KR102054044B1 - Surface treated copper foil - Google Patents

Abstract

[PROBLEMS] To provide a surface-treated copper foil excellent in adhesion to an insulating substrate at room temperature and capable of suppressing blister generation when a copper clad laminate is formed to give a thermal load of solder reflow. [Measures] A surface-treated copper foil having a surface-treated surface, wherein (1) N concentration is 1.5 to 7.5 by XPS measurement at a depth of 0.5 min sputtering under a condition of 1.1 nm / min (SiO ₂ equivalent) rate from the surface-treated surface. surface which satisfies any one or more of the following: atom%, (2) C concentration of 12-30 atom%, (3) Si concentration of 3.1 atom% or more, and O concentration of 40-48 atom%. Treatment copper foil.

Description

Surface Treatment Copper Foil {SURFACE TREATED COPPER FOIL}

This invention relates to the surface-treated copper foil for copper clad laminated boards.

A printed wiring board is generally manufactured by adhering an insulating substrate to copper and a copper alloy foil (hereinafter referred to as "copper foil") to form a copper clad laminate, followed by a step of forming a conductor pattern on the copper foil surface by etching. And a printed circuit board is manufactured by connecting and mounting an electronic component by soldering etc. on a printed wiring board.

As one of the characteristics required for copper foil for printed wiring boards, good adhesion with an insulating base material can be given, and various techniques have been developed so far, mainly on the roughening treatment technology of the copper foil surface (for example, WO2011 / 138876, JP 2011-168887).

On the other hand, it is also known that the adhesiveness with an insulating base material improves by processing the copper foil surface with a silane coupling agent (for example, Unexamined-Japanese-Patent No. 2011-168887, Unexamined-Japanese-Patent No. 2008-118163). Furthermore, since N concentration and Si concentration of the copper foil surface have a beneficial effect on the adhesion to the insulating substrate, a technique of controlling the N concentration and Si concentration such as treating the copper foil surface with a silane coupling agent having a predetermined concentration is also known (for example, For example, WO2013 / 147116).

Patent Document 1: WO2011 / 138876 Patent Document 2: Japanese Unexamined Patent Publication No. 2011-168887 Patent Document 3: Japanese Unexamined Patent Publication No. 2008-118163 Patent Document 4: WO2013 / 147116

The technique which controlled the N concentration and Si concentration of the copper foil surface described in WO2013 / 147116 is an effective technique in improving adhesiveness with an insulating base material. On the other hand, in the manufacturing process of a printed circuit board as mentioned above, mounting of electronic components is often performed by soldering, and heat load is also applied to copper foil and an insulating base material at the time of solder reflow. In recent years, 300 degreeC or more tolerance is calculated | required with respect to the reliability with respect to the high temperature heat load by solder reflow. However, although the copper clad laminated board which surface-treated with the silane coupling agent as described in WO2013 / 147116 obtained favorable adhesiveness, it is easy to produce a blister (swelling) in a copper clad laminated board by the heat load of a solder reflow of 300 degreeC or more. I knew that. In a copper clad laminated board in which blisters are likely to occur due to a heat load, circuit deformation and peeling are likely to occur at the time of electronic component mounting. For this reason, it is advantageous to provide a copper clad laminated board in which blister generation is suppressed at the time of thermal load as well as good adhesion at normal temperature.

The present invention has been made in view of the above circumstances, and provides a surface-treated copper foil which is excellent in adhesion to an insulating substrate at room temperature and which is capable of suppressing blister generation when a copper clad laminate is formed to give a thermal load of solder reflow. It is one task to do it. Moreover, another object of this invention is to provide the copper clad laminated board provided with such a surface-treated copper foil.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined that the said subject should be solved, but WO2013 / 147116 controlled N and Si density | concentration in XPS_survey measurement of a surface-treated copper foil surface, but in order to suppress the blister at the time of heating, It has been found to be important to control the N concentration, C concentration or the combination of Si and O concentrations in the depth direction.

In one aspect, the present invention provides a surface-treated copper foil having a surface-treated surface, wherein the N concentration by the XPS measurement at a depth after 0.5 min sputtering under conditions of a rate of 1.1 nm / min (in terms of SiO ₂ ) from the surface-treated surface is 1.5 to 1.5. It is surface-treated copper foil which is 7.5 atom%.

In another aspect, the present invention is a surface-treated copper foil having a surface-treated surface, wherein the C concentration by XPS measurement at a depth after 0.5 min sputtering under a condition of 1.1 nm / min (in terms of SiO ₂ ) from the surface-treated surface is 12 to 12. It is surface-treated copper foil which is 30 atom%.

According to still another aspect of the present invention, there is provided a surface-treated copper foil having a surface-treated surface, wherein Si concentration by XPS measurement at a depth of 0.5 min sputtering under a condition of 1.1 nm / min (SiO ₂ conversion) at a rate of 1.1 nm / min is 3.1. It is a surface-treated copper foil which is more than atom% and whose O concentration is 40-48 atom%.

In yet another aspect, the present invention is a surface-treated copper foil having a surface-treated surface, which is a surface-treated copper foil that satisfies any one or more of the following conditions.

The N concentration is 1.5 to 7.5 atom% by XPS measurement at a depth after 0.5 min sputtering under conditions of rate 1.1 nm / min (SiO ₂ equivalent) from the surface treated surface;

A C concentration of 12-30 atom% by XPS measurement at a depth after 0.5 min sputtering under conditions of rate 1.1 nm / min (SiO ₂ equivalent) from the surface-treated surface;

Si concentration by XPS measurement at a depth of 0.5 min sputtering at a rate of 1.1 nm / min (in terms of SiO ₂ ) from the surface-treated surface is 3.1 atom% or more, and an O concentration is 40 to 48 atom%.

In one embodiment, the surface-treated copper foil according to the present invention, the surface-treated side the density N by XPS measurement in the depth after 1.0min sputter rate in terms 1.1nm / min (in terms of SiO ₂₎ 0.5 ~ 6.0atom% to be.

In another embodiment, the surface-treated copper foil according to the present invention may have a C concentration of 8 to 25 atom% by XPS measurement at a depth of 1.0 min sputtering under a condition of 1.1 nm / min (SiO ₂ equivalent) rate from a surface-treated surface. to be.

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

In another embodiment, the surface-treated copper foil which concerns on this invention is copper foil which is a rolled copper foil or an electrolytic copper foil.

In another embodiment, the surface-treated copper foil which concerns on this invention is for bonding with a liquid crystal polymer.

In another embodiment, the surface-treated copper foil which concerns on this invention is for joining with polyimide resin.

In another embodiment, the surface-treated copper foil which concerns on this invention is used for the printed circuit board used under the high frequency exceeding 1 GHz.

In another embodiment, the surface-treated copper foil which concerns on this invention WHEREIN: At least 1 sort (s) selected from the group which consists of a roughening process layer, a heat resistant process layer, an rustproof process layer, a chromate treatment layer, and a silane coupling process layer on the copper foil surface. Has a layer.

The surface-treated copper foil which concerns on this invention WHEREIN: In another embodiment, the surface of copper foil has 1 or more types chosen from the group which consists of a heat-resistant processing layer, an antirust process layer, a chromate treatment layer, and a silane coupling process layer.

In still another embodiment, the surface-treated copper foil according to the present invention has a heat-resistant layer or an rust-preventing layer on the surface of the copper foil, has a chromate-treated layer on the heat-resistant layer or rust-prevented layer, and the chromate-treated layer. It has a silane coupling process layer on it.

In another embodiment, the surface-treated copper foil which concerns on this invention has a heat-resistant processing layer on the copper foil surface, has a rustproof treatment layer on the said heat-resistant treatment layer, and has a chromate treatment layer on the said rustproof treatment layer, A silane coupling treatment layer is provided on the chromate treatment layer.

In another embodiment, the surface-treated copper foil which concerns on this invention has a chromate treatment layer on the copper foil surface, and has a silane coupling treatment layer on the said chromate treatment layer.

In another embodiment, the surface-treated copper foil which concerns on this invention has a roughening process layer on the copper foil surface, has a chromate treatment layer on the said roughening process layer, and provides a silane coupling process layer on the said chromate treatment layer. Have

In another embodiment, the surface-treated copper foil which concerns on this invention has a roughening process layer on the copper foil surface, and is 1 or more types chosen from the group which consists of an antirust process layer and a heat-resistant process layer on the said roughening process layer. Has a chromate treatment layer on at least one layer selected from the group consisting of the rustproof treatment layer and the heat resistant treatment layer, and a silane coupling treatment layer on the chromate treatment layer.

In another embodiment, the surface-treated copper foil which concerns on this invention has a roughening process layer on the copper foil surface, has a rustproof process layer on the said roughening process layer, and has a chromate process layer on the said rustproof process layer, A silane coupling treatment layer is provided on the chromate treatment layer.

In another embodiment, the surface-treated copper foil which concerns on this invention has a roughening process layer on the copper foil surface, and has a silane coupling process layer on the said roughening process layer.

In another embodiment, the surface-treated copper foil which concerns on this invention has a silane coupling process layer on the copper foil surface.

In another embodiment, the surface-treated copper foil which concerns on this invention has a roughening process layer on the copper foil surface, and the said roughening process layer has a secondary particle layer on a primary particle layer and this primary particle layer.

In another embodiment, the surface-treated copper foil which concerns on this invention is the said secondary particle layer formed from the ternary alloy which consists of copper, cobalt, and nickel.

In another embodiment of the surface-treated copper foil which concerns on this invention, the average particle diameter of the said primary particle layer is 0.25-0.45 micrometer, and the average particle diameter of the said secondary particle layer is 0.05-0.25 micrometer.

In yet another aspect, the present invention is a copper foil laminated plate comprising a surface-treated surface of a surface-treated copper foil according to the present invention bonded to an insulating substrate.

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

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

ADVANTAGE OF THE INVENTION According to this invention, the surface-treated copper foil which is excellent in adhesiveness with the insulated substrate at normal temperature, and can suppress blister generation when a heat load is applied by forming a copper clad laminated board is provided. For this reason, since deformation | transformation and peeling of a circuit are suppressed by the heat which arises when mounting an electronic component by soldering to a printed wiring board, it contributes to manufacture of a printed circuit board with high quality reliability.

In one embodiment of the present invention, the rate is 1.1 nm / min (SiO ₂₎ from the surface-treated surface of the surface-treated copper foil. At least one selected from the combination of N atom concentration, C atom concentration and Si and O atom concentration by XPS measurement at a depth after 0.5 min sputtering (hereinafter referred to as "0.5 min sputter depth") under the Doing. According to the inventor's examination result, controlling at least one selected from the combination of N atom concentration, C atom concentration and Si and O atom concentration at 0.5 min sputter depth is excellent in adhesion to the insulating substrate at room temperature, It is effective for suppressing blister generation when a copper clad laminate is formed to give a heat load.

N concentration by XPS measurement at 0.5 min sputter depth is preferably 1.5 atom% or more, more preferably 3.7 atom% or more, and even more preferably 4.0 atom% or more from the viewpoint of increasing the adhesion strength with the insulating substrate. . In addition, the N concentration by XPS measurement at the depth is preferably 7.5 atom% or less, more preferably 6.7 atom% or less, and even more preferably 6.6 atom% or less from the viewpoint of suppressing blister generation.

In addition, the C concentration by XPS measurement at 0.5 min sputter depth is preferably 12 atom% or more, more preferably 18 atom% or more, and even more preferably 21.6 atom% or more from the viewpoint of increasing the adhesion strength with the insulating substrate. . Further, the C concentration by XPS measurement at the depth is preferably 30 atom% or less, more preferably 28.6 atom% or less, and even more preferably 23.8 atom% or less from the viewpoint of suppressing blister generation.

In addition, the combination of Si and O concentrations by XPS measurement at 0.5 min sputter depth 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 substrate, and Si: 4.3 tom. It is more preferable that it is% or more, O: 43.4 atom% or more, and it is still more preferable that it is Si: 5.8 atom% or more and O: 44.6 atom% or more. Further, the combination of Si and O concentration by XPS measurement at the depth is preferably from Si: 12.6 atom% or less and from O: 48 atom% or less from the viewpoint of suppressing blister generation, and from Si: 12.4 atom% or less and from O: It is more preferable that it is 47 atom% or less, and it is still more preferable that it is Si: 11.9 atom% or less and O: 46.4 atom% or less.

Since at least one of the combination of N atom concentration, C atom concentration and Si and O atom concentration by XPS measurement at 0.5 min sputter depth satisfies the above concentration condition, the adhesion strength with the insulating substrate is improved and the bliss is improved. Although generation | occurrence | production of a site | part can be suppressed advantageously, it is preferable to satisfy | fill two or more types of concentration requirements among these three types of concentration requirements, and it is more preferable to satisfy all three types of concentration requirements.

In a preferred embodiment of the present invention, the surface treatment surface of the surface-treated copper foil at a rate of 1.1 nm / min (in terms of SiO ₂ ) after 1.0 min sputtering (hereinafter referred to as "1.0 min sputter depth"). At least one selected from N and C atomic concentrations by XPS measurement is controlled. According to the inventor's examination result, controlling at least one selected from the N and C atomic concentrations at 1.0 min sputter depth and preferably at both the 0.5 min sputter depth, and excellent adhesion to the insulating substrate at room temperature, Moreover, it is more effective in suppressing blister generation when a copper clad laminated board is comprised and heat load is applied.

The N concentration by XPS measurement at 1.0 min sputter depth is preferably 0.5 atom% or more, more preferably 1.0 atom% or more, and even more preferably 1.8 atom% or more from the viewpoint of increasing the adhesion strength with the insulating substrate. . Further, the N concentration by XPS measurement at the depth is preferably 6.0 atom% or less, more preferably 4.7 atom% or less, and even more preferably 4.2 atom% or less from the viewpoint of suppressing blister generation.

In addition, the C concentration by XPS measurement at 1.0 min sputter depth is preferably 8 atom% or more, more preferably 16.8 atom% or more, even more preferably 18.4 atom% or more from the viewpoint of increasing the adhesion strength with the insulating substrate. Do. Further, the C concentration by XPS measurement at the depth is preferably 25 atom% or less, more preferably 21.3 atom% or less, even more preferably 20.7 atom% or less from the viewpoint of suppressing blister generation.

The atomic concentration measurement of each element at the depth by XPS measurement is possible by performing XPS depth direction analysis on the surface-treated surface of surface-treated copper foil.

In the Example, it analyzed on condition of the following.

Device: Albackpie Co., Ltd. product 5600MC

Reach Vacuum Degree: 5.7 × 10 ^-7 Pa

Excitation source: monochrome MgKα

Output: 400W

Detecting Area: 800㎛Ø

Incident angle: 81 °

Blowout angle: 45 °

No Chinese gun

<Sputter condition>

Ionic species: Ar

Acceleration voltage: 1 kV

Stamp area: 3mm × 3mm

Rate: 1.1 nm / min (SiO ₂ equivalent)

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

The method of treating the copper foil surface with a silane coupling agent as one means for forming the surface treatment surface in which the combination of N concentration, C concentration, and Si and O concentration is controlled in the said range is 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.

Although there is no restriction | limiting in particular as a silane coupling agent, The aminosilane which N and Si contain in a molecule | numerator can be used suitably. As the aminosilane, silanes containing at least one amino group or imino group can be used. The number of amino groups or imino groups contained in aminosilane can be 1-4 pieces, respectively, Preferably it is 1-3 pieces, respectively, More preferably, it is 1-2 pieces. In a suitable embodiment, the number of amino groups and / or imino groups contained in aminosilane can be made into one each.

The aminosilane in which the sum of the number of amino groups and imino groups included in the aminosilane is one may be particularly called monoaminosilane, two aminosilanes are particularly diaminosilane, and three aminosilanes may be particularly called triaminosilane. Monoaminosilane and diaminosilane can be used suitably in this invention. In a suitable embodiment, monoaminosilane comprising one amino group can be used as the aminosilane. In a suitable embodiment, the aminosilane may be comprised of at least one, for example one amino group, at the end of the molecule, preferably at the end of a straight or branched chain molecule.

As aminosilane, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimeth Methoxysilane, 1-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, 1, 2-diaminopropyltrimethoxysilane, 3-amino-1-propenyltrimethoxysilane, 3-amino- 1-propyltrimethoxysilane, 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 And N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and 3- (N-phenyl) aminopropyltrimethoxysilane.

Moreover, in preferable embodiment, the silane coupling agent which has a structural formula of following formula I can be used.

H ₂ NR ¹ -Si (OR ² ) ₂ (R ³ ) (Formula I)

(In formula I,

R ¹ is a divalent group of a C ₁ to C ₁₂ hydrocarbon having a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, heterocyclic ring or no heterocyclic ring,

R ₂ is an alkyl group of C ₁ ~ C ₅ ,

R ³ is a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ alkoxy group.)

R ¹ is a substituted or unsubstituted C ₁ to C ₁₂ linear saturated hydrocarbon divalent, a substituted or unsubstituted C ₁ to C ₁₂ branched saturated hydrocarbon divalent, substituted or unsubstituted C ₁ to C ₁₂ Divalent, substituted or unsubstituted C ₁ to C ₁₂ linear unsaturated hydrocarbon divalent, substituted or unsubstituted C ₁ to C ₁₂ cyclic hydrocarbon divalent, substituted or unsubstituted C ₁ to C ₁₂ 2 to the top of the heterocyclic hydrocarbon is preferably selected from the group the group consisting of divalent aromatic hydrocarbons substituted or unsubstituted Whanin C ₁ ~ C _12.

R ¹ is-(CH ₂ ) _n -,-(CH ₂ ) _n- (CH) _m- (CH2) _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- Group consisting of (CH) NH _2- (CH ₂ ) _m-1 -,-(CH ₂ ) _n-1- (CH) NH _2- (CH ₂ ) _m-1 -NH- (CH ₂ ) _j- It is preferable that the group chosen from (wherein n, m, j is an integer of 1 or more).

R ¹ is - (CH _{2) n} - or _{- (CH 2) n -NH- (} CH 2) m - which is more preferred.

It is preferable that n, m, j are 1, 2 or 3 each independently.

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.

It is important for the silane coupling treatment to have a higher concentration (eg, 1.0 vol% or more) than the usual concentration in the water of the silane coupling agent in order to obtain high adhesion with the insulating substrate, but if it is too high, the concentration of N, C or O is too high. Is excessive, and blister suppression becomes difficult. For example, the concentration of the silane coupling agent in water may be 1.5 to 6 vol%, and preferably 2.0 to 4.0 vol%.

Since a silane coupling agent can mix silane and water and provide it as an aqueous solution, it is important to set the stirring time at the time of mixing both suitably according to the kind and concentration of a silane coupling agent. Since the optimum stirring time varies depending on the type and concentration of the silane coupling agent, it is difficult to generalize and discuss, but as a standard, it can be selected within the range of 1 to 24 hours. When the stirring time is short, such as less than 0.5 hours, since hydrolysis of the silane coupling agent does not proceed sufficiently, OR ² or R ³ in Si (OR ² ) ₂ (R ³ ) represented by the above-described formula (I) is When not substituted sufficiently with an OH group (hydroxyl group), the adhesiveness assumed may not be acquired. In this case, many C ₁ -C ₅ alkyl groups corresponding to R ² or R ³ remain in the silane coupling layer. Using more than the optimal amount of silane coupling agent to further increase the adhesion increases not only C concentration but also N concentration and O concentration. Preferable stirring time is 2 hours or more, more preferable stirring time is 5 hours or more, and more preferable stirring time is 12 hours or more. It becomes easy to be fluctuate | varied in pH and temperature by stirring for a long time, and the amino group containing N, the hydroxyl group containing O, etc. will form hydrogen bonds between silane coupling agents, and will not have a crosslinked structure between the metal and resin assumed. Furthermore, amino groups and hydroxyl groups are susceptible to pH, so the silane coupling agent may deteriorate. In such a case, industrial use becomes difficult.

As the stirring time, when the total number of amino groups and imino groups in the silane coupling agent is large, short stirring time and, on the other hand, lengthening the stirring time, it is easy to satisfy the concentration condition of the surface-treated surface according to the present invention described above. In addition, 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, whereby the concentration conditions of the surface-treated surface according to the present invention described above are easily satisfied.

The surface treatment method of the copper foil by a silane coupling agent is anything, such as spray adhesion, coater application | coating, immersion, and letting out of the silane coupling agent aqueous solution. In addition, after a silane coupling process, it is necessary not to make drying temperature too high, and not to make drying time too long. It is because the silane coupling agent which exists in the copper foil surface may decompose when drying temperature is too high or drying time is too long. As an example, a drying temperature may be 70-150 degreeC and a drying time may be 1 second-10 minutes.

Although there is no restriction | limiting in particular in the kind of copper foil (source foil) used as a surface treatment object, A rolled copper foil and an electrolytic copper foil can be used suitably. Copper foil contains pure copper foil and copper alloy foil, and can be made into arbitrary compositions known as a circuit formation use. In addition, the copper foil used for surface treatment may be a carrier, a peeling layer, and an ultrathin copper layer in this order, and the ultra-thin copper layer of the copper foil with a carrier may be sufficient as it, and the copper foil used for surface treatment may have a carrier. Copper foil with a carrier and a carrier may be used for the above-mentioned copper foil with a carrier and carrier, A well-known copper foil with a carrier and a carrier can be used.

In addition, in the present invention, since adhesion to the insulating substrate is improved by controlling at least one kind of the combination of the N concentration, the C concentration, and the Si and O concentration combinations on the surface treatment surface, the surface of the surface is improved to improve the adhesion with the insulating substrate. There is little need to increase roughness. For this reason, conductor loss can be reduced by reducing the surface roughness in the surface treatment surface of a surface-treated copper foil, ensuring adhesiveness with an insulating base material. The low conductor losses are advantageous for applications to printed circuit boards, for example as used under high frequencies above 1 GHz. As surface roughness in surface treatment surface, when measured using a stylus roughness meter specifically based on JIS # B0601-1982, it is preferable that 10-point average roughness Rz is 1.5 micrometers or less, and it is more preferable that it is 1.2 micrometers or less. It is more preferable that it is 1.0 micrometer or less, for example, it can be 0.2-1.5 micrometers.

The combination of N concentration, C concentration, and Si and O concentration as a means of forming a surface-treated surface controlled in the above range, N, C, Si and O on the copper foil surface by dry plating such as sputtering, CVD and PVD After sticking, the method of heating and setting a temperature and time suitably after that is also mentioned. By adjusting the heating conditions, the concentrations of N, C, Si and O on the surface treated surface can be controlled.

In one embodiment, the surface-treated copper foil which concerns on this invention WHEREIN: The copper foil surface has 1 or more types chosen from the group which consists of a roughening process layer, a heat-resistant process layer, an rustproof process layer, a chromate treatment layer, and a silane coupling process layer. Can have. In addition, the surface-treated copper foil which concerns on this invention can have one or more types chosen from the group which consists of a heat-resistant processing layer, an rust-proof processing layer, a chromate treatment layer, and a silane coupling treatment layer in the copper foil surface in one Embodiment. have.

The said roughening process layer is not specifically limited, Any roughening process layer or a well-known roughening process layer can be applied. The heat resistant layer is not particularly limited, and any heat resistant layer or a known heat treated layer can be applied. The rustproof treatment layer is not particularly limited, and any rustproof treatment layer or a known rustproof treatment layer may be applied. The plating layer is not particularly limited, and any plating layer or a known plating layer can be applied. The chromate treatment layer is not particularly limited, and any chromate treatment layer or a known chromate treatment layer can be applied.

In one embodiment of the surface-treated copper foil which concerns on this invention, you may form a roughening process layer by applying the roughening process for improving adhesiveness with an insulating substrate, etc. to the copper foil surface, for example. A roughening process can be performed by forming roughening particle | grains with copper or a copper alloy, for example. The roughening process may be fine. The roughening treatment layer may be a layer composed of an alloy containing any one member selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or any one or more thereof. Furthermore, after forming roughening particle | grains with copper or a copper alloy, you may further perform the roughening process which forms secondary particle | grains or tertiary particle | grains with the single substance, alloy, etc. of nickel, cobalt, copper, and zinc. Especially, the roughening process layer in which the secondary particle layer which consists of ternary alloys which consist of copper, cobalt, and nickel was formed on the primary particle layer of copper and this primary particle layer is preferable. It is more preferable that the average particle diameter of the said primary particle layer is 0.25-0.45 micrometer, and the average particle diameter of this secondary particle layer is 0.05-0.25 micrometer.

In one embodiment of the surface-treated copper foil which concerns on this invention, after a roughening process, you may form a heat resistant layer or an antirust process layer with the single substance, alloy, etc. of nickel, cobalt, copper, zinc, etc. Furthermore, the surface is chromate-treated, You may perform processes, such as a silane coupling process. Alternatively, the heat-resistant layer or the rust-preventing layer may be formed of a single element or an alloy of nickel, cobalt, copper, zinc, or the like, and the surface may be subjected to chromate treatment, silane coupling treatment, or the like.

That is, at least one layer selected from the group consisting of a heat resistant layer, an rustproof layer, a chromate treated layer, and a silane coupling layer may be formed on the surface of the roughened layer, and the heat resistant layer and the antirust layer are formed on the surface of the copper foil. Or at least one layer selected from the group consisting of chromate treated layers and silane coupling treated layers. In addition, the above-mentioned heat-resistant layer, antirust process layer, chromate process layer, and silane coupling process layer may be respectively formed from several layer (for example, 2 or more layers, 3 or more layers, etc.). In addition, in this invention, a "rustproof process layer" contains the "chromate process layer." When adhesiveness with resin is considered, it is preferable to form a silane coupling process layer in the outermost layer of surface treatment copper foil.

The following treatments can be used as a waterproofing or chromate treatment.

<Ni plating>

(Liquid Composition) Ni-ion: 10-40 g / L

(pH) 1.0 to 5.0

(Liquid temperature) 30-70 degrees Celsius

(Current Density) 1 ~ 9A / dm ²

(Current time) 0.1-3 seconds

<Ni-Co Plating>: Ni-Co Alloy Plating

(Liquid Composition) Co: 1-20 g / L, Ni: 1-20 g / L

(pH) 1.5 to 3.5

(Liquid temperature) 30-80 degreeC

(Current density) 1 ~ 20A / dm ²

(Live time) 0.5-4 seconds

<Zn-Ni Plating>: Zn-Ni Alloy Plating

(Liquid composition) Zn: 10 to 30 g / L, Ni: 1 to 10 g / L

(pH) 3 ~ 4

(Liquid temperature) 40-50 degrees Celsius

(Current density) 0.5 ~ 5A / dm ²

(Current time) 1-3 seconds

<Ni-Mo Plating>: Ni-Mo Alloy Plating

(Liquid composition) Nickel sulfate: 270-280 g / L, nickel chloride: 35-45 g / L, nickel acetate: 10-20 g / L, molybdenum (added as sodium molybdate): 0.1-10 g / L, trisodium citrate: 15-25 g / L, Polishing agent: Saccharin, Butyndiol, etc. Sodium dodecyl sulfate: 55-75 ppm

(pH) 4 ~ 6

(Liquid temperature) 55-65 ℃

(Current Density) 1 ~ 11A / dm ²

(Current time) 1-20 seconds

<Cu-Zn Plating>: Cu-Zn Alloy Plating

(Liquid composition) NaCN: 10-30 g / L, NaOH: 40-100 g / L, Cu: 60-120 g / L, Zn: 1-10 g / L

(Liquid temperature) 60-80 ℃

(Current Density) 1 ~ 10A / dm ²

(Current time) 1-10 seconds

Electrolytic Chromate

(Liquid composition) Chromic anhydride, chromic acid or potassium dichromate: 1 to 10 g / L, zinc (if added, zinc sulfate is added): 0 to 5 g / L

(pH) 0.5 to 10

(Liquid temperature) 40-60 ° C

(Current density) 0.1 ~ 2.6A / dm ²

0.5 to 90 As / dm ²

(Current time) 1-30 seconds

<Immersion Chromate>

(Liquid composition) Chromic anhydride, chromic acid or potassium dichromate: 1 to 10 g / L, zinc (if added, zinc sulfate is added): 0 to 5 g / L

(pH) 2 ~ 10

(Liquid temperature) 20-60 ° C

(Processing time) 1-30 seconds

The copper foil laminated sheet can be formed by bonding the surface treatment surface of the surface-treated copper foil which concerns on this invention with an insulating base material. It is good also as a single layer copper clad laminated board with an insulating base material, and a multilayer copper clad laminated board with an insulating base material of two or more layers. The copper foil laminated sheet may be either flexible or rigid. Although there is no restriction | limiting in particular as an insulating base material, Epoxy resin, a phenol resin, a polyimide resin, a polyimide amide resin, a polyester resin, a polyphenylene sulfide resin, a polyetherimide resin, a fluororesin, a liquid crystal polymer (LCP), and mixing them The one which was made. In addition, the insulating base material which impregnated the glass cloth with an epoxy resin, bismaleimide triazine resin, a polyimide resin, etc. is mentioned. In particular, the liquid crystal polymer has a great advantage of low dielectric constant, low dielectric loss tangent, low water absorption, small change in the above characteristics and further small dimensional change, and is suitable for high frequency applications.

The surface-treated copper foil which concerns on this invention is especially useful as copper foil for flexible printed circuit boards (FPC) which laminated | stacked copper foil on the liquid crystal polymer. Among insulating substrates, liquid crystal polymers have a weak strength, and a material in which copper foil is laminated has a big problem that peel strength is hard to come out. When the roughness of the copper foil surface is increased, the physical anchoring effect can be obtained, and thus the peeling strength tends to increase. However, the electrical properties at high frequencies are deteriorated under the influence of the surface effect described above. However, according to one embodiment of the surface-treated copper foil according to the present invention, even if the surface roughness is small, the adhesion to the insulating substrate can be ensured, so that the advantages of the liquid crystal polymer described above can be utilized.

A printed wiring board can be manufactured using a copper clad laminated board. There is no restriction | limiting in particular in the processing method from a copper clad laminated board to a printed wiring board, It is enough to use a well-known etching process. A printed circuit board can also be manufactured by mounting various electronic components on a printed wiring board. The printed circuit board can also be mounted on various electronic devices.

(Example)

Hereinafter, an Example demonstrates this invention. In addition, a present Example shows a suitable example and this invention is not limited to this Example. Accordingly, all modifications, other embodiments or aspects included in the technical spirit of the present invention are included in the present invention. In addition, a comparative example is written together for the contrast with this invention. In addition, the balance part of the liquid used for the roughening process, plating, silane coupling process, heat resistant process, waterproofing process, etc. which were described in the experiment example of this application was also made into water unless there is particular notice.

(Examples 1, 4 to 6 and Comparative Examples 1, 3 and 4)

A rolled copper foil (tough pitch copper (JIS # H3100 alloy number C1100, manufactured by JX Nikko Nippon Petroleum Metal Co., Ltd.)) having a thickness of 12 µm was prepared. After wash | cleaning the surface of this rolled copper foil with electrolytic resin, water, and oxygen, the process which forms primary particles of copper on the surface of this rolled copper foil is performed, and the process which forms secondary particles after that is performed. The roughening process was performed by doing this. The detailed conditions of a roughening process are as follows.

<Harmonic processing condition>

(Plating conditions of the primary particles of copper)

Liquid composition: copper 10g / L, sulfuric acid 50g / L

Liquid temperature: 26 ℃

Current density: 50 A / dm ²

Plating time: 1.5 seconds

(Plating Conditions of Secondary Particles)

Liquid composition: Copper 16g / L, Nickel 9g / L, Cobalt 8g / L

pH: 2.4

Liquid temperature: 35 ℃

Current density: 25 A / dm ₂

Plating time: 1.5 seconds

After the roughening treatment was applied, Ni-Co alloy plating (heat-resistant waterproofing) and chromate treatment were sequentially performed.

<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) 12 A / dm ²

(Current time) 0.8 seconds

Electrolytic Chromate

(Liquid composition) potassium dichromate: 4 g / L, zinc (added in zinc sulfate form): 0.5 g / L

(pH) 3.5

(Liquid temperature) 60 ° C

(Current density) 2.0A / dm ²

(Current time) 2 seconds

The chromatographed surface was photographed using a scanning electron microscope (SEM). And the particle | grain observation of a roughening process was performed using this photograph. As a result, the average particle diameter of the primary particle layer of copper was 0.25-0.45 micrometer, and the average particle diameter of the secondary particle layer was 0.05-0.25 micrometer. In addition, the diameter of the smallest circle surrounding the particles was measured as the particle diameter, and the average particle diameter was calculated. In addition, the size of the roughened particles hardly changes before and after heat-resistant waterproofing and chromate treatment.

Next, the silane coupling process was performed to the surface after chromate treatment. The silane coupling agent was prepared by mixing silanes of the kind shown in Table 1 so that it may become water of 25 degreeC, and the silane concentration shown in Table 1, and stirring the time stirring speed shown in Table 1 at 900 rpm. After apply | coating the obtained silane coupling agent solution to the surface treatment surface of copper foil, the liquid suspension of the excess silane coupling agent solution was performed, rolling the SUS rod against the copper foil surface. Then, the silane coupling process was performed by drying on 100 degreeC * 5 minutes conditions.

(Examples 2, 7, 8 and Comparative Examples 5, 6, 9)

A rolled copper foil (manufactured by JX Nikko Nippon Petroleum Co., Ltd.) having a thickness of 50 µm to 100 ppm by mass of Ag was prepared. The roughening process, heat-resistant waterproofing process, and chromate treatment similar to Example 1 were given to the surface of this rolled copper foil in order. The silane coupling process was performed to the surface after chromate treatment. The silane coupling agent was prepared by mixing the silanes of the kind shown in Table 1 so that it might become water of 25 degreeC, and the silane concentration shown in Table 1, and stirring the time stirring speed of Table 1 at 900 rpm. After apply | coating the obtained silane coupling agent solution to the surface treatment surface of copper foil, the liquid suspension of the excess silane coupling agent solution was performed, rolling the SUS rod against the copper foil surface. Then, the silane coupling process was performed by drying on 100 degreeC * 5 minutes conditions.

(Examples 3, 9-11 and Comparative Examples 2, 7, 8)

An ingot in which 1200 ppm of Sn was added to anoxic 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 rolled to 9 micrometer thick copper foil, and the rolled copper foil was obtained.

Next, Ni plating was performed to the said rolled copper foil on the following conditions (do not carry out a roughening process).

Ni-ion: 40g / L

Temperature: 50 ℃

Current Density: 7.0 A / dm ²

 Plating time: 2.0 seconds

 pH: 4.0

Next, the silane coupling process was performed to the Ni plating surface. The silane coupling agent was prepared by mixing the silanes of the kind shown in Table 1 so that it may become water of 25 degreeC, and the silane concentration of Table 1, and stirring the time stirring speed of Table 1 at 900 rpm. After apply | coating the obtained silane coupling agent solution to the surface treatment surface of copper foil, the liquid suspension of the excess silane coupling agent solution was performed, rolling the SUS rod against the copper foil surface. Then, the silane coupling process was performed by drying on 100 degreeC * 5 minutes conditions.

<XPS depth direction analysis>

With respect to the surface-treated side of each surface-treated copper foil obtained albaek pie Co., Ltd. using the 5600MC, was subjected to XPS analysis and sputter depth direction as in the above-described conditions, the rate 1.1nm / min (in terms of SiO _2). The element to be analyzed was N1s, O1s, C1s, Si2s, Cr2p ³ , Zn2p ³ , Cu2p ³ , Ni2p ³ , 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 obtained surface-treated copper foil was measured using Surfcorder SE-3C tactile roughness meter manufactured by Kosaka Laboratory Co., Ltd. based on JIS # B0601-1982. The results are shown in Table 1.

<Peel strength>

The surface-treated surface of each obtained surface-treated copper foil was bonded to a liquid crystal polymer having a thickness of 50 µm (Kuraray Co., Vecstar CT-Z, a copolymer of hydroxybenzoic acid (ester) and naphthohydroxide (ester)) by heat pressing and A laminated board was obtained.

Thermal conditions: heating at an elevated rate of about 5.1 ° C./min (reach 305 ° C. after 60 minutes)

Natural cooling after holding for 10 minutes

Pressure condition: 4.0MPa pressurization after 50 minutes from heating start

Zero pressure after 30 minutes of pressurization

The 90 degree peeling strength at normal temperature (25 degreeC) was measured using the copper clad laminated board obtained in this way. Peeling strength is 3 mm in circuit width, and is a value at the time of peeling copper foil from a liquid crystal polymer at a speed | rate of 50 mm / min at a 90 degree angle. This peeling strength measurement is based on JISC6471-1995 (hereinafter, the same). It measured twice and made the average value the measured value. The results are shown in Table 1.

<Soldering Blister Test>

The surface treatment surface of each obtained surface-treated copper foil was bonded together by the heat press on both surfaces of the liquid-crystal polymer (Curare product, Vecstar CT-Z) of thickness 50micrometer, and the copper clad laminated board was obtained.

Thermal conditions: heating at a rate of temperature rise of about 5.1 ° C./min (reach 305 ° C. after 60 minutes)

Natural cooling after holding for 10 minutes

Pressure condition: 4.0 MPa pressurized after 50 minutes from the start of heating

Zero pressure after 30 minutes of pressurization

The copper clad laminate was cut to a size of 40 mm x 40 mm and then lubricated to prevent solder adhesion to the copper clad laminate surface. Then, the blister appearance which formed on the surface of the copper clad laminated board when floating in the 300 degreeC-330 degreeC hander bath for 10 second was visually evaluated by the following criteria. The results are shown in Table 1.

◎: When blister does not occur in 40mm × 40mm sample

(Circle): When blister occurrence was seen in the 40 mm x 40 mm sample, but the area which a blister occupies is 10% or less

(Triangle | delta): When the blister occupies more than 10% and is less than 20% in a 40 mm x 40 mm sample.

X: When the blister occupies more than 20% of the 40 mm x 40 mm sample

<High Frequency Characteristic Test>

The surface treatment surface of each obtained surface-treated copper foil was bonded together by the heat press on both surfaces of 50 micrometers liquid crystal polymer (Vecstar CT-Z by Kuraray), and the microstrip line structure was formed in order to investigate a high frequency characteristic. At this time, the circuit was formed by etching so that the characteristic impedance was 50?. The transmission loss measurement was performed using this circuit, and when the transmission loss (TL: unit dB / cm) at 30 GHz frequency was 0≥TL≥-0.8, the high frequency characteristic was set to (circle). In addition, when the transmission loss was -0.8> TL≥-1.2, (triangle | delta) was made and (x) when the transmission loss is -1.2> TL≥-10. The results are shown in Table 1.

(Examples 12, 13 and Comparative Example 10)

In Example 12, a surface-treated copper foil was produced in the same manner as in Example 1. Example 13 produced the surface-treated copper foil similarly to Example 6. In Comparative Example 10, a surface-treated copper foil was produced in the same manner as in Comparative Example 1.

U-Nice A, manufactured by Ube Heungsan Co., Ltd., composed of polyamic acid (about 20 wt%) and N-methyl-2-pyrrolidone (about 80 wt%) on the surface treatment of each obtained surface-treated copper foil, is a doctor blade manufactured by Yoshimitsu Seiki Coating was carried out using YD-3 type. After coating, it dried for 20 minutes in 100 degreeC oven, after heating up to 350 degreeC in the nitrogen substitution oven at the temperature increase rate of about 3 degree-C / min, about 350 hours, and carrying out the curing process of polyimide resin by maintaining 350 degreeC * 30 minutes. The copper foil laminated board was obtained by this.

<Peel strength>

The 90 degree peeling strength at normal temperature (25 degreeC) was measured using the copper clad laminated board obtained in this way. Peeling strength is 3 mm in circuit width, and is a value at the time of peeling copper foil from polyimide resin at a speed | rate of 50 mm / min at 90 degree | times. This peeling strength measurement is based on JIS C6471-1995 (hereinafter, the same). It measured twice and made the average value the measured value. The results are shown in Table 1.

<Soldering Blister Test>

The copper clad laminate thus obtained was cut to a size of 40 mm x 40 mm, and then lubricating oil was applied to the copper clad laminate to prevent solder adhesion. Then, the blister appearance which formed on the surface of the copper clad laminated board when it floated in the 300 degreeC-330 degreeC hander bath for 10 second was visually evaluated by the following criteria. The results are shown in Table 1.

◎: When blister does not occur in 40mm × 40mm sample

(Circle): When the blister generate | occur | produced in the 40 mm x 40 mm sample, but the area which a blister occupies is 10% or less.

(Triangle | delta): When the area which a blister occupies in 40 mm x 40 mm sample is more than 10%-20% or less

×: when the blister occupies more than 20% of the 40 mm × 40 mm sample

Table 1-1

TABLE 1-2

Table 1-3

Table 1-4

<Consideration>

Surface-treated copper foil that satisfies at least one concentration requirement selected from the combination of N concentration, C concentration, and Si and O concentration at 0.5 min sputter depth from the surface treatment surface defined in the present invention is combined with the liquid crystal polymer at room temperature. When adhesiveness was high and a copper clad laminated board was comprised and heat load was applied, it turned out that blister generation is suppressed. In addition, in Examples 1, 2, 4 to 6, 8, 10, and 11, where atomic concentrations of N and C at a 1.0 min sputter depth as well as a 0.5 min sputter depth are desired, blister suppression occurs even when a heat load of 320 ° C. is given. The effect was excellent. Moreover, Examples 1, 6, and 8, where N concentration, C concentration, and Si and O concentrations are more preferable at 0.5 min sputter depth, were excellent in blister suppression effect even under a heat load of 330 ° C. In addition, although the experimental data are not shown, the same tendency was observed even when polyamide, prepreg or fluorine resin was used as the insulating substrate, so that the effects of the present invention can be obtained not only when bonding with a liquid crystal polymer but also when bonding with other insulating substrates. It can be said.

On the other hand, Comparative Examples 1, 2, 4, 6, and 7 have high silane coupling concentrations, and thus, Comparative Examples 2, 3, 5, and 7 have insufficient stirring time due to the formation of a thick silane coupling film in the outermost layer of the surface treatment. Therefore, due to the reason that the hydrolysis reaction of the silane coupling agent was insufficient, Comparative Examples 8 and 9 were all prescribed in the present invention because of the reason that the silane coupling concentration was thin so that the silane coupling film having a sufficient thickness was not formed in the outermost layer of the surface treatment. The requirements for the combination of N concentration, C concentration and Si and O concentration at 0.5 min sputter depth from the surface treated surface could not be satisfied. For this reason, even when adhesiveness with the liquid crystal polymer at normal temperature is high, the blister generation was not able to be suppressed when the copper clad laminated board was comprised and heat load was applied. Moreover, although blister generation was suppressed in Comparative Examples 8 and 9, adhesiveness with the liquid crystal polymer at normal temperature was insufficient.

Claims (27)

A surface-treated copper foil having a surface-treated surface, wherein the C concentration is 12-30 atom% by XPS measurement at a depth of 0.5 min sputtering under conditions of a rate of 1.1 nm / min (in terms of SiO ₂ ) from the surface-treated surface. A surface-treated copper foil having a surface-treated surface, wherein the Si concentration by XPS measurement at a depth of 0.5 min sputtering at a rate of 1.1 nm / min (in terms of SiO ₂ ) from the surface-treated surface is 3.1 atom% or more, and the O concentration is Surface-treated copper foil which is 40 to 48 atom%. The surface-treated copper foil which satisfy | fills any two or more of the following conditions with the surface-treated copper foil which has a surface treatment surface.
N concentration is 1.5 to 7.5 atom% by XPS measurement at a depth after 0.5 min sputtering under conditions of rate 1.1 nm / min (SiO ₂ equivalent) from the surface treated surface.
C concentration is 12 to 30 atom% by XPS measurement at a depth after 0.5 min sputtering at a rate of 1.1 nm / min (SiO 2 equivalent) from the surface treated surface.
Si concentration by XPS measurement at a depth of 0.5 min sputtering at a rate of 1.1 nm / min (in terms of SiO ₂ ) from the surface-treated surface is 3.1 atom% or more, and an O concentration is 40 to 48 atom%. The method according to any one of claims 1 to 3,
From the surface-treated surface rate 1.1nm / min (SiO ₂ basis) of the N concentration measured by XPS in the depth after sputtering 1.0min 0.5 ~ 6.0atom% under the condition, the surface treated copper foil. The method according to any one of claims 1 to 3,
From the surface-treated surface rate 1.1nm / min (SiO ₂ basis) of the C concentration measured by XPS in the depth after sputtering 1.0min 8 ~ 25atom% under the condition, the surface treated copper foil. The method according to any one of claims 1 to 3,
Surface-treated copper foil whose Rz of a surface-treated surface is 1.5 micrometers or less. The method according to any one of claims 1 to 3,
Surface-treated copper foil whose copper foil is a rolled copper foil or an electrolytic copper foil. The method according to any one of claims 1 to 3,
Surface-treated copper foil for bonding with a liquid crystal polymer. The method according to any one of claims 1 to 3,
Surface-treated copper foil for bonding with polyimide resin. The method according to any one of claims 1 to 3,
Surface-treated copper foil used for printed circuit boards used under high frequencies above 1 GHz. The method according to any one of claims 1 to 3,
The surface-treated copper foil which has at least 1 sort (s) of layer chosen from the group which consists of a roughening process layer, a heat resistant process layer, a rustproof process layer, a chromate treatment layer, and a silane coupling process layer on the copper foil surface. The method according to any one of claims 1 to 3,
The surface-treated copper foil which has at least 1 sort (s) of layer chosen from the group which consists of a heat-resistant processing layer, a rust-proof processing layer, a chromate treatment layer, and a silane coupling treatment layer on the copper foil surface. The method according to any one of claims 1 to 3,
The surface-treated copper foil which has a heat-resistant processing layer or an rust-preventing layer on the copper foil surface, has a chromate treatment layer on the said heat-resistant treatment layer or an rustproof treatment layer, and has a silane coupling process layer on the said chromate treatment layer. The method according to any one of claims 1 to 3,
Surface-treated copper foil which has a heat-resistant treatment layer on the copper foil surface, has a rustproof treatment layer on the said heat-resistant treatment layer, has a chromate treatment layer on the said rustproof treatment layer, and has a silane coupling treatment layer on the said chromate treatment layer. . The method according to any one of claims 1 to 3,
The surface-treated copper foil which has a chromate treatment layer on the copper foil surface, and has a silane coupling process layer on the said chromate treatment layer. The method according to any one of claims 1 to 3,
The surface-treated copper foil which has a roughening process layer on the copper foil surface, has a chromate process layer on the said roughening process layer, and has a silane coupling process layer on the said chromate process layer. The method according to any one of claims 1 to 3,
It has a roughening process layer on the copper foil surface, and has 1 or more types chosen from the group which consists of an antirust process layer and a heat resistant process layer on the said roughening process layer, and is selected from the group which consists of the said rustproof process layer and a heat resistant process layer. The surface-treated copper foil which has a chromate treatment layer on one or more types of layers, and has a silane coupling process layer on the said chromate treatment layer. The method according to any one of claims 1 to 3,
Surface-treated copper foil which has a roughening process layer on the copper foil surface, has a rustproof process layer on the said roughening process layer, has a chromate process layer on the said rustproof process layer, and has a silane coupling process layer on the said chromate process layer. . The method according to any one of claims 1 to 3,
Surface-treated copper foil which has a roughening process layer on the copper foil surface, and has a silane coupling process layer on the said roughening process layer. The method according to any one of claims 1 to 3,
Surface-treated copper foil which has a silane coupling process layer on the copper foil surface. The method according to any one of claims 1 to 3,
Surface-treated copper foil which has a roughening process layer on the copper foil surface, and the said roughening process layer has a secondary particle layer on a primary particle layer and this primary particle layer. The method of claim 21,
The surface-treated copper foil with which the said secondary particle layer is formed from the ternary alloy which consists of copper, cobalt, and nickel. The method of claim 21,
The surface-treated copper foil whose average particle diameter of the said primary particle layer is 0.25-0.45 micrometer, and whose average particle diameter of the said secondary particle layer is 0.05-0.25 micrometer. The copper foil laminated board formed by bonding the surface treatment surface of the surface treatment copper foil in any one of Claims 1-3 with an insulating base material. The printed wiring board using the surface-treated copper foil in any one of Claims 1-3. The electronic device using the printed wiring board of Claim 25. delete