JP6854114B2 - Surface-treated copper foil - Google Patents

Description

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

The printed wiring board is formed by adhering an insulating base material to copper and a copper alloy foil (hereinafter referred to as "copper foil") to form a copper-clad laminate, and then etching to form a conductor pattern on the copper foil surface. It is generally manufactured after that. Then, a printed circuit board is manufactured by connecting and mounting electronic components on the printed wiring board with solder or the like.

One of the characteristics required for copper foil for printed wiring boards is that it has good adhesion to the insulating base material, and various technologies have been used so far, centering on the copper foil surface roughening treatment technology. It has been developed (for example, WO2011 / 138876, JP-A-2011-16887).

On the other hand, it is also known that the adhesion to the insulating base material is improved by treating the surface of the copper foil with a silane coupling agent (for example, JP-A-2011-16887, JP-A-2008-118163). Gazette). Furthermore, assuming that the N concentration and Si concentration on the copper foil surface have a significant effect on the adhesion to the insulating base material, the N concentration and Si concentration can be adjusted by treating the copper foil surface with a silane coupling agent having a predetermined concentration. Controlled techniques are also known (eg, WO2013 / 147116).

WO2011 / 138876 JP-A-2011-16887 Japanese Unexamined Patent Publication No. 2008-118163 WO2013 / 147116

The technique of controlling the N concentration and the Si concentration of the copper foil surface described in WO2013 / 147116 is an effective technique for improving the adhesion to the insulating base material. On the other hand, as described above, in the manufacturing process of the printed circuit board, the electronic components are often mounted by solder, and the copper foil and the insulating base material are also subjected to a heat load during the solder reflow. Recently, resistance of 300 ° C. or higher is required for reliability against a high temperature heat load due to solder reflow. However, the copper-clad laminates that have been surface-treated with a silane coupling agent as described in WO2013 / 147116 can obtain good adhesion, but are copper-clad laminates due to the heat load of solder reflow of 300 ° C. or higher. It was found that blister (swelling) is likely to occur in the solder. Copper-clad laminates, which are prone to blisters due to heat load, are prone to circuit deformation and peeling when mounting electronic components. Therefore, in addition to good adhesion at room temperature, it would be advantageous to provide a copper-clad laminate in which the generation of blisters is suppressed during a heat load.

The present invention was created in view of the above circumstances, has excellent adhesion to an insulating substrate at room temperature, and generates blister when a copper-clad laminate is formed and a heat load of solder reflow is applied. One of the issues is to provide a surface-treated copper foil that can be suppressed. Another object of the present invention is to provide a copper-clad laminate provided with such a surface-treated copper foil.

As a result of diligent studies to solve the above problems, the present inventors control the concentrations of N and Si in the XPS surveillance measurement of the surface of the surface-treated copper foil in WO2013 / 147116, but suppress the blister during heating. It has been found that it is important to control the combination of N concentration, C concentration, or Si and O concentration in the depth direction of the surface of the surface-treated copper foil.

The present invention is a surface-treated copper foil having a surface-treated surface on one side, and N by XPS measurement at a depth of 0.5 _{min after sputtering at a rate of 1.1 nm / min (SiO 2 conversion) from the surface-treated surface.} A surface-treated copper foil having a concentration of 1.5 to 7.5 atom%.

In another aspect, the present invention is a surface-treated copper foil having a surface-treated surface, and XPS measurement at a depth of 0.5 _{min after sputtering at a rate of 1.1 nm / min (SiO 2 conversion) from the surface-treated surface.} This is a surface-treated copper foil having a C concentration of 12 to 30 atom%.

In yet another aspect, the present invention is a surface-treated copper foil having a surface-treated surface, and XPS at a depth of 0.5 _{min after sputtering at a rate of 1.1 nm / min (SiO 2 conversion) from the surface-treated surface.} A surface-treated copper foil having a measured Si concentration of 3.1 atom% or more and an O concentration of 40 to 48 atom%.

In yet another aspect, the present invention is a surface-treated copper foil having a surface-treated surface, which satisfies any one or more of the following conditions.
-The N concentration measured by XPS at the depth after 0.5 min sputtering under the condition of 1.1 nm / min (SiO _{2 conversion) from the surface treated surface is 1.5 to 7.5 atom%;}
-The C concentration by XPS measurement at the depth after 0.5 min sputtering under the condition of 1.1 nm / min (SiO _{2 conversion) from the surface treated surface is 12 to 30 atom%;}
-Si concentration by XPS measurement at a depth after 0.5 min sputtering under the condition of rate 1.1 nm / min (SiO ₂ conversion) from the surface treated surface is 3.1 atom% or more, and O concentration is 40 to 48 atom%. Is.

In one embodiment, the surface-treated copper foil according to the present invention has an N concentration of 0.5 to 0.5 by XPS measurement at a depth of 1.0 _{min after sputtering at a rate of 1.1 nm / min (SiO 2 conversion) from the surface-treated surface.} It is 6.0 atom%.

In another embodiment, the surface-treated copper foil according to the present invention has a C concentration of 8 to 8 to a depth measured by XPS at a depth of 1.0 _{min after sputtering at a rate of 1.1 nm / min (SiO 2 conversion) from the surface-treated surface.} It is 25 atom%.

In still another embodiment, the surface-treated copper foil according to the present invention has an Rz of 1.5 μm or less on the surface-treated surface.

In still another embodiment, the surface-treated copper foil according to the present invention is a rolled copper foil or an electrolytic copper foil.

In yet another embodiment, the surface-treated copper foil according to the present invention is for bonding with a liquid crystal polymer.

In still another embodiment, the surface-treated copper foil according to the present invention is for bonding with a polyimide resin.

In yet another embodiment, the surface-treated copper foil according to the present invention is used for a printed circuit board used at a high frequency exceeding 1 GHz.

In still another embodiment, the surface-treated copper foil according to the present invention is selected from the group consisting of a roughening treatment layer, a heat-resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the copper foil. It has one or more layers.

In still another embodiment, the surface-treated copper foil according to the present invention is one or more selected from the group consisting of a heat-resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the copper foil. Has a layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a heat-resistant treatment layer or a rust-preventive treatment layer on the surface of the copper foil, and has a chromate-treatment layer on the heat-resistant treatment layer or the rust prevention treatment layer. Then, a silane coupling treatment layer is provided on the chromate treatment layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a heat-resistant treatment layer on the surface of the copper foil, has a rust-preventive treatment layer on the heat-resistant treatment layer, and is on the rust-preventive treatment layer. Has a chromate-treated layer, and has a silane coupling-treated layer on the chromate-treated layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a chromate-treated layer on the surface of the copper foil and a silane coupling-treated layer on the chromate-treated layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a roughening-treated layer on the surface of the copper foil, a chromate-treated layer on the roughening-treated layer, and a chromate-treated layer on the chromate-treated layer. Has a silane coupling treatment layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a roughening-treated layer on the surface of the copper foil, and is selected from the group consisting of a rust-preventive treatment layer and a heat-resistant treatment layer on the roughening treatment layer. It has one or more layers to be coated, has a chromate-treated layer on one or more layers selected from the group consisting of the rust-preventive treatment layer and the heat-resistant treatment layer, and has a silane on the chromate-treated layer. It has a coupling treatment layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a roughening-treated layer on the surface of the copper foil, a rust-preventive treatment layer on the roughening-treated layer, and the rust-preventive treatment layer. A chromate-treated layer is provided on the top, and a silane coupling-treated layer is provided on the chromate-treated layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a roughening-treated layer on the surface of the copper foil and a silane coupling-treated layer on the roughening-treated layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a silane coupling-treated layer on the surface of the copper foil.

In still another embodiment, the surface-treated copper foil according to the present invention has a roughening-treated layer on the surface of the copper foil, and the roughening-treated layer is a primary particle layer and a secondary particle layer on the primary particle layer. It has a particle layer.

In still another embodiment, the surface-treated copper foil according to the present invention has the secondary particle layer formed of a ternary alloy composed of copper, cobalt and nickel.

In still another embodiment, the surface-treated copper foil according to the present invention has an average particle size of 0.25 to 0.45 μm of the primary particle layer and an average particle size of 0.05 to 0.45 μm of the secondary particle layer. It is 0.25 μm.

In yet another aspect, the present invention is a copper foil laminated plate obtained by laminating the surface-treated surface of the surface-treated copper foil according to the present invention with an insulating base material.

In yet another aspect, the present invention is a printed wiring board using the surface-treated copper foil according to the present invention.

In yet another aspect, the present invention is an electronic device using a printed wiring board according to the present invention.

According to the present invention, it is possible to provide a surface-treated copper foil having excellent adhesion to an insulating substrate at room temperature and capable of suppressing the generation of blisters when a copper-clad laminate is formed and a heat load is applied. it can. Therefore, deformation and peeling of the circuit are suppressed by the heat generated when the electronic component is mounted on the printed wiring board by soldering, which contributes to the production of the printed circuit board with high quality reliability.

In one embodiment of the present invention, the depth after 0.5 min sputtering from the surface treated surface of the surface treated copper foil under the _{condition of a rate of 1.1 nm / min (SiO 2} conversion) (hereinafter, “0.5 min sputtering depth””. It controls at least one selected from the combination of N atomic concentration, C atomic concentration, and Si and O atomic concentrations measured by XPS in (). According to the results of the study by the present inventor, it is possible to control at least one selected from a combination of N atomic concentration, C atomic concentration, and Si and O atomic concentrations at a sputtering depth of 0.5 min at room temperature. It has excellent adhesion to the insulating substrate, and is effective in suppressing the generation of blister when a copper-clad laminate is formed and a heat load is applied.

The N concentration measured by XPS at a sputtering depth of 0.5 min is preferably 1.5 atom% or more, more preferably 3.7 atom% or more, from the viewpoint of increasing the adhesion strength with the insulating base material. Even more preferably, it is 0.0 atom% or more. Further, the N concentration measured by XPS at the above depth is preferably 7.5 atom% or less, more preferably 6.7 atom% or less, and 6.6 atom% or less from the viewpoint of suppressing the generation of blisters. Is even more preferable.

Further, the C concentration measured by XPS at a sputtering depth of 0.5 min is preferably 12 atom% or more, more preferably 18 atom% or more, and 21.6 atom from the viewpoint of increasing the adhesion strength with the insulating base material. % Or more is even more preferable. Further, the C concentration measured by XPS at the above depth is preferably 30 atom% or less, more preferably 28.6 atom% or less, and 23.8 atom% or less from the viewpoint of suppressing the generation of blisters. Is even more preferable.

Further, the combination of Si and O concentrations measured by XPS at a sputtering depth of 0.5 min is preferably Si: 3.1 atom% or more and O: 40 atom% or more from the viewpoint of increasing the adhesion strength with the insulating base material. , Si: 4.3 tom% or more, O: 43.4 atom% or more, and even more preferably Si: 5.8 atom% or more, O: 44.6 atom% or more. Further, the combination of Si and O concentrations measured by XPS at the above depth is preferably Si: 12.6 atom% or less, O: 48 atom% or less, and Si: 12.4 atom from the viewpoint of suppressing the generation of blisters. % Or less, O: 47 atom% or less, and even more preferably Si: 11.9 tom% or less, O: 46.4 atom% or less.

When at least one combination of N-atom concentration, C-atom concentration, and Si and O atomic concentrations measured by XPS at a sputter depth of 0.5 min satisfies the above concentration conditions, the adhesion strength with the insulating substrate is increased. Although it can be improved and the occurrence of blister can be significantly suppressed, it is preferable that two or more of these three types of concentration requirements are satisfied, and all three types of concentration requirements are satisfied. More preferred.

In a preferred embodiment of the present invention, the depth after 1.0 min sputtering from the surface treated surface of the surface treated copper foil under the _{condition of a rate of 1.1 nm / min (SiO 2} conversion) (hereinafter, “1.0 min sputtering depth”). At least one selected from the atomic concentrations of N and C by XPS measurement in) is controlled. According to the results of the study by the present inventor, in addition to the 0.5 min sputtering depth, at least one selected from the atomic concentrations of N and C at the 1.0 min sputtering depth, preferably both, is controlled at room temperature. It is excellent in adhesion to the insulating substrate in the above, and is more effective in suppressing the generation of blister when a copper-clad laminate is formed and a heat load is applied.

The N concentration measured by XPS at a sputtering depth of 1.0 min is preferably 0.5 atom% or more, more preferably 1.0 atom% or more, from the viewpoint of increasing the adhesion strength with the insulating base material. It is even more preferable that the content is 0.8 atom% or more. Further, the N concentration measured by XPS at the above depth is preferably 6.0 atom% or less, more preferably 4.7 atom% or less, and 4.2 atom% or less from the viewpoint of suppressing the generation of blisters. Is even more preferable.

Further, the C concentration measured by XPS at a sputtering depth of 1.0 min is preferably 8 atom% or more, more preferably 16.8 atom% or more, and more preferably 16.8 atom% or more, from the viewpoint of increasing the adhesion strength with the insulating base material. It is even more preferable that the content is 4 atom% or more. Further, the C concentration measured by XPS at the above depth is preferably 25 atom% or less, more preferably 21.3 atom% or less, and 20.7 atom% or less from the viewpoint of suppressing the generation of blisters. Is even more preferable.

The atomic concentration of each element at the above depth by XPS measurement can be measured by performing XPS depth direction analysis on the surface-treated surface of the surface-treated copper foil.
In the examples, the analysis was performed under the following conditions.
Equipment: 5600MC manufactured by ULVAC PHI Co., Ltd.
Ultimate vacuum: 5.7 x 10 ^-7 Pa
Excitation source: Monochromatic MgKα
Output: 400W
Detection area: 800 μmφ
Incident angle: 81 ° degree Extraction angle: 45 ° degree No neutralizing gun <Sputtering conditions>
Ion species: Ar +
Acceleration voltage: 1kV
Sweep area: 3mm x 3mm
Rate: 1.1 nm / min (SiO ₂ conversion)

In the present invention, the atomic concentrations of N, C, Si and O in the XPS measurement are measured for N1s, O1s, C1s, Si2s, Cr2p ³ , Zn2p ³ , Cu2p ³ , Ni2p ³ and Co2p ³ , and the total mole fraction thereof. It is given as the mole fraction of each of N1s, C1s, Si2s and O1s when the number is 100%.

As one means for forming a surface-treated surface in which the combination of N concentration, C concentration, and Si and O concentration is controlled in the above range, a method of treating the copper foil surface with a silane coupling agent can be mentioned. When treating the copper foil surface with a silane coupling agent, it is important to appropriately select the type of silane coupling agent, the concentration of the silane coupling agent in water, and the stirring time.

The silane coupling agent is not particularly limited, but aminosilane containing N and Si in the molecule can be preferably used. As the aminosilane, a silane containing one or more amino groups or imino groups can be used. The number of amino groups or imino groups contained in aminosilane can be, for example, 1 to 4, preferably 1 to 3, and more preferably 1 to 2, respectively. In a preferred embodiment, the number of amino groups and / or imino groups contained in aminosilane can be one each.

Aminosilane having a total number of amino groups and imino groups contained in aminosilane of 1 can be referred to as monoaminosilane in particular, aminosilane having 2 can be referred to as diaminosilane, and aminosilane having 3 can be referred to as triaminosilane. .. Monoaminosilane and diaminosilane can be suitably used in the present invention. In a preferred embodiment, a monoaminosilane containing one amino group can be used as the aminosilane. In a preferred embodiment, the aminosilane can contain at least one, eg, one amino group, at the end of the molecule, preferably at the end of a linear or branched chain molecule.

Examples of aminosilanes include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 1-. Aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, 1,2-diaminopropyltrimethoxysilane, 3-amino-1-propenyltrimethoxysilane, 3-amino-1-propynyltrimethoxysilane, 3- Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane can be mentioned.

Further, in a preferred embodiment, a silane coupling agent having the following structural formula I can be used.
H ₂ N-R ^1- Si (OR ² ) ₂ (R ³ ) (Formula I)
(However, in the above formula I,
R ¹ has linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic or heterocyclic, C _{1 to} C ₁₂ It is a divalent group of hydrocarbons and
R ² is an alkyl group of _{C 1 to} C _{5 and}
R ³ is an alkyl group of C ₁ -C _5, or an alkoxy group of C ₁ -C _5. )

R ¹ is a substituted or unsubstituted _{divalent group of linear saturated hydrocarbons C 1 to} C ₁₂ , a substituted or unsubstituted divalent group of branched saturated hydrocarbons _{C 1 to} C _12, substituted or unsubstituted, straight-chain unsaturated hydrocarbon divalent radical of hydrogen C ₁ -C _12, a substituted or unsubstituted, branched unsaturated hydrocarbon divalent radical of hydrogen C ₁ -C _12, substituted or Unsubstituted, _{divalent groups of C 1 to} C ₁₂ cyclic hydrocarbons, substituted or unsubstituted, C _{1 to} C ₁₂ heterocyclic hydrocarbon divalent groups, substituted or unsubstituted, C ₁ to It is preferably a group selected from the group consisting of divalent groups of C _{12 aromatic hydrocarbons.}

R ¹ is − (CH ₂ ) _n −, − (CH ₂ ) _n − (CH) _m − (CH ₂ ) _j-1 −, − (CH ₂ ) _n − (CC) − (CH ₂ ) _{n- 1} −, − (CH ₂ ) _n −NH − (CH ₂ ) _m −, − (CH ₂ ) _n −NH − (CH ₂ ) _m −NH − (CH ₂ ) _j −, − (CH ₂ ) _{n- 1} − (CH) NH ₂ − (CH ₂ ) _m-1 −, − (CH ₂ ) _n-1 − (CH) NH ₂ − (CH ₂ ) _m-1 − NH − (CH ₂ ) _j − It is preferably a group selected from the group (where n, m, j are integers greater than or equal to 1).
It is more preferable that R ¹ is − (CH ₂ ) _n − or − (CH ₂ ) _n −NH − (CH ₂ ) _{m −.}
It is preferable that n, m, and j are 1, 2, or 3 independently of each other.
R ² is preferably a methyl group or an ethyl group.
R ³ is preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group.

The concentration of the silane coupling agent in water is higher than usual (for example, 1.0 vol% or more), and it is important to perform the silane coupling treatment in order to obtain high adhesion to the insulating base material, but it is high. Note that if it is too much, the N, C or O concentration will be excessive and it will be difficult to suppress the blister. Illustratively, the concentration of the silane coupling agent in water can be 1.5 to 6 vol%, preferably 2.0 to 4.0 vol%.

Since the silane coupling agent can be provided as an aqueous solution by mixing silane and water, it is important to appropriately set the stirring time when mixing the two according to the type and concentration of the silane coupling agent. is there. Since the optimum stirring time varies depending on the type and concentration of the silane coupling agent, it is difficult to generalize and discuss it, but as a guide, it can be selected in the range of 1 to 24 hours. When the stirring time is short, such as less than 0.5 hours, the hydrolysis of the silane coupling agent does not proceed sufficiently, so that in Si (OR ² ) ₂ (R ³ ) represented by the above formula (I), If OR ² or R ³ is not sufficiently substituted with an OH group (hydroxyl group), the expected adhesion may not be obtained. In this case, a large amount of _{C 1 to} C ₅ alkyl groups corresponding to ^{R 2} or R ^{3 remains in the silane coupling layer.} If an optimum amount or more of the silane coupling agent is used in order to further increase the adhesion, not only the C concentration but also the N concentration and the O concentration will increase. The preferable stirring time is 2 hours or more, the more preferable stirring time is 5 hours or more, and the more preferable stirring time is 12 hours or more. Stirring for a long time makes it susceptible to fluctuations in pH and temperature, and amino groups containing N and hydroxyl groups containing O form hydrogen bonds between the silane coupling agents, and between the assumed metal and resin. Does not have the cross-linked structure of. Furthermore, since amino groups and hydroxyl groups are easily affected by pH, the silane coupling agent may be altered. In such a case, it becomes difficult to use industrially.
As the stirring time, when the total number of amino groups and imino groups in the silane coupling agent is large, the stirring time is short, and when the total number is small, the stirring time is long. It is easy to meet the surface density condition. Further, when the concentration of the silane coupling agent in water is high, the stirring time is short, and when the concentration is low, the stirring time is long, so that the above-mentioned concentration condition of the surface-treated surface according to the present invention can be easily satisfied.

The surface treatment method of the copper foil with the silane coupling agent may be any of spray spraying of an aqueous solution of the silane coupling agent, coating with a coater, dipping, pouring and the like. Further, after the silane coupling treatment, it is necessary not to raise the drying temperature too high and not to make the drying time too long. This is because if the drying temperature is set too high or the drying time is set too long, the silane coupling agent present on the surface of the copper foil may be decomposed. Illustratively, the drying temperature can be 70 to 150 ° C. and the drying time can be 1 second to 10 minutes.

The type of copper foil (raw foil) to be surface-treated is not particularly limited, but rolled copper foil and electrolytic copper foil can be preferably used. The copper foil includes a pure copper foil and a copper alloy foil, and can have any composition known for circuit forming applications. The copper foil to be surface-treated may be an ultra-thin copper layer of a copper foil with a carrier having a carrier, a release layer, and an ultra-thin copper layer in this order, and the copper foil to be surface-treated is a carrier. May have. Any kind of carrier-attached copper foil or carrier may be used for the above-mentioned carrier-attached copper foil or carrier, and known carrier-attached copper foil or carrier can be used.

Further, in the present invention, since the adhesion to the insulating base material is improved by controlling one or more combinations of N concentration, C concentration, and Si and O concentration on the surface-treated surface, the insulating group is used. There is little need to increase the surface roughness in order to improve the adhesion with the material. Therefore, the conductor loss can be reduced by reducing the surface roughness of the surface-treated surface of the surface-treated copper foil while ensuring the adhesion to the insulating base material. The low conductor loss is advantageous for application to printed circuit boards such as those used at high frequencies above 1 GHz. Specifically, the surface roughness of the surface-treated surface is that the ten-point average roughness Rz is 1.5 μm or less when measured using a stylus type roughness meter in accordance with JIS B0601-1982. Is more preferable, 1.2 μm or less is more preferable, 1.0 μm or less is even more preferable, and for example, it can be 0.2 to 1.5 μm.

As another means for forming a surface-treated surface in which the combination of N concentration, C concentration, and Si and O concentration is controlled in the above range, N is applied to the surface of the copper foil by dry plating such as sputtering, CVD, and PVD. , C, Si and O are attached, and then the temperature and time are appropriately set for heating. The N, C, Si and O concentrations of the surface-treated surface can be controlled by adjusting the heating conditions.

In one embodiment, the surface-treated copper foil according to the present invention is one selected from the group consisting of a roughening treatment layer, a heat-resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the copper foil. It can have the above layers. Further, in one embodiment, the surface-treated copper foil according to the present invention is one or more layers selected from the group consisting of a heat-resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the copper foil. Can have.

The roughening treatment layer is not particularly limited, and any roughening treatment layer or a known roughening treatment layer can be applied. The heat-resistant treatment layer is not particularly limited, and any heat-resistant treatment layer or a known heat-resistant treatment layer can be applied. The rust preventive treatment layer is not particularly limited, and any rust preventive treatment layer or a known rust preventive treatment layer can be applied. The plating-treated layer is not particularly limited, and any plating-treated layer or a known plating-treated layer can be applied. The chromate-treated layer is not particularly limited, and any chromate-treated layer or a known chromate-treated layer can be applied.

In one embodiment of the surface-treated copper foil according to the present invention, a roughening-treated layer is provided on the surface of the copper foil by, for example, roughening treatment for improving adhesion with an insulating substrate. May be good. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening treatment may be fine. The roughened layer is a layer made of any simple substance selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc, or an alloy containing any one or more of them. May be good. Further, after forming the roughened particles with copper or a copper alloy, it is also possible to carry out a roughening treatment in which secondary particles or tertiary particles are further provided with a simple substance or alloy of nickel, cobalt, copper or zinc. In particular, a roughened treatment layer in which a primary particle layer of copper and a secondary particle layer made of a ternary alloy composed of copper, cobalt and nickel is formed on the primary particle layer is preferable. It is more preferable that the average particle size of the primary particle layer is 0.25 to 0.45 μm, and the average particle size of the secondary particle layer is 0.05 to 0.25 μm.

In one embodiment of the surface-treated copper foil according to the present invention, a heat-resistant treatment layer or a rust-prevention treatment layer may be formed from a simple substance or alloy of nickel, cobalt, copper, zinc, or the like after the roughening treatment. The surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Alternatively, a heat-resistant treatment layer or a rust-preventive treatment layer is formed from a simple substance or alloy of nickel, cobalt, copper, zinc, etc. without roughening treatment, and the surface thereof is further subjected to treatment such as chromate treatment and silane coupling treatment. You may.

That is, one or more layers selected from the group consisting of a heat resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer, and the copper foil surface may be formed. In addition, one or more layers selected from the group consisting of a heat-resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer and a silane coupling treatment layer may be formed. The heat-resistant layer, the rust-preventive treatment layer, the chromate treatment layer, and the silane coupling treatment layer may each be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.). In the present invention, the "rust preventive treatment layer" includes a "chromate treatment layer". Considering the adhesion to the resin, it is preferable to provide a silane coupling-treated layer on the outermost layer of the surface-treated copper foil.

The following treatments can be used as the rust preventive treatment or the chromate treatment.
<Ni plating>
(Liquid composition) Ni ion: 10-40 g / L
(PH) 1.0-5.0
(Liquid temperature) 30-70 ° C
(Current density) 1-9A / dm ²
(Energizing time) 0.1 to 3 seconds

<Ni-Co plating>: Ni-Co alloy plating (liquid composition) Co: 1 to 20 g / L, Ni: 1 to 20 g / L
(PH) 1.5-3.5
(Liquid temperature) 30-80 ° C
(Current density) 1 to 20 A / dm ²
(Energizing time) 0.5-4 seconds

<Zn-Ni plating>: Zn-Ni alloy plating (liquid composition) Zn: 10 to 30 g / L, Ni: 1 to 1 to 10 g / L
(PH) 3-4
(Liquid temperature) 40-50 ° C
(Current density) 0.5 to 5 A / dm ²
(Energizing time) 1-3 seconds

<Ni-Mo plating>: Ni-Mo alloy plating (liquid composition) Nickel sulfate: 270 to 280 g / L, nickel chloride: 35 to 45 g / L, nickel acetate: 10 to 20 g / L, molybdate (added as sodium molybdate) ): 0.1 to 10 g / L, trisodium citrate: 15-25 g / L, brightener: saccharin, butinediol, etc., sodium dodecyl sulfate: 55 to 75 ppm
(PH) 4-6
(Liquid temperature) 55-65 ° C
(Current density) 1 to 11 A / dm ²
(Energizing time) 1 to 20 seconds

<Cu-Zn plating>: Cu-Zn alloy plating (liquid composition) NaCl: 10 to 30 g / L, NaOH: 40 to 100 g / L, Cu: 60 to 120 g / L, Zn: 1 to 10 g / L
(Liquid temperature) 60-80 ° C
(Current density) 1 to 10 A / dm ²
(Energizing time) 1 to 10 seconds

<Electrolytic chromate>
(Liquid composition) Chromic anhydride, chromic acid, or potassium dichromate: 1-10 g / L, zinc (added in the form of zinc sulfate if added): 0-5 g / L
(PH) 0.5-10
(Liquid temperature) 40-60 ° C
(Current density) 0.1 to 2.6 A / dm ²
(Amount of coulomb) 0.5 to 90 As / dm ²
(Energizing time) 1 to 30 seconds

<Immersion chromate>
(Liquid composition) Chromic anhydride, chromic acid, or potassium dichromate: 1-10 g / L, zinc (added in the form of zinc sulfate if added): 0-5 g / L
(PH) 2-10
(Liquid temperature) 20-60 ° C
(Processing time) 1 to 30 seconds

A copper foil laminated plate can be formed by laminating the surface-treated surface of the surface-treated copper foil according to the present invention with an insulating base material. A single-layer copper-clad laminate having a single-layer insulating base material may be used, or a multi-layer copper-clad laminate having two or more layers of an insulating base material may be used. The copper foil laminate can be either flexible or rigid. The insulating base material is not particularly limited, but is an epoxy resin, a phenol resin, a polyimide resin, a polyimideamide resin, a polyester resin, a polyphenylene sulfide resin, a polyetherimide resin, a fluororesin, a liquid crystal polymer (LCP), and a mixture thereof. The ones that have been made can be mentioned. In addition, an insulating base material obtained by impregnating a glass cloth with an epoxy resin, a bismaredo triazine resin, a polyimide resin, or the like can be mentioned. In particular, the liquid crystal polymer has the great advantages of low dielectric constant, low dielectric loss tangent, low water absorption, little change in electrical characteristics, and little change in dimensions, and is suitable for high frequency applications.

The surface-treated copper foil according to the present invention is particularly useful as a copper foil for a flexible printed circuit board (FPC) in which a copper foil is laminated on a liquid crystal polymer. Among the insulating base materials, the liquid crystal polymer has a weak strength, and the material in which the copper foil is laminated has a big problem that the peel strength is hard to be obtained. When the roughness of the copper foil surface is increased, the peel strength tends to be increased because a physical anchor effect is obtained, but the electric characteristics at high frequencies are deteriorated due to the influence of the above-mentioned skin effect. However, according to one embodiment of the surface-treated copper foil according to the present invention, the adhesion to the insulating base material can be ensured even if the surface roughness is small, so that the above-mentioned advantages of the liquid crystal polymer can be utilized. You can.

A printed wiring board can be manufactured using a copper-clad laminate. The processing method from the copper-clad laminate to the printed wiring board is not particularly limited, and a known etching processing process may be used. A printed circuit board can also be manufactured by mounting various electronic components on a printed wiring board. Further, the printed circuit board can be mounted on various electronic devices.

Hereinafter, the present invention will be described with reference to Examples. It should be noted that this example shows a suitable example, and the present invention is not limited to these examples. Therefore, all modifications, other examples or embodiments included in the technical idea of the present invention are included in the present invention. A comparative example is also described for comparison with the present invention. Further, the rest of the liquid used for the roughening treatment, plating, silane coupling treatment, heat resistance treatment, rust prevention treatment, etc. described in the experimental examples of the present application was also water unless otherwise specified.

(Examples 1, 4 to 6 and Comparative Examples 1, 3, 4)
A rolled copper foil having a thickness of 12 μm (Tough pitch copper manufactured by JX Nippon Mining & Metals Co., Ltd. (JIS H3100 alloy number C1100)) was prepared. After the surface of the rolled copper foil is electrolytically degreased, washed with water, and pickled, a treatment of providing primary copper particles on the surface of the rolled copper foil is performed, and then a treatment of providing secondary particles is performed to roughen the surface. Processing was performed. The detailed conditions for the roughening process are as follows.

<Roughening treatment conditions>
(Plating conditions for primary copper particles)
Liquid composition: copper 10 g / L, sulfuric acid 50 g / L
Liquid temperature: 26 ° C
Current density: 50A / dm ²
Plating time: 1.5 seconds

(Plating conditions for secondary particles)
Liquid composition: Copper 16 g / L, Nickel 9 g / L, Cobalt 8 g / L
pH: 2.4
Liquid temperature: 35 ° C
Current density: 25A / dm ²
Plating time: 1.5 seconds

After the above roughening treatment, Ni—Co alloy plating (heat-resistant rust-preventive treatment) and chromate treatment were performed in this order.
<Ni-Co plating>: Ni-Co alloy plating (liquid composition) Co: 4 g / L, Ni: 12 g / L
(PH) 2.3
(Liquid temperature) 50 ° C
(Current density) 12A / dm ²
(Energizing time) 0.8 seconds

<Electrolytic chromate>
(Liquid composition) Potassium dichromate: 4 g / L, Zinc (added in the form of zinc sulfate): 0.5 g / L
(PH) 3.5
(Liquid temperature) 60 ° C
(Current density) 2.0A / dm ²
(Energizing time) 2 seconds

Photographs were taken on the chromate-treated surface using a scanning electron microscope (SEM). Then, the particles of the roughening treatment were observed using the photograph. As a result, the average particle size of the copper primary particle layer was 0.25 to 0.45 μm, and the average particle size of the secondary particle layer was 0.05 to 0.25 μm. The diameter of the smallest circle surrounding the particles was measured as the particle diameter, and the average particle diameter was calculated. The size of the roughened particles hardly changes before and after the heat-resistant rust preventive treatment and the chromate treatment.

Next, the surface after the chromate treatment was subjected to a silane coupling treatment. A silane coupling agent was prepared by mixing the types of silanes shown in Table 1 with water at 25 ° C. so as to have the silane concentration shown in Table 1 and stirring the time stirring speed shown in Table 1 at 900 rpm. After applying the obtained silane coupling agent solution to the surface-treated surface of the copper foil, the excess silane coupling agent solution was drained while rolling the SUS rod against the surface of the copper foil. Then, the silane coupling treatment was carried out by drying under the condition of 100 ° C. × 5 minutes.

(Examples 2, 7, 8 and Comparative Examples 5, 6, 9)
A rolled copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd.) having a thickness of 12 μm having a composition of adding 50 to 100 mass ppm of Ag to oxygen-free copper (OFC) was prepared. The surface of the rolled copper foil was subjected to the same roughening treatment, heat-resistant rust prevention treatment, and chromate treatment as in Example 1 in this order. A silane coupling treatment was performed on the surface after the chromate treatment. A silane coupling agent was prepared by mixing the types of silanes shown in Table 1 with water at 25 ° C. so as to have the silane concentration shown in Table 1 and stirring the time stirring speed shown in Table 1 at 900 rpm. After applying the obtained silane coupling agent solution to the surface-treated surface of the copper foil, the excess silane coupling agent solution was drained while rolling the SUS rod against the surface of the copper foil. Then, the silane coupling treatment was carried out by drying under the condition of 100 ° C. × 5 minutes.

(Examples 3, 9 to 11 and Comparative Examples 2, 7, 8)
An ingot in which 1200 ppm of Sn was added to oxygen-free copper was melted, and the ingot was hot-rolled from 900 ° C. to obtain a plate having a thickness of 10 mm. Then, cold rolling and annealing were repeated, and finally cold rolling was performed on a copper foil having a thickness of 9 μm to obtain a rolled copper foil.

Next, the rolled copper foil was subjected to Ni plating under the following conditions (no roughening treatment was performed).
Ni ion: 40 g / L
Temperature: 50 ° C
Current density: 7.0A / dm ²
Plating time: 2.0 seconds pH: 4.0

Next, the Ni-plated surface was subjected to a silane coupling treatment. A silane coupling agent was prepared by mixing the types of silanes shown in Table 1 with water at 25 ° C. so as to have the silane concentration shown in Table 1 and stirring the time stirring speed shown in Table 1 at 900 rpm. After applying the obtained silane coupling agent solution to the surface-treated surface of the copper foil, the excess silane coupling agent solution was drained while rolling the SUS rod against the surface of the copper foil. Then, the silane coupling treatment was carried out by drying under the condition of 100 ° C. × 5 minutes.
<XPS depth direction analysis>
XPS depth was applied to the surface-treated surface of each of the obtained surface-treated copper foils _{while sputtering at a rate of 1.1 nm / min (SiO 2} conversion) under the above-mentioned conditions using 5600MC manufactured by ULVAC PFI Co., Ltd. Directional analysis was performed. The elements to be analyzed were N1s, O1s, C1s, Si2s, Cr2p ³ , Zn2p ³ , Cu2p ³ , Ni2p ³ , and Co2p ³ . Table 1 shows the atomic concentrations of N, C, Si and O after 0.5 min sputtering and 1.0 min sputtering.

<Surface roughness of surface-treated copper foil>
The ten-point average roughness Rz of the surface-treated surface of each of the obtained surface-treated copper foils was measured using a Surfcoder SE-3C stylus type roughness meter manufactured by Kosaka Research Institute Co., Ltd. in accordance with JIS B0601-1982. did. The results are shown in Table 1.

<Peel strength>
The surface-treated surface of each of the obtained surface-treated copper foils is hot-pressed on a liquid crystal polymer having a thickness of 50 μm (Kuraray, Vectstar CT-Z, a copolymer of hydroxybenzoic acid (ester) and hydroxynaphthoic acid (ester)). To obtain a copper-clad laminate.
Thermal conditions: Heating at a heating speed of about 5.1 ° C / min (reaches 305 ° C after 60 minutes)
Natural cooling pressure condition after holding for 10 minutes: 4.0 MPa pressurization 50 minutes after the start of heating
Zero pressure after holding pressure for 30 minutes

Using the copper-clad laminate thus obtained, the 90-degree peel strength at room temperature (25 ° C.) was measured. The peel strength is a value when the copper foil is peeled off from the liquid crystal polymer at a speed of 50 mm / min at an angle of 90 degrees with a circuit width of 3 mm. This peel strength measurement conforms to JIS C6471-1995 (hereinafter, the same applies). The measurement was performed twice, and the average value was used as the measured value. The results are shown in Table 1.

<Solder blister test>
The surface-treated surface of each of the obtained surface-treated copper foils was bonded to both sides of a liquid crystal polymer (Vecstar CT-Z manufactured by Kuraray) having a thickness of 50 μm by a hot press to obtain a copper-clad laminate.
Thermal conditions: Heating at a heating speed of about 5.1 ° C / min (reaches 305 ° C after 60 minutes)
Natural cooling pressure condition after holding for 10 minutes: 4.0 MPa pressurization 50 minutes after the start of heating
Zero pressure after holding pressure for 30 minutes

After cutting the copper-clad laminate into a size of 40 mm × 40 mm, grease was applied to the surface of the copper-clad laminate to prevent solder adhesion. Then, the appearance of the blisters formed on the surface of the copper-clad laminate when floated in a solder bath at 300 ° C. to 330 ° C. for 10 seconds was visually evaluated according to the following criteria. The results are shown in Table 1.
⊚: When no blister was generated in the 40 mm × 40 mm sample ○: When blister was observed in the 40 mm × 40 mm sample, but the area occupied by the blister was 10% or less Δ: 40 mm × 40 mm When the area occupied by the blister exceeds 10% in the sample and is 20% or less ×: When the area occupied by the blister exceeds 20% in the 40 mm × 40 mm sample

<High frequency characteristic test>
After the surface-treated surface of each of the obtained surface-treated copper foils is bonded to both sides of a 50 μm liquid crystal polymer (Vecstar CT-Z manufactured by Kuraray) by a hot press, a microstrip line structure is formed in order to investigate high-frequency characteristics. did. At this time, the circuit was formed by etching so that the characteristic impedance was 50Ω. The transmission loss was measured using this circuit, and when the transmission loss (TL: unit dB / cm) at a frequency of 30 GHz was 0 ≧ TL ≧ −0.8, the high frequency characteristic was set to ◯. Further, the case where the transmission loss was −0.8> TL ≧ −1.2 was evaluated as Δ, and the case where the transmission loss was −1.2> TL ≧ −10 was evaluated as ×. The results are shown in Table 1.

(Examples 12 and 13 and Comparative Example 10)
In Example 12, a surface-treated copper foil was prepared in the same manner as in Example 1. In Example 13, a surface-treated copper foil was prepared in the same manner as in Example 6. In Comparative Example 10, a surface-treated copper foil was prepared in the same manner as in Comparative Example 1.

U-Varnish A manufactured by Ube Industries, Ltd. composed of polyamic acid (about 20 wt%) and N-methyl-2-pyrrolidone (about 80 wt%) was produced by Yoshimitsu Seiki on the surface-treated surface of each of the obtained surface-treated copper foils. The coating was performed using a doctor blade YD-3 type. After coating, it is dried in an oven at 100 ° C. for 20 minutes, then heated to 350 ° C. in a nitrogen replacement oven at a heating speed of about 3 ° C./min in about 2 hours, and then held at 350 ° C. for 30 minutes. Then, a copper foil laminated plate was obtained by performing a curing step of the polyimide resin.

<Peel strength>
Using the copper-clad laminate thus obtained, the 90-degree peel strength at room temperature (25 ° C.) was measured. The peel strength is a value when the copper foil is peeled off from the polyimide resin at a speed of 50 mm / min at an angle of 90 degrees with a circuit width of 3 mm. This peel strength measurement conforms to JIS C6471-1995 (hereinafter, the same applies). The measurement was performed twice, and the average value was used as the measured value. The results are shown in Table 1.

<Solder blister test>
The copper-clad laminate thus obtained was cut into a size of 40 mm × 40 mm, and then grease was applied to the surface of the copper-clad laminate to prevent solder adhesion. Then, the appearance of the blisters formed on the surface of the copper-clad laminate when floated in a solder bath at 300 ° C. to 330 ° C. for 10 seconds was visually evaluated according to the following criteria. The results are shown in Table 1.
⊚: When no blister was generated in the 40 mm × 40 mm sample ○: When blister was observed in the 40 mm × 40 mm sample, but the area occupied by the blister was 10% or less Δ: 40 mm × 40 mm When the area occupied by the blister exceeds 10% in the sample and is 20% or less ×: When the area occupied by the blister exceeds 20% in the 40 mm × 40 mm sample

<Discussion>
A surface-treated copper foil satisfying at least one concentration requirement selected from a combination of N concentration, C concentration, and Si and O concentration at a sputtering depth of 0.5 min from the surface-treated surface specified in the present invention is at room temperature. It can be seen that the adhesion to the liquid crystal polymer is high, and the generation of blister is suppressed when a copper-clad laminate is formed and a heat load is applied. Further, in Examples 1, 2, 4 to 6, 8, 10 and 11, in which the atomic concentrations of N and C at a sputtering depth of 1.0 min are preferable in addition to the sputtering depth of 0.5 min, a heat load of 320 ° C. is applied. Even when given, the effect of suppressing blister was excellent. Further, Examples 1, 6 and 8 in which the N concentration and the C concentration at the sputtering depth of 0.5 min and the Si and O concentrations are more preferable are excellent in the effect of suppressing the blister even when a heat load of 330 ° C. is applied. Was there. Although experimental data is not shown, the same tendency was observed even when polyamide, prepreg, or fluororesin was used as the insulating substrate. Therefore, the effect of the present invention is not limited to when bonded to a liquid crystal polymer. It can be said that it can be obtained even when it is bonded to another insulating base material.

On the other hand, Comparative Examples 1, 2, 4, 6 and 7 had a high silane coupling concentration, and a thick silane coupling film was formed on the outermost layer of the surface treatment. Therefore, Comparative Examples 2, 3, 5, 7 Because the hydrolysis reaction of the silane coupling agent was insufficient due to insufficient stirring time, Comparative Examples 8 and 9 had a low silane coupling concentration and thus had a sufficient thickness for the outermost layer of the surface treatment. Because of the reason that the silane coupling film was not formed, all of them satisfy the requirements regarding the combination of N concentration, C concentration, and Si and O concentration at a sputter depth of 0.5 min from the surface-treated surface specified in the present invention. I couldn't. Therefore, even when the adhesion to the liquid crystal polymer at room temperature is high, it is not possible to suppress the generation of blisters when a copper-clad laminate is formed and a heat load is applied. Further, in Comparative Examples 8 and 9, the generation of blisters was suppressed, but the adhesion to the liquid crystal polymer at room temperature was insufficient.

Claims (27)

A surface-treated copper foil having a surface-treated surface in a state before being bonded to an insulating base material, and XPS at a depth of 0.5 _{min after sputtering at a rate of 1.1 nm / min (SiO 2 conversion) from the surface-treated surface.} A surface-treated copper foil having a measured N concentration of 1.5 to 7.5 atom%. A surface-treated copper foil having a surface-treated surface, with a C concentration of 12 to 30 atom% measured by XPS at a depth of 0.5 _{min after sputtering at a rate of 1.1 nm / min (SiO 2 conversion) from the surface-treated surface.} A surface-treated copper foil. A surface-treated copper foil having a surface-treated surface, the Si concentration measured by XPS at a depth of 0.5 _{min after sputtering under the condition of 1.1 nm / min (SiO 2 conversion) from the surface-treated surface is 3.1 atom% or more.} A surface-treated copper foil having an O concentration of 40 to 48 atom%. A surface-treated copper foil having a surface-treated surface and satisfying any one or more of the following conditions.
-The N concentration measured by XPS at the depth after 0.5 min sputtering under the condition of 1.1 nm / min (SiO _{2 conversion) from the surface treated surface is 1.5 to 7.5 atom%;}
-The C concentration by XPS measurement at the depth after 0.5 min sputtering under the condition of 1.1 nm / min (SiO _{2 conversion) from the surface treated surface is 12 to 30 atom%;}
-Si concentration by XPS measurement at a depth after 0.5 min sputtering under the condition of rate 1.1 nm / min (SiO ₂ conversion) from the surface treated surface is 3.1 atom% or more, and O concentration is 40 to 48 atom%. Is. Any of claims 1 to 4 in which the N concentration measured by XPS at a depth after 1.0 min sputtering under the condition of a rate of 1.1 nm / min (SiO _{2 conversion) from the surface-treated surface is 0.5 to 6.0 atom%.} The surface-treated copper foil according to item 1. The present invention according to any one of claims 1 to 5, wherein the C concentration measured by XPS at a depth after 1.0 min sputtering at a rate of 1.1 nm / min (SiO _{2 conversion) from the surface-treated surface is 8 to 25 atom%.} Surface treatment copper foil. The surface-treated copper foil according to any one of claims 1 to 6, wherein the Rz of the surface-treated surface is 1.5 μm or less. The surface-treated copper foil according to any one of claims 1 to 7, wherein the copper foil is a rolled copper foil or an electrolytic copper foil. The surface-treated copper foil according to any one of claims 1 to 8, which is used for bonding to a liquid crystal polymer. The surface-treated copper foil according to any one of claims 1 to 8, which is used for bonding with a polyimide resin. The surface-treated copper foil according to any one of claims 1 to 10, which is used for a printed circuit board used at a high frequency exceeding 1 GHz. Any one of claims 1 to 11 having one or more layers selected from the group consisting of a roughening treatment layer, a heat resistance treatment layer, a rust prevention treatment layer, a chromate treatment layer and a silane coupling treatment layer on the surface of a copper foil. The surface-treated copper foil described in the section. The surface according to any one of claims 1 to 11, wherein the surface of the copper foil has one or more layers selected from the group consisting of a heat-resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer and a silane coupling treatment layer. Treated copper foil. A claim having a heat-resistant treatment layer or a rust-preventive treatment layer on the copper foil surface, a chromate-treatment layer on the heat-resistant treatment layer or the rust-prevention treatment layer, and a silane coupling treatment layer on the chromate treatment layer. Item 2. The surface-treated copper foil according to any one of Items 1 to 11. A heat-resistant treatment layer is provided on the surface of the copper foil, a rust-preventive treatment layer is provided on the heat-resistant treatment layer, a chromate treatment layer is provided on the rust prevention treatment layer, and a silane cup is provided on the chromate treatment layer. The surface-treated copper foil according to any one of claims 1 to 11, which has a ring-treated layer. The surface-treated copper foil according to any one of claims 1 to 11, which has a chromate-treated layer on the surface of the copper foil and has a silane coupling-treated layer on the chromate-treated layer. Any one of claims 1 to 11 having a roughening-treated layer on a copper foil surface, a chromate-treated layer on the roughening-treated layer, and a silane coupling-treated layer on the chromate-treated layer. The surface-treated copper foil described in the section. A roughening treatment layer is provided on the surface of the copper foil, and one or more layers selected from the group consisting of a rust prevention treatment layer and a heat resistance treatment layer are provided on the roughening treatment layer. The invention according to any one of claims 1 to 11, which has a chromate-treated layer on one or more layers selected from the group consisting of heat-resistant treatment layers and a silane coupling-treated layer on the chromate-treated layer. The surface-treated copper foil described. It has a roughening treatment layer on the copper foil surface, a rust prevention treatment layer on the roughening treatment layer, a chromate treatment layer on the rust prevention treatment layer, and a chromate treatment layer on the chromate treatment layer. The surface-treated copper foil according to any one of claims 1 to 11, which has a silane coupling-treated layer. The surface-treated copper foil according to any one of claims 1 to 11, which has a roughening-treated layer on the surface of the copper foil and has a silane coupling-treated layer on the roughening-treated layer. The surface-treated copper foil according to any one of claims 1 to 11, which has a silane coupling-treated layer on the surface of the copper foil. Any one of claims 1 to 12, 17 to 20, which has a roughening-treated layer on the surface of a copper foil, and the roughening-treated layer has a primary particle layer and a secondary particle layer on the primary particle layer. The surface-treated copper foil described in the section. The surface-treated copper foil according to claim 22, wherein the secondary particle layer is formed of a ternary alloy composed of copper, cobalt, and nickel. The surface-treated copper foil according to claim 22 or 23, wherein the primary particle layer has an average particle size of 0.25 to 0.45 μm and the secondary particle layer has an average particle size of 0.05 to 0.25 μm. .. A copper foil laminated plate obtained by laminating the surface-treated surface of the surface-treated copper foil according to any one of claims 1 to 24 with an insulating base material. A printed wiring board using the surface-treated copper foil according to any one of claims 1 to 24. An electronic device using the printed wiring board according to claim 26.