WO2019188262A1

WO2019188262A1 - Surface-treated copper foil and copper-clad laminate

Info

Publication number: WO2019188262A1
Application number: PCT/JP2019/010096
Authority: WO
Inventors: 友希大理
Original assignee: Ｊｘ金属株式会社
Priority date: 2018-03-29
Filing date: 2019-03-12
Publication date: 2019-10-03
Also published as: MY194720A; KR20200100138A; CN111655900B; JP6413039B1; KR102502018B1; TWI687527B; JP2019173139A; CN111655900A; TW201942369A; PH12020551281A1

Abstract

A surface-treated copper foil, wherein a surface treatment layer comprising a silane compound is present on a copper foil surface. When the surface treatment layer comprising the silane compound of this surface-treated copper foil is measured according to TOF-SIMS, a peak is detected in the location of at least one mass number (m/z) selected from the group consisting of 240.9-241.1, 241.9-242.1, 242.9-243.1, 243.9-244.1, 244.9-245.1, 260.9-261.1, 261.9-262.1 and 262.9-263.1.

Description

Surface treated copper foil and copper clad laminate

The present invention relates to a surface-treated copper foil and a copper clad laminate.

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

In recent years, in electronic devices such as personal computers and mobile terminals, with the increase in communication speed and capacity, the frequency of electrical signals has been increased, and a flexible printed wiring board that can cope with this has been demanded. In particular, as the frequency of the electrical signal increases, the loss (attenuation) of the signal power increases as the frequency increases, and data cannot be read easily. Therefore, it is required to reduce the loss of signal power.

The loss of signal power in electronic circuits can be roughly divided into two. One is conductor loss, that is, loss due to copper foil, and the other is dielectric loss, that is, loss due to resin base material.
The conductor loss has a skin effect in a high frequency region and has a characteristic that the current flows on the surface of the conductor. Therefore, if the copper foil surface is rough, the current flows along a complicated path. Therefore, in order to reduce the conductor loss, it is desirable to reduce the surface roughness of the copper foil.

On the other hand, since the dielectric loss depends on the type of the resin base material, it is desirable to use a resin base material formed from a low dielectric material (for example, a liquid crystal polymer or a low dielectric polyimide). Moreover, since dielectric loss is also influenced by the adhesive agent which adhere | attaches between copper foil and a resin base material, it is desirable to adhere | attach between copper foil and a resin base material, without using an adhesive agent.
Then, in order to adhere | attach between copper foil and a resin base material without an adhesive agent, while providing a roughening process to copper foil, the method of providing the surface treatment layer of a silane compound between copper foil and a resin base material Has been proposed (for example, Patent Document 1). In the roughening treatment of the copper foil, since the roughened particles are formed in a tree shape on the surface of the copper foil, the adhesion between the copper foil and the resin base material can be enhanced by the anchor effect.

JP 2012-112009 A

However, the roughened particles electrodeposited on the surface of the copper foil increase the conductor loss due to the skin effect, and cause the phenomenon that the roughened particles, which are called powder fall off, are peeled off. It is desirable to reduce the amount of roughened particles. On the other hand, if the number of roughened particles to be electrodeposited on the surface of the copper foil is reduced, the anchor effect by the roughened particles is lowered, and sufficient adhesion between the copper foil and the resin base material cannot be obtained. In particular, resin base materials formed from low dielectric materials such as liquid crystal polymers and low dielectric polyimides are less likely to adhere to copper foils than conventional resin base materials. There is a need for another means to enhance.
Moreover, although the surface treatment layer of a silane compound has the effect which improves the adhesiveness between copper foil and a resin base material, it cannot be said that the adhesive improvement effect is sufficient depending on the kind.

An embodiment of the present invention has been made to solve the above-described problems, and is a surface-treated copper foil capable of improving the adhesion with 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 adhesion between a resin substrate, particularly a resin substrate suitable for high frequency applications, and a surface-treated copper foil.

As a result of intensive studies to solve the above problems, the present inventors have found that the position (mass number: m / z) at which the peak is detected when the surface treatment layer of the silane compound is measured by TOF-SIMS. The present inventors have found that it is related to the adhesion between the surface treatment layer of the silane compound and the resin substrate, and have completed the surface-treated copper foil and the copper clad laminate according to the embodiment of the present invention.

That is, the surface-treated copper foil according to the embodiment of the present invention has a surface-treated layer of a silane compound on the surface of the copper foil, and when the surface-treated layer of the silane compound is measured by TOF-SIMS, 240.9 To 241.1, 241.9 to 242.1, 242.9 to 243.1, 243.9 to 244.1, 244.9 to 245.1, 260.9 to 261.1, 261.9 to 262 .1 and 262.9 to 263.1, a peak is detected at the position of at least one mass number (m / z) selected from the group consisting of.

Moreover, the copper clad laminated board which concerns on embodiment of this invention contains the resin base material joined on the surface treatment layer of the said silane compound of the said surface treatment copper foil and the said surface treatment copper foil.

According to the embodiment of the present invention, it is possible to provide a surface-treated copper foil capable of enhancing the adhesion with a resin base material, particularly a resin base material suitable for high frequency applications.
Moreover, according to embodiment of this invention, the copper clad laminated board excellent in the adhesiveness between a resin base material, especially the resin base material suitable for a high frequency use, and surface-treated copper foil can be provided.

FIG. 2 is a TOF-SIMS spectrum (mass number (m / z) is in the range of 240 to 260) in the surface treatment layer of the silane compound of the surface-treated copper foil obtained in Example 1 and Comparative Examples 1 and 2. FIG. FIG. 3 is a TOF-SIMS spectrum (mass number (m / z) is in the range of 260 to 263.5) in the surface treatment layer of the silane compound of the surface-treated copper foil obtained in Example 1 and Comparative Examples 1 and 2. FIG.

Hereinafter, embodiments of the present invention will be specifically described. However, the present invention should not be construed as being limited thereto, and various modifications can be made based on the knowledge of those skilled in the art without departing from the gist of the present invention. Can be changed and improved. A plurality of constituent elements disclosed in each embodiment can form various inventions by an appropriate combination. For example, some constituent elements may be deleted from all the constituent elements shown in each embodiment, or constituent elements of different embodiments may be appropriately combined.

The surface-treated copper foil which concerns on embodiment of this invention has the surface treatment layer of a silane compound on the copper foil surface.
In this specification, the “surface treatment layer of a silane compound” means a film formed from a silane compound. The “copper foil” includes not only copper foil but also copper alloy foil.

When the surface treatment layer of the silane compound is measured by TOF-SIMS (time-of-flight secondary ion mass spectrometry), the surface-treated copper foil according to the embodiment of the present invention is 240.9 to 241.1, 241. 9 to 242.1, 242.9 to 243.1, 243.9 to 244.1, 244.9 to 245.1, 260.9 to 261.1, 261.9 to 262.1, and 262.9 to A peak is detected at the position of at least one mass number (m / z) selected from the group consisting of 263.1. Although the detailed reason is not clear, if it is a surface treatment layer of such a silane compound in which a peak is detected at the position of mass number, the adhesion of the surface-treated copper foil to the resin substrate can be improved.

The mass number of 240.9 to 241.1 is preferably 241.03, and the mass number of 241.9 to 242.1 is preferably 242.03, and 242.9 to 243.1. The mass number is preferably 243.03, the mass number of 243.9 to 244.1 is preferably 244.05, and the mass number of 244.9 to 245.1 is preferably 245.05. The mass number of 260.9 to 261.1 is preferably 261.01, the mass number of 261.9 to 262.1 is preferably 262.01, and 262.9 to 263.1. The mass number is preferably 263.03.

The silane compound is not particularly limited as long as a peak is detected at the position of the above mass number when the surface treatment layer of the silane compound is measured by TOF-SIMS. Typically, the silane compound has a reactive functional group and a hydrolyzable group.
Here, in the present specification, the “reactive functional group” refers to a chemical interaction with a resin substrate (for example, an interaction by van der Waals force, an interaction by Coulomb force, but is not limited thereto). ) Means a reactive group capable of exhibiting The “hydrolyzable group” means a reactive group that can be hydrolyzed by moisture and chemically bonded to the copper foil.

Although it does not specifically limit as a reactive functional group of a silane compound, From an adhesive viewpoint with respect to a resin base material, at least 1 sort (s) selected from an amino group, a (meth) acryl group, a thiol group (mercapto group), and an epoxy group. At the end. The “(meth) acryl group” means both an acryl group and a methacryl group.
Although it does not specifically limit as a hydrolysable group of a silane compound, Alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group; An acyloxy group etc. are mentioned. Among these, alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group are preferable because they have a high effect of improving the adhesion between the resin base material and the surface-treated copper foil.

Although a silane compound can be manufactured by a well-known method, you may use a commercial item. Examples of commercially available products that can be used as the silane compound include KBM series and KBE series manufactured by Shin-Etsu Chemical Co., Ltd. However, when a commercially available silane compound is used alone, when the surface treatment layer of the silane compound is measured by TOF-SIMS, a peak is hardly detected at the position of the above mass number. Therefore, when using a commercially available silane compound, it is preferable to use a mixture of two or more silane compounds. Among them, a preferable mixture of silane compounds is a mixture of KBM603 (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane) and KBM503 (3-methacryloxypropyltrimethoxysilane), KBM602 (N-2- A mixture of (aminoethyl) -3-aminopropyldimethoxysilane) and KBM503 (3-methacryloxypropyltrimethoxysilane), KBM603 (N-2- (aminoethyl) -3-aminopropyltrimethoxysilane) and KBE503 ( A mixture of 3-methacryloxypropyltriethoxysilane), KBM602 (N-2- (aminoethyl) -3-aminopropyldimethoxysilane) and KBE503 (3-methacryloxypropyltriethoxysilane), KBM903 (3 -A Nopropyltrimethoxysilane) and KBM503 (3-methacryloxypropyltrimethoxysilane), KBE903 (3-aminotriethoxysilane) and KBM503 (3-methacryloxypropyltrimethoxysilane), KBE903 (3 -Aminotriethoxysilane) and KBE503 (3-methacryloxypropyltriethoxysilane), KBM903 (3-aminopropyltrimethoxysilane) and KBE503 (3-methacryloxypropyltriethoxysilane).
When the mixture of two or more silane compounds is used, the mixing ratio is not particularly limited, and may be appropriately adjusted according to the type of the silane compound to be used.

The surface roughness of the surface treatment layer of the silane compound is not particularly limited, but the ten-point average roughness Rz is preferably 0.1 to 2.0 μm, more preferably 0.50 to 1.0 μm. The arithmetic average roughness Ra is preferably 0.01 to 0.30, more preferably 0.05 to 0.16. By controlling the surface roughness of the surface treatment layer of the silane compound within the above range, it is possible to improve adhesion to conventional resin base materials, particularly resin base materials suitable for high-frequency applications that are difficult to adhere to copper foil. .
Here, in this specification, “ten-point average roughness Rz” and “arithmetic average roughness Ra” mean those measured in accordance with JIS B0601: 1982.

It does not specifically limit as copper foil, A rolled copper foil or an electrolytic copper foil can be used. Among them, the rolled copper foil is preferable because the surface roughness is small and the conductor loss can be reduced. Moreover, copper foil with a carrier provided with the carrier, the intermediate | middle layer laminated | stacked on the carrier, and the copper foil laminated | stacked on the intermediate | middle layer may be sufficient as copper foil. The carrier and the intermediate layer are not particularly limited, and known ones can be used.
A roughening treatment layer may be formed on the surface of the copper foil by subjecting it to a roughening treatment from the viewpoint of enhancing the adhesion to the resin base material. Here, the “roughening treatment layer” in this specification means a layer of roughening particles electrodeposited on a copper foil.
The roughened particles are not particularly limited, and are formed from copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, zinc, or an alloy containing one or more of them, which is generally used for the roughening treatment. Fine particles.
However, the roughened particles electrodeposited on the surface of the copper foil increase the conductor loss due to the skin effect, and can cause the phenomenon that the roughened particles called powder fall off, so the copper foil can be used as necessary. It is good also as an aspect which makes the roughening particle | grains electrodeposited on the surface small or few, or does not perform a roughening process.

Between the copper foil and the surface treatment layer of the silane compound, one or more layers selected from the group consisting of a heat resistant treatment layer, a rust prevention treatment layer and a chromate treatment layer are provided from the viewpoint of improving various properties. Also good. These layers may be a single layer or a plurality of layers.

A surface-treated copper foil having a surface-treated layer of a silane compound having the above characteristics on the surface of the copper foil is manufactured by preparing a solution containing the silane compound and then surface-treating the copper foil using this solution. Can do.
The solution containing a silane compound can contain a solvent such as water in addition to the silane compound. The concentration of the silane compound in the solution is not particularly limited, but it is preferable that the silane concentration of the silane compound in the solution is 0.5 volume% to 10 volume%. From the viewpoint of solubility in a solvent in the solution, the silane concentration of the entire silane compound in the solution is preferably 0.1% to 5.0% by volume.
The solution containing the silane compound can be prepared, for example, by adding the silane compound to a solvent and mixing.

The surface treatment conditions may be appropriately adjusted according to the type of silane compound used. Specifically, the temperature of the solution is 10 to 30 ° C., the pH of the solution is 1 to 12, the treatment time is 1 to 5 seconds, the drying temperature is 100 to 150 ° C., and the drying time is 10 to 300 seconds. A surface treatment may be performed. The pH of the solution is particularly preferably around neutral, that is, 3 to 10. When the silane compound contains an amino group, the pH of the solution is preferably 6-12.

The surface treatment method is not particularly limited, and a known method such as a coating method or a dipping method can be used. In particular, when the coating method is used, the adhesion amount of the silane compound can be controlled by changing the coating means such as showering and spraying or adjusting the number of coatings. It is also possible to control the adhesion amount of the silane compound by adjusting the concentration of the silane compound in the solution containing the silane compound.

When a roughening treatment is performed on the surface of the copper foil before the surface treatment, an electroplating method can be used. The amount of electrodeposition of the roughened particles on the copper foil surface can be controlled mainly by adjusting the current density and the electrodeposition time. The amount of electrodeposition of the roughened particles mainly affects the surface roughness of the surface-treated copper foil.
As the roughening treatment, for example, the following roughening treatment method (1) or roughening treatment method (2) can be used.
<Roughening treatment method (1)>
Liquid composition: copper 10-20 g / L, nickel 7-10 g / L, cobalt 7-10 g / L
Liquid temperature: 30-60 ° C
Current density: 1 to 50 A / dm ²
pH: 2.0 to 3.0
Electrodeposition time: 0.12 to 1.15 seconds The amount of each metal per 1 dm ² deposited by the roughening treatment is preferably 15 to 40 mg of copper, 100 to 1500 μg of nickel, and 700 to 2500 μg of cobalt.

<Roughening treatment method (2)>
Primary particle plating (1)
Liquid composition: copper 10-15 g / L, nickel 0-10 g / L, cobalt 0-20 g / L, sulfuric acid 10-60 g / L
Liquid temperature: 20-40 ° C
Current density: 10 to 50 A / dm ²
Electrodeposition time: 0.2-5 seconds Primary particle plating (2)
Liquid composition: copper 10-30 g / L, sulfuric acid 70-120 g / L
Liquid temperature: 30-50 ° C
Current density: 3 to 30 A / dm ²
Electrodeposition time: 0.2 to 5 seconds Secondary particle plating Liquid composition: Copper 10 to 20 g / L, nickel 0 to 15 g / L, cobalt 0 to 10 g / L
Liquid temperature: 30-40 ° C
Current density: 10 to 35 A / dm ²
Electrodeposition time: 0.2-5 seconds

When providing a heat-resistant, anti-rust or chromate treatment layer between the copper foil and the surface treatment layer of the silane compound, the heat treatment, anti-rust treatment or chromate treatment should be applied before the surface treatment of the silane compound. What is necessary is just to go to the foil surface. These treatment methods are not particularly limited, and can be performed according to known methods.

The surface-treated copper foil produced as described above has a surface treatment layer of a silane compound in which a peak is detected at a specific position (mass number: m / z) when measured by TOF-SIMS. Therefore, the adhesiveness between the surface treatment layer of the silane compound and the resin base material is high. In particular, this surface-treated copper foil can improve the adhesion to the resin substrate even when there are few roughened particles electrodeposited on the copper foil surface by the roughening treatment or when the roughening treatment is not performed. it can. Therefore, this surface-treated copper foil is suitable not only for conventional resin base materials but also for resin base materials suitable for high frequency applications that are harder to adhere to copper foil than conventional resin base materials (liquid crystal polymers, low dielectric materials such as low dielectric polyimides). It can also be used for bonding to a resin base material formed from a material.

A copper clad laminate according to an embodiment of the present invention includes the above-described surface-treated copper foil and a resin base material bonded onto the surface-treated layer of the silane compound of the surface-treated copper foil. The resin base material is preferably a resin base material formed from a low dielectric material.
Here, “low dielectric” in this specification means that the dielectric loss tangent (1 GHz) is 0.01 or less.
Examples of the low dielectric material include, but are not limited to, liquid crystal polymer (LCP), low dielectric polyimide, low dielectric epoxy resin, fluorine resin, polyphenylene ether resin, and the like.
As used herein, “liquid crystal polymer” means an aromatic polyester that exhibits optical anisotropy in the liquid phase. The liquid crystal polymer is generally commercially available, and for example, Vecstar (registered trademark) series manufactured by Kuraray Co., Ltd. can be used.
In the present specification, “low dielectric polyimide” means, for example, a polyimide having a relative dielectric constant (1 GHz) of 3.3 or less and a dielectric loss tangent (1 GHz) of 0.005 or less. The low dielectric polyimide is generally commercially available, and for example, U varnish, Upilex (registered trademark) manufactured by Ube Industries, Ltd. can be used.
Examples of the fluororesin include PTFE.
Polyphenylene ether resins also include compounds with other resins such as polystyrene.

The copper clad laminate having the above-described configuration is formed by placing a resin base material on the surface treatment layer of the silane compound of the surface-treated copper foil, and then applying pressure between the surface-treated copper foil and the resin base material. Can be manufactured.
The applied pressure is not particularly limited, and may be appropriately set according to the type of the surface-treated copper foil and the resin base material to be used.

The copper clad laminate produced as described above is a surface-treated copper having a surface-treated layer of a silane compound in which a peak is detected at a specific position (mass number: m / z) when measured by TOF-SIMS. Since the foil is provided, the adhesiveness between the surface-treated copper foil and the resin base material is excellent. Therefore, this copper-clad laminate is suitable for use in applications such as flexible wiring boards, rigid wiring boards, shield materials, RF-IDs, planar heating elements, and radiators.

Hereinafter, the surface-treated copper foil and the copper-clad laminate according to the embodiment of the present invention will be described in detail by way of examples, but these limit the surface-treated copper foil and the copper-clad laminate according to the embodiment of the present invention. It is not a thing.
The silane compounds used in each example and comparative example are as follows.
・ KBM603 (Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropyltrimethoxysilane)
・ KBM503 (Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxysilane)

Example 1
In accordance with the roughening method (2) described above, a roughened layer is obtained by subjecting a rolled copper foil of 12 μm thickness (BHZ-Z-HA-V2 manufactured by JX Metals Co., Ltd.) to the following conditions. Formed.
<Primary particle plating (1)>
Liquid composition: copper 11g / L, sulfuric acid 52g / L
Liquid temperature: 22 ° C
Current density: 40 A / dm ²
Electrodeposition time: 1 second <Primary particle plating (2)>
Liquid composition: copper 19g / L, sulfuric acid 101g / L
Liquid temperature: 42 ° C
Current density: 4 A / dm ²
Electrodeposition time: 3 seconds <Secondary particle plating>
Liquid composition: copper 15g / L, nickel 10g / L, cobalt 7g / L
Liquid temperature: 37 ° C
Current density: 30 A / dm ²
Electrodeposition time: 1 second

Next, after sequentially forming a heat-resistant treatment layer and a chromate layer on the roughening treatment layer, a surface treatment layer is formed using a solution containing a silane compound under the following conditions to form a surface treatment layer of the silane compound. A treated copper foil was obtained.
Silane compound: A mixture of KBM603 and KBM503 (volume ratio of KBM603 to KBM503 is 75:25)
Concentration of silane compound in solution: 1% by volume
Solution temperature: 20 ° C
Solution pH: 4.5
Processing time: 3 seconds Application frequency: 1 time Drying temperature: 110 ° C
Drying time: 30 seconds

Next, on the surface-treated layer of the silane compound of the surface-treated copper foil obtained above, a resin substrate made of a liquid crystal polymer (Vecstar (registered trademark) CT-Z manufactured by Kuraray Co., Ltd.) having a thickness of 50 μm was disposed. Then, the copper clad laminated board was obtained by pressurizing and joining. At this time, the applied pressure was set to 4 MPa.

(Comparative Example 1)
A surface-treated copper foil and a copper clad laminate were prepared in the same manner as in Example 1 except that KBM603 was used as the silane compound, the concentration of the silane compound in the solution was changed to 4% by volume, and the pH of the solution was changed to 11.
(Comparative Example 2)
A surface-treated copper foil and a copper clad laminate were prepared in the same manner as in Example 1 except that KBM503 was used as the silane compound.

The surface-treated copper foils obtained in the above examples and comparative examples were subjected to TOF-SIMS analysis of the silane compound surface treatment layer. The analysis conditions are shown below.
Equipment: Ion-tof TOF-SIMS 4S
Primary ion species: Bi ³⁺
Measurement mode: positive
Measurement area: 200 μm × 200 μm
Neutralizing gun used: None

The results of TOF-SIMS analysis are shown in FIGS. FIG. 1 shows a spectrum of TOF-SIMS in the range of mass number (m / z) from 240 to 260. FIG. 2 shows a spectrum of TOF-SIMS in the range of mass number (m / z) from 260 to 263.5. It is a spectrum.
As shown in FIGS. 1 and 2, in Example 1, the mass number (m / z) is position A at 240.9 to 241.1, position B at 241.9 to 242.1, 242.9 to 243. 1 position C, 243.9 to 244.1 position D, 244.9 to 245.1 position E, 260.9 to 261.1 position F, 261.9 to 262.1 positions G and 262 A peak was detected at position H between .9 and 263.1. More specifically, in Example 1, the mass numbers (m / z) are 241.03, 242.03, 243.03, 244.05, 245.05, 261.01, 262.01, and 263.03. A peak was detected at the position of. In contrast, in Comparative Examples 1 and 2, no peak was detected at any of the positions A to H.

Next, the 10-point average roughness Rz and arithmetic average roughness Ra of the surface treatment layer of the silane compound were measured for the surface-treated copper foils obtained in the above Examples and Comparative Examples. The results are shown in Table 1.
The ten-point average roughness Rz and arithmetic average roughness Ra of the surface treatment layer of the silane compound were measured according to JIS B0601: 1982 using a contact roughness meter Surfcoder SE-600 manufactured by Kosaka Laboratory. In this measurement, the measurement reference length is 0.8 mm, the evaluation length is 4 mm, the cutoff value is 0.25 mm, the feeding speed is 0.1 mm / second, and the measurement position is changed in the width direction of the surface-treated copper foil. 10 times, and the average of the 10 measurements was taken as the evaluation result.

Next, 90 degree peel strength was measured about the copper clad laminated board obtained by said Example and comparative example. The results are shown in Table 1.
The 90 degree peel strength was measured in accordance with JIS C6471: 1995. Specifically, the strength when the conductor (surface-treated copper foil) width was 3 mm and the resin substrate and the surface-treated copper foil were peeled at a speed of 50 mm / min at an angle of 90 degrees was measured. The measurement was performed twice, and the average value was taken as the result of 90 degree peel strength.

As shown in Table 1, it can be seen that Example 1 has a 90 degree peel strength higher than that of Comparative Examples 1 and 2, and has high adhesion between the surface treatment layer of the silane compound and the resin substrate. It was.

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 improving the adhesion with a resin substrate, particularly a resin substrate suitable for high frequency applications. . Moreover, according to embodiment of this invention, the copper clad laminated board excellent in the adhesiveness between a resin base material, especially the resin base material suitable for a high frequency use, and surface-treated copper foil can be provided.

Since the surface-treated copper foil according to the embodiment of the present invention has a surface-treated layer of a silane compound that has high adhesion to the resin substrate, it can be used for the production of a copper-clad laminate. In addition, the copper-clad laminate according to the embodiment of the present invention is excellent in adhesion between the resin base material and the surface-treated copper foil. Therefore, the flexible wiring board, the rigid wiring board, the shield material, the RF-ID, It can be used for applications such as planar heating elements and radiators.

Claims

A surface-treated copper foil having a surface-treated layer of a silane compound on the surface of the copper foil,
When the surface treatment layer of the silane compound was measured by TOF-SIMS, 240.9 to 241.1, 241.9 to 242.1, 242.9 to 243.1, 243.9 to 244.1, 244 .9 to 245.1, 260.9 to 261.1, 261.9 to 262.1, and at least one mass number (m / z) selected from the group consisting of 262.9 to 263.1 Surface-treated copper foil where peaks are detected.
Position of at least one mass number (m / z) selected from the group consisting of 241.03, 242.03, 243.03, 244.05, 245.05, 261.01, 262.01, and 263.03 The surface-treated copper foil according to claim 1, wherein the peak is detected.
240.9 to 241.1, 241.9 to 242.1, 242.9 to 243.1, 243.9 to 244.1, 244.9 to 245.1, 260.9 to 261.1, 261. The surface-treated copper foil according to claim 1, wherein the peak is detected at positions of mass numbers (m / z) of 9 to 262.1 and 262.9 to 263.1.
The peak is detected at the positions of mass numbers (m / z) of 241.03, 242.03, 243.03, 244.05, 245.05, 261.01, 262.01, and 263.03, Item 4. The surface-treated copper foil according to Item 3.
The surface-treated copper foil according to any one of claims 1 to 4, wherein the silane compound is a mixture of two or more silane compounds.
The surface according to any one of claims 1 to 5, wherein the silane compound is a mixture containing N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane. Treated copper foil.
7. One or more layers selected from the group consisting of a heat-resistant treatment layer, a rust-proof treatment layer, and a chromate treatment layer are provided between the copper foil and the surface treatment layer of the silane compound. The surface-treated copper foil as described in one.
The surface-treated copper foil according to any one of claims 1 to 7, wherein a ten-point average roughness Rz of the surface treatment layer of the silane compound is 0.50 to 1.0 µm.
The surface-treated copper foil according to any one of claims 1 to 8, which is bonded to a resin base material.
A copper-clad laminate comprising the surface-treated copper foil according to any one of claims 1 to 9 and a resin base material bonded onto the surface-treated layer of the silane compound of the surface-treated copper foil.
The copper-clad laminate according to claim 10, wherein the resin base material is a liquid crystal polymer, a low dielectric polyimide, a low dielectric epoxy resin, a fluororesin or a polyphenylene ether resin.
The copper-clad laminate according to claim 10 or 11, which is used for a flexible wiring board, a rigid wiring board, a shield material, RF-ID, a planar heating element or a radiator.