WO2021117339A1

WO2021117339A1 - Surface-treated copper foil, copper-clad laminate plate, and printed wiring board

Info

Publication number: WO2021117339A1
Application number: PCT/JP2020/038989
Authority: WO
Inventors: 郁浩五刀
Original assignee: Ｊｘ金属株式会社
Priority date: 2019-12-13
Filing date: 2020-10-15
Publication date: 2021-06-17
Also published as: TW202122642A; KR20220087525A; CN114761622A; CN114761622B; JP2021095596A

Abstract

A surface-treated copper foil comprising a copper foil and a surface treatment layer formed on at least one surface of the copper foil. In the surface-treated copper foil, the load area ratio SMr2 that separates a protruding valley and the core section of the surface treatment layer is 91-96%.

Description

Surface-treated copper foil, copper-clad laminate and printed wiring board

This disclosure relates to surface-treated copper foil, copper-clad laminates, and printed wiring boards.

Copper-clad laminates are widely used in various applications such as flexible printed wiring boards. This flexible printed wiring board is mounted by etching the copper foil of a copper-clad laminate to form a conductor pattern (also called a "wiring pattern") and connecting electronic components on the conductor pattern with solder. Manufactured.

In recent years, in electronic devices such as personal computers and mobile terminals, the frequency of electric signals has been increasing along with the increase in communication speed and capacity, and a flexible printed wiring board capable of coping with this has been required. In particular, as the frequency of the electric signal becomes higher, the loss (attenuation) of the signal power becomes larger and the data tends to be unreadable. Therefore, it is required to reduce the loss of the signal power.

The loss of signal power (transmission loss) in an electronic circuit can be roughly divided into two. The first is the conductor loss, that is, the loss due to the copper foil, and the second is the dielectric loss, that is, the loss due to the resin base material.
The conductor loss has a skin effect in the high frequency region and has the characteristic that the current flows on the surface of the conductor. Therefore, if the surface of the copper foil is rough, the current will flow along a complicated path. Therefore, in order to reduce the conductor loss of the high frequency signal, it is desirable to reduce the surface roughness of the copper foil. Hereinafter, when the terms "transmission loss" and "conductor loss" are simply used in the present specification, they mainly mean "transmission loss of high frequency signal" and "conductor loss of high frequency signal".

On the other hand, since the dielectric loss depends on the type of the resin base material, it is possible to use a resin base material formed of a low dielectric material (for example, a liquid crystal polymer or a low dielectric polyimide) in a circuit board through which a high frequency signal flows. desirable. Further, since the dielectric loss is also affected by the adhesive that adheres between the copper foil and the resin base material, it is desirable to adhere between the copper foil and the resin base material without using an adhesive.
Therefore, it has been proposed to form a surface treatment layer on at least one surface of the copper foil in order to bond the copper foil and the resin base material without using an adhesive. For example, Patent Document 1 proposes a method of providing a roughening treatment layer formed of roughened particles on a copper foil and forming a silane coupling treatment layer on the outermost surface layer.

Japanese Unexamined Patent Publication No. 2012-112009

The roughened layer can enhance the adhesiveness between the copper foil and the resin base material by the anchor effect of the roughened particles, but it may increase the conductor loss due to the skin effect, so that it can be applied to the copper foil surface. It is desirable to reduce the amount of coarsened particles to be electrodeposited. On the other hand, if the number of roughened particles electrodeposited on the surface of the copper foil is reduced, the anchoring effect of the roughened particles is reduced, and sufficient adhesiveness between the copper foil and the resin base material cannot be obtained. In particular, a resin base material formed of a low-dielectric material such as a liquid crystal polymer or a low-dielectric polyimide is more difficult to adhere to a copper foil than a conventional resin base material, so that the adhesiveness between the copper foil and the resin base material is improved. The development of a method to enhance it is desired.
Further, although the silane coupling treatment layer has an effect of improving the adhesiveness between the copper foil and the resin base material, the effect of improving the adhesiveness may not be sufficient depending on the type.

An embodiment of the present invention has been made to solve the above problems, and is a surface-treated copper foil capable of enhancing adhesiveness to a resin base material, particularly a resin base material suitable for high-frequency applications. The purpose is to provide.
Another object of the present invention is to provide a copper-clad laminate having excellent adhesiveness between a resin base material, particularly a resin base material suitable for high-frequency applications and a surface-treated copper foil.
Further, an embodiment of the present invention aims to provide a printed wiring board having excellent adhesion between a resin base material, particularly a resin base material suitable for high frequency applications, and a circuit pattern.

As a result of diligent research on the surface-treated copper foil in order to solve the above problems, the present inventors have conducted a load area ratio that separates the protruding valley portion and the core portion among various indexes of the surface roughness of the surface-treated layer. Based on the finding that SMr2 is closely related to the adhesiveness between the surface-treated copper foil and the resin base material, by controlling SMr2 to a specific range, the surface-treated copper foil and the resin base material can be combined. They have found that the adhesiveness between them can be enhanced, and have completed the embodiment of the present invention.

That is, the embodiment of the present invention has a copper foil and a surface-treated layer formed on at least one surface of the copper foil, and has a load area ratio that separates the protruding valley portion and the core portion of the surface-treated layer. The present invention relates to a surface-treated copper foil having an SMr2 of 91 to 96%.
Further, an embodiment of the present invention relates to a copper-clad laminate comprising the surface-treated copper foil and a resin base material adhered to the surface-treated layer of the surface-treated copper foil.
Further, an embodiment of the present invention relates to a printed wiring board including a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate.

According to the embodiment of the present invention, it is possible to provide a surface-treated copper foil capable of enhancing the adhesiveness with a resin base material, particularly a resin base material suitable for high frequency applications.
Further, according to the embodiment of the present invention, it is possible to provide a copper-clad laminate having excellent adhesiveness between a resin base material, particularly a resin base material suitable for high-frequency applications and a surface-treated copper foil.
Further, according to the embodiment of the present invention, it is possible to provide a printed wiring board having excellent adhesiveness between a resin base material, particularly a resin base material suitable for high frequency applications, and a circuit pattern.

It is sectional drawing of the surface-treated copper foil which has a roughening treatment layer on one surface of a copper foil. 3 is an SEM photograph of the surface-treated layer in the surface-treated copper foil of Example 1 and Comparative Example 1.

Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention should not be construed as being limited to these, and shall be based on the knowledge of those skilled in the art as long as the gist of the present invention is not deviated. , Various changes and improvements can be made. The plurality of components disclosed in the following embodiments can form various inventions by appropriate combinations. For example, some components may be removed from all the components shown in the following embodiments.

The surface-treated copper foil according to the embodiment of the present invention has a copper foil and a surface-treated layer formed on at least one surface of the copper foil. That is, the surface treatment layer may be formed on only one surface of the copper foil, or may be formed on both surfaces of the copper foil. Further, when the surface treatment layers are formed on both surfaces of the copper foil, the types of the surface treatment layers may be the same or different.

The surface treatment layer has a load area ratio SMr2 that separates the protruding valley portion and the core portion from 91 to 96%.
Here, the load area ratio SMr2 that separates the protruding valley portion and the core portion represents the ratio of the protruding valley portion below the core portion, and the smaller the ratio of the protruding valley portion, the larger the value of SMr2. SMr2 is measured according to ISO 25178. When the resin base material is adhered to the surface treatment layer of the surface treatment copper foil, if the proportion of the protruding valleys of the surface treatment layer is large, the particles (for example, roughened particles) forming the surface treatment layer are often small. And / or because the area of the portion where the particles are absent becomes large, the anchor effect is not sufficiently exhibited. Therefore, the anchor effect can be enhanced by setting SMr2 of the surface treatment layer to 91% or more (reducing the proportion of protruding valleys). As a result, the adhesive force between the surface-treated copper foil and the resin base material is increased. On the other hand, by setting SMr2 of the surface treatment layer to 96% or less, it is possible to suppress an increase in transmission loss due to the skin effect.

The surface treatment layer has a load area ratio SMr1 that separates the protruding peak portion and the core portion, preferably 16 to 28%.
Here, the load area ratio SMr1 that separates the protruding mountain portion and the core portion represents the ratio of the protruding peak portion above the core portion, and the larger the ratio of the protruding peak portion, the larger the value of SMr1. SMr1 is measured according to ISO 25178. When the resin base material is adhered to the surface treatment layer of the surface-treated copper foil, if the proportion of the protruding peaks of the surface treatment layer is small, the force when the resin base material is peeled from the surface treatment layer (hereinafter, "peeling force"). ) Concentrates on the surface of the core part. Therefore, by setting SMr1 of the surface treatment layer to 16% or more (increasing the ratio of the protruding peaks), it is possible to easily disperse the peeling force in the height direction of the protruding peaks due to the presence of the protruding peaks. it can. As a result, the adhesive force between the surface-treated copper foil and the resin base material is increased. On the other hand, by setting SMr1 of the surface treatment layer to 28% or less, it is possible to suppress an increase in transmission loss due to the skin effect.

The surface-treated layer has a protruding peak height Spk of preferably 1.2 to 2.5 μm.
Here, the protruding peak height Spk is measured in accordance with ISO 25178. When the resin base material is adhered to the surface-treated layer of the surface-treated copper foil, if the protruding peak portion of the surface-treated layer is low, the peeling force is concentrated on the surface of the core portion. Therefore, by setting the Spk of the surface treatment layer to 1.2 μm or more (increasing the protruding ridge), it is possible to easily disperse the peeling force in the height direction of the protruding ridge due to the presence of the protruding ridge. .. As a result, the adhesive force between the surface-treated copper foil and the resin base material is increased. On the other hand, by setting the Spk of the surface treatment layer to 2.5 μm or less, it is possible to suppress an increase in transmission loss due to the skin effect.

In the surface treatment layer, the level difference Sk of the core portion of the surface treatment layer is preferably 1.0 to 2.0 μm.
Here, the level difference Sk of the core portion of the surface treatment layer represents the degree of variation in the height of the portion (core portion) excluding the protruding peak portion and the protruding valley portion, and is measured in accordance with ISO 25178. When the resin base material is adhered to the surface-treated layer of the surface-treated copper foil, if the height variation of the core portion is small, the core portion becomes substantially flat and the peeling force is concentrated on the upper surface thereof. Therefore, by setting the Sk of the surface treatment layer to 1.0 μm or more (increasing the variation in the height of the core portion), the upper surface of the core portion is made uneven and the peeling force is increased in the height direction of the core portion. It can be easily dispersed. As a result, the adhesive force between the surface-treated copper foil and the resin base material is increased. On the other hand, by setting the Sk of the surface treatment layer to 2.0 μm or less, it is possible to suppress an increase in transmission loss due to the skin effect.

The type of the surface treatment layer is not particularly limited, and various surface treatment layers known in the art can be used.
Examples of the surface treatment layer include a roughening treatment layer, a heat resistance treatment layer, a rust prevention treatment layer, a chromate treatment layer, a silane coupling treatment layer and the like. These layers may be used alone or in combination of two or more. Among them, the surface treatment layer preferably has a roughening treatment layer from the viewpoint of adhesiveness to the resin base material.
When the surface treatment layer has one or more layers selected from the group consisting of a heat resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer and a silane coupling treatment layer, these layers are on the roughening treatment layer. It is preferable that it is provided in.

Here, as an example, FIG. 1 shows a schematic cross-sectional view of a surface-treated copper foil having a roughening-treated layer on one surface of the copper foil.
As shown in FIG. 1, the roughening treatment layer formed on one surface of the copper foil 10 includes a primary roughening particle 20, a cover plating layer 30 covering the primary roughening particle 20, and a cover plating layer 30. Includes the secondary roughened particles 40 formed above. It is preferable that the primary roughened particles 20 coated with the cover plating layer 30 are substantially spherical, and the secondary roughened particles 40 are formed so as to spread in a dendritic shape. With such a structure, it becomes easy to control SMr2, SMr1, Spk and Sk of the surface treatment layer within the above range.

The primary roughened particles 20 are not particularly limited, but are formed from an element selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, or an alloy containing two or more kinds of elements. be able to. Among them, the primary roughened particles 20 are preferably formed from copper or a copper alloy, particularly copper.
The cover plating layer 30 is not particularly limited, but can be formed of copper, silver, gold, nickel, cobalt, zinc, or the like.
The secondary roughened particles 40 are not particularly limited, but can be formed from a metal selected from the group consisting of nickel, cobalt, copper, and zinc, or an alloy containing two or more kinds of metals. Among them, the secondary roughened particles 40 are preferably formed from a copper alloy, particularly a Cu—Co—Ni alloy.

The roughened layer can be formed by electroplating. The conditions may be adjusted according to the electroplating apparatus used and are not particularly limited, but typical conditions are as follows.
(Formation condition R1 of primary roughened particles 20)
Plating solution composition: 5 to 15 g / L Cu, 40 to 100 g / L sulfuric acid Plating solution temperature: 20 to 50 ° C.
Electroplating Conditions: current density 30 ~ 60A / dm ^2, coulombs 40 ~ 100As / dm ²

(Formation condition R2 of the cover plating layer 30)
Plating solution composition: 10 to 30 g / L Cu, 70 to 130 g / L sulfuric acid Plating solution temperature: 30 to 60 ° C.
Electroplating conditions: Current density 4.8 to 15 A / dm ² , Coulomb amount 10 to 35 As / dm ²

(Formation condition Y of secondary roughened particles 40)
Plating solution composition: 10 to 20 g / L Cu, 5 to 15 g / L Co, 5 to 15 g / L Ni
pH: 2-3
Plating liquid temperature: 30-40 ° C
Electroplating Conditions: current density 15 ~ 45A / dm ^2, coulombs 15 ~ 55As / dm ²

Under the formation condition R1 of the primary roughened particles 20, as the amount of coulomb decreases, the growth of the primary roughened particles 20 in the Z direction (direction perpendicular to the copper foil 10) is suppressed. Further, under the formation condition R2 of the cover plating layer 30, as the amount of coulomb increases, the layer grows uniformly and thickly in the XYZ direction. Therefore, by controlling the amount of coulomb (R1) / amount of coulomb (R2) to 6.0 or less, preferably 4.0 or less, the shape of the primary roughened particles 20 coated with the cover plating layer 30 is substantially spherical. It can be controlled to have a substantially hemispherical shape. Then, by controlling the primary roughened particles 20 coated with the cover plating layer 30 into a substantially spherical to substantially hemispherical shape and then forming the secondary roughened particles 40, the secondary coarse particles 20 are formed on the cover plating layer 30. The chemical particles 40 are likely to be formed so as to spread in a dendritic shape.
When the amount of coulomb (R1) / amount of coulomb (R2) exceeds 6.0, the growth of the primary roughened particles 20 in the Z direction becomes large, so that the primary roughened particles 20 coated with the cover plating layer 30 The shape is approximately ellipsoidal to semi-ellipsoidal. Therefore, the secondary roughened particles 40 formed on the cover plating layer 30 are less likely to spread like dendritic particles.

The heat-resistant treatment layer and the rust-prevention treatment layer are not particularly limited, and can be formed from materials known in the art. Since the heat-resistant treatment layer may also function as a rust-preventive treatment layer, one layer having both the functions of the heat-resistant treatment layer and the rust-preventive treatment layer is formed as the heat-resistant treatment layer and the rust-preventive treatment layer. May be good.
The heat-resistant layer and / or rust-preventive layer includes nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. It can be a layer containing one or more elements (which may be in any form such as metal, alloy, oxide, nitride, sulfide, etc.) selected from the group of. Among them, the heat-resistant treatment layer and / or the rust-prevention treatment layer is preferably a Ni—Zn layer or a Zn layer. In particular, if the Ni—Zn layer has a lower Ni content than the Zn content or the Zn layer does not contain Ni, the conductor loss can be reduced without significantly reducing the heat resistance effect and the rust preventive effect. It is preferable because it becomes.

The heat-resistant treatment layer and the rust-prevention treatment layer can be formed by electroplating. The conditions may be adjusted according to the electroplating apparatus to be used and are not particularly limited, but the conditions for forming the heat resistant treatment layer (Ni—Zn layer) using a general electroplating apparatus are as follows. is there.
Plating solution composition: 1 to 30 g / L Ni, 1 to 30 g / L Zn
Plating solution pH: 2-5
Plating liquid temperature: 30 to 50 ° C
Electroplating conditions: current density 1-10 A / dm ² , time 0.1-5 seconds

The chromate-treated layer is not particularly limited and can be formed from a material known in the art.
Here, the term "chromate-treated layer" as used herein means a layer formed of a solution containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate-treated layer can be any element (metal, alloy, oxide, nitride, sulfide, etc.) such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. It can be a layer containing (may be in the form). Examples of the chromate-treated layer include a chromate-treated layer treated with an aqueous solution of chromic anhydride or potassium dichromate, and a chromate-treated layer treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc.

The chromate-treated layer can be formed by a known method such as immersion chromate treatment and electrolytic chromate treatment. These conditions are not particularly limited, but for example, the conditions for forming a general immersion chromate-treated layer are as follows.
Chromate solution composition: 1 to 10 g / L K ₂ Cr ₂ O ₇ , 0.01 to 10 g / L Zn
Chromate solution pH: 2-5
Chromate liquid temperature: 30-55 ° C

The silane coupling treatment layer is not particularly limited, and can be formed from a material known in the art.
Here, the term "silane coupling-treated layer" as used herein means a layer formed of a silane coupling agent.
The silane coupling agent is not particularly limited, and those known in the art can be used. Examples of silane coupling agents include amino-based silane coupling agents, epoxy-based silane coupling agents, mercapto-based silane coupling agents, metharoxy-based silane coupling agents, vinyl-based silane coupling agents, and imidazole-based silane coupling agents. , Triazine-based silane coupling agent and the like. Among these, amino-based silane coupling agents and epoxy-based silane coupling agents are preferable. The above-mentioned silane coupling agent can be used alone or in combination of two or more.
As a typical method for forming a silane coupling treatment layer, a 1.2% by volume aqueous solution (pH: 10) of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.) ) Is applied and dried to form a silane coupling treatment layer.

The copper foil is not particularly limited, and may be either an electrolytic copper foil or a rolled copper foil. Electrolytic copper foil is generally produced by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath, but a flat S-plane (shine surface) formed on the drum side and an S-plane. It has an M surface (matte surface) formed on the opposite side. Generally, since the M surface of the electrolytic copper foil has irregularities, the surface treatment layer and the resin are formed by forming a surface treatment layer on the M surface of the electrolytic copper foil and adhering the surface treatment layer to the resin base material. Adhesion with the base material can be improved.

The material of the copper foil is not particularly limited, but when the copper foil is a rolled copper foil, tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number) usually used as a circuit pattern of a printed wiring board are used. High-purity copper such as C1020 or JIS H3510 alloy number C1011) can be used. Further, for example, copper alloys such as Sn-containing copper, Ag-containing copper, copper alloys to which Cr, Zr, Mg and the like are added, and Corson-based copper alloys to which Ni and Si and the like are added can also be used. In addition, in this specification, "copper foil" is a concept including copper alloy foil.

The thickness of the copper foil is not particularly limited, but may be, for example, 1 to 1000 μm, 1 to 500 μm, 1 to 300 μm, 3 to 100 μm, 5 to 70 μm, 6 to 35 μm, or 9 to 18 μm. ..

The surface-treated copper foil having the above-mentioned structure can be produced according to a method known in the art. Here, SMr2, SMr1, Spk and Sk of the surface treatment layer can be controlled by adjusting the formation conditions of the surface treatment layer, particularly the formation conditions of the roughening treatment layer described above.

In the surface-treated copper foil according to the embodiment of the present invention, the load area ratio SMr2 that separates the protruding valley portion and the core portion of the surface-treated layer is controlled to 91 to 96%, so that the surface-treated copper foil is a surface-treated copper foil. The anchor effect can be enhanced when a resin base material is adhered to the surface. Therefore, this surface-treated copper foil can enhance the adhesiveness to a resin base material, particularly a resin base material suitable for high-frequency applications.

The copper-clad laminate according to the embodiment of the present invention includes the above-mentioned surface-treated copper foil and a resin base material adhered to the surface-treated layer of the above-mentioned surface-treated copper foil. This copper-clad laminate can be manufactured by adhering a resin base material to the surface-treated layer of the above-mentioned surface-treated copper foil.
The resin base material is not particularly limited, and those known in the art can be used. Examples of resin base materials include paper base material phenol resin, paper base material epoxy resin, synthetic fiber cloth base material epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass non-woven fabric base material epoxy resin, and glass. Examples thereof include cloth-based epoxy resins, polyester films, polyimide films, liquid crystal polymers, and fluororesins.

The method for adhering the surface-treated copper foil to the resin base material is not particularly limited, and can be performed according to a method known in the art. For example, the surface-treated copper foil and the resin base material may be laminated and thermocompression bonded.
The copper-clad laminate manufactured as described above can be used for manufacturing a printed wiring board.

Since the copper-clad laminate according to the embodiment of the present invention uses the above-mentioned surface-treated copper foil, it is possible to improve the adhesiveness to a resin base material, particularly a resin base material suitable for high-frequency applications.

The printed wiring board according to the embodiment of the present invention includes a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate. This printed wiring board can be manufactured by etching the surface-treated copper foil of the copper-clad laminate to form a circuit pattern. The method for forming the circuit pattern is not particularly limited, and a known method such as a subtractive method or a semi-additive method can be used. Among them, the subtractive method is preferable as the method for forming the circuit pattern.

When the printed wiring board is manufactured by the subtractive method, it is preferable to carry out as follows. First, a predetermined resist pattern is formed by applying, exposing and developing a resist on the surface of the surface-treated copper foil of the copper-clad laminate. Next, the surface-treated copper foil of the portion (unnecessary portion) where the resist pattern is not formed is removed by etching to form a circuit pattern. Finally, the resist pattern on the surface-treated copper foil is removed.
The various conditions in this subtractive method are not particularly limited, and can be performed according to the conditions known in the art.

Since the printed wiring board according to the embodiment of the present invention uses the above-mentioned copper-clad laminate, it is excellent in adhesiveness between a resin base material, particularly a resin base material suitable for high-frequency applications, and a circuit pattern. ..

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
A rolled copper foil A (young rate after recrystallization of 120 GPa, thickness of 12 μm) is prepared, one surface is degreased and pickled, and then a roughened treated layer is formed as a surface treated layer to form a surface treated copper. I got the foil. The conditions for forming the roughened layer were as follows.
<Conditions for forming primary roughened particles R1>
Plating solution composition: 11 g / L Cu, 50 g / L sulfuric acid Plating solution temperature: 25 ° C.
Electroplating conditions: current density 35.6 A / dm ² , coulomb amount 72.7 As / dm ²

(Conditions for forming the cover plating layer R2)
Plating solution composition: 20 g / L Cu, 100 g / L sulfuric acid Plating solution temperature: 50 ° C.
Electroplating conditions: current density 9.9 A / dm ² , coulomb amount 30.3 As / dm ²

(Formation condition Y of secondary roughened particles 40)
Plating solution composition: 15.5 g / L Cu, 7.5 g / L Co, 9.5 g / L Ni
pH: 2.4
Plating liquid temperature: 36 ° C
Electroplating conditions: current density 33.1 A / dm ² , coulomb amount 44.8 As / dm ²

(Examples 2 to 14 and Comparative Example 1)
A surface-treated copper foil was obtained in the same manner as in Example 1 except that at least one of the type of rolled copper foil, the current density and the amount of coulomb in R1, R2 and Y was changed as shown in Table 1. In Table 1, the rolled copper foil B is a rolled copper foil having a Young's modulus of 85 GPa and a thickness of 12 μm after recrystallization.

With respect to the surface-treated copper foils obtained in the above Examples and Comparative Examples, the surface state of the surface-treated layer was observed using a scanning electron microscope (SEM). As a result, in Examples 1 to 14, many structures in which the roughened particles (particularly secondary roughened particles) were spread in a dendritic shape were confirmed, whereas in Comparative Example 1, the structure was hardly confirmed. As a representative example, FIG. 2 shows SEM photographs (20,000 times, inclination of 40 °) of the surface-treated layer (roughened layer) in the surface-treated copper foils of Example 1 and Comparative Example 1.

Next, the following characteristic evaluations were performed on the surface-treated copper foils obtained in the above Examples and Comparative Examples.
<SMr2, SMr1, Spk, Sk of the surface treatment layer>
Images were taken using a laser microscope (LEXT OLS4000) manufactured by Olympus Corporation. The captured image was analyzed using the analysis software of a laser microscope (LEXT OLS4100) manufactured by Olympus Corporation. Measurements of SMr2, SMr1, Spk and Sk were performed in accordance with ISO 25178, respectively. In addition, as these measurement results, the average value of the values measured at any three places was used as the measurement result. The temperature at the time of measurement was 23 to 25 ° C. The main setting conditions for the laser microscope and analysis software are as follows.
Objective lens: MPLAPON50XLEXT (magnification: 50x, numerical aperture: 0.95, immersion type: air, mechanical lens barrel length: ∞, cover glass thickness: 0, field of view: FN18)
Optical zoom magnification: 1x Scanning mode: XYZ High accuracy (height resolution: 10 nm, number of pixels of captured data: 1024 x 1024)
Captured image size [number of pixels]: 257 μm in width × 258 μm in length [1024 × 1024]
(Since it is measured in the lateral direction, the evaluation length is equivalent to 257 μm)
DIC: Off Multi-layer: Off Laser intensity: 100
Offset: 0
Confocal level: 0
Beam diameter Aperture: Off Image average: 1 time Noise reduction: On Brightness unevenness correction: On Optical noise filter: On Cutoff: None (λc, λs, λf all none)
Filter: Gaussian filter Noise removal: Measurement pretreatment Surface (tilt) correction: Implementation

<Peel strength>
Surface-treated copper foil is used as a resin base material [LCP: liquid crystal polymer resin (copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)) film (Vectar (registered trademark) CTQ manufactured by Kuraray Co., Ltd .; thickness 50 μm or After bonding with 100 μm)], a circuit having a width of 3 mm was formed in the TD direction (width direction of the rolled copper foil). Next, the strength (TD180 ° peel strength) when the circuit (surface-treated copper foil) is peeled off from the surface of the resin base material at a speed of 50 mm / min in the TD180 ° direction is based on JIS C6471: 1995. Was measured. The measurement was performed three times, and the average value was used as the result of peel strength. If the peel strength is 0.50 kgf / cm or more, it can be said that the adhesiveness between the circuit (surface-treated copper foil) and the resin base material is good.
The circuit width was adjusted by a normal subtractive etching method using a copper chloride etching solution.

Table 2 shows the results of the above characteristic evaluation.

As shown in Table 1, the surface-treated copper foils of Examples 1 to 14 in which SMr2 of the surface-treated layer was within a predetermined range had high peel strength.
On the other hand, the surface-treated copper foil of Comparative Example 1 in which SMr2 of the surface-treated layer was out of the predetermined range had low peel strength.

As can be seen from the above results, according to the embodiment of the present invention, it is possible to provide a surface-treated copper foil capable of enhancing the adhesiveness with a resin base material, particularly a resin base material suitable for high frequency applications. .. Further, according to the embodiment of the present invention, it is possible to provide a copper-clad laminate having excellent adhesiveness between a resin base material, particularly a resin base material suitable for high-frequency applications and a surface-treated copper foil. Further, according to the embodiment of the present invention, it is possible to provide a printed wiring board having excellent adhesiveness between a resin base material, particularly a resin base material suitable for high frequency applications, and a circuit pattern.

Claims

It has a copper foil and a surface treatment layer formed on at least one surface of the copper foil.
A surface-treated copper foil having a load area ratio SMr2 of 91 to 96% that separates the protruding valley portion and the core portion of the surface-treated layer.
The surface-treated copper foil according to claim 1, wherein the load area ratio SMr1 for separating the protruding peak portion and the core portion of the surface-treated layer is 16 to 28%.
The surface-treated copper foil according to claim 1 or 2, wherein the protruding peak height Spk of the surface-treated layer is 1.2 to 2.5 μm.
The surface-treated copper foil according to any one of claims 1 to 3, wherein the level difference Sk of the core portion of the surface-treated layer is 1.0 to 2.0 μm.
The surface-treated copper foil according to any one of claims 1 to 4, wherein the surface-treated layer has a roughened-treated layer.
The fifth aspect of the present invention, wherein the roughening treatment layer includes primary roughened particles, a cover plating layer covering the primary roughened particles, and secondary roughened particles formed on the cover plating layer. Surface-treated copper foil.
The surface treatment layer further comprises one or more layers selected from the group consisting of a heat resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer and a silane coupling treatment layer on the roughening treatment layer. The surface-treated copper foil according to 5 or 6.
The surface-treated copper foil according to any one of claims 1 to 7, wherein the copper foil is a rolled copper foil.
A copper-clad laminate comprising the surface-treated copper foil according to any one of claims 1 to 8 and a resin base material adhered to the surface-treated layer of the surface-treated copper foil.
A printed wiring board having a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate according to claim 9.