KR101824827B1 - Surface-treated copper foil - Google Patents

Abstract

Wherein the Si concentration is 2.0% or more and the N concentration is 2.0% or more in the XPS survey measurement of the surface of the copper foil. A copper foil for a flexible printed circuit board (FPC) in which a copper foil is laminated on a liquid crystal polymer (LCP) preferable for high frequency use is provided.

Description

SURFACE-TREATED COPPER FOIL}

The present invention relates to a surface-treated copper foil for a copper clad laminate for manufacturing a flexible printed wiring board (FPC) capable of performing efficient transmission of a high-frequency electrical signal.

The flexible printed circuit board is manufactured by etching a copper foil of a substrate to form various wiring patterns, and connecting the electronic components by soldering. The copper foil is classified into an electrolytic copper foil and a rolled copper foil from its production method, and a rolled copper foil having excellent flexibility is favorably used for a copper foil for a flexible substrate. In electronic devices such as PCs and mobile communications, as the communication speed and capacity increase, electric signals are being made higher in frequency, and printed wiring boards and copper foils capable of coping with them are required.

In electronic apparatuses such as PCs and mobile communications, electric signals are made to have a high frequency. However, when the frequency of electric signals becomes 1 GHz or more, the influence of the skin effect on the surface of the conductor only becomes significant, And the influence of the increase of the conductor loss can not be ignored. Also in this respect, it is desired that the surface roughness of the copper foil is small.

The surface of the electrolytic copper foil of green foil is formed by electrodeposited particles of copper, and the surface of the rolled copper foil is formed by contact with the rolling roll. Therefore, in general, the surface roughness of rolled copper foil is smaller than the surface roughness of electrolytic copper foil. The electrodeposited particles in the roughening treatment are finer in the rolled copper foil. For this reason, the rolled copper foil is considered to be excellent as a copper foil for a high-frequency circuit.

On the other hand, the higher the frequency, the larger the data transfer amount, but the loss (attenuation) of the signal power becomes larger, and the data can not be read, so that the circuit length of the FPC is limited. In order to reduce the loss (attenuation) of such signal power, the surface roughness of the copper foil on the conductor side is small and the transition from polyimide to liquid crystal polymer on the resin side tends to occur. From the viewpoint of the skin effect, it is most preferable that the copper foil does not have a roughening treatment and has a low roughness.

The loss (attenuation) of the signal power in the electronic circuit can largely be divided into two. The first one is the conductor loss, that is, the loss due to the copper foil. The second one is the dielectric loss, that is, the loss due to the substrate. In conductor loss, there is a skin effect at high frequencies, and current has the property of flowing through the surface of a conductor. Therefore, if the surface of the copper foil is rough, a complicated path follows and a current flows. As described above, since the roughness of the rolled copper foil is smaller than that of the electrolytic copper foil, the conductor loss tends to be small.

On the other hand, a liquid crystal polymer (LCP) is required to be laminated without a glue to a copper foil as a polymer exhibiting optical anisotropy in a liquid phase (melting or solution). The entire aromatic polyester-based liquid crystal polymer is a halogen-free material exhibiting the orientation properties of molecules even in a molten state and maintaining this state even in a solid state and exhibiting thermoplasticity.

Liquid crystal polymer (LCP) is characterized by low dielectric constant and low dielectric loss tangent. In addition, the relative dielectric constant of polyimide is 3.5 and the dielectric loss tangent of LCP is 0.002, while that of polyimide is 0.01, so that the liquid crystal polymer (LCP) is more excellent in characteristics . In addition, the liquid crystal polymer (LCP) has the advantage of being low in absorbency and having a low moisture absorption rate, having little change in electrical characteristics, and having a small dimensional change.

In the rolled copper foil, the rolling finish material which is rolled after the final annealing is optimized (see, for example, Patent Document 1) for the purpose of maintaining the handling property.

However, the liquid crystal polymer (LCP) has a weaker strength than the polyimide, and a material in which the copper foil is laminated has a large problem that peel strength is hard to be obtained. When the roughness of the copper foil is increased, the peel strength tends to increase because a physical anchor effect can be obtained. However, the electrical characteristics at high frequencies are deteriorated by the influence of the above-described skin effect.

Although there are several proposals for a copper foil for a high-frequency circuit (see, for example, Patent Documents 2, 3, 4 and 5), from the viewpoint of simplifying the manufacturing process of the rolled copper foil and reducing the high- This is the current situation.

Japanese Patent Application Laid-Open No. 2003-193211 Japanese Patent Publication No. 61-54592 Japanese Patent Publication No. 3-34679 Japanese Patent Publication No. 7-10564 Japanese Unexamined Patent Publication No. 5-55746

SUMMARY OF THE INVENTION It is an object of the present invention to provide a copper foil for a flexible printed circuit board (FPC) in which a copper foil is laminated on a liquid crystal polymer (LCP) suitable for high frequency applications, And a copper foil having an improved copper foil.

The present inventors have found that transmission loss can be reduced by the following reasons.

The first is that the surface of the copper foil is greatly affected in the high frequency region. As the surface roughness increases, the transmission loss increases. Therefore, it is effective to adjust the surface roughness of the copper foil as small as possible.

The second is the use of a liquid crystal polymer (LCP) laminated substrate. However, for this purpose, it is necessary to increase the adhesive strength (peel strength) to the copper foil.

By solving the above problems, it has been found that a flexible printed circuit board (FPC) in which signal power loss (attenuation) is suppressed can be provided.

From the above findings, the present invention provides the following inventions.

1) A surface-treated copper foil having a Si concentration of 2.0% or more and an N concentration of 2.0% or more in XPS survey measurement of the surface of the copper foil.

2) The surface-treated copper foil according to 1) above, which is a copper foil for a flexible printed circuit board.

3) The surface-treated copper foil according to any one of 1) to 2) above, wherein the copper foil is a rolled copper foil or an electrolytic copper foil.

(4) The surface-treated copper foil according to any one of (1) to (3) above, which is a copper foil bonded to a flexible printed circuit board made of a liquid crystal polymer.

(5) The surface-treated copper foil according to any one of (1) to (4) above, wherein the state fill strength at 90 degrees when bonded to a flexible printed circuit board made of a liquid crystal polymer is 0.3 kg / cm or more.

6) The surface-treated copper foil according to any one of 1) to 5) above, which is bonded to a flexible printed circuit board usable under high frequencies exceeding 1 GHz.

According to the present invention, it is possible to manufacture a surface-treated copper foil that can be used for a high-frequency circuit application, and the copper foil can be applied to a liquid crystal polymer (LCP) A flexible printed circuit board which can be used under a high frequency exceeding the above range can be realized.

The surface-treated copper foil usable for high frequency circuit applications is characterized in that the Si concentration is 2.0% or more and the N concentration is 2.0% or more in the XPS survey measurement of the surface of the copper foil. This makes it possible to increase the adhesive strength (peel strength) when bonding the copper foil to the liquid crystal polymer (LCP) laminated substrate. As one means for achieving the Si concentration and the N concentration on the surface of the copper foil, the copper foil surface is subjected to a silane treatment. It is also effective to use the surface-treated copper foil of the present invention for a copper foil for a high-frequency circuit.

When the Si concentration is less than 2.0% and the N concentration is less than 2.0% in the XPS survey measurement of the surface of the copper foil surface, the bonding strength is not sufficient and in the XPS survey measurement of the copper foil surface, the Si concentration exceeds 20.0% If the concentration exceeds 40.0%, foaming occurs at the time of laminating with the LCP, so that an excessively large amount is not preferable.

The silane application method may be any of spraying, coating, immersion, pouring, etc. of the silane coupling agent solution. Since these are known techniques (see, for example, Japanese Patent Application Laid-open No. 60-15654), detailed description thereof will be omitted.

With respect to the concentrations of Si and N on the surface of the copper foil, the surface of the copper foil bonded to the surface of the resin was measured by XPS to determine the Si concentration and N concentration of the outermost surface. The analysis conditions are shown below.

Device: manufactured by ULVAC PY LTD 5600MC

Reaching vacuum degree: 2.0 × 10 ^-9 Torr

Here the circle: Monochromated AlKα

Output: 210 W

Detection area: 800 탆

Angle of incidence: 45 °

Extraction angle: 45 °

No Chunghwa

The copper foil having an increased bonding strength is a copper foil for a high-frequency circuit most suitable for a flexible printed circuit board made of a liquid crystal polymer. That is, the state fill strength at 90 degrees in the case of bonding to a flexible printed circuit board made of a liquid crystal polymer can be 0.3 kg / cm or more.

In addition, since the bonding strength of the copper foil can be increased, the copper foil can be applied to the rolled copper foil and the electrolytic copper foil which have less surface roughness (less conductor loss) and obtain the optimum copper foil for a high frequency circuit. The copper foil for a high frequency circuit makes it possible to manufacture a flexible printed circuit board which can be used under a high frequency exceeding 1 GHz.

The surface-treated copper foil according to the present invention may have a roughening treatment layer and / or heat-resistant treatment layer and / or a rust-preventive treatment layer and / or a chromate treatment layer and / or a plating treatment layer and / or a silane coupling treatment layer . 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 layer is not particularly limited, and any heat-resistant layer or a known heat-resistant layer may be used. The rust-preventive treatment layer is not particularly limited, and all rust-inhibited treatment layers and known rust-inhibited treatment layers can be applied. The plating treatment layer is not particularly limited, and any plating treatment layer or a known plating treatment 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.

For example, the surface-treated copper foil according to the invention of the present application may be subjected to a roughening treatment for improving the adhesion with, for example, an insulating substrate to the surface thereof, thereby forming the roughened layer. The roughening treatment can be carried out, for example, by forming coarse particles with copper or a copper alloy. The harmonic treatment may be fine. The roughening treatment layer may be a layer made of an alloy containing any one or more selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc.

It is also possible to carry out a harmonizing treatment for forming secondary particles or tertiary particles with nickel, cobalt, copper, zinc alone, or an alloy of nickel, cobalt, zinc, or the like after the roughening particles are formed of copper or a copper alloy. Thereafter, the heat-resistant layer or rust-preventive layer may be formed of a single body of nickel, cobalt, copper, zinc, or an alloy, or the surface may further be subjected to chromate treatment, silane coupling treatment or the like. Even if a heat-resistant treatment layer or rust-preventive treatment layer is formed of a single body of nickel, cobalt, copper, zinc or an alloy or the like and the surface is further subjected to a treatment such as a chromate treatment or a silane coupling treatment do.

That is, at least one layer selected from the group consisting of heat-resistant treatment layer, rust-preventive treatment layer, chromate treatment layer and silane coupling treatment layer may be formed on the surface of the roughened treatment layer, , An anti-rust treatment layer, a chromate treatment layer, and a silane coupling treatment layer may be formed. The heat-resistant layer, rust-preventive treatment layer, chromate treatment layer and silane coupling treatment layer described above may be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.). In the present invention, the " anti-rust treatment layer " includes a " chromate treatment layer ".

Further, in consideration of the adhesion with the resin, it is preferable to form a silane coupling treatment layer on the outermost layer of the surface-treated copper foil.

As the coarsened layer, it is preferable that a primary particle layer of copper and a secondary particle layer of a ternary alloy composed of copper, cobalt and nickel are formed on the primary particle layer.

It is more preferable that the primary particle layer has an average particle diameter of 0.25 - 0.45 탆 and the secondary particle layer has an average particle diameter of 0.05 - 0.25 탆.

As the rust-preventive treatment or the chromate treatment, the following treatments can be used.

≪ Ni-Co plating >: Ni-Co alloy plating

(Liquid composition) Co: 1 to 20 g / l, Ni: 1 to 20 g / l

(pH) 1.5 to 3.5

(Liquid temperature) 30 to 80 DEG C

(Current density) 1 to 20 A / dm 2

(Energization time) 0.5 to 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 to 4

(Liquid temperature) 40 to 50 DEG C

(Current density) 0.5 to 5 A / dm &lt; 2 &gt;

(Energization time) 1 to 3 seconds

&Lt; Ni-Mo plating &gt;: Ni-Mo alloy plating

Molybdenum (added as sodium molybdate): 0.1 to 10 g / l, nickel chloride: 35 to 45 g / l, nickel acetate: 10 to 20 g / Sodium citrate: 15-25 g / l Brightener: Saccharin, Butynediol, etc. Dodecylsulfate: 55-75 ppm

(pH) 4 to 6

(Liquid temperature) 55 to 65 ° C

(Current density) 1 to 11 A / dm &lt; 2 &gt;

(Energization time) 1 to 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 /

(Liquid temperature) 60 to 80 DEG C

(Current density) 1 to 10 A / dm &lt; 2 &gt;

(Energization time) 1 to 10 seconds

<Electrolytic chromate>

1 to 10 g / l of zinc chloride (added in the form of zinc sulfate if added): 0 to 5 g / l

(pH) 0.5 to 10

(Liquid temperature) 40 to 60 DEG C

(Current density) 0.1 to 2.6 A / d &lt;

(Coulomb amount) 0.5 to 90 As / dm &lt; 2 &gt;

(Energization time) 1 to 30 seconds

<Immersion Chromate>

1 to 10 g / l of zinc chloride (added in the form of zinc sulfate if added): 0 to 5 g / l

(pH) 2 to 10

(Liquid temperature) 20 to 60 DEG C

(Processing time) 1 to 30 seconds

When Si and N are attached to the surface of the copper foil in the silane coupling treatment, aminosilane is used for the silane coupling treatment. It is also necessary to perform the silane coupling treatment at a higher concentration (for example, 1.5 vol% or more) than that of the prior art in the concentration of the silane coupling agent in the silane coupling treatment liquid. It is also necessary that the drying temperature after the silane coupling treatment is not excessively increased and that the drying time is not excessively long. If the drying temperature is excessively high or the drying time is too long, the silane coupling agent present on the surface of the copper foil may be desorbed.

The drying after the silane coupling treatment is preferably carried out at a drying temperature of 90 to 110 캜, preferably 95 to 105 캜, for a drying time of 1 to 10 seconds, preferably 1 to 5 seconds.

In a preferred embodiment, a silane containing at least one amino group and / or an imino group as an aminosilane can be used. The number of amino groups and imino groups contained in the aminosilane may 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 imino groups contained in the aminosilane may be one each.

The aminosilane having one amino group and the total number of imino groups contained in the aminosilane is particularly monoaminosilane, the two aminosilanes are particularly diaminosilane, and the three aminosilanes are particularly called triaminosilane. Monoaminosilane and diaminosilane can be preferably used in the present invention. In a preferred embodiment, a monoaminosilane containing one amino group as the aminosilane can be used. In a preferred embodiment, the aminosilane can contain at least one amino group, for example one amino group, at the end of the molecule, preferably at the end of a linear or branched chain-like molecule.

Examples of the aminosilane include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, Aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, 1,2-diaminopropyltrimethoxysilane, 3-amino-1-propenyltrimethoxysilane, 3-amino Propyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-amino-3-aminopropyltrimethoxysilane), N- Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and 3- (N-phenyl) aminopropyltrimethoxysilane.

In a preferred embodiment, it is preferable to use silane having the following formula I for the silane coupling treatment.

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

(In the above formula I,

R1 is a divalent group of C1 to C12 hydrocarbon, having a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, having a heterocyclic ring or not having a heterocyclic ring,

R2 is a C1-C5 alkyl group,

R3 is a C1 to C5 alkyl group or a C1 to C5 alkoxy group)

R1 is a substituted or unsubstituted linear saturated hydrocarbon of a divalent group, a substituted or unsubstituted C1 to C12 branched saturated hydrocarbon divalent group, a substituted or unsubstituted C1 to C12 linear unsaturated A divalent group of a hydrocarbon, a substituted or unsubstituted C1 to C12 branched unsaturated hydrocarbon, a divalent group of a substituted or unsubstituted C1 to C12 cyclic hydrocarbon, a substituted or unsubstituted C1 to C12 heterocyclic A divalent group of a hydrocarbon, a substituted or unsubstituted divalent group of a C1 to C12 aromatic hydrocarbon, and the like.

In addition, R1 _{a, - (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 - in (Provided that n, m, and j are integers equal to or greater than 1).

It is preferable that R1 is - (CH ₂ ) _n - or - (CH ₂ ) _n -NH- (CH ₂ ) _m -.

n, m and j are each independently 1, 2 or 3.

R 2 is preferably a methyl group or an ethyl group.

R3 is preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group.

In another embodiment, a layer containing Si and N may be formed on the surface of the copper foil by dry plating such as sputtering, CVD, or PDV. Then, it may be heated at a heating temperature of 150 to 250 ° C for 1 second to 300 seconds. Si and N present in the surface layer are diffused toward the copper foil side by heating so that the concentration of Si and N on the surface of the copper foil can be easily controlled to a predetermined range.

An example of the conditions of the sputtering is shown below.

(Target): 15 to 65 mass% of Si, 25 to 55 mass% of N, and a total of 50 mass% or more of Si concentration and N concentration. The remainder may be any element.

(Apparatus) Sputtering apparatus manufactured by ULVAC Co., Ltd.

(Output) DC 50 W

(Argon pressure) 0.2 Pa

Example

Hereinafter, the present invention will be described by way of examples. It should be noted that the present embodiment shows a preferable example, and the present invention is not limited to these embodiments. Accordingly, all modifications, other embodiments or aspects included in the technical idea of the present invention are included in the present invention. For comparison with the present invention, a comparative example is also described.

(Example 1)

An ingot in which 1200 ppm of Sn was added to oxygen-free copper was melted, and the ingot was hot-rolled from 900 占 폚 to obtain a plate having a thickness of 10 mm. Thereafter, cold rolling and annealing were repeated, and finally cold rolled with a copper foil having a thickness of 9 탆. The surface roughness of the rolled copper foil was Rz 0.63 탆.

Next, the rolled copper foil was plated with Ni under the following conditions (no coarsening treatment).

The remainder of the Ni plating solution is water. The balance of the solution used in the coarsening treatment, the plating treatment, the silane treatment, the heat-resistant treatment and the rust-inhibitive treatment described in the present application was also made with water unless otherwise specified.

Ni ion: 10 to 40 g / l

Temperature: 30 ~ 70 ℃

Current density: 1 to 9 A / dm 2

Plating time: 0.1 ~ 3.0 seconds

pH: 1.0-5.0

Next, the above-mentioned Ni-plated rolled copper foil was subjected to an immersion chromate treatment under the following conditions.

K ₂ Cr ₂ O ₇ : 1 to 10 g / l

Temperature: 20 ~ 60 ℃

Processing time: 1 to 5 seconds

Next, silane coupling treatment shown in Table 1 was carried out.

Type of silane: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane

Silane concentration: 1.5 vol%

Temperature: 10 ~ 60 ℃

Processing time: 1 to 5 seconds

Drying after silane treatment: 100 占 폚 × 3 seconds

As a result, the copper foil surface roughness Rz (10-point average roughness) after the silane coupling treatment was 0.63 mu m. Rz was measured using a contact roughness tester Surfcorder SE-3C, a contact-type roughness meter manufactured by Kosaka Laboratory Co., Ltd., in accordance with JIS B 0601-1982. With respect to the Si concentration and the N concentration on the surface of the copper foil, the Si concentration was 2.2% and the N concentration was 5.0% by XPS survey measurement, and the high-frequency characteristics were also good. Also, the Si concentration and the N concentration measured by the XPS survey measurement are the atom concentration (atom%). Further, when Si and N are detected in this measurement, it can be judged that a silane coupling treatment layer made of aminosilane exists in the surface-treated copper foil.

Since the measurement method (evaluation method) of the Si concentration and the N concentration of the copper foil surface in the following examples and comparative examples is carried out in the same manner, the explanations thereof are omitted in order to avoid complication.

The above results achieved the conditions of the present invention in which the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the XPS survey measurement of the surface of the copper foil.

The silane-treated rolled copper foil thus produced was bonded to a resin of a liquid crystal polymer (Vecstar CT-Z, manufactured by Kuraray Co., Ltd.) having a thickness of 50 占 퐉 by a press. The sample thus obtained was used to measure the 90 degree peel strength.

The peel strength is a case where the resin and the copper foil are peeled off at a speed of 50 mm / min at an angle of 90 degrees with a circuit width of 3 mm. The measurement was carried out twice, and the average value was determined.

The measurement of the peel strength is in accordance with JIS C 6471-1995 (hereinafter the same). As a result, a 90 degree fill strength of 0.32 kg / cm was obtained. The results are shown in Table 1. As shown in Example 1, the surface-treated rolled copper foil of Example 1 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

After bonding the copper foil to a liquid crystal polymer having a thickness of 50 탆, a microstrip line structure was formed to investigate high frequency characteristics. At this time, the circuit was formed so as to have a characteristic impedance of 50 OMEGA. The transmission loss was measured using this circuit, and when the transmission loss at a frequency of 30 GHz was smaller than -0.6, the high frequency characteristic was marked as?.

Also, -0.6 to -0.8 was rated as?, -0.8 to -1.2 was evaluated as?, And when the transmission loss was larger than -1.2, it was evaluated as?. This measurement value is shown as a reference and does not limit the scope.

(Example 2)

The conditions for the silane treatment in Example 1 were changed (the silane concentration was 1.7 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.61 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 3.7% and the N concentration was 8.5%, indicating that the Si concentration was 2.0% or more and the N concentration was 2.0% Respectively. The high-frequency characteristics were also good.

As a result, the 90 degree peel strength was 0.48 kg / cm. These are shown in Table 1. As shown in Example 2, the surface-treated rolled copper foil of Example 2 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 3)

The conditions of the silane treatment in Example 1 were changed (the silane concentration was 2.0 vol%), and the other conditions were the same as in Example 1. [ As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.61 mu m.

The Si concentration and the N concentration of the copper foil surface were found to be 5.7% and 10.7% in the same manner as in Example 1. As a result, the Si concentration and the N concentration were found to be 2.0% Respectively. The high-frequency characteristics were also good.

As a result, the 90 degree peel strength was 0.55 kg / cm. These are shown in Table 1. As shown in Example 3, the surface-treated rolled copper foil of Example 3 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 4)

The conditions of the silane treatment in Example 1 were changed (the silane concentration was set to 3.0 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.67 mu m.

The Si concentration and the N concentration of the surface of the copper foil were measured in the same manner as in Example 1 to find that the Si concentration was 5.5% and the N concentration was 10.1%, and the Si concentration was 2.0% or more and the N concentration was 2.0% Respectively. The high-frequency characteristics were also good.

As a result, the 90 degree peel strength was 0.63 kg / cm. These are shown in Table 1. As shown in Example 4, the surface-treated rolled copper foil of Example 4 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 5)

The conditions of the silane treatment in Example 1 were changed (the silane concentration was 4.0 vol%), and the other conditions were the same as in Example 1. [ As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.65 mu m.

The Si concentration and the N concentration of the copper foil surface were found to be 6.6% and 10.8%, respectively, in the same manner as in Example 1. As a result, the Si concentration and the N concentration were 2.0% Respectively. The high-frequency characteristics were also good.

As a result, the 90 degree peel strength was 0.63 kg / cm. These are shown in Table 1. As shown in Example 5, the surface-treated rolled copper foil of Example 5 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 6)

The conditions of the silane treatment in Example 1 were changed (the silane concentration was 5.0 vol%), and the other conditions were the same as those in Example 1. [ As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.61 mu m.

The Si concentration and the N concentration of the copper foil surface were found to be 8.5% and 14.1%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively. The high-frequency characteristics were also good.

As a result, the 90 degree peel strength was 0.77 kg / cm. These are shown in Table 1. As shown in Example 6, the surface-treated rolled copper foil of Example 6 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 7)

The conditions of the silane treatment in Example 1 were changed (the silane concentration was 6.5 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.60 mu m.

The Si concentration and the N concentration of the copper foil surface were found to be 9.0% and 12.1%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively. The high-frequency characteristics were also good.

As a result, the 90 degree peel strength was 0.83 kg / cm. These are shown in Table 1. As shown in Example 7, it can be seen that the surface-treated rolled copper foil of Example 7 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 8)

Before the nickel plating in Example 1, the roughening treatment was carried out and then the heat resistance and rustproofing treatment were carried out and the conditions of the silane treatment were changed (the silane concentration was 5.0 vol%). Other conditions were the same as those of Example 1. (That is, roughening treatment, heat resistance and anti-rust treatment, immersion chromate treatment and silane treatment were performed on the rolled copper foil which was cold rolled and made to a thickness of 9 mu m in Example 1. Did not do it). As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 0.90 mu m. An example of the blending treatment conditions will be described below. In this embodiment, the coarsening treatment (coarsening treatment plating) was carried out under the following plating conditions.

This plating condition represents a preferable example, and plating conditions other than those shown below are acceptable.

(Plating conditions of primary particles of copper)

Liquid composition: copper 10 to 20 g / l, sulfuric acid 50 to 100 g / l

Solution temperature: 25 ~ 50 ℃

Current density: 1 to 58 A / dm 2

Plating time: 0.1 to 10 seconds

(Plating conditions of secondary particles)

Liquid composition: copper 10 to 20 g / l, nickel 5 to 15 g / l, cobalt 5 to 15 g / l

pH: 2-3

Temperature: 30 ~ 50 ℃

Current density: 24 ~ 50 A / dm2

Plating time: 0.5 to 4 seconds

The Si concentration and the N concentration of the surface of the copper foil were measured in the same manner as in Example 1 to find that the Si concentration and the N concentration were 7.2% and 15.2%, respectively, and that the Si concentration was 2.0% Respectively. The high-frequency characteristics were also good although slightly lower than those of Examples 1 to 7.

As a result, the 90-degree peel strength was 0.95 kg / cm. These are shown in Table 1. As shown in Example 8, the surface-treated rolled copper foil of Example 8 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 9)

Before the nickel plating in Example 1, the roughening treatment was carried out, and then the heat resistance and rustproofing treatment were carried out, and the conditions of the silane treatment were changed (the silane concentration was 7.5 vol%). Other conditions were the same as those of Example 1. (That is, roughening treatment, heat resistance and anti-rust treatment, immersion chromate treatment and silane treatment were performed on the rolled copper foil which was cold rolled and made to a thickness of 9 mu m in Example 1. Did not do it). As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.92 mu m. Further, in this embodiment, roughening treatment (roughening treatment plating) was performed under the same plating conditions as in Example 8. [

The Si concentration and the N concentration of the copper foil surface were found to be 9.9% and 22.4%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively. The high-frequency characteristics were also good although slightly lower than those of Examples 1 to 7.

As a result, the 90 degree peel strength was 1.13 kg / cm. These are shown in Table 1. As shown in Example 9, the surface-treated rolled copper foil of Example 9 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 10)

Before the nickel plating in Example 1, the roughening treatment was carried out, and then the heat resistance and rustproofing treatment were carried out, and the conditions of the silane treatment were changed (the silane concentration was 7.5 vol%). Other conditions were the same as those of Example 1. (That is, roughening treatment, heat resistance and anti-rust treatment, immersion chromate treatment and silane treatment were performed on the rolled copper foil which was cold rolled and made to a thickness of 9 mu m in Example 1. Did not do it). As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 1.48 mu m.

The Si concentration and the N concentration of the copper foil surface were found to be 14.6% and 25.3%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively. Although it is slightly lower than those of Examples 1 to 7, the high-frequency characteristics are also at a normal level and are not particularly problematic.

As a result, the 90 degree peel strength was 1.31 kg / cm. These are shown in Table 1. As shown in Example 10, the surface-treated rolled copper foil of Example 10 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 11)

The conditions and conditions for the silane treatment in Example 1 were changed (N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, silane concentration was 5.0 vol%) and other conditions were the same as in Example 1 . As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.62 mu m.

The Si concentration and the N concentration of the copper foil surface were determined in the same manner as in Example 1. As a result, the Si concentration and the N concentration were found to be 10.1% and 19.8%, respectively, and the Si concentration and the N concentration were 2.0% Respectively. The high-frequency characteristics were also good.

As a result, the 90-degree peel strength was 0.71 kg / cm. These are shown in Table 1. As shown in Example 11, the surface-treated rolled copper foil of Example 11 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 12)

The conditions and conditions of the silane treatment in Example 1 were changed (3-aminopropylmethoxysilane and silane concentration: 7.0 vol%), and other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.65 mu m.

The Si concentration and the N concentration of the copper foil surface were found to be 12.3% and 11.9%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively. The high-frequency characteristics were also good.

As a result, a 90 degree peel strength of 0.81 kg / cm was obtained. These are shown in Table 1. As shown in Example 12, the surface-treated rolled copper foil of Example 12 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 13)

(3-triethoxysilyl-N-1,3-dimethyl-butylidenepropylamine, silane concentration: 5.5 vol%) and the other conditions were the same as in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.64 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 8.3% and the N concentration was 8.5%, and the Si concentration was 2.0% or more and the N concentration was 2.0% Respectively. The high-frequency characteristics were also good.

As a result, the 90-degree peel strength was 0.71 kg / cm. These are shown in Table 1. As shown in Example 13, the surface-treated rolled copper foil of Example 13 has industrially sufficient surface performance as a material for a high-frequency circuit board.

(Example 14)

The conditions and conditions for the silane treatment in Example 1 were changed (N-phenyl-3-aminopropylmethoxysilane, silane concentration: 7.5 vol%). As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.60 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 18.5% and the N concentration was 16.5%, and the Si concentration was 2.0% or more and the N concentration was 2.0% Respectively. The high-frequency characteristics were also good.

As a result, the 90 degree peel strength was 0.79 kg / cm. These are shown in Table 1. As shown in Example 14, the surface-treated rolled copper foil of Example 14 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Comparative Example 1)

The conditions of the silane treatment in Example 1 were changed (the silane concentration was 0.5 vol%), and the 90 degree peel strength was measured in the same manner. The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.60 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration and the N concentration were 1.1% and 3.3%, respectively, and that the Si concentration was 2.0% .

As a result, the 90 - degree peel strength was as low as 0.11 ㎏ / ㎝. These are shown in Table 1. As shown in Comparative Example 1, the surface-treated rolled copper foil of Comparative Example 1 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 2)

The conditions of the silane treatment in Example 1 were changed (the silane concentration was 1.0 vol%), and the 90 degree peel strength was measured in the same manner. The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.61 mu m.

The Si concentration and the N concentration of the surface of the copper foil were found to be 1.4% and 3.5%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 .

As a result, the 90 - degree peel strength was as low as 0.12 ㎏ / ㎝. These are shown in Table 1. As shown in Comparative Example 2, the surface-treated rolled copper foil of Comparative Example 2 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 3)

The silane treatment in Example 1 was not carried out. Therefore, there is no Si or N on the surface of the copper foil. The 90 degree peel strength was measured in the same manner. The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.61 mu m.

Si and N on the surface of the copper foil were not present. Therefore, the Si concentration on the copper foil surface was 2.0% or more and the N concentration was 2.0% or more.

As a result, the 90 degree peel strength was remarkably low as 0.03 kg / cm. These are shown in Table 1. As shown in Comparative Example 3, the rolled copper foil having no Si or N on the surface of the copper foil could not have industrially sufficient surface performance as a material for a high frequency circuit board.

(Comparative Example 4)

The steel sheet was subjected to a roughening treatment before the nickel plating in Example 1, and then heat-resistant and rust-preventive treatment were carried out. However, no silane treatment was carried out (in other words, the rolled copper foil was cold- Treatment, heat resistance and rust prevention treatment, and immersion chromate treatment were carried out. Therefore, there is no Si or N on the surface of the copper foil. The 90 degree peel strength was measured in the same manner. The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.92 mu m. Further, in this embodiment, roughening treatment (roughening treatment plating) was performed under the same plating conditions as in Example 8. [

Si and N on the surface of the copper foil were not present. Therefore, the Si concentration on the copper foil surface was 2.0% or more and the N concentration was 2.0% or more.

As a result, the 90 - degree peel strength was as low as 0.32 ㎏ / ㎝. These are shown in Table 1. Compared with Examples 8 and 9, the rolled copper foil having no Si or N on the surface of the copper foil could not have industrially sufficient surface performance as a material for a high frequency circuit board.

(Comparative Example 5)

The steel sheet was subjected to a roughening treatment before the nickel plating in Example 1, and then heat-resistant and rust-preventive treatment were carried out. However, no silane treatment was carried out (in other words, the rolled copper foil was cold- Treatment, heat resistance and rust prevention treatment, and immersion chromate treatment were carried out. Therefore, there is no Si or N on the surface of the copper foil. The 90 degree peel strength was measured in the same manner. The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 1.53 탆. Further, in this embodiment, roughening treatment (roughening treatment plating) was carried out under the same plating conditions as in Example 10.

Si and N on the surface of the copper foil were not present. Therefore, the Si concentration on the copper foil surface was 2.0% or more and the N concentration was 2.0% or more.

As a result, the 90 degree peel strength was 0.66 kg / cm. These are shown in Table 1. Compared with Example 10, the rolled copper foil with no Si or N on the surface of the copper foil could not be regarded as the optimum surface performance industrially as a material for a high frequency circuit board.

(Comparative Example 6)

The steel sheet was subjected to a roughening treatment before the nickel plating in Example 1, and then heat-resistant and rust-preventive treatment were carried out. However, no silane treatment was carried out (in other words, the rolled copper foil was cold- Treatment, heat resistance and rust prevention treatment, and immersion chromate treatment were carried out. Therefore, there is no Si or N on the surface of the copper foil. The 90 degree peel strength was measured in the same manner. The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 3.21 탆.

Si and N on the surface of the copper foil were not present. Therefore, the Si concentration on the copper foil surface was 2.0% or more and the N concentration was 2.0% or more.

As a result, the 90 degree peel strength was 0.89 kg / cm. These are shown in Table 1. Compared with other comparative examples, the peel strength is high, but this is a physical effect of roughness of the surface. As described above, if the roughness is large, the loss increases due to the skin effect. It can not be said that it has industrially optimum surface performance.

(Comparative Example 7)

The roughening treatment was performed before the nickel plating in Example 1, and then the heat resistance and rustproofing treatment were performed. However, the conditions of the silane treatment were further changed (the silane concentration was 10.0 vol%). Other conditions were the same as those of Example 1. (That is, roughening treatment, heat resistance and anti-rust treatment, immersion chromate treatment and silane treatment were performed on the rolled copper foil which was cold rolled and made to a thickness of 9 mu m in Example 1. Did not do it). As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 1.51 탆. Further, in this embodiment, roughening treatment (roughening treatment plating) was carried out under the same plating conditions as in Example 10.

The Si concentration and the N concentration of the copper foil surface were 20.6% and 40.1%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 , But there was a problem in the presence of a large amount, and foaming occurred at the time of lamination with liquid crystal polymer (LCP). Therefore, the peel strength of the copper foil was not measured. These are shown in Table 1. As shown in Comparative Example 7, the surface-treated rolled copper foil of Comparative Example 7 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 8)

The conditions for the silane treatment in Example 1 were changed (glycidoxypropyltrimethoxysilane was used and the concentration was 1.5 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.62 mu m.

The Si concentration and the N concentration were found to be 2.2% and 0.0%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1. As a result, Was not satisfied.

As a result, the 90 - degree peel strength was as low as 0.13 ㎏ / ㎝. These are shown in Table 1. As shown in Comparative Example 8, the surface-treated rolled copper foil of Comparative Example 8 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 9)

The conditions for the silane treatment in Example 1 were changed (glycidoxypropyltrimethoxysilane was used, and the concentration was 5.0 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.63 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 9.5% and the N concentration was 0.0%, and the Si concentration was 2.0% or more and the N concentration was 2.0% Was not satisfied.

As a result, the 90 - degree peel strength was as low as 0.19 ㎏ / ㎝. These are shown in Table 1. As shown in Comparative Example 9, the surface-treated rolled copper foil of Comparative Example 9 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 10)

The conditions for the silane treatment in Example 1 were changed (3-methacryloxypropyltrimethoxysilane was used and the concentration was 2.0 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.67 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration and the N concentration were 5.2% and 0.0%, respectively, and that the Si concentration was 2.0% Was not satisfied.

As a result, the 90 degree peel strength was remarkably low as 0.04 kg / cm. These are shown in Table 1. As shown in Comparative Example 10, the surface-treated rolled copper foil of Comparative Example 10 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 11)

The conditions of the silane treatment in Example 1 were changed (vinyltrimethoxysilane was used, and the concentration was 0.5 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.65 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 1.4% and the N concentration was 0.0%, indicating that the Si concentration was 2.0% or more and the N concentration was 2.0% Was not satisfied.

As a result, the 90 degree peel strength was remarkably low as 0.07 kg / cm. These are shown in Table 1. As shown in Comparative Example 11, the surface-treated rolled copper foil of Comparative Example 11 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 12)

The conditions for the silane treatment in Example 1 were changed (vinyltrimethoxysilane was used and the concentration was 2.0 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.65 mu m.

The Si concentration and the N concentration of the copper foil surface were found to be 5.8% and 0.0%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Was not satisfied.

As a result, the 90 degree peel strength was remarkably low as 0.09 kg / cm. These are shown in Table 1. As shown in Comparative Example 12, the surface-treated rolled copper foil of Comparative Example 12 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 13)

The conditions of the silane treatment in Example 1 were changed (vinyltrimethoxysilane was used, and the concentration was 5.0 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.65 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 11.1% and the N concentration was 0.0%, and the Si concentration was 2.0% or more and the N concentration was 2.0% Was not satisfied.

As a result, the 90 degree peel strength was remarkably low at 0.11 kg / cm. These are shown in Table 1. As shown in Comparative Example 13, the surface-treated rolled copper foil of Comparative Example 13 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 14)

The conditions for the silane treatment in Example 1 were changed (3-mercaptopropyltrimethoxysilane was used and the concentration was 2.0 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.64 mu m.

The Si concentration and the N concentration of the copper foil surface were found to be 5.6% and 0.0%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Was not satisfied.

As a result, the 90 degree peel strength was remarkably low as 0.07 kg / cm. These are shown in Table 1. As shown in Comparative Example 14, the surface-treated rolled copper foil of Comparative Example 14 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 15)

The conditions for the silane treatment in Example 1 were changed (tetramethoxysilane was used, and the concentration was 2.0 vol%), and the other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.67 mu m.

The Si concentration and the N concentration were found to be 5.7% and 0.0%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Was not satisfied.

As a result, the 90 degree peel strength was remarkably low as 0.07 kg / cm. These are shown in Table 1. As shown in Comparative Example 15, the surface-treated rolled copper foil of Comparative Example 15 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 16)

The conditions for the silane treatment in Example 1 were changed (tetramethoxysilane and 3-mercaptopropyltrimethoxysilane were mixed and the concentration was 0.2 + 0.5 vol%), and the other conditions were the same as in Example 1 Likewise. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.64 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration and the N concentration were 3.2% and 0.0%, respectively, and that the Si concentration was 2.0% Was not satisfied.

As a result, the 90 degree peel strength was remarkably low as 0.05 kg / cm. These are shown in Table 1. As shown in Comparative Example 16, the surface-treated rolled copper foil of Comparative Example 16 could not have industrially sufficient surface performance as a material for a high-frequency circuit board.

Next, examples of the case where the kind of the copper foil, the roughening treatment, the heat-resistant treatment, and the anti-rust treatment are changed. This example also includes examples in which the heat-resistant treatment and / or the rust-preventive treatment are not performed (Examples 28, 29, 31 to 33). In this case, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as the silane, and the silane concentration was 5.0 vol%. The drying after the silane treatment was performed at 100 ° C for 3 seconds. Further, in the heat resistance treatment, heat resistance can be ensured at the time of laminating the copper foil and the liquid crystal polymer (LCP), and the metal species is not a problem.

Examples thereof include single or alloy platings of Zn, Ni, Co, Mo, P, Cr, W and the like. The heat-treated layer may be Zn-free. The manufacturing conditions and the evaluation (of the peel strength) from the following Examples 21 to 33 and Comparative Examples 21 to 27 were the same as those of Example 1 except that each was described individually. The processing conditions of the Ni-Co plating treatment, the Zn-Ni plating treatment, the Ni-Mo plating treatment, the Cu-Zn plating treatment, the electrolytic chromate treatment and the immersion chromate treatment were as described above. The conditions of the immersion chromate treatment were the same as those in Example 1.

(Example 21)

The rolled copper foil having a thickness of 6 占 퐉 was roughened and subjected to Ni-Co plating treatment as a heat-resistant treatment. In addition, electrolytic chromate treatment was performed as the rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 5.0 vol%. The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.82 mu m. Table 2 shows the treatment conditions.

The Si concentration and the N concentration of the copper foil surface were found to be 6.6% and 8.2%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively.

As a result, a high value of 0.88 kg / cm was obtained for the 90 degree peel strength.

The results are shown in Table 3. As shown in Example 21, the surface-treated rolled copper foil of Example 21 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 22)

The rolled copper foil having a thickness of 12 占 퐉 was subjected to a roughening treatment and subjected to a Zn-Ni plating treatment as a heat-resistant treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 5.0 vol%.

The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 0.90 mu m. Table 2 shows the treatment conditions.

The Si concentration and the N concentration of the copper foil surface were found to be 6.8% and 9.0%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively.

As a result, a high value of 0.93 kg / cm was obtained for the 90 degree peel strength. The results are shown in Table 3. As shown in Example 22, the surface-treated rolled copper foil of Example 22 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 23)

A rolled copper foil having a thickness of 35 탆 was roughened and subjected to Ni-Mo plating treatment as a heat-resistant treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 5.0 vol%.

The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 1.55 mu m. Table 2 shows the treatment conditions.

The Si concentration and the N concentration of the surface of the copper foil were found to be 5.5% and 7.3%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively.

As a result, the 90 degree peel strength was as high as 1.30 kg / cm. The results are shown in Table 3. As shown in Example 23, the surface-treated rolled copper foil of Example 23 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 24)

A rolled copper foil having a thickness of 18 탆 was subjected to a roughening treatment and subjected to a Cu-Zn plating treatment as a heat-resistant treatment. Further, electrolytic chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 5.0 vol%.

The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 0.81 탆. Table 2 shows the treatment conditions.

The Si concentration and the N concentration of the copper foil surface were found to be 3.8% and 4.3%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively.

As a result, a high value of 0.85 kg / cm was obtained for the 90 degree peel strength. The results are shown in Table 3. As shown in the twenty-fourth embodiment, the surface-treated rolled copper foil of the twenty-fourth embodiment has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 25)

The surface of the electrolytic copper foil having a plate thickness of 18 占 퐉 was subjected to a roughening treatment and subjected to Ni-Co plating treatment as heat treatment. Further, electrolytic chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 5.0 vol%.

The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 1.62 mu m. Table 2 shows the treatment conditions.

The Si concentration and the N concentration were found to be 4.6% and 8.9%, respectively, and the Si concentration and the N concentration were 2.0% or more and 2.0% or more, respectively, in the same manner as in Example 1 Respectively.

As a result, the 90 degree peel strength was as high as 1.29 kg / cm. The results are shown in Table 3. As shown in Example 25, it is found that the surface-treated electrolytic copper foil of Example 25 has industrially sufficient surface performance as a material for a high-frequency circuit board.

(Example 26)

The surface of the electrolytic copper foil having a thickness of 5 占 퐉 was subjected to a roughening treatment and subjected to a Zn-Ni plating treatment as a heat treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 5.0 vol%.

The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 1.31 탆. Table 2 shows the treatment conditions.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 5.2% and the N concentration was 5.9%, the Si concentration was 2.0% or more and the N concentration was 2.0% Respectively.

As a result, the 90 degree peel strength was as high as 1.01 kg / cm. The results are shown in Table 3. As shown in Example 26, it can be seen that the surface-treated electrolytic copper foil of Example 26 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 27)

The shiny surface of the electrolytic copper foil having a thickness of 12 占 퐉 was subjected to a roughening treatment and subjected to a Ni-Mo plating treatment as a heat-resistant treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 5.0 vol%.

The other conditions were the same as those in Example 1. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 1.42 mu m. Table 2 shows the treatment conditions.

The Si concentration and the N concentration of the copper foil surface were found to be 5.4% and 6.4%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively.

As a result, the 90 - degree peel strength was as high as 1.18 kg / cm. The results are shown in Table 3. As shown in Example 27, it can be seen that the surface-treated electrolytic copper foil of Example 27 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

Next, examples of the case where the kind of the copper foil, the roughening treatment, the heat resistance treatment and the anti-rust treatment are changed. In this case, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as the silane, and the silane concentration was set to 0.5 vol%. The drying after the silane treatment was performed at 100 ° C for 3 seconds.

In Comparative Examples 21 to 27, the conditions of the base material, the roughening treatment, the rust-preventive treatment and the chromate treatment were the same as those in Examples 21 to 27. When only the silane concentration was changed (inevitably, Si and The amount of deposition of N is changed).

(Example 28)

A roughened copper foil having a thickness of 9 占 퐉 (JIS H 3100 alloy No. C1100 manufactured by JX Nikkus Nisseki Metal Co., Ltd.) was subjected to a roughening treatment under the following conditions, and then subjected to a silane coupling treatment. The roughening treatment was carried out by subjecting the surface of the rolled copper foil to a treatment of forming primary particles of copper and then forming a secondary particle. N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as the silane for the silane treatment, and the silane concentration was 5.0 vol%. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.91 mu m.

&Lt; Harmonizing treatment condition &

(Plating conditions of primary particles of copper)

Liquid composition: copper 10 to 20 g / l, sulfuric acid 50 to 100 g / l

Solution temperature: 25 ~ 50 ℃

Current density: 1 to 58 A / dm 2

Plating time: 0.1 to 10 seconds

(Plating conditions of secondary particles)

Liquid composition: copper 10 to 20 g / l, nickel 5 to 15 g / l, cobalt 5 to 15 g / l

pH: 2-3

Temperature: 30 ~ 50 ℃

Current density: 24 ~ 50 A / dm2

Plating time: 0.5 to 4 seconds

The Si concentration and the N concentration of the surface of the copper foil were measured in the same manner as in Example 1 to find that the Si concentration and the N concentration were 7.3% and 15.1%, respectively, and that the Si concentration was 2.0% Respectively. As a result, the 90-degree peel strength was 0.95 kg / cm.

The surface of the surface-treated copper foil after the silane treatment was photographed using a scanning electron microscope (SEM). Then, the grains of the roughening treatment were observed using the photographs. As a result, the average particle diameter of the primary particle layer of copper was 0.25 to 0.45 mu m, and the average particle diameter of the secondary particle layer was 0.05 to 0.25 mu m. Further, the diameter of the minimum circle surrounding the particles was measured as the particle diameter, and the average particle diameter was calculated.

These are shown in Table 3. As shown in Example 28, it can be seen that the surface-treated copper foil of Example 28 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 29)

(JIS H 3100 alloy No. C1100) manufactured by JX Nikko Nisseki Metal Co., Ltd.) having a thickness of 9 탆 was subjected to a roughening treatment under the following conditions and then subjected to electrolytic chromate treatment, Silane coupling treatment. The roughening treatment was carried out by subjecting the surface of the rolled copper foil to a treatment of forming primary particles of copper and then forming a secondary particle. N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as the silane for the silane treatment, and the silane concentration was 5.0 vol%. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.91 mu m.

&Lt; Harmonizing treatment condition &

(Plating conditions of primary particles of copper)

Liquid composition: copper 10 to 20 g / l, sulfuric acid 50 to 100 g / l

Solution temperature: 25 ~ 50 ℃

Current density: 1 to 58 A / dm 2

Plating time: 0.1 to 10 seconds

(Plating conditions of secondary particles)

Liquid composition: copper 10 to 20 g / l, nickel 5 to 15 g / l, cobalt 5 to 15 g / l

pH: 2-3

Temperature: 30 ~ 50 ℃

Current density: 24 ~ 50 A / dm2

Plating time: 0.5 to 4 seconds

The Si concentration and the N concentration of the surface of the copper foil were found to be 7.5% and 15.4%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively. As a result, the 90 degree peel strength was 0.96 kg / cm.

The surface of the surface-treated copper foil after the silane treatment was photographed using a scanning electron microscope (SEM). Then, the grains of the roughening treatment were observed using the photographs. As a result, the average particle diameter of the primary particle layer of copper was 0.25 to 0.45 mu m, and the average particle diameter of the secondary particle layer was 0.05 to 0.25 mu m. Further, the diameter of the minimum circle surrounding the particles was measured as the particle diameter, and the average particle diameter was calculated.

These are shown in Table 3. As shown in Example 29, the surface-treated copper foil of Example 29 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 30)

A roughening treatment was carried out on a rolled copper foil having a thickness of 9 占 퐉 (JIS H 3100 alloy No. C1100 manufactured by JX Nikkus Nisseki Metal Co., Ltd., JIS H 3100 alloy No. C1100) under the following conditions and then subjected to Ni-Co plating treatment, Followed by a subsequent electrolytic chromate treatment, and then further subjected to a silane coupling treatment. The roughening treatment was performed by subjecting the surface of the rolled copper foil to a treatment of forming primary particles of copper and then forming a secondary particle. N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as the silane for the silane treatment, and the silane concentration was 5.0 vol%. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 0.90 mu m.

&Lt; Harmonizing treatment condition &

(Plating conditions of primary particles of copper)

Liquid composition: copper 10 to 20 g / l, sulfuric acid 50 to 100 g / l

Solution temperature: 25 ~ 50 ℃

Current density: 1 to 58 A / dm 2

Plating time: 0.1 to 10 seconds

(Plating conditions of secondary particles)

Liquid composition: copper 10 to 20 g / l, nickel 5 to 15 g / l, cobalt 5 to 15 g / l

pH: 2-3

Temperature: 30 ~ 50 ℃

Current density: 24 ~ 50 A / dm2

Plating time: 0.5 to 4 seconds

The Si concentration and the N concentration of the copper foil surface were found to be 7.6% and 15.6%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively. As a result, the 90 degree peel strength was 0.96 kg / cm.

The surface of the surface-treated copper foil after the silane treatment was photographed using a scanning electron microscope (SEM). Then, the grains of the roughening treatment were observed using the photographs. As a result, the average particle diameter of the primary particle layer of copper was 0.25 to 0.45 mu m, and the average particle diameter of the secondary particle layer was 0.05 to 0.25 mu m. Further, the diameter of the minimum circle surrounding the particles was measured as the particle diameter, and the average particle diameter was calculated.

These are shown in Table 3. As shown in Example 30, the surface-treated copper foil of Example 30 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 31)

(JIS H 3100 alloy No. C1100) manufactured by JX Nikko Nisseki Metal Co., Ltd.) having a thickness of 12 탆 was subjected to electrolytic chromate treatment, and then further subjected to a silane coupling treatment. N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as the silane-treated silane, and the silane concentration was 5.0 vol%. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.62 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 8.4% and the N concentration was 14.0%, and the Si concentration was 2.0% or more and the N concentration was 2.0% Respectively. As a result, the 90-degree peel strength was 0.67 kg / cm.

These are shown in Table 3. As shown in Example 31, it can be seen that the surface-treated copper foil of Example 31 has industrially sufficient surface performance as a material for a high-frequency circuit board.

(Example 32)

(JIS H 3100 alloy No. C1100, manufactured by JX Nikko Nisseki Metal Co., Ltd. (JIS H 3100 alloy No. C1100), 60 ° specular surface glossiness of 500% or more) having a thickness of 12 탆 was subjected to silane coupling treatment. N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was used as the silane-treated silane, and the silane concentration was 5.0 vol%. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.31 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration and the N concentration were 8.2% and 13.8%, respectively, and that the Si concentration was 2.0% Respectively. As a result, the 90-degree peel strength was 0.61 kg / cm.

These are shown in Table 3. As shown in Example 32, the surface-treated copper foil of Example 32 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Example 33)

A SiN film was formed under the following sputtering conditions on a high-gloss rolled copper foil having a thickness of 12 占 퐉 (JIS H 3100 alloy No. C1100 manufactured by JX Nikkus Nisseki Metal Co., Ltd .; For 5 minutes. The copper foil surface roughness Rz after sputtering was 0.30 mu m.

(Target): more than 59.5 mass% of Si, more than 39.5 mass% of N.

(Apparatus) Sputtering apparatus manufactured by ULVAC Co., Ltd.

(Output) DC 50 W

(Argon pressure) 0.2 Pa

The Si concentration and the N concentration of the copper foil surface were found to be 8.5% and 11.3%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Respectively. As a result, the 90 degree fill strength was 0.65 kg / cm.

These are shown in Table 3. As shown in Example 33, the surface-treated copper foil of Example 33 has industrially satisfactory surface performance as a material for a high-frequency circuit board.

(Comparative Example 21)

The rolled copper foil having a thickness of 6 占 퐉 was roughened and subjected to Ni-Co plating treatment as a heat-resistant treatment. In addition, electrolytic chromate treatment was performed as the rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%. Also, the silane concentration of 0.5 vol% is generally the concentration set in the silane treatment. Also, since the specific gravity of silane is about 1.0, 0.5 vol% means about 0.5 wt%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.82 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 0.3% and the N concentration was 0.4%, indicating that the Si concentration was 2.0% or more and the N concentration was 2.0% Was not satisfied.

As a result, the 90 - degree peel strength decreased to 0.29 ㎏ / ㎝. The results are shown in Table 3. As shown in this Comparative Example 21, the surface-treated rolled copper foil of Comparative Example 21 did not have an industrially satisfactory surface performance expected as a material for a high-frequency circuit board.

(Comparative Example 22)

The rolled copper foil having a thickness of 12 占 퐉 was subjected to a roughening treatment and subjected to a Zn-Ni plating treatment as a heat-resistant treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 0.90 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 0.3% and the N concentration was 0.5%, and the Si concentration was 2.0% or more and the N concentration was 2.0% Was not satisfied.

As a result, the 90-degree peel strength became 0.32 kg / cm and decreased. The results are shown in Table 3. As shown in this Comparative Example 22, the surface-treated rolled copper foil of Comparative Example 22 did not reach an industrially satisfactory surface performance expected as a material for a high-frequency circuit board.

(Comparative Example 23)

A rolled copper foil having a thickness of 35 탆 was roughened and subjected to Ni-Mo plating treatment as a heat-resistant treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 1.55 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration and the N concentration were 0.7% and 0.8%, respectively, and that the Si concentration was 2.0% Was not satisfied.

As a result, the 90 - degree peel strength decreased to 0.70 ㎏ / ㎝. The results are shown in Table 3. As shown in this Comparative Example 23, the surface-treated rolled copper foil of Comparative Example 23 did not reach an industrially satisfactory surface performance expected as a material for a high-frequency circuit board.

(Comparative Example 24)

A rolled copper foil having a thickness of 18 탆 was subjected to a roughening treatment and subjected to a Cu-Zn plating treatment as a heat-resistant treatment. Further, electrolytic chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 0.81 탆.

The Si concentration and the N concentration of the copper foil surface were found to be 0.4% and 0.7%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Was not satisfied.

As a result, the 90 degree peel strength was remarkably decreased to 0.30 kg / cm. The results are shown in Table 3. As shown in Comparative Example 24, the surface-treated rolled copper foil of Comparative Example 24 did not have industrially sufficient surface performance as a material for a high-frequency circuit board.

(Comparative Example 25)

The surface of the electrolytic copper foil having a plate thickness of 18 占 퐉 was subjected to a roughening treatment and subjected to Ni-Co plating treatment as heat treatment. Further, electrolytic chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 1.62 mu m.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration and the N concentration were 1.0% and 1.1%, respectively, and the Si concentration and the N concentration were 2.0% Was not satisfied.

As a result, the 90 - degree peel strength decreased to 0.65 ㎏ / ㎝. The results are shown in Table 3. As shown in this Comparative Example 25, the surface-treated electrolytic copper foil of Comparative Example 25 did not reach an industrially satisfactory surface performance expected as a material for a high-frequency circuit board.

(Comparative Example 26)

An electrolytic copper foil having a thickness of 5 占 퐉 was subjected to a roughening treatment and subjected to a Zn-Ni plating treatment as a heat-resistant treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 1.31 탆.

The Si concentration and the N concentration of the surface of the copper foil were found to be 0.8% and 1.3%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Was not satisfied.

As a result, the 90 - degree peel strength decreased to 0.44 ㎏ / ㎝. The results are shown in Table 3. As shown in this Comparative Example 26, the surface-treated electrolytic copper foil of Comparative Example 26 did not reach an industrially satisfactory surface performance expected as a material for a high-frequency circuit board.

(Comparative Example 27)

An electrolytic copper foil having a thickness of 12 占 퐉 was subjected to a roughening treatment and subjected to a Ni-Mo plating treatment as a heat-resistant treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment became 1.42 mu m.

The Si concentration and the N concentration of the surface of the copper foil were measured in the same manner as in Example 1 to find that the Si concentration and the N concentration were 1.1% and 1.1%, respectively, and that the Si concentration was 2.0% Was not satisfied.

As a result, the 90 - degree peel strength decreased to 0.45 ㎏ / ㎝. The results are shown in Table 3. As shown in Comparative Example 27, the surface-treated electrolytic copper foil of Comparative Example 27 did not reach an industrially satisfactory surface performance expected as a material for a high-frequency circuit board.

(Comparative Example 28)

Ni-Zn plating treatment was performed on the glossy surface of the electrodeposited copper foil having a thickness of 12 占 퐉 as heat resistance treatment. Further, electrolytic chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.60 mu m. The adhesion amounts of Ni and Zn at this time were 600 占 퐂 / dm 2 and 90 占 퐂 / dm 2, respectively.

The Si concentration and the N concentration of the surface of the copper foil were determined in the same manner as in Example 1 to find that the Si concentration was 0.7% and the N concentration was 0.9%, and the Si concentration was 2.0% or more and the N concentration was 2.0% Was not satisfied.

As a result, the 90 degree peel strength was as low as 0.10 kg / cm. The results are shown in Table 3. As shown in this Comparative Example 28, the surface-treated electrolytic copper foil of Comparative Example 28 did not reach an industrially satisfactory surface performance expected as a material for a high-frequency circuit board.

When the copper foil and the polyimide were bonded to each other to measure the fill strength, it was found to be 0.8 kg / cm and the resin had a large difference in fill strength.

(Comparative Example 29)

An electrolytic copper foil having a thickness of 12 占 퐉 was subjected to a roughening treatment and subjected to a Ni-Mo plating treatment as a heat-resistant treatment. Further, an immersion chromate treatment was performed as a rust-preventive treatment. Silane treatment was carried out on this. The silane concentration was 0.5 vol%.

The other conditions were the same as those in Example 1. Table 2 shows the treatment conditions. As a result, the surface roughness Rz of the copper foil after the silane coupling treatment was 0.61 mu m. The deposition amounts of Ni and Zn at this time were 2850 占 퐂 / dm 2 and 190 占 퐂 / dm 2, respectively.

The Si concentration and the N concentration of the surface of the copper foil were determined to be 0.9% and 1.3%, respectively, and the Si concentration was 2.0% or more and the N concentration was 2.0% or more in the same manner as in Example 1 Was not satisfied.

As a result, the 90 - degree peel strength was as low as 0.11 ㎏ / ㎝. The results are shown in Table 3. As shown in this Comparative Example 29, the surface-treated electrolytic copper foil of Comparative Example 29 did not reach an industrially satisfactory surface performance expected as a material for a high-frequency circuit board. Further, when the peel strength was measured by bonding the copper foil and the polyimide, it was found to be 1.2 kg / cm, and it was confirmed that the resin had a large difference in the peel strength.

Industrial availability

The present invention can manufacture a copper foil for a high-frequency circuit, and the copper foil can be applied to a liquid crystal polymer (LCP) laminate substrate to increase the adhesive strength (fill strength), and also to provide a flexible An excellent effect that a printed circuit board can be realized can be obtained, which is industrially very useful.

Claims (34)

Wherein the Si concentration is not less than 2.2 atomic% and not more than 18.5 atomic%, the N concentration is not less than 4.3 atomic% and not more than 25.3 atomic%, and the 10-point average roughness Rz of the surface-treated copper foil surface is 1.62 Mu m or less,
Characterized in that the roughening treatment layer on the surface of the copper foil has a primary particle layer of copper and a secondary particle layer composed of a ternary alloy of copper, cobalt and nickel on the primary particle layer. Copper foil. Wherein the Si concentration is not less than 2.2 atomic% and not more than 18.5 atomic%, the N concentration is not less than 5.0 atomic% and not more than 25.3 atomic%, and the 10 point average roughness Rz of the surface-treated copper foil surface is 1.62 Mu m or less,
Characterized in that the roughening treatment layer on the surface of the copper foil has a primary particle layer of copper and a secondary particle layer composed of a ternary alloy of copper, cobalt and nickel on the primary particle layer. Copper foil. Wherein the Si concentration is at least 3.7 atomic% and not more than 18.5 atomic%, the N concentration is at least 8.5 atomic% and not more than 25.3 atomic%, and the 10-point average roughness Rz of the surface-treated copper foil surface is 1.62 Mu m or less,
Characterized in that the roughening treatment layer on the surface of the copper foil has a primary particle layer of copper and a secondary particle layer composed of a ternary alloy of copper, cobalt and nickel on the primary particle layer. Copper foil. Wherein the Si concentration is not less than 5.5 atomic% and not more than 18.5 atomic%, the N concentration is not less than 10.1 atomic% and not more than 25.3 atomic%, and the ten-point average roughness Rz of the surface-treated copper foil surface is 1.62 Mu m or less,
Characterized in that the roughening treatment layer on the surface of the copper foil has a primary particle layer of copper and a secondary particle layer composed of a ternary alloy of copper, cobalt and nickel on the primary particle layer. Copper foil. Wherein the Si concentration is 6.6 atomic% or more and 18.5 atomic% or less, the N concentration is 10.8 atomic% or more and 25.3 atomic% or less, and the 10-point average roughness Rz of the surface-treated copper foil surface is 1.62 Mu m or less,
Characterized in that the roughening treatment layer on the surface of the copper foil has a primary particle layer of copper and a secondary particle layer composed of a ternary alloy of copper, cobalt and nickel on the primary particle layer. Copper foil. Wherein the Si concentration is 8.5 atom% or more and 18.5 atom% or less, the N concentration is 12.1 atom% or more and 25.3 atom% or less, and the 10-point average roughness Rz of the surface-treated copper foil surface is 1.62 Mu m or less,
Characterized in that the roughening treatment layer on the surface of the copper foil has a primary particle layer of copper and a secondary particle layer composed of a ternary alloy of copper, cobalt and nickel on the primary particle layer. Copper foil. 7. The method according to any one of claims 1 to 6,
Wherein the surface roughness Rz of the surface-treated copper foil surface is 0.92 占 퐉 or less. 7. The method according to any one of claims 1 to 6,
Wherein the surface roughness Rz of the surface-treated copper foil surface is 0.82 탆 or more and 1.62 탆 or less. 7. The method according to any one of claims 1 to 6,
Wherein the copper foil is a copper foil for a flexible printed wiring board. 7. The method according to any one of claims 1 to 6,
Wherein the copper foil is a rolled copper foil or an electrolytic copper foil. 7. The method according to any one of claims 1 to 6,
Wherein the copper foil is a copper foil bonded to a liquid crystal polymer. 7. The method according to any one of claims 1 to 6,
The state peel strength at 90 degrees in accordance with JIS C6471-1995 when the liquid crystal polymer of Vecstar (registered trademark) CT-Z manufactured by Kuraray is bonded by press with a circuit width of 3 mm is 0.3 kg / cm or more Treated copper foil. 7. The method according to any one of claims 1 to 6,
A surface-treated copper foil used for a flexible printed circuit board used under a high frequency exceeding 1 GHz. 7. The method according to any one of claims 1 to 6,
And at least one layer selected from the group consisting of a heat-resistant treatment layer, a rust-preventive treatment layer, a chromate treatment layer and a silane coupling treatment layer on the roughening treatment layer. 7. The method according to any one of claims 1 to 6,
A surface-treated copper foil having a chromate treatment layer on the roughening treatment layer and a silane coupling treatment layer on the chromate treatment layer. 7. The method according to any one of claims 1 to 6,
And at least one layer selected from the group consisting of a rust preventive treatment layer and a heat resistant treatment layer on the roughening treatment layer and having a chromate treatment layer on at least one layer selected from the group consisting of the anti-rust treatment layer and the heat resistant treatment layer, A surface treated copper foil having a silane coupling treatment layer on the treatment layer. 7. The method according to any one of claims 1 to 6,
A surface-treated copper foil having a heat-resistant treatment layer on a roughening treatment layer, a rust-inhibitive treatment layer on the heat-resistant treatment layer, a chromate treatment layer on the rust-inhibitive treatment layer, and a silane coupling treatment layer on the chromate treatment layer. 15. The method of claim 14,
Wherein the primary particle layer has an average particle diameter of 0.25 - 0.45 탆 and the secondary particle layer has an average particle diameter of 0.05 - 0.25 탆. 18. The method of claim 17,
Wherein the primary particle layer has an average particle diameter of 0.25 - 0.45 탆 and the secondary particle layer has an average particle diameter of 0.05 - 0.25 탆. 15. The method of claim 14,
A surface-treated copper foil having a chromate treatment layer on the roughening treatment layer and a silane coupling treatment layer on the chromate treatment layer. 15. The method of claim 14,
A surface-treated copper foil having a roughening treatment layer on the roughening treatment layer, a chromate treatment layer on the rust-preventive treatment layer, and a silane coupling treatment layer on the chromate treatment layer. A copper-clad laminate for manufacturing a flexible printed wiring board (FPC) having the surface-treated copper foil according to any one of claims 1 to 6. A flexible printed wiring board using the surface-treated copper foil according to any one of claims 1 to 6. A flexible printed circuit board using the surface-treated copper foil according to any one of claims 1 to 6. An electronic device comprising the flexible printed wiring board according to claim 23. delete delete delete delete delete delete delete delete delete