is formed is washed with water and then a predetermined thickness (for example, 1 nm or more and 70 nm or less) Rust-preventive layer 5 is formed. That is, the anticorrosive layer 5 is formed by electrolytic plating in the plating liquid forming the anticorrosive layer 5. The thickness of the anticorrosive layer 5 has a constant relationship with the plating amount. That is, when the plating amount is increased, the thickness of the rust preventive layer 5 becomes thick. Therefore, the electrolytic plating treatment for forming the anticorrosive layer 5 so as to have a predetermined plating amount may be performed.

In the anticorrosive layer forming step (S14), for example, a Ni plating process for forming a Ni plating layer, a Zn plating process for forming a Zn plating layer, a chromate treatment (trivalent chromation treatment) for forming a chromate treatment layer, Followed by a silane coupling treatment for forming a silane coupling layer.

<Ni plating treatment>

After completing the coarsened copper plating layer forming step (S13), the copper foil base material (2) on which the coarsened copper plating layer (4) is formed is washed with water and then subjected to Ni plating to form a predetermined thickness 10 nm or more and 50 nm or less) is formed. (Plating bath) containing not less than 320 g / L of nickel sulfate hexahydrate, not less than 40 g / L and not more than 50 g / L of nickel chloride, and not less than 40 g / L and not more than 60 g / L of boric acid, To form an Ni plating layer. The thickness of the Ni plating layer is adjusted by adjusting the plating time.

<Zn plating treatment>

After completion of the Ni plating process, the copper foil substrate 2 on which the Ni plating layer is formed is washed with water and then subjected to Zn plating treatment to form a Zn plating layer having a predetermined thickness (for example, 1 nm or more and 10 nm or less) on the Ni plating layer. For example, an electrolytic plating treatment is performed using a plating solution containing zinc sulfate at 80 g / L or more and 120 g / L or less and sodium sulfate at 60 g / L or more and 80 g / L or less, thereby forming a Zn plating layer. The thickness of the Zn plating layer is adjusted by adjusting the plating time.

<Chromate treatment>

After completion of the Zn plating treatment, the copper foil base material 2 on which the Zn plating layer is formed is washed with water and then subjected to chromate treatment to form a chromate treatment layer having a predetermined thickness (for example, 1 nm or more and 10 nm or less) on the Zn plating layer . For example, a chromate treatment layer is formed by chemical conversion treatment using a reactive chromate solution of trivalent chromium type as a treatment liquid. The thickness of the chromate treatment layer is adjusted by adjusting the chemical treatment time or the like.

&Lt; Silane coupling treatment >

After completion of the chromate treatment, the copper foil base material 2 on which the chromate treatment layer is formed is washed with water and then subjected to silane coupling treatment to form a very thin silane coupling layer on the chromate treatment layer. For example, a silane coupling liquid is used as a treatment liquid to form a silane coupling layer. The thickness of the silane coupling layer is adjusted by adjusting the chemical conversion treatment time and the concentration of the treatment liquid. Thus, the surface-treated copper foil 1 according to the present embodiment is manufactured.

[Laminating step (S20)]

Subsequently, the laminated board 10 is formed by using the surface-treated copper foil 1. First, the surface-treated copper foil 1 is cut to a predetermined size. A resin substrate 11 (for example, a polyimide (PI) resin film) on which a thermoplastic layer is formed on any one main surface is prepared. Treated copper foil 1 so that the surface of the surface-treated copper foil 1 on the side where the copper plating layer is formed and the thermoplastic layer of the resin substrate 11 are in contact with each other, 1) and the resin base material 11 are arranged. Subsequently, the surface-treated copper foil 1 and the resin substrate 11 are heated to a predetermined temperature (for example, 150 DEG C or more and 350 DEG C or less) using, for example, a vacuum press machine or the like, The surface-treated copper foil 1 and the resin substrate 11 are bonded together by applying a predetermined pressure (for example, 0.5 MPa or more and 3.0 MPa or less) to the substrate 11 for a predetermined time (for example, To form a two-layer CCL as the laminate 10.

Recrystallization of the copper foil base material 2 (rolled copper foil), which is work-hardened by the final cold rolling treatment, is caused by heating when bonding the surface-treated copper foil 1 and the resin base material 11, do. That is, the recrystallization annealing of the copper foil base material 2 is performed while bonding the surface-treated copper foil 1 and the resin base material 11. As the rolled copper foil is recrystallized, the rolled copper foil is provided with a recrystallized structure, so that the bending resistance of the rolled copper foil is improved. At this time, at least part of the copper plating layer 3 is also recrystallized together with the copper foil base 2 by heating.

[Haze value inspection step (S30)]

Subsequently, the haze value of the resin base material 11 is measured. First, the surface-treated copper foil 1 of at least a part (for example, a haze value and an area necessary for measuring the transparency described later) is removed from the laminate 10 by etching to expose the resin substrate 11 . The resin base material 11 (the portion of the laminate 10 where the resin base material 11 is exposed) to cover the light oil inlet 21a of the integrating sphere 21 is arranged (see Fig. 2). With the lid 24 covering the light outlet port 21b, light is emitted from the light source 22 and the amount of transmitted light through the detector 23 is measured. Then, the lid 24 is peeled off, and light is emitted from the light source 22 and the amount of diffused transmission light is measured by the detector 23 while the light distribution port 21b is open. Then, the haze value of the resin base material 11 where the surface-treated copper foil 1 is removed is calculated from the above-mentioned equation (1). When the haze value of the resin substrate 11 is 80% or less, it is judged that the surface-treated copper foil 1 is acceptable. When the haze value of the resin substrate 11 exceeds 80%, the surface-treated copper foil 1 is judged to be a defective product.

[Transparency inspection step (S40)]

When the haze value measured in the haze value inspection step (S30) is 80% or less, the transparency of the resin base material 11 where the surface treated copper foil 1 is removed from the laminate 10 is measured. First, the resin base material 11 is arranged at the light output position of the light source 22 (see Fig. 3 (a)). The light emitted from the light source 22 is emitted from the light source inlet 21a through the resin substrate 11 by the center sensor 31a and the ring sensor 31b And measures the light amount of the light introduced into the integrating sphere 21. The transparency of the resin base material 11 is calculated from the above equation (2) by using the light amount IC received by the center sensor 31a and the light amount IR received by the ring sensor 31b. When the transparency of the resin substrate 11 is 70% or more, it is determined that the surface-treated copper foil 1 is acceptable. When the transparency of the resin substrate 11 is less than 70%, the surface-treated copper foil 1 is judged to be a defective product. Then, the manufacturing process of the laminate 10 is finished.

(4) Effect of the present embodiment

According to this embodiment, one or a plurality of effects shown below can be obtained.

(a) According to the present embodiment, the surface-treated copper foil 1 is bonded on both main surfaces of the resin base material so that the side of the copper-plated layer 4 is in contact with the resin base material Treated copper foil 1 is formed so that the haze value of the resin base material is 80% or less and the transparency is 70% or more when the surface-treated copper foil 1 is removed on both main surfaces of the resin base material. This makes it possible to easily visually recognize the alignment mark on the resin substrate after etching even in the case where the resin substrate after etching is in close contact with the alignment mark as well as in the case where the resin substrate after etching is disposed at a position spaced apart from the alignment mark. Therefore, when mounting an electronic part or the like on the FPC formed by the laminated board 10 formed by using the surface-treated copper foil 1, it is possible to easily position the mounting position, and the mounting workability can be improved.

That is, by setting the haze value of the resin substrate after etching to 80% or less, the alignment mark can be visually recognized beyond the resin substrate after the etching when the resin substrate after etching and the alignment mark are in close contact with each other. Further, by setting the transparency of the resin substrate after etching to 70% or more, the alignment mark can be visually recognized beyond the resin substrate after the etching, even when the resin substrate after etching is disposed at a position spaced apart from the alignment mark. Therefore, in the present embodiment, positioning of the mounting position can be facilitated with high accuracy even when mounting of an electronic component or the like is performed while the FPC is being carried. As described above, the present embodiment is particularly effective in the case where mounting of an electronic component or the like is performed while the FPC is carried.

(b) The surface-treated copper foil 1 is formed so that the peel strength between the surface-treated copper foil 1 and the resin substrate is 0.6 N / mm or more, whereby the surface-treated copper foil 1 Can be suppressed from being peeled off from the resin base material (11). It is possible to suppress peeling of the surface-treated copper foil 1 from the resin base material 11 even when copper wiring of a predetermined shape is formed, for example, by removing the surface-treated copper foil 1 at a predetermined place from the laminated board 10 have. That is, the reliability of the FPC can be improved.

(c) The copper plating layer 3 can be formed by using a copper plating solution to which an organic compound having a mercapto group is added, whereby deterioration of the transparency of the resin substrate after etching can be suppressed without lowering the adhesion. Concretely, when the amount of the organic compound having a mercapto group used as a brightening agent is larger than an appropriate amount (for example, 1.5 mg / L or less) when it is used as a brightening agent, deterioration of transparency can be suppressed have. That is, other uses of an organic compound additive having a mercapto group which is usually used as a brightening agent have been found. As a result, the effects (a) and (b) described above can be further obtained.

Generally, the transparency and adhesiveness of a resin substrate are in a relationship of a front and a back side, and as the transparency of the resin substrate after etching, for example, becomes higher, the adhesiveness decreases. In order to improve the transparency of the resin substrate, it is necessary to reduce the size of the coarsened copper plating layer. However, if the size of the harmonic ribs is made smaller, the anchoring effect obtained becomes smaller, so that the adhesiveness is lowered. On the other hand, by forming the copper plating layer 3 using a copper plating solution to which an organic compound having a mercapto group is added, deterioration of adhesion can be suppressed while increasing the transparency of the resin substrate. These action factors are being studied extensively.

(d) The effect of (a) and (b) can be further obtained by forming the copper plating layer 3 to have a thickness of not less than 0.1 μm and not more than 0.6 μm. Further, when the copper foil base material 2 is recrystallized, the copper plating layer 3 can be recrystallized together with the copper foil base 2 (rolled copper foil).

(e) The cohesive copper plating layer 4 is formed so as to have a thickness of not less than 0.05 탆 and not more than 0.3 탆, whereby the adhesiveness can be maintained while suppressing a decrease in transparency of the resin substrate. That is, the effects (a) and (b) can be further obtained. In addition, the processing time (plating time) for forming the coarsened copper plating layer 4 can be suppressed from becoming unnecessarily long, and productivity can be improved.

(f) By subjecting the surface-treated copper foil 1 and the resin base material 11 to bonding to perform the recrystallization annealing of the copper foil base material 2 by heating at the time of forming the laminate 10, . That is, when a rolled copper foil is used, for example, as the copper foil base material 2, the copper foil base material 2 before being subjected to the recrystallization annealing treatment is in a cured state. Therefore, when the surface-treated copper foil 1 is transported before the laminate 10 is formed, the surface-treated copper foil 1 is reduced, elongated or broken, wrinkles are generated in the surface-treated copper foil 1, . Thus, the interruption of the production of the surface-treated copper foil 1 can be reduced, and the productivity can be improved. The resin base material 11 can be bonded to the surface-treated copper foil 1 which is not deformed when the surface-treated copper foil 1 and the resin base material 11 are bonded.

(Another embodiment of the present invention)

Although the embodiment of the present invention has been specifically described above, the present invention is not limited to the above-described embodiment, but can be appropriately changed without departing from the gist of the present invention.

The distance L between the light emitting position of the light source 22 and the center position of the light oil inlet 21a of the integrating sphere 21 coincides with the mounting distance, But the present invention is not limited to this. That is, the integrating sphere 21 and the light source 22 may be arranged so that the distance L between the light output position of the light source 22 and the center position of the light oil inlet 21a is longer than the mounting distance. In this case, when measuring the transparency of the resin base material 11, 25 to be measured, the distance between the optical axis of the light source 22 and the distance between the resin base material 11 to be measured and the light oil inlet 21a becomes a mounting distance The resin base material 11 may be disposed. The resin base material 11 may be disposed at a position where the distance between the resin base material 11 and the light oil inlet 21a is longer than the mounting distance. That is, the distance between the light source 22 and the light oil inlet 21a or the distance between the resin base 11 and the light oil inlet 21a can be set to any distance and does not necessarily match the mounting distance.

In the above embodiment, the organic sulfur compound, the surfactant and the leveling agent are separately added, but the present invention is not limited thereto. For example, an additive in which two or more kinds of organic sulfur compounds, surfactants, leveling agents and the like are blended in advance may be used. These additives may be used singly or in combination with the organic sulfur compounds, surfactants and leveling agents described in the above embodiments.

Although the rust preventive layer 5 is formed in the above embodiment, the present invention is not limited to this. That is, the anticorrosive layer 5 may not be formed depending on the purpose or purpose of the surface-treated copper foil 1. In the above embodiment, the rust preventive layer 5 is composed of a Ni plating layer, a Zn plating layer, a chromate treatment layer and a silane coupling layer, but is not limited thereto. That is, the layer structure of the anticorrosive layer 5 may be appropriately changed depending on the purpose or purpose of the surface-treated copper foil 1, or the like. The Ni plating layer may be formed of a Ni alloy containing other metal elements such as Co. The Zn plating layer may be formed of a Zn alloy containing another metal.

In the above embodiment, the case where the rust preventive layer 5 is formed only on the roughened copper plating layer 4 has been described, but the present invention is not limited to this. (Hereinafter referred to as the surface-treated copper foil 1 (the surface of the copper foil base material 2) on the opposite side to the side where the copper coplanar plating layer 4 is formed in the copper foil base material 2 of the surface-treated copper foil 1, (Also referred to as &quot; back surface &quot;)) of the substrate. Namely, for example, a Ni plating layer, a Zn plating layer and a chromate treatment layer may be formed on the back surface of the copper foil base material 2 as a rust preventive layer in this order from the side of the copper foil base material 2. As a result, the heat resistance and chemical resistance of the surface-treated copper foil 1 can be further improved.

In the above embodiment, the laminated board 10 having the surface-treated copper foil 1 formed on both surfaces of the resin substrate 11 has been described, but the present invention is not limited thereto. That is, the surface-treated copper foil 1 may be formed on any one of the resin substrates 11.

In the above embodiment, the bonding of the surface-treated copper foil 1 and the resin base material 11 is not made using an adhesive, but the present invention is not limited to this. For example, the surface-treated copper foil 1 and the resin base material may be bonded via an adhesive. That is, a three-layer CCL may be formed as the laminate 10. [

For example, in the step of forming a copper plating layer, the copper plating layer 4 may be formed by adding a copper plating layer 3 to the copper plating layer 3 followed by a capsule copper plating treatment. In other words, the capsulated copper plating layer (so-called covering plating layer) may cover the copper plating layer 3 attached to the copper plating layer 3. Accordingly, the coarse rib can be grown as a nodule-shaped protrusion. That is, the size of the coarse rib can be increased. When the capsule copper plating treatment is performed, the haze value of the resin substrate is set to 80% or less and the transparency is set to 70% or more.

In the above-described embodiment, the cleaning step for performing electrolytic degreasing treatment and pickling treatment in the copper plating layer forming step is performed, but the invention is not limited thereto. For example, the cleaning step may be either electrolytic degreasing treatment or pickling treatment. In addition to the electrolytic degreasing treatment and pickling treatment in the cleaning process, other treatment may be performed. The cleaning process may be omitted.

Although the rust preventive layer 5 is formed only on the coarsened copper plating layer 4 in the above embodiment, the present invention is not limited thereto. For example, a rust preventive layer (hereinafter also referred to as a back rust prevention layer) may be formed on the main surface of the copper foil base 2 opposite to the side where the roughened copper plating layer 4 is formed. In this case, the rust preventive layer 5 and the back rust prevention layer may be formed at the same time. The rust preventive layer 5 and the back rust prevention layer may be respectively formed. For example, the step of forming the antirust layer 5 may be performed after the step of forming the antirust layer 5. The layer structure of the backing rustproofing layer may be the same as that of the anticorrosive layer 5 or may be different from that of the anticorrosive layer 5. For example, the backing rust prevention layer may not be provided with a silane coupling layer.

In the above embodiment, the recrystallization annealing process of the copper foil base material 2 provided in the surface-treated copper foil 1 while bonding the surface-treated copper foil 1 to the resin base material is performed. However, the present invention is not limited thereto. That is, the bonding of the surface-treated copper foil 1 and the resin substrate and the recrystallization annealing treatment of the copper foil base 2 may be separately performed.

In the above embodiment, the case where the surface-treated copper foil 1 is used for the FPC has been described, but the invention is not limited thereto. The surface-treated copper foil 1 according to the present embodiment can also be used as a negative current collecting copper foil of a lithium ion secondary battery, an electromagnetic wave shield for a plasma display, an antenna of an IC card, or the like.

Example

Examples of the present invention will be described below, but the present invention is not limited thereto.

<Preparation of sample>

First, a surface-treated copper foil serving as samples of Samples 1 to 21 was prepared.

(Sample 1)

In Sample 1, a rolled copper foil having a thickness of 11 탆 was formed from oxygen-free copper (OFC) as a copper foil substrate. The copper foil base was subjected to electrolytic degreasing treatment and pickling treatment to clean the surface of the copper foil base. First, an electrolytic degreasing treatment was performed using an aqueous solution containing 40 g / L of sodium hydroxide and 20 g / L of sodium carbonate. At this time, the solution temperature was set to 40 degrees, the current density was set to 10 A / dm 2 , and the treatment (plating) time was set to 10 seconds. After completion of the electrolytic degreasing treatment, the copper foil substrate was washed with water. Thereafter, the substrate for copper foil was immersed in an aqueous solution containing 150 g / L of sulfuric acid and having a liquid temperature of 25 DEG C for 10 seconds to conduct a pickling treatment. After the pickling treatment was completed, the copper foil substrate was washed with water.

Next, a copper plating layer was formed on one of the main surfaces of the copper foil base. First, 170 g / L of copper sulfate pentahydrate, 70 g / L of sulfuric acid, 30 mg / L of powder reagent of SPS as an organic sulfur compound, and 10 g / L of a CU-BRITE TH-RIII series of surfactants 5 ml / L of leveling agent solution of CU-BRITE TH-RIII series manufactured by Eva Yasei Light Co., Ltd. as the leveling agent, 0.15 ml / L of hydrochloric acid (aqueous HCl solution) as chloride ion, Aqueous solution. Then, a copper plating layer having a thickness of 0.1 占 퐉 was formed by electrolytic plating the copper plating solution at a liquid temperature of 35 캜, a current density of 7 A / dm 2 and a treatment time of 10 seconds.

After the copper plating layer was formed, the copper foil substrate on which the copper plating layer was formed was washed with water. Thereafter, a copper plating layer was formed on the copper plating layer. An aqueous solution containing 100 g / L of copper sulfate pentahydrate, 70 g / L of sulfuric acid, and 20 g / L of iron sulfate heptahydrate was prepared as a coarse copper plating solution. Then, the copper plating layer having a thickness of 0.05 탆 was formed, which was mainly formed of a coarsened liquor, at a solution temperature of 30 캜, a current density of 60 A / dm 2 and a treatment time of 0.5 sec. That is, plating conditions were set so that the thickness (average thickness) when the coarsened copper plating layers were uniformly adjusted to be equal to 0.05 占 퐉 to form a coarsened copper plating layer.

After forming the coarsened copper plating layer, the copper foil substrate on which the coarsened copper plating layer was formed was washed with water. Thereafter, a rust preventive layer was formed on the coarsened copper plating layer. Specifically, first, an aqueous solution (Ni plating solution) containing 300 g / L of nickel sulfate hexahydrate, 45 g / L of nickel chloride and 50 g / L of boric acid was prepared. Then, a nickel plating layer having a thickness of 25 nm was formed on the coarsened copper plating layer by setting the solution temperature of the Ni plating solution to 50 DEG C, the current density to be 2 A / dm 2 , and the treatment time to 5 seconds. After the Ni plating layer was formed, the copper foil substrate was washed with water. Thereafter, an aqueous solution (Zn plating solution) containing 90 g / L of zinc sulfate and 70 g / L of sodium sulfate was produced. Then, a Zn plating layer having a thickness of 7 nm was formed on the Ni plating layer by setting the liquid temperature of the Zn plating solution to 30 degrees, the current density to 1.5 A / dm 2 , and the treatment time to 4 seconds. After the Zn plating layer was formed, the copper foil substrate was washed with water. Subsequently, trivalent chromium plating was performed to form a chromate treatment layer having a thickness of 5 nm on the Zn plating layer. After the chromate treatment layer was formed, the copper foil substrate was washed with water. Then, the copper foil base material having the chromate treatment layer formed thereon was immersed in a silane coupling solution having a concentration of 3-aminopropyltrimethoxysilane of 5% and a liquid temperature of 25 ° C for 5 seconds, and then dried at a temperature of 200 ° C to obtain a chromate- A silane coupling treatment layer having an extremely thin thickness was formed.

(Back side anticorrosion layer) is formed on the main surface of the copper foil base opposite to the side where the copper-clad coating layer is formed in parallel with formation of the anticorrosive layer on the copper-clad plating layer (simultaneously with formation of the anticorrosive layer on the copper- A Ni plating layer, a Zn plating layer and a chromate treatment layer were formed in this order from the side of the copper foil substrate. The method of forming the Ni plating layer, the Zn plating layer, and the chromate treatment layer is the same as that of the Ni plating layer, the Zn plating layer, and the chromate treatment layer, which are formed on the copper plating layer. Thus, a surface-treated copper foil was prepared and used as sample 1.

(Samples 2 to 3)

In the samples 2 to 3, the thickness of the copper plating layer was changed as shown in Table 3, respectively. A surface-treated copper foil was produced in the same manner as in Sample 1 except for the above.

(Samples 4 to 6)

In Sample 4, the average thickness of the coarsened copper plating layer was set to 0.11 탆. That is, the plating treatment conditions at the time of forming the coarsened copper plating layer were changed to reduce the size of the coarsened plating. A surface-treated copper foil was produced in the same manner as in Sample 1 except for the above. In the samples 5 to 6, the thickness of the copper plating layer was changed as shown in Table 3, respectively. Otherwise, a surface-treated copper foil was prepared in the same manner as in the case of the sample 4.

(Samples 7 to 9)

In Sample 7, the average thickness of the coarsened copper plating layer was set to 0.3 mu m. That is, the plating condition for forming the coarsened copper plating layer was changed to increase the size of the coarsened plating. A surface-treated copper foil was produced in the same manner as in Sample 1 except for the above. In the samples 8 to 9, the thickness of the copper plating layer was changed as shown in Table 3, respectively. Otherwise, a surface-treated copper foil was prepared in the same manner as in the sample 7.

(Samples 10 to 11)

In Sample 10, the average thickness of the coarsened copper plating layer was 0.03 mu m. A surface-treated copper foil was produced in the same manner as in Sample 2 except for the above. In Sample 11, a copper plating layer was formed using a copper plating solution not containing SPS as an organic sulfur compound. Otherwise, a surface-treated copper foil was prepared in the same manner as in Sample 10.

(Samples 12 to 13)

In Sample 12, the coarsened copper plating layer was formed by using a copper plating solution not containing iron sulfate heptahydrate. Otherwise, a surface-treated copper foil was prepared in the same manner as in Sample 10. In the sample 13, a copper plating layer was not formed. A surface-treated copper foil was produced in the same manner as in Sample 12 except for the above.

(Samples 14 to 16)

In Sample 14, the average thickness of the coarsened copper plating layer was 0.35 mu m. A surface-treated copper foil was produced in the same manner as in Sample 2 except for the above. In Sample 15, a copper plating layer was formed using a copper plating solution to which SPS as an organic sulfur compound was not added. Otherwise, the surface-treated copper foil was prepared in the same manner as in the sample 14. In Sample 16, the coarsened copper plating layer was formed using a coarsened copper plating solution to which no iron sulfate heptahydrate was added. Otherwise, the surface-treated copper foil was prepared in the same manner as in the sample 14.

(Samples 17 to 21)

In Sample 17, a copper plating layer was formed using a copper plating solution to which SPS as an organic sulfur compound was not added. Otherwise, a surface-treated copper foil was produced in the same manner as in the sample 5. In Sample 18, the coarsened copper plating layer was formed by using a copper plating solution not containing iron sulfate heptahydrate. Otherwise, a surface-treated copper foil was produced in the same manner as in the sample 5. In the sample 19, a copper plating layer was not formed. A surface-treated copper foil was produced in the same manner as in Sample 1 except for the above. In the sample 20, the copper plating layer was not formed. Otherwise, a surface-treated copper foil was prepared in the same manner as in the case of the sample 4. In the sample 21, the copper plating layer was not formed. Otherwise, a surface-treated copper foil was prepared in the same manner as in the sample 7.

Figure 112015032418930-pat00003

&Lt; Fabrication of laminates &

Two-sided FCCL (Flexible Copper Clad Laminate) was produced as a laminate by using each of the surface-treated copper foils of Samples 1 to 21. As a resin substrate, a polyimide resin film (PIXEO (registered trademark) of KANEKA CORPORATION) having a thickness of 25 mu m was used. Each surface-treated copper foil and the resin base material of Samples 1 to 21 were cut into a predetermined size (100 mm in length x 60 mm in width). Then, the surface-treated copper foils, each of which was cut into a predetermined shape on both sides of the resin substrate, were laminated. At this time, each sample was laminated so that the surface of the surface-treated copper foil, which is the sample, on the side where the copper-clad coating layer was formed, was in contact with the resin base. Thereafter, a surface-treated copper foil of each sample and a resin substrate were bonded to each other under the conditions of 300 deg. C, 5 MPa, and 15 minutes using a vacuum press machine to produce a double-sided FCCL. The bonding conditions by the vacuum press machine are such that the surface treated copper foil as the sample is recrystallized to give the surface treated copper foil the heat amount to provide the recrystallized structure and satisfies the recommended conditions of the polyimide resin film maker, So that it is possible to bond the resin base material.

<Evaluation of transparency>

The transparency of the resin substrate was evaluated for the laminate formed by using the surface-treated copper foils of Samples 1 to 21. As evaluation of the transparency of the resin base material, haze value and transparency of the resin base material after the surface-treated copper foil as each sample were removed from the laminate were measured. Specifically, the surface-treated copper foils were all removed from the laminate by spray-etching using the ferric chloride for the laminate produced using each sample. That is, the entire surface of both sides (both main surfaces) of the resin substrate was exposed. Each of the resin substrates from which the surface-treated copper foil was removed was measured for haze value and transparency using a haze-gard plus manufactured by BYK Corporation.

&Lt; Evaluation of adhesion &

The adhesion of the laminate formed using each of the surface-treated copper foils of Samples 1 to 21 was evaluated by measuring the peel strength at the time of peeling the surface-treated copper foil from the resin substrate. The peel strength was measured as follows. First, on each of the main surfaces (the surface opposite to the side of the surface-treated copper foil which is in contact with the resin base material) of each of the laminate plates formed by using the surface-treated copper foils of Samples 1 to 21, Masking tape. A masking tape was attached to the entire surface of the other main surface of each laminated plate. Each of the laminates having the masking tape attached thereto was subjected to spray etching treatment using ferric chloride to remove predetermined portions of the surface-treated copper foil (places where no masking tape was adhered) from the laminate. The masking tape was then removed. Subsequently, the strength at the time of peeling the surface-treated copper foil from the resin base was measured. Specifically, the force required when the surface-treated copper foil which had been etched to have a width of 1 mm was removed from the resin base at an angle of 90 degrees (so that the angle formed between the peeled surface-treated copper foil and the resin base was 90 degrees) . The larger the value of the peel strength measured as described above, the higher the adhesion.

&Lt; Evaluation result >

The evaluation results of the transparency (haze value, transparency) of the resin base material and the adhesion property between the surface-treated copper foil and the resin base material are shown in Table 3 for Samples 1 to 21, respectively. When the haze value of the resin base material is 80% or less and the transparency of the resin base material is 70% or more from Samples 1 to 9, the mounting of electronic parts or the like to the FPC formed by using the surface- And workability was improved. That is, it is possible to easily identify a positioning mark for determining the mounting position of the electronic component or the like beyond the resin substrate when the electronic component or the like is mounted. Concretely, even when the resin base material and the positioning mark are in close contact with each other, the positioning mark can easily be confirmed over the resin base material even when the resin base material is disposed at a position separated from the positioning mark.

A comparison between the sample 1 and the sample 19, the sample 4 and the sample 20, the sample 7 and the sample 21, and the sample 12 and the sample 13 are compared to each other. When the copper plating layer is formed, Confirmed. That is, it was confirmed that the haze value of the resin base material can be made lower and the transparency of the resin base material can be further increased.

From the comparison between the samples 5 and 17, and the comparison between the samples 10 and 11, it was confirmed that the transparency of the resin substrate could be improved by forming a copper plating layer with a copper plating solution containing an organic sulfur compound.

From the comparison of the sample 2 and the sample 10, it was confirmed that when the average thickness of the copper plating layer was less than 0.05 탆, the transparency of the resin substrate could be improved, but the adhesion tended to be lowered. Further, when the average thickness of the copper-clad plating layer was thicker than 0.30 占 퐉, it was confirmed that the adhesiveness was improved but the transparency of the resin substrate was lowered by comparison of the samples 8 and 14. From samples 14 and 15, it was found that if the average thickness of the coarsened copper plating layer was excessively large (thicker than 0.30 탆), whether or not a copper plating layer was formed of a copper plating solution containing an organic sulfur compound However, it was confirmed that the effect of improving the transparency of the resin substrate can not be exhibited.

From the comparison between the samples 5 and 18 and the comparison between the samples 10 and 12, the copper plating layer was formed by using a copper plating solution containing an organic sulfur compound, and the copper plating layer was formed into a copper plating solution containing iron sulfate heptahydrate It was confirmed that the growth of the coarse grains constituting the coarsened copper plating layer was suppressed and the size of the coarse grains could be made uniform. As a result, it was confirmed that the transparency of the resin substrate was improved. Further, when the average thickness of the coarsened copper plating layer was too thick from the comparison of the specimen 14 and the specimen 16, the copper plating layer was formed by using a copper plating solution containing an organic sulfur compound, and the coarsened copper plating layer was formed by adding iron sulfate heptahydrate It was confirmed that the effect of improving the transparency of the resin substrate can not be exerted even when the copper plating solution is used.

<Preferred embodiment of the present invention>

Hereinafter, preferred embodiments of the present invention will be described.

[Appendix 1]

According to one aspect of the present invention,

A copper foil substrate,

A copper plating layer formed on the copper foil substrate,

And a copper plating layer formed on the copper plating layer,

Treating the surface-treated copper foil on both main surfaces of the resin substrate so as to face the surface-treated copper foil so that the surface on the side where the copper-clad coating layer is formed is in contact with the resin substrate, Wherein a haze value of the resin base material is 80% or less and a transparency is 70% or more when the copper foil is removed, and a surface treatment is performed so that a peel strength between the surface-treated copper foil and the resin base material is 0.6 N / A copper foil is provided.

[Note 2]

As the surface-treated copper foil of App. 1, preferably,

The copper plating layer is formed using a copper plating solution to which an organic compound having a mercapto group is added.

[Note 3]

As the surface-treated copper foil of App. 2, preferably,

The copper plating solution contains 5 mg / L or more and 60 mg / L or less of the organic compound having the mercapto group.

[Note 4]

The surface-treated copper foil according to any one of Notes 1 to 3,

The copper plating layer is formed to have a thickness of 0.1 占 퐉 or more and 0.6 占 퐉 or less.

[Note 5]

The surface-treated copper foil of any one of claims 1 to 4,

The copper-clad plating layer is formed so that the average thickness is 0.05 μm or more and 0.30 μm or less.

[Note 6]

According to another aspect of the present invention,

A surface-treated copper foil having a copper foil base, a copper plating layer formed on the copper foil base and a copper plating layer formed on the copper plating layer,

And a resin base material formed so as to be in contact with a side of the copper plating layer side,

Treating the surface-treated copper foil on both main surfaces of the resin base material after bonding the surface-treated copper foil on both main surfaces of the resin base material so that the surface-treated copper foil is opposed to the resin base material, A haze value of 80% or less and a transparency of 70% or more, and a fill strength between the surface-treated copper foil and the resin base material is 0.6 N / mm or more.

1 Surface treated copper foil
2 Copper base material
3 Copper plated layer
4 Harmonious copper plating layer

Claims (6)

A copper foil substrate (copper foil base material)
A copper plating layer formed on the copper foil substrate,
A copper plating layer (roughened copper plating layer) formed on the copper plating layer
A surface treated copper foil (surface treated copper foil)
Treating the surface-treated copper foil so that the surface on the side where the copper-clad coating layer is formed is brought into contact with the resin base material on both main surfaces of the resin substrate, Treated copper foil, the resin substrate has a haze value of 80% or less and a transparency of 70% or more,
The peel strength between the surface-treated copper foil and the resin base material is 0.6 N / mm or more,
Wherein the copper plating layer is formed so that the average thickness is 0.05 占 퐉 or more and 0.30 占 퐉 or less. The method according to claim 1,
Wherein the copper plating layer is formed using a copper plating solution to which an organic compound having a mercapto group is added.
The method according to claim 1,
Wherein the copper plating layer is formed to have a thickness of 0.1 占 퐉 or more and 0.6 占 퐉 or less.
3. The method of claim 2,
Wherein the copper plating layer is formed to have a thickness of 0.1 占 퐉 or more and 0.6 占 퐉 or less.
A surface-treated copper foil having a copper foil base, a copper plating layer formed on the copper foil base and a copper plating layer formed on the copper plating layer,
And a resin substrate formed to contact the surface of the copper plating layer on the side where the copper plating layer is formed
Respectively,
Treating the surface-treated copper foil on both main surfaces of the resin substrate after bonding the surface-treated copper foil to both main surfaces of the resin substrate so as to oppose the surface-treated copper foil; The haze value is 80% or less and the transparency is 70% or more, and the peel strength between the surface-treated copper foil and the resin base material is 0.6 N / mm or more,
Wherein the copper plating layer is formed so as to have an average thickness of not less than 0.05 mu m and not more than 0.30 mu m. delete
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