TWI645759B - Surface-treated copper foil for printed wiring board, copper-clad laminated board for printed wiring board, and printed wiring board - Google Patents

Abstract

A surface-treated copper foil for a printed wiring board includes a silane coupling agent layer on a surface on which roughened particles are formed, and an average height of the roughened particles on the surface of the silane coupling agent layer is 0.05 μm or more and less than 0.5 μm. The BET surface area ratio of the surface of the silane coupling agent layer is 1.2 or more, and the fine surface coefficient Cms is 2.0 or more and less than 8.0.

Description

Surface-treated copper foil for printed wiring board, copper-clad laminated board for printed wiring board, and printed wiring board

The present invention relates to a surface-treated copper foil for a printed wiring board. The present invention also relates to a copper-clad laminate for a printed wiring board using the surface-treated copper foil for a printed wiring board and a printed wiring board using the surface-treated copper foil for the printed wiring board.

In recent years, with the development of high performance and high performance of computers or information communication equipment, or the development of the Internet, it is necessary to transfer and process large-capacity information at a higher speed. Therefore, the transmitted signals tend to be more high-frequency, and printed wiring boards are required to suppress the transmission loss of high-frequency signals. In the production of a printed wiring board, a copper foil and an insulating base material (resin base material) are usually laminated, and a copper-clad laminated board which is heated and pressurized is produced, and a conductor circuit is formed using the copper-clad laminated board . When transmitting high-frequency signals (high-frequency transmission) to the conductor circuit, the transmission loss is related to the three elements of conductor loss, dielectric loss, and radiation loss.

Conductor loss is caused by the surface resistance of the conductor circuit. After a high-frequency signal is transmitted in a conductor circuit formed using a copper-clad laminated board, a skin-effect phenomenon occurs. That is, when alternating current flows in a conductor circuit, the magnetic beam changes, and a back electromotive force is generated in the center portion of the conductor circuit. As a result, it is difficult for a current to flow in the center portion of the conductor, and instead, a conductor surface portion (skin portion) is generated. The phenomenon of increased current density. Such a skin effect phenomenon is that in order to reduce the effective cross-sectional area of a conductor, so-called surface resistance is generated. The thickness (skin depth) of the epidermal portion through which the current flows is inversely proportional to the square root of the frequency.

In recent years, high-frequency compatible devices such as those exceeding 20 GHz have been developed. When a high-frequency signal in the GHz band is transmitted in a conductor circuit at a frequency, the skin depth is formed to be about 2 μm or less, causing current to flow only on the extreme surface layer of the conductor. Therefore, in the copper-clad laminated board used in this high-frequency-compatible device, if the surface roughness of the copper foil becomes larger, the transmission path of the conductor formed by the copper foil (that is, the transmission path of the skin portion) also becomes It becomes longer and increases transmission loss. Therefore, it is desirable to reduce the surface roughness of the copper foil of the copper-clad laminated board used in the high-frequency corresponding equipment.

On the other hand, the copper foil generally used in printed wiring boards uses a method such as plating or etching to form a roughened layer (a layer that forms roughened particles) on the surface, and uses a physical effect (anchoring Effect, Anchoring Effect) to improve adhesion to the resin substrate. However, if the roughened particles formed on the surface of the copper foil are increased in order to effectively improve the adhesion with the resin substrate, as described above, the transmission loss will increase.

Dielectric loss is caused by the dielectric constant or tangent loss of the resin substrate. When a pulse signal flows through a conductor circuit, the electric field around the conductor circuit changes. When the period (frequency) at which the electric field changes is close to the relaxation time (moving time of the charged body that generates the polarization) of the resin substrate (that is, after the high frequency is generated), a delay occurs in the electric field change. In this state, molecular friction is generated inside the resin, and heat is generated, causing transmission loss. In order to suppress the dielectric loss, as the resin substrate of the copper-clad laminated board, a resin having a large polarity and a small amount of substitution group must be used, or a resin having no substitution group having a large polarity must be used, so that It is difficult to generate a polarization of the resin substrate accompanying the change in the electric field.

On the other hand, in addition to forming the roughened layer, the copper foil used in the printed wiring board is treated with a silane coupling agent to treat the surface of the copper foil. Time between forces. When the adhesion between the silane coupling agent and the resin substrate is chemically improved, it is necessary for the resin substrate to have a somewhat polar displacement agent. However, in order to suppress the dielectric loss, it is necessary to reduce the When a low-dielectric base material having a large amount of a substituent group is used, the chemical adhesion force is lowered, and it is difficult to ensure sufficient adhesion between the copper foil and the resin base material.

As described above, in a copper clad laminate, there is a trade-off relationship between suppression of transmission loss and improvement (improvement in durability) of the adhesion (adhesion) between the copper foil and the resin substrate.

In recent years, high-frequency compatible printed wiring boards have been rapidly developed in areas where reliability is more required. For example, the use of printed wiring boards for mobile communications such as automotive applications requires high reliability even in severe environments such as high-temperature environments. In order to meet such requirements, in terms of copper clad laminates, it is necessary to highly improve the adhesion between the copper foil and the resin substrate.

To meet these needs, various technologies have been developed. For example, Patent Document 1 describes a surface-treated copper foil that forms a roughened surface having a surface roughness Rz of 1.5 to 4.0 μm and a lightness value of 30 or less in order to adhere the roughened particles to the copper foil. It has a slightly uniform distribution at a specified density, and the surface-treated copper foil has protrusions formed of the roughened particles, the protrusions have a specified height and width, and are also described in Patent Document 1, By using such a surface-treated copper foil, the adhesion between a liquid crystal polymer and a resin base material for a high-frequency circuit board can be improved.

In a small electronic device such as a smart phone or a tablet, a flexible printed wiring board (hereinafter, referred to as FPC) is used from the viewpoint of easy wiring and light weight. near Over the years, along with the high performance of these small electronic devices, and the tendency of high-speed signal transmission, the impedance matching (matching of output impedance and input impedance) of FPC has become an important issue. In order to achieve high-speed impedance matching for signal transmission speeds, measures have been taken to thicken a resin substrate (typically polyfluorene), which is the basis of FPC.

FDC is bonded to a liquid crystal substrate, or mounted with an IC chip, and is subjected to a predetermined process. Regarding the alignment during the processing, the positioning pattern that can be identified through the resin substrate removed by etching is used as an index. Therefore, when the above positions are blended, the permeability (identifiability) of the resin substrate becomes important. The transmittance of such a resin substrate is generally evaluated and managed using the total light transmittance and haze (haze value) in the visible range. In recent years, with the development of thickening of resin substrates and the diversification of position adjustment procedures, the level of permeability required for resin substrates after etching has also increased. The permeability of the resin substrate after the etching method has a large influence on the shape of the surface of the copper foil bonded to the resin substrate in addition to the characteristics of the resin itself.

Flexible resin substrates such as polyimide and liquid crystal polymers will be bonded to copper foil under high temperature and high pressure conditions. In this case, because the resin penetrates into the roots of the roughened particles formed on the roughened surface of the copper foil, the larger the roughened particles, the deeper the unevenness that is transferred to the resin, resulting in after-etching. The light of the resin substrate is easy to be scattered, and the light transmittance tends to be deteriorated.

In addition, Patent Document 2 concerning FPC describes an FPC suitable for a die flexible mold package (COF) format. The FPC has an electrolytic copper foil structure that is provided on a bonding surface that is bonded to an insulating layer. An anti-rust treatment layer made of a nickel-zinc alloy, the surface roughness (Rz) of the bonding surface is 0.05 to 1.5 μm, and the specular gloss at an angle of incidence of 60 ° is more than 250; it is also described that the FPC shows excellent Light transmittance and adhesion between copper foil and resin As excellent.

In addition, Patent Document 3 describes a surface-treated copper foil. In order to form roughened particles by roughening, the roughened surface has an average roughness Rz of 0.5 to 1.3 μm and a gloss of 4.8. To 68. The ratio A / B between the surface area A of the roughened particles and the area B of the roughened particles as viewed from the surface of the copper foil is 2.00 to 2.45; and it is described that the surface-treated copper foil and the resin substrate The copper-clad laminated board formed by the lamination has good resin transparency after etching the copper foil, and excellent adhesion between the copper foil and the resin.

[Advanced technical literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 4833556

Patent Document 2: Japanese Patent No. 4090467

Patent Document 3: Japanese Patent No. 5497808

The surface-treated copper foil described in the above-mentioned Patent Document 1 has good adhesion to a high-frequency-resisting resin substrate, but the copper-clad laminated board using the surface-treated copper foil has a transmission loss in the high-frequency band of the GHz band. High, can not fully meet the high requirements of high frequency corresponding printed wiring board.

In addition, the electrolytic copper foil used in the FPC described in the above-mentioned Patent Document 2 has not been subjected to a roughening treatment, and in addition to COF, the high-tightness and resin substrate required for a printed wiring board cannot be achieved. Sex.

Moreover, the surface-treated copper foil described in the said patent document 3 is that when the low-dielectric base material is used as a resin base material, sufficient adhesiveness with a resin base material cannot be obtained.

The object of the present invention is to provide a surface-treated copper foil for a printed wiring board, which will be described later. By using the surface-treated copper foil for a printed wiring board, it is possible to achieve a high degree of transmission suppression even when transmitting high-frequency signals in the GHz band. Loss, printed wiring board that can still improve the adhesion between the copper foil and the resin substrate, and has superior durability and recognizability. Another object of the present invention is to provide a copper-clad laminated board for a printed wiring board using the surface-treated copper foil for a printed wiring board, and a printed wiring board (circuit board) using the surface-treated copper foil for the printed wiring board.

The above-mentioned problems of the present invention can be solved by the following means.

[1] A surface-treated copper foil for a printed wiring board, which has a silane coupling agent layer on a surface on which roughened particles are formed, and an average height of the roughened particles on the surface of the silane coupling agent layer is 0.05 μm or more and less than 0.5 μm, the BET surface area ratio on the surface of the silane coupling agent layer is 1.2 or more, and the fine surface coefficient Cms is 2.0 or more and less than 8.0.

[2] The surface-treated copper foil for a printed wiring board according to (1), wherein the average height of the roughened particles on the surface of the silane coupling agent layer is 0.05 μm or more and less than 0.3 μm.

[3] (1) or (2) of the printed wiring board surface treated copper foil, wherein, in the L ^* a ^* b surface layer of the silane-coupling agent ^* color system of L ^* is 40 or more and less than 60.

[4] The surface-treated copper foil for printed wiring boards according to (1) to (3), which has a surface on which the roughened particles have been formed, is provided with a material selected from the group consisting of chromium (Cr), iron (Fe), and cobalt (Co). , Nickel (Ni), copper (Cu), zinc (Zn), molybdenum (Mo), and tin (Sn) at least one metal metal treatment layer, or preferably has a metal selected from the group consisting of chromium, iron, cobalt A metal-treated layer of an alloy formed of at least two metals of nickel, copper, zinc, molybdenum, and tin.

[5] The surface-treated copper foil for a printed wiring board according to any one of (1) to (4), wherein the amount of the silicon element contained in the silane coupling agent layer is 0.5 μg / dm ² or more and less than 15 μg / dm ² .

[6] The surface-treated copper foil for a printed wiring board according to any one of (1) to (5), wherein the silane coupling agent has a member selected from the group consisting of an epoxy group, an amino group, a vinyl group, and a (meth) acrylic acid. At least one of functional groups, such as methyl, styryl, urea, isocyanurate, mercapto, sulfide, and isocyanate.

[7] A copper-clad laminated board for a printed wiring board, comprising a resin layer of the silane coupling agent layer surface area layer of the surface-treated copper foil for a printed wiring board according to any one of (1) to (6).

[8] A printed wiring board using the copper-clad laminated board for a printed wiring board of (7).

The surface-treated copper foil for a printed wiring board of the present invention is such that by using it in a conductor circuit of a printed wiring board, it is possible to obtain a high degree of suppression of transmission loss when transmitting high-frequency signals in the GHz band, and to improve the copper foil. A printed wiring board with excellent adhesion to a resin substrate (resin layer) and superior durability and recognizability.

The copper-clad laminated board for a printed wiring board of the present invention is such that by using it as a substrate for a printed wiring board, the transmission loss of the obtained printed wiring board when transmitting high-frequency signals in the GHz band can be highly suppressed. And it can improve the adhesion between the copper foil and the resin substrate, and has superior durability and recognizability.

The printed wiring board of the present invention is such that the transmission loss when transmitting high-frequency signals in the GHz band is highly suppressed, and the adhesion between the copper foil and the resin substrate is improved, and it has excellent durability and recognizability. Printed wiring board.

The above and other features and advantages of the present invention will be made clear with reference to the drawings and the following description, as appropriate.

FIG. 1 is an explanatory diagram showing an example of a method for measuring the height of roughened particles.

FIG. 2 is an explanatory diagram showing an example of a method for measuring the height of roughened particles.

The preferable embodiment of the surface-treated copper foil for printed wiring boards of this invention is demonstrated below.

[Surface-treated copper foil for printed wiring boards]

The surface-treated copper foil for a printed wiring board of the present invention (hereinafter, simply referred to as the "surface-treated copper foil of the present invention") is treated with a silane coupling agent (that is, having a silane on the surface on which roughened particles have been formed). Coupling agent layer) The surface of roughened particles has been formed (the surface with anti-corrosion metal attached if necessary). On the surface of the silane coupling agent layer (the surface of the surface-treated copper foil), the average height of the roughened particles is 0.05 μm or more. And less than 0.5 μm, the BET surface area ratio of the surface of the silane coupling agent layer is 1.2 or more. The fine surface area coefficient (Cms) of the surface of the silane coupling agent layer is 2.0 or more and less than 8.0. The surface-treated copper foil of the present invention is the surface of the silane coupling agent layer, and the average height of the roughened particles measured on the surface is 0.05 μm or more and less than 0.5 μm, and the BET surface area ratio of the surface is 1.2 or more, and the surface with a Cms of 2.0 or more and less than 8.0 is simply called a "roughened surface". Although the roughened surface is preferably covered with a silane coupling agent as a whole, as long as the effect of the present invention can be achieved, the silane coupling agent can also cover only a part of the roughened surface (that is, as long as the According to the effect of the invention, even if a film defect occurs in a part of the silane coupling agent layer on the roughened surface, this form is also included in the form of "having a silane coupling agent layer" in the present invention).

The surface-treated copper foil of the present invention only needs to be a roughened surface on at least one side, or both sides may be roughened surfaces. The surface-treated copper foil of the present invention generally has a form in which only one surface is a roughened surface.

In the surface-treated copper foil of the present invention, even if the roughened surface shows an average height of less than 0.5 μm of roughened particles, the BET surface area ratio is still larger than 1.2. Therefore, when the copper foil and the resin layer are processed through the surface of the roughened area layer to produce a copper-clad laminate, the anchoring effect of the roughened particles and a large surface area can be used to highly enhance the copper foil and Adhesiveness between resin layers to obtain a copper-clad laminate with superior heat resistance. In addition, since the The roughened surface has an average height of the roughened particles that is less than 0.5 μm and appears relatively low, so the influence of the presence of the roughened particles on the length of the transmission path can be reduced. Therefore, in the conductor circuit using the copper-clad laminated board, when transmitting high-frequency signals in the GHz band, transmission loss can also be effectively suppressed.

Prior to this, it was not known how to increase the BET surface area ratio to 1.2 or more while forming micro-roughened particles with an average height of less than 0.5 μm on the surface of the copper foil. Under these circumstances, the present inventors have successfully produced roughened particles having an average height of 0.05 μm or more and less than 0.5 μm, and a BET surface area ratio of 1.2 or more by using specific roughening plating treatment conditions described later. Surface of the copper foil to complete the present invention.

From the viewpoint of more effectively reducing transmission loss while maintaining high adhesion to the resin substrate, the average height of the roughened particles on the roughened surface is preferably 0.05 μm or more and less than 0.5 μm. , More preferably 0.05 μm or more and less than 0.3 μm.

In the present invention, the roughened particles are preferably formed so as to be uniform (homogeneous) over the entire roughened surface. The average height of the roughened particles was measured by a method described in Examples described later.

The above-mentioned BET surface area ratio is calculated by a BET method based on a measurement method of a surface area. That is, the above-mentioned BET surface area ratio is such that a gas molecule having a known adsorption occupied area is adsorbed on the sample surface, and the surface area (BET measurement surface area) of the sample is obtained based on the adsorption amount, and the BET measurement surface area is subtracted from The value of the surface area (sample cut-out area) where the surface of the sample has no unevenness, and the ratio of this value to the sample cut-out area is the BET surface area ratio, and is measured by the method described in the examples described later.

In the surface-treated copper foil of the present invention, the BET surface area ratio of the roughened surface is such that the larger the value, the larger the surface area. Therefore, the larger the above-mentioned BET surface area ratio of the roughened surface, the more the interaction with the resin is improved, and the anchoring effect of the roughened particles increases the product. The adhesion between the copper foil and the resin layer when the resin layer is laminated. In the surface-treated copper foil of the present invention, the BET surface area ratio of the roughened surface is preferably 1.2 or more and 10 or less, and more preferably 4 or more and 8 or less.

In the measurement of the surface area of copper foil, the surface area measurement using a laser microscope is generally used. In principle, it is impossible to measure the formation of the "negative" part due to the shape of the roughened particles, which is not reached by laser light. In addition, it is difficult to detect the surface area of extremely fine uneven portions by a high sensitivity method. For example, even rough particles with the same height and diameter, compared with roughened particles with root shrinkage and roughened particles without shrinkage, although the former has a large area of close contact with the resin, it is performed by a laser microscope. In the measurement of the surface area, almost the same measured value is displayed.

In contrast, in the measurement of the surface area by the BET method, since the surface area is measured by the adsorption of gas molecules, it has a high sensitivity to fine unevenness, and it can also be measured that the laser light forms "negative" "part. Therefore, as compared with the case where the measurement is performed using a laser microscope, the surface area of the sample on which the roughened particles have been formed can generally be measured with higher accuracy.

The present inventors have succeeded in increasing the ratio of the surface area of the "negative" portion or the fine uneven portion that cannot be measured in a laser microscope by performing a specific roughening plating process described later. It was found that by suppressing the average height of the coarse particles, it can effectively suppress the transmission loss when transmitting high-frequency signals, and at the same time, it can greatly improve the adhesion with the resin substrate, and can maintain the resin after etching. The identifiability of the base material further reaches the invention.

The fine surface area coefficient (Cms) refers to a comparison value of the surface area ratio measured by the BET method with respect to the surface area ratio measured by a laser microscope, and is a portion of the "yin" that cannot be measured by a laser microscope or Numerically quantify the ratio of the surface area of fine unevenness the result of. The details of the Cms calculation method are the same as those described in the examples described later. In the surface-treated copper foil of the present invention, the Cms of the roughened surface is 2.0 or more and less than 8.0. By setting the average height of the roughened particles on the roughened surface and the BET surface area ratio of the roughened surface within the range specified in the present invention, and setting the Cms of the roughened surface to 2.0 or more and less than 8.0, the The adhesion between the surface and the resin substrate is highly improved, and at the same time, the identifiability of the resin after etching is well maintained. Cms is preferably 2.5 or more and less than 5.0.

In addition, between the surface area measured by a laser microscope and the surface area measured by the BET method, since the principle of measuring the surface area is different, there may be cases where the Cms does not reach 1 depending on the shape of the roughened surface.

In the surface-treated copper foil of the present invention, the lightness index L ^* (Lightness) of the roughened surface is preferably 40 or more, preferably 60 or less, more preferably 40 or more, and 55 or less. If it is a dark brown to black treated surface (a surface formed by an alloy and copper oxide) like a so-called blackening treatment, L ^* tends to be small and the transmission loss tends to increase. On the other hand, if the shape of the roughened particles is rounded, L ^* tends to increase and the adhesion to the resin matrix tends to decrease. L ^* is measured by the method described in Examples described later.

In the surface-treated copper foil of the present invention, the surface on which the roughened particles have been formed before the silane coupling agent treatment is provided with a layer made of chromium (Cr), iron (Fe), cobalt (Co), nickel (Ni), copper ( Cu), zinc (Zn), molybdenum (Mo), and tin (Sn) at least one metal selected from a metal treatment layer, or preferably has a metal treatment layer comprising chromium, iron, cobalt, nickel, copper, zinc, molybdenum And a metal treatment layer of an alloy formed of at least two metals selected from tin and tin. The metal treatment layer is a metal treatment layer including at least one metal selected from nickel, zinc, and chromium, or preferably a metal treatment layer including two or more metals selected from nickel, zinc, and chromium. Formed alloy metal Processing layer.

The copper-clad laminated board or printed wiring board used for the surface-treated copper foil of the present invention is often heated during the manufacturing process, such as a bonding process between a resin and a copper foil, or a soldering process. By this heating, copper is diffused to the resin side, and the adhesion between copper and resin is reduced. However, by providing the above-mentioned metal treatment layer, copper diffusion can be prevented, and the resin substrate can be more stably maintained. High degree of tightness. In addition, the metal constituting the metal treatment layer can also function as a rust preventive metal for preventing patina.

From the viewpoint of further improving the etchability of copper foil, it is also important to control the amount of nickel as a rust-preventive metal on the surface where roughened particles have been formed before the silane coupling agent is processed. That is, when there is a large amount of nickel attached, although it is difficult to generate patina and to improve the adhesion with the resin at a high temperature, nickel remains easily after etching, and it is difficult to obtain sufficient insulation reliability. . When the surface-treated copper foil of the present invention has a metal-treated layer, the amount of the nickel element contained on the roughened surface is preferably 0.1 mg / dm from the viewpoint of both adhesion and etching at high temperatures. ² or more and less than 0.3 mg / dm ² .

[Surface-treated copper foil for manufacturing printed wiring boards] <Copper foil>

As the copper foil used in the production of the surface-treated copper foil of the present invention, a rolled copper foil, an electrolytic copper foil, or the like can be selected depending on the application or other purposes. The thickness of the copper foil used in the surface-treated copper foil of the present invention is not particularly limited, and can be appropriately selected according to the purpose. The thickness of the foil is generally 4 to 120 μm, preferably 5 to 50 μm, and more preferably 6 to 18 μm.

<Roughening Plating Treatment>

In the production of the surface-treated copper foil of the present invention, the formation of the above-mentioned roughened surface can be carried out by appropriately using specific roughened plating conditions. That is, the present invention is based on the fact that the inventors have set the molybdenum concentration within a specific range and performed the plating treatment under specific conditions described later, and have found out that the roughened surface can be formed.

(Roughening Plating Treatment Conditions)

In order to form the roughened surface, it is necessary to control the molybdenum concentration to be 50 mg / L or more and 600 mg / L or less in the roughening plating treatment (plating treatment). In addition, if the concentration of molybdenum is less than 50 mg / L, problems such as powder dropping will occur. If it exceeds 600 mg / L, although other characteristics can be satisfied, it is difficult to treat the surface of the silane coupling agent (that is, the rough surface). The chemically treated surface) has a BET surface area ratio of 1.2 or more.

In order to form the roughened surface, it is necessary to set the flow velocity between the electrode gaps to be not less than 0.15 m / s and not more than 0.4 m / s during the roughening plating process. If the flow velocity between the electrode gaps is less than 0.15 m / sec, the hydrogen detachment operation on the copper foil cannot be performed, and it is difficult to obtain the effect of molybdenum, causing problems such as powder peeling. In addition, when the flow velocity between the electrode gaps exceeds 0.4m / sec, the supply of copper ions to the fine recesses will be excessive, making the recesses buried by electroplating, and it is difficult to increase the BET surface area ratio of the surface treated by the silane coupling agent to 1.2. the above.

In order to form the above-mentioned roughened surface, it is necessary to set the current density multiplied by the processing time to 20 (A / dm ² ) in the roughening plating process. More than 250 seconds (A / dm ² ). Below seconds. When the value does not reach 20 (A / dm ² ). In seconds, since the average height of the roughened particles on the roughened surface after the silane coupling agent treatment is difficult to form 0.05 μm or more, it is not easy to ensure sufficient adhesion to the laminated resin. In addition, if it exceeds 250 (A / dm ² ). In seconds, since the average height of the roughened particles formed is difficult to be less than 0.5 μm, the transmission loss is likely to deteriorate. The current density multiplied by the processing time is preferably 20 (A / dm ² ). More than seconds, less than 160 (A / dm ² ). second.

In order to form the above roughened surface, the current density must be multiplied by the processing time in the roughening plating process, and the value divided by the concentration of molybdenum must be set to 1.0 {(A / dm ² ). Seconds} / (mg / L) or more, 3.0 {(A / dm ² ). Seconds} / (mg / L) or less. When the value does not reach 1.0 {(A / dm ² ). At sec} / (mg / L), it is difficult to obtain a sufficient BET surface area ratio, although other characteristics can be satisfied. In addition, if the value exceeds 3.0 {(A / dm ² ). Seconds} / (mg / L), but it is difficult to form Cms below 8.0. The current density is multiplied by the processing time and divided by the concentration of molybdenum, preferably 1.2 (A / dm ² ). More than seconds and less than 2.4 (A / dm ² ). second.

In order to form the above-mentioned roughening treatment surface, preferable roughening plating treatment conditions are disclosed below.

-Roughening plating treatment conditions-

Cu: 10 to 30 g / L

H ₂ SO ₄ : 100 to 200 g / L

Bath temperature: 20 to 30 ° C

Molybdenum concentration: 50 to 600 mg / L

Velocity between electrode gaps: 0.15 to 0.4 m / s

Current density: 15 to 70A / dm ²

Current density × processing time: 0.1 to 10 seconds

Current density × processing time: 20 to 250 (A / dm ² ). second

Current density × treatment time ÷ molybdenum concentration: 1.0 to 3.0 {(A / dm ² ). Seconds) / (mg / L)

In addition, adding molybdenum to the plating solution refers to a form in which molybdenum is dissolved as ions, and as long as it does not include a change in the pH of the copper sulfate plating solution and incorporates metallic impurities into the copper plating film, there is no special limit. For example, an aqueous solution of a molybdate (for example, sodium or potassium molybdate) can be added to the copper sulfate plating solution.

<Metal treatment layer>

When the surface-treated copper foil of the present invention has a metal-treated layer, the method for forming the metal-treated layer is not particularly limited, and it can be formed by a general method. For example, in the case where a metal-treated layer having nickel, zinc, and chromium is formed as an example, the metal-treated layer may be formed in the following conditions, for example, in the order of nickel plating, zinc plating, and chromium plating.

[Nickel plating]

Ni: 10 to 100g / L

H ₃ BO ₃ : 1 to 50g / L

PO ₂ : 0 to 10g / L

Bath temperature: 10 to 70 ° C

Current density: 1 to 50A / dm ²

Processing time: 1 second to 2 minutes

pH: 2.0 to 4.0

〔Galvanized〕

Zn: 1 to 30g / L

NaOH: 10 to 300g / L

Bath temperature: 5 to 60 ° C

Current density: 0.1 to 10A / dm ²

Processing time: 1 second to 2 minutes

〔chrome〕

Cr: 0.5 to 40g / L

Bath temperature: 20 to 70 ° C

Current density: 0.1 to 10A / dm ²

Processing time: 1 second to 2 minutes

pH: below 3.0

In the surface-treated copper foil of the present invention, the amount of silicon element (that is, the amount of silicon element contained in the silane coupling agent layer) present on the roughened surface is preferably 0.5 μg / dm ² or more and less than 15 μg. / dm ² . By setting the amount of the silicon element to be 0.5 μg / dm ² or more and less than 15 μg / dm ² , it is possible to effectively improve the adhesiveness with the resin while suppressing the use amount of the silane coupling agent. The amount of silicon element contained in the silane coupling agent layer is preferably 3 μg / dm ² or more, less than 15 μg / dm ² , more preferably 5 μg / dm ² or more, and less than 15 μg / dm ² .

The silane coupling agent is appropriately selected in accordance with the molecular structure (type of functional group, etc.) of the resin constituting the resin layer laminated with the surface-treated copper foil of the present invention. Among them, the silane coupling agent is preferably an epoxy group, an amino group, a vinyl group, a (meth) acryl group, a styryl group, a urea group, an isocyanurate group, a mercapto group, a sulfide group, and an isocyanate The group is selected from at least one kind of functional group. "(Meth) acrylfluorenyl" means "acrylfluorenyl and / or methacrylfluorenyl" Meaning.

The treatment with the silane coupling agent on the surface of the copper foil on which the roughened particles have been formed can be performed in a general manner. For example, a solution (coating solution) of a silane coupling agent is prepared, and the coating solution is coated on the surface of the copper foil on which the roughened particles have been formed, and dried, whereby the silane coupling agent can be adsorbed or even bonded to The surface of the copper foil on which the roughened particles have been formed. As the coating liquid, for example, the solution used may be a silane coupling agent having a concentration of 0.05 wt% to 1 wt% using pure water.

The coating method of the coating liquid is not particularly limited. For example, the coating liquid may be uniformly flowed on the surface on which the roughened particles have been formed in a state where the copper foil is inclined, and a roller is used to remove the excess. After the liquid is heated and dried, the coating liquid is sprayed on the copper foil with the surface of the roughened particles facing downwards and spread between the rollers, and then the roller is used to remove the excess liquid and then perform heating and drying operations. Apply coating. The coating temperature is not particularly limited, and is usually implemented at 10 to 40 ° C.

[Copper-clad laminated board for printed wiring board]

The copper-clad laminated board for a printed wiring board of the present invention (hereinafter referred to as "copper-clad laminated board of the present invention") is a roughened surface of the surface-treated copper foil of the present invention, and has a laminated resin layer ( Resin substrate). The resin layer is not particularly limited, and the resin layer to be used may be a resin layer generally used in a copper-clad laminated board used to produce a printed wiring board. For example, a halogen-free low-dielectric resin substrate used in a rigid board (hard printed wiring board), or a low-dielectric polyfluorene imide commonly used in flexible substrates .

The method of laminating the surface-treated copper foil and the resin substrate is not particularly limited. For example, the copper foil and the resin substrate are bonded by a hot-press molding method using a hot-pressing machine or the like. In the hot press above The pressing temperature in the molding method is preferably set to about 150 to 400 ° C. The pressure on the pressurizing surface is preferably set to about 1 to 50 MPa.

The thickness of the copper-clad laminated board is preferably 10 to 1000 μm.

〔Printed wiring board〕

The printed wiring board of this invention is manufactured using the copper clad laminated board of this invention. That is, the copper-clad laminated board of the present invention is subjected to a process such as etching to form a conductor circuit pattern, and is formed in a general manner or formed by mounting other members in accordance with needs.

[Example]

Hereinafter, the present invention will be described in more detail based on examples. In addition, the following is an example of the present invention. In the practice of the present invention, various forms can be adopted as long as they do not depart from the gist of the present invention.

[Manufacture of copper foil]

As the copper foil used as a base material for the roughening treatment, an electrolytic copper foil or a rolled copper foil is used.

In Examples 1, 2, 4, 5, 7, and 8, Comparative Examples 1 to 4, and 7, and Reference Example 1, an electrolytic copper foil having a thickness of 12 μm manufactured under the following conditions was used.

<Manufacturing conditions of electrolytic copper foil>

CuSO ₄ : 280g / L

H ₂ SO ₄ : 70g / L

Chlorine concentration: 25mg / L

Bath temperature: 55 ℃

Current density: 45A / dm ²

additive

． Sodium 3-mercapto 1-propane sulfonate: 2mg / L

． Hydroxyethyl cellulose: 10mg / L

． Low molecular weight gum (molecular weight 3000): 50mg / L

In Examples 3 and 6, and Comparative Examples 5 and 6, a commercially available 12 μm refined copper rolled foil (manufactured by UACJ Co., Ltd.) was obtained by degreasing under the following conditions.

<Degreasing processing conditions>

Degreasing solution: Aqueous solution of cleaning agent 160S (Meltec)

Concentration: 60g / L aqueous solution

Bath temperature: 60 ℃

Current density: 3A / dm ²

Power on time: 10 seconds

[Forming a roughened surface]

By the electroplating process, a roughened electroplated surface is formed on one side of the copper foil. This roughened plating treatment surface uses the following roughening plating bath basic bath composition, sets the molybdenum concentration as described in Table 1 below, and sets the flow velocity, current density, and processing time between the electrode gaps as follows Table 1 describes the roughened plated surface. The concentration of molybdenum is adjusted by adding an aqueous solution in which sodium molybdate has been dissolved in pure water to a basic bath.

<Basic bath composition of roughened plating solution>

Cu: 25g / L

H ₂ SO ₄ : 180g / L

Bath temperature: 25 ℃

<Forming a metal-treated layer>

Next, on the roughened plated surface formed as described above, metal plating was performed in the order of Ni, Zn, and Cr under the following plating conditions to form a metal-treated layer. In addition, in Reference Example 1, a metal-treated layer was not formed.

<Nickel plating>

Ni: 40g / L

H ₃ BO ₃ : 5g / L

Bath temperature: 20 ℃

pH: 3.6

Current density: 0.2A / dm ²

Power on time: 10 seconds

<Galvanized>

Zn: 2.5g / L

NaOH: 40g / L

Bath temperature: 20 ℃

Current density: 0.3A / dm ²

Power on time: 5 seconds

〔chrome〕

Cr: 5g / L

Bath temperature: 30 ℃

pH: 2.2

Current density: 5A / dm ²

Power on time: 5 seconds

<Coating Silane Coupling Agent (Roughened Surface)>

The entire surface of the metal-treated layer was coated with a solution (30 ° C) of a commercially available silane coupling agent described in Table 2, and the excess solution was removed with a squeegee, followed by drying at 120 ° C for 30 seconds in the atmosphere. . The method of preparing each silane coupling agent solution is as follows.

3-Glycidoxypropylmethyldimethoxysilane (KBM-402 manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.3 wt% solution was prepared with pure water.

3-Aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.): A 0.25% by weight solution was prepared with pure water.

Vinyltrimethoxysilane (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.): Add sulfuric acid to pure water to adjust the solution to pH 3 to prepare a 0.2 wt% solution.

3-Methacryloxypropylmethyldimethoxysilane (KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.): Add sulfuric acid to pure water to adjust the solution to pH 3 to prepare a 0.25% solution .

3-Isocyanatopropyl triethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.): sulfuric acid was added to pure water to adjust the solution to pH 3 to prepare a 0.2 wt% solution.

3-Ureidopropyltriethoxysilane (KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.): Ethanol and pure water were mixed at 1: 1, and the mixed solution was prepared as a 0.3 wt% solution.

[Measure the average height of the roughened particles]

A cross section parallel to the thickness direction of the copper foil obtained by the ion polishing treatment was observed with an SEM image, and the average height of the roughened particles on the roughened surface was obtained. Details are explained below.

The SEM image shown in FIG. 1 is a cross section parallel to the thickness direction of the roughened surface (surface after silane coupling agent treatment) of the surface-treated copper foil manufactured in Comparative Example 6. Similarly, in the cross section of each copper foil, the top and bottom of the roughened particles can be confirmed in the visual field, and the magnification is adjusted so that about ten roughened particles can be observed. SEM observations are performed for five different fields. Measure the height of the roughest particles with the highest height within the five fields of view of a copper foil, and average the five measured values (maximum values) obtained. The average height of the roughened particles on the roughened surface of the copper foil.

The method of measuring the height of the roughened particles will be described in detail using drawings. As shown in FIG. 1, for the roughened particles to be measured, the shortest distance between the straight line connecting the left and right bottoms (the straight line connecting points a and b) is the longest, and the top of the roughened particle (point c) and The shortest distance between the lines connecting point a and point b is the height H of the roughened particles.

The SEM image shown in FIG. 2 is a cross section parallel to the thickness direction of the roughened surface (the surface treated with the silane coupling agent) of the surface-treated copper foil produced in Example 2. When the roughened particles form a branched state as shown, the whole including the branched structure is regarded as one roughened particle. That is, the shortest distance between the left and right straight lines (straight lines connecting point d and e) of the roughened particles formed into dendritic shapes is the longest, and the top of the roughened particles (point f) and the point d are connected. The shortest distance between the straight line and point e is the height H of the roughened particles.

The results are shown in Table 3 below.

[Measurement of BET surface area ratio A]

The calculation of the BET surface area ratio A is obtained by dividing the surface area of the roughened surface (BET measurement surface area) measured by the BET method by the cut-out area of the sample forming the plan view area.

The BET measurement surface area was measured using a gas adsorption pore distribution measuring device ASAP2020, manufactured by Micromeritics, using a radon adsorption BET multipoint method. Prior to the measurement, as a pretreatment, drying under reduced pressure was performed at a temperature of 150 ° C for 6 hours.

The sample (copper foil) used in the measurement was cut out to form about 3 g of 3 dm ² , cut into a 5 mm square, and then introduced into a measurement device.

In the surface area measurement by the BET method, the total amount of the sample introduced into the device is measured. Because of the surface area of the surface, it is not possible to measure only the surface area of only the roughened surface of the surface-treated copper foil that has been subjected to the single-side roughening treatment. Here, the BET surface area ratio A is actually calculated by the following formula.

<BET surface area ratio A>

The surface area ratio of the surface on which the roughening treatment has not been performed (the surface opposite to the roughening treatment surface) is set to 1, that is, the surface area ratio is regarded as the same as the cut-out area of the sample, and the BET surface area ratio A is calculated by the following formula.

(BET surface area ratio A) = [(BET measured surface area)-(sample cut-out area)] / (sample cut-out area)

In terms of surface area measurement by the BET method, the surface area of the roughened surface and the surface (side surface) other than the surface not subjected to the roughening treatment is also measured. However, the foil thickness estimated in the present invention (for example, even the largest (Also at about 120 μm), the proportion of the side surface in the total plan view area is very small, which can actually be ignored.

As shown in Reference Example 1, there may be cases where the surface area of the BET measurement is smaller than the cut-out area due to the measurement principle of the BET method in the object without roughening the surface (that is, the BET surface area ratio A is less than 1). Happening). On the other hand, when the surface with fine unevenness is formed by the roughening treatment, the BET method is applied, so that the fine unevenness and the like can be detected with high sensitivity. As a result, the BET surface area ratio A exceeds 1.

[Measurement of laser surface area ratio B]

The laser surface area ratio B is calculated based on a surface area measurement value using a laser microscope VK8500 (manufactured by Keyence). In more detail, the roughened surface of the sample (copper foil) was observed at a magnification of 1000 times, and the three-dimensional surface area of the plane viewing area of 6550 μm ^{2 was} measured. The three-dimensional surface area was divided by 6550 μm ² to obtain the laser surface area ratio B . The measurement pitch was set to 0.01 μgm. The results are shown in Table 3.

〔Calculate fine surface coefficient Cms〕

The fine surface coefficient Cms is calculated from the following formula using the BET surface area ratio A and the laser surface area ratio B. The results are shown in Table 3 below.

Fine surface coefficient Cms = BET surface area ratio A / laser surface area ratio B

[Determination of Silicon]

The silicon element content (μg / dm ² ) of the roughened surface was measured by marking the surface of the sample without the roughening plating treatment with a paint, and then cutting out a 10 cm square to heat the mixed acid (nitrate 2) to 80 ° C. : Hydrochloric acid 1: pure water 5 (volume ratio)) After dissolving only the surface portion, the mass of silicon in the obtained solution was measured using an atomic absorption spectrometer (type: Z-2300) manufactured by Hitachi High-Tech Science. Quantitative analysis was performed by atomic absorption spectrometry. The results are shown in Table 3 below in terms of the amount of silicon element.

[Measurement of Lightness Index L ^* ]

Lightness index L ^* color system L ^* a ^* b ^* in the L Table prescribed in JIS-Z8729 ^*. The lightness index L ^* was measured using a UV-visible spectrophotometer V-660 (integrating sphere unit) made by Japan Spectroscopy. In the range of wavelengths from 870 to 200 nm, the total light spectral reflectance of the roughened surface was measured. Based on the obtained spectrum, the brightness index L ^* value was calculated using the software attached to the analyzer. The results are shown in Table 3.

[Evaluation of high-frequency characteristics]

The transmission loss in the high-frequency band was measured as an evaluation of the high-frequency characteristics. The roughened surface (surface treated with a silane coupling agent) of the surface-treated copper foil having a roughened surface prepared in the above-mentioned examples and comparative examples, under a condition of a surface pressure of 3 MPa and 200 ° C paste Combined with polyphenylene ether-based low-dielectric-resistance resin substrate MEGTRON6 (thickness: 50 to 100 μm) made by Panasonic Corporation, a copper-clad laminated board was produced. The obtained laminated board was subjected to circuit processing, and MEGTRON6 was further bonded on top of it to finally form a three-layer copper foil base board. A microstrip line having a width of 100 μm and a length of 40 mm is formed in the transmission path. In this transmission path, a network analyzer is used to transmit high-frequency signals up to 100 GHz, and the transmission loss is measured. The characteristic impedance is 50Ω.

The measured value of the transmission loss is that the smaller the absolute value, the smaller the transmission loss, which means that it has good high-frequency characteristics. Table 4 shows the evaluation results of the transmission loss in 20 GHz and 70 GHz. The evaluation criteria are as follows.

<20GHz transmission loss evaluation standard>

◎: Transmission loss is -6.2dB or more

○: Transmission loss does not reach -6.2dB to -6.5dB or more

×: Transmission loss does not reach -6.5dB

<70GHz Transmission Loss Evaluation Standard>

◎: Transmission loss is -20.6dB or more

○: Transmission loss does not reach -20.6dB to -24.0dB or more

×: less than -24.0dB

Furthermore, based on the evaluation results of the transmission loss described above, the high-frequency characteristics based on the following evaluation criteria are comprehensively evaluated. The results are shown in Table 4 below.

<Standard for Comprehensive Evaluation of High Frequency Characteristics>

◎ (Excellent): The evaluation results of the transmission loss of 20 GHz and the transmission loss of 70 GHz are both ◎.

○ (Good): The evaluation result of the transmission loss at 20 GHz was ◎, and the evaluation result of the transmission loss at 70 GHz was ○.

△ (Passed): Although the evaluation result of the transmission loss at 70 GHz is ×, the transmission loss at 20 GHz is ◎ or ○.

× (Fail): The evaluation results of the transmission loss of 20GHz and the transmission loss of 70GHz are both ×.

[Evaluation of identifiability]

As the evaluation of the discriminability, a haze, that is, a haze value measurement was performed. The roughened surfaces of the samples produced in the examples and comparative examples were used as resin bonding surfaces, and laminated on both sides of a lamination polyimide PIXEO (FRS-522 thickness 12.5 μm) manufactured by KANEKA Co., Ltd. to produce a coating. Copper laminate. With respect to these copper laminated laminates, the copper foils laminated on both sides were etched and removed with a copper chloride solution to produce a sample film for measuring the haze value.

About the produced sample film, the haze value was measured based on the method described in JIS K 7136: 2000 using an integrating sphere unit V-660, which is an ultraviolet-visible spectrophotometer made by Japan Spectroscopy. Calculated using (Td / Tt) × 100 (%) as the haze value. (Tt: total light transmittance, Td: diffuse transmittance).

The haze value indicates the haze of the sample film. The smaller the value is, the lower the haze is, and it is good as the distinguishability. The relevant identifiability was evaluated based on the evaluation criteria described below. The results are shown in Table 4 below.

<Evaluation Criteria for Identifiability>

◎: The haze value is less than 30%

：: The haze value is 30% or more and less than 60%.

△: The haze value is 60% or more and less than 80%.

×: The haze value is 80% or more.

If the identifiability is ◎, ○, or △, it can be said that it has identifiability that is allowable in practical applications.

Evaluation of tightness-1

Adhesion was evaluated by a peel test. A copper-clad laminate was produced in the same manner as the copper-clad laminate produced in the above [Evaluation of High Frequency Characteristics], and the copper foil portion of the obtained copper-clad laminate was marked with a tape having a width of 10 mm. After the copper-clad laminated board was subjected to copper chloride etching, the tape was removed, and a 10 mm wide circuit wiring board was produced. Using a Tensilon tester manufactured by Toyo Seiki Seisakusho Co., Ltd., a circuit wiring portion (copper foil portion) with a width of 10 mm of the circuit wiring board was measured at a speed of 50 mm / min in a 90-degree direction at the time of peeling from the resin substrate. strength. Using the obtained measured value as an index, the adhesion was evaluated based on the following evaluation criteria. In addition, compared with PIXEO resin, MEGTRON6 resin has a greater contribution to the anchoring effect of adhesion. The results are shown in Table 4 below.

<Evaluation Criteria for Adhesion>

○: Peeling strength is 0.6 kN / m or more

△: Peel strength is 0.5 kN / m or more and less than 0.6 kN / m

×: Peel strength is less than 0.5kN / m

Evaluation of tightness -2

A copper-clad laminate was produced in the same manner as the copper-clad laminate produced in the above [Evaluability Evaluation], and the copper foil portion of the obtained copper-clad laminate was marked with a tape having a width of 10 mm. After the copper-clad laminated board was subjected to copper chloride etching, the tape was removed, and a 10 mm wide circuit wiring board was produced. Using a Tensilon tester manufactured by Toyo Seiki Seisakusho Co., Ltd., a circuit wiring portion (copper foil portion) with a width of 10 mm of the circuit wiring board was measured at a speed of 50 mm / min in a 90-degree direction at the time of peeling from the resin substrate. strength. Using the obtained measured value as an index, the adhesion was evaluated based on the following evaluation criteria. The results are shown in Table 4 below.

<Evaluation Criteria for Adhesion>

○: peeling strength is 1 kN / m or more,

×: Peel strength is less than 1kN / m

Furthermore, based on the above-mentioned evaluation results of the tightness, the tightness based on the following evaluation criteria is comprehensively evaluated. The results are shown in Table 4 below.

<Comprehensive Evaluation Criteria for Adhesion>

((Excellent): Both of the above [adhesion evaluation-1] and [adhesion evaluation-2] evaluation results were ○.

○ (Pass): The two evaluation results of the above [adhesion evaluation-1] evaluation result were △, and the adhesion evaluation-2] were ○.

× (Failure): At least one of the above two evaluation results of [Adhesiveness Evaluation-1] and [Adhesiveness Evaluation-2] was evaluated as ×.

〔Comprehensive Evaluation〕

Comprehensive information on the above-mentioned high-frequency characteristics, identifiability and tightness is comprehensively evaluated based on the following evaluation criteria.

<Evaluation Criteria for Comprehensive Evaluation>

A (Excellent): The comprehensive evaluation results of high-frequency characteristics, the evaluation of identifiability, and the comprehensive evaluation of tightness are all ◎.

B: (Pass): Although the above-mentioned A was not satisfied, there was no × in the comprehensive evaluation results of the high-frequency characteristics, the evaluation of the identifiability, and the comprehensive evaluation of the tightness.

C (Fail): At least one of the comprehensive evaluation results of high-frequency characteristics, the evaluation of identifiability, and the comprehensive evaluation of tightness is ×.

Here, the results shown in the above tables will be discussed.

As shown in Comparative Example 1, the average height of the roughened particles existing on the roughened surface of the surface-treated copper foil is smaller than that specified in the present invention. When the copper-clad laminated board was produced using the surface-treated copper foil of Comparative Example 1, the heat-resistant adhesiveness between the copper foil and the resin substrate deteriorated.

As shown in Comparative Examples 2, 3, and 7, the BET surface area ratio and Cms of the roughened surface of the surface-treated copper foil were all smaller than those specified in the present invention. When the copper-clad laminated board was produced using the surface-treated copper foils of Comparative Examples 2, 3, and 7, the heat-resistant adhesiveness between the copper foil and the resin substrate deteriorated.

As shown in Comparative Examples 4 and 5, the average heights of the roughened particles existing on the roughened surface of the surface-treated copper foil were larger than those specified in the present invention. When the surface-treated copper foils of Comparative Examples 4 and 5 were used to produce a copper-clad laminated board and a conductor circuit was formed, both the high-frequency characteristics and the discernability were significantly deteriorated.

Comparative Example 6 shows an example in which Cms is smaller than that specified in the present invention. When the surface-treated copper foil of Comparative Example 6 was used to produce a copper-clad laminated board, the MEGTRON6 resin, which contributes a large amount to the anchoring effect of the adhesion, had a deterioration in adhesion.

In addition, Reference Example 1 is an example in which the copper foil is not subjected to a roughening treatment, a metal treatment layer is not further formed, and a silane coupling agent layer treatment is not performed. When the copper-clad laminated board was produced using the copper foil of Reference Example 1, the result was that the adhesion between the copper foil and the resin substrate was significantly deteriorated.

In comparison, the average height of the roughened particles that have been formed on the roughened surface of the surface-treated copper foil is within the range specified in the present invention, and the BET surface area ratio of the roughened surface and Cms also satisfy In the surface-treated copper foils of Examples 1 to 8 specified in the present invention, when the surface-treated copper foil is used to produce a copper-clad laminated board, the copper foil and the resin substrate exhibit excellent adhesion. In addition, the guide formed by the copper clad laminated board using the surface-treated copper foils of Examples 1 to 8 was used. The body circuit can effectively suppress transmission loss even when transmitting high-frequency signals. Furthermore, the resin substrates laminated with the surface-treated copper foils of Examples 1 to 8 will be presented after the copper foils are removed by etching. Out of the distinguishability.

This application claims the priority of Patent Application No. 2015-240007, filed in Japan on December 9, 2015, and the contents of this specification are hereby incorporated by reference with reference to this priority.

Claims (8)

A surface-treated copper foil for a printed wiring board, comprising a silane coupling agent layer on a surface on which roughened particles are formed, characterized in that the average height of the roughened particles on the surface of the silane coupling agent layer is 0.05 μm or more and When the thickness is less than 0.5 μm, the BET surface area ratio of the surface of the silane coupling agent layer is 1.2 or more, and the fine surface coefficient Cms is 2.0 or more and less than 8.0. For example, the surface-treated copper foil for a printed wiring board of the scope of application for a patent, wherein the average height of the roughened particles on the surface of the silane coupling agent layer is 0.05 μm or more and less than 0.3 μm. The scope of the patent or the printed wiring board 2 of surface treated copper foil 1, wherein the L ^* a ^* b in the surface layer of the silane-coupling agent ^* color system of L ^* is 40 or more and less than 60. For example, the surface-treated copper foil for a printed wiring board for which the scope of patent application is item 1 or 2, wherein the surface on which the roughened particles are formed is provided with a material selected from the group consisting of chromium (Cr), iron (Fe), cobalt (Co), A metal treatment layer of at least one metal selected from the group consisting of nickel (Ni), copper (Cu), zinc (Zn), molybdenum (Mo), and tin (Sn), or a metal treatment layer having a material selected from the group consisting of chromium, iron, cobalt, nickel, and copper A metal-treated layer of an alloy formed of at least two or more metals of zinc, molybdenum, and tin. For example, the surface-treated copper foil for a printed wiring board according to the first or second application scope of the patent, wherein the amount of the silicon element contained in the silane coupling agent layer is 0.5 μg / dm ² or more and less than 15 μg / dm ² . For example, the surface-treated copper foil for a printed wiring board according to item 1 or 2 of the patent application scope, wherein the silane coupling agent has a material selected from the group consisting of epoxy, amino, vinyl, (meth) acrylfluorenyl, styryl, At least one of a ureido group, an isocyanurate group, a mercapto group, a sulfide group, and an isocyanate group. A copper-clad laminated board for a printed wiring board is a resin layer on the surface area of the silane coupling agent layer of the surface-treated copper foil for a printed wiring board according to any one of claims 1 to 6. A printed wiring board using a copper-clad laminated board for a printed wiring board according to item 7 of the patent application.