JP3330925B2 - Copper foil for laser drilling - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper foil excellent in laser drilling property which can efficiently form interlayer connection holes in a printed circuit board. In addition, the copper foil of the present invention includes not only the copper foil itself but also a copper-clad laminate or a product in which copper is directly formed on a laminate (including a plated product).

[0002]

2. Description of the Related Art In recent years, in the production of electronic parts and wiring boards using copper foil as a conductor, finer processing is possible as compared with a conventional mechanical drill with the increase in wiring density. Laser drilling has been used. However, when a highly versatile carbon dioxide laser is irradiated to make a hole in the copper foil surface, the reflectance of copper near the wavelength of 10 μm of the carbon dioxide laser becomes close to 100%, and the laser processing efficiency is increased. Is extremely bad. In order to compensate for this reduction in processing rate, a high-output carbon dioxide laser processing device is required.When such high-output carbon dioxide laser is used for laser processing with high energy, There is a problem that the resin substrate to be opened is damaged due to excessive processing, and it is not possible to form a hole in an intended shape. In addition, the amount of scattered matter accompanying the processing increases, and problems such as contamination of the apparatus and the non-processed part of the processed object occur.

Therefore, in order to avoid such a problem, a hole is formed in the copper foil portion by chemical etching in advance, and then a resin portion is formed by laser. But,
In this case, there is a disadvantage that the number of steps is increased and the cost is increased as compared with the case where the copper foil and the resin portion are punched at once. On the other hand, in general, as a means of laser processing, metal with high reflectance at the wavelength of laser light is provided with a material with high absorptance on the surface, so that the material can absorb laser light and generate heat to process it. It is also known that processing efficiency can be similarly increased by making the surface uneven. further,
Proposals have also been made, such as to perform an oxidized surface treatment of copper (blackening treatment) in order to increase the absorptivity when drilling a copper foil.

[0004] However, all of the above proposals require complicated operations and treatments, so that sufficient laser processing efficiency cannot be obtained, and those provided with the above-mentioned surface treatment layer have a weak treatment layer and are thus peeled. For example, there is a problem that it becomes a contamination source during the process. Further, a proposal has been made in which the copper foil itself is thinned so that a hole can be formed even with low energy. However, since the thickness of the copper foil actually used is different from 9 to 36 μm, only a part of the material can make the copper foil thin. Further, in order to make a hole under the same low energy condition, it is necessary to make the copper foil extremely thin to about 3 to 5 μm, and in this case, handling becomes a problem. As described above, some proposals in which conventional copper foils are improved are not sufficient for drilling holes by laser light, and at present, a copper foil material suitable for laser processing has not been obtained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to improve the surface of a copper foil in manufacturing a printed circuit board. Another object of the present invention is to provide a copper foil suitable for forming a small-diameter interlayer connection hole, in which drilling with a laser becomes extremely easy.

[0006]

From the above SUMMARY OF THE INVENTION The present invention provides a copper foil for drilled hole machining using 1 laser, at least on the laser incident surface of the copper foil, containing copper C
u, Ni, Co, Sn, Zn, In and alloys thereof, and at least one or more metal platings.
Copper foil for laser drilling characterized by forming a particle layer of 1 to 3 μm 2 On the surface on which the particle layer is formed by the metal plating, a covering film is formed without further changing the surface shape. 2. The copper foil for laser drilling according to 1 above, wherein

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention focuses on the surface morphology formed by surface plating, and as a result of study, it has been found that when a particle layer of 0.01 to 3 μm is formed on the surface by plating, a favorable It has been found that perforation characteristics can be obtained. The roughened surface of the copper foil formed by this fine particle layer of 0.01 to 3 μm irregularly reflects laser light, and can achieve the same effect as light absorption. It has become possible to ensure a proper drilling property. At this time, as the plating metal containing copper, Ni, Co, S, which has been confirmed to absorb laser light by itself and to be effective for laser drilling, have been confirmed.
n, ZnIn and alloys thereof can be used. But,
It is not necessary to limit to these, and other metals can be used.
By applying metal plating containing copper to the laser light incident surface of the copper foil as in the present invention and forming particles of 0.01 to 3 μm, it has become possible to obtain even higher laser workability. .

The above-mentioned Ni, Co, S containing no copper
0.01 to 3 using n, ZnIn and their alloys.
It is also conceivable to form a particle layer of μm to improve the laser drilling property. Certainly, by forming the particle layer by such plating, the laser drilling property was improved.
However, such a peeling or dropping of the plating layer occurred, and in some cases, a phenomenon of easy peeling due to rubbing or the like was observed. For example, when unevenness plating of Co alone was performed on copper foil, sufficient hole-piercing properties were confirmed, but the plating treatment layer was brittle, and particles were detached by rubbing. In an attempt to improve the problem of the drop-out and peeling phenomena, the amount of plating was reduced and the protrusions were reduced. Therefore, even if the above-described metal layer is formed alone, the laser drilling property and the like can be improved, but it cannot be said that it is actually an appropriate treatment layer, and there is a problem. In view of the above, as a result of further studying various metal layers to be plated on copper foil, by adding copper to the electroplating composition forming the particle layer, the adhesion of plating is increased, and the treatment layer is peeled off. And that it can be effectively prevented from falling off.

Further, in order to prevent the above-mentioned peeling or falling off,
It is more effective to cover the roughened surface with one or more metals. The overplating may be performed under normal plating conditions (normal plating), and plating is performed without damaging the particle layer of 0.01 to 3 μm formed by the roughened surface treatment. That is, a particle layer of 0.01 to 3 μm is in this range so as not to lower the perforation by laser light,
It needs to be substantially present. The plating for forming the cover film may be the same plating as the rough plating for forming the particle layer, or may be a different plating. Preferably, as in the rough plating for forming the particle layer, N
i, Co, Sn, Zn, In and alloys thereof are good;
Further, the laser drilling property can be improved. In this manner, by performing the overplating on the roughening treatment, it is possible to ensure sufficient laser drilling without peeling or falling off.

[0010] The copper foil used in the present invention can be applied to either an electrolytic copper foil or a rolled copper foil. Further, the thickness of the copper foil is desirably 18 μm or less for use as a high-density wiring. However, the copper foil with improved laser drilling properties of the present invention is not limited to this thickness,
Naturally, it can be applied to a thickness larger than this. The particle layer (roughening treatment) formed by plating or the like can be partially applied to the laser beam irradiation surface of the copper foil or the entire copper foil. It is natural that these plating treatments and the like are required not to impair the properties of the copper foil applied to the circuit board, and the treatment of the present invention sufficiently satisfies these conditions.

After the above plating treatment, a rust-preventive treatment containing chromium and / or zinc can be performed. The technique or treatment solution for this rust prevention treatment is not particularly limited. This rust prevention treatment can be performed on the surface of the plating treatment, that is, partially on the laser beam irradiation surface of the copper foil or on the entire copper foil. As described above, it is natural that this rust prevention treatment is not required to impair the properties as copper foil applied to the circuit board, and the rust prevention treatment of the present invention sufficiently satisfies these conditions. I have. In addition, this rust prevention treatment hardly affects the laser drillability.

As the metal plating of the present invention, for example, Cu,
In order to form a plating layer of Ni, Co, Sn, Zn, In, and an alloy thereof, the following plating treatment can be applied. The following is a typical example. By appropriately setting the conditions within this range, the roughening treatment and the cover plating can be performed. It should be noted that this plating process shows only a preferred example, and the present invention is not limited to these examples.

(Copper plating treatment) Cu concentration: 1 to 30 g / L Electrolyte temperature: 20 to 60 ° C, pH: 1.0 to 4.0 Current density: 5 to 60 A / dm ² , Plating time: 0.1 5 to 4 seconds (nickel plating treatment) Ni concentration: 1 to 30 g / L Electrolyte temperature: 25 to 60 ° C, pH: 1.0 to 4.0 Current density: 0.5 to 5 A / dm ² , plating time : 0.5 to 4 seconds (cobalt plating treatment) Co concentration: 1 to 30 g / L Electrolyte temperature: 25 to 60 ° C, pH: 1.0 to 4.0 Current density: 0.5 to 5 A / dm ² Plating time: 0.5 to 4 seconds (tin plating treatment) Sn concentration: 5 to 100 g / L Sulfuric acid: 40 to 150 g / L Electrolyte temperature: 25 to 40 ° C, pH: 1.0 to 4.0 Current density: 1.0~5A / ^dm 2, plating time: 0.5-4 seconds (indium plated In concentration: 10 to 50 g / L sulfuric acid: 10 to 50 g / L electrolyte solution temperature: 20~40 ° C, pH: 1.0~4.0 current density: 1.0~20A / ^dm 2, plating time: 0 0.5 to 4 seconds (zinc-cobalt plating treatment) Zn concentration: 1 to 20 g / L, Co concentration: 1 to 30 g / L Electrolyte temperature: 25 to 50 ° C, pH: 1.5 to 4.0 Current density : 0.5 to 5 A / dm ² , Plating time: 1 to 3 seconds (copper-nickel plating treatment) Cu concentration: 5 to 20 g / L, Ni concentration: 5 to 20 g / L Electrolyte temperature: 25 to 50 ° C PH: 1.0 to 4.0 Current density: 10 to 45 A / dm ² Plating time: 1 to 3 seconds (copper-cobalt plating treatment) Cu concentration: 5 to 20 g / L, Co concentration: 5 to 20 g / L Electrolyte temperature: 25 to 50 ° C, pH: 1.0 to 4.0 Current density: 10 45A / ^dm 2, plating time: 1-3 seconds (zinc - nickel-plated) zinc concentration: 1 to 10 g / L, Ni concentration: 10 to 30 g / L electrolyte solution temperature: 40~50 ° C, pH: 3 . 0 to 4.0 Current density: 0.5 to 5 A / dm ² , Plating time: 1 to 3 seconds (cobalt-nickel plating treatment) Co concentration: 5 to 20 g / L, Ni concentration: 5 to 20 g / L Electrolyte Temperature: 20 to 50 ° C, pH: 1.0 to 4.0 Current density: 0.5 to 10 A / dm ² , Plating time: 1 to 180 seconds (copper-cobalt-nickel plating treatment) Co concentration: 1 to 15 g / L, Ni concentration: 1 to 15 g / L Cu concentration: 5 to 25 g / L Electrolyte temperature: 20 to 50 ° C, pH: 1.0 to 4.0 Current density: 1.0 to 30 A / dm ² , Plating time: 1 to 180 seconds

[0014]

Next, an embodiment will be described. Note that the present embodiment shows a preferred example, and the present invention is not limited to these embodiments. Therefore, all modifications, other examples or aspects included in the technical concept of the present invention are included in the present invention. For comparison with the present invention, a comparative example is described in a later stage.

(Example 1) A copper-cobalt-nickel alloy was plated on a glossy surface (S surface) of an electrolytic copper foil having a thickness of 12 μm under the above conditions to form a particle layer of about 0.1 to 0.8 μm. It was done. FIG. 1 is a micrograph of the roughened surface on which the particle layer is formed.

(Example 2) A copper-cobalt-nickel alloy is plated on a glossy surface (S surface) of an electrolytic copper foil having a thickness of 12 μm under the above conditions to form a particle layer of about 0.1 to 0.8 μm. Further, a cover plating (forming a coating layer) with a cobalt-nickel alloy under the above plating conditions is further performed thereon.

Comparative Example 1 An electrolytic copper foil having a thickness of 12 μm was used as it was. FIG. 2 is a micrograph of the surface of the electrolytic copper foil.

Comparative Example 2 A glossy surface (S surface) of a 12 μm thick electrolytic copper foil was plated with cobalt under the above conditions to form a particle layer of about 0.3 to 1 μm. FIG.
Is a micrograph of the roughened surface on which the particle layer is formed.

The samples of Examples 1 and 2 and Comparative Examples 1 and 2 were made into single-sided substrates using prepreg (FR-4), and 100 points were irradiated with carbon dioxide laser light under the following conditions. The piercing rates were compared. Table 1 shows the results. (Laser irradiation conditions) Apparatus used: Carbon dioxide laser processing equipment Spot size: 144 μm φ Pulse width: 32 μsec Frequency: 400 Hz, number of shots: 1 shot Laser irradiation energy: (Condition 1: 25 mJ / pulse, Condition 2: 32 mJ / pulse)

[0020]

[Table 1]

In Example 1, both the condition 1 and the condition 2 showed a drilling rate of 100%, showing a very excellent drilling rate. In this case, a small amount of powder falling off (peeling off or falling off of the plating layer) due to rubbing was observed, but this was not a problematic level. This was confirmed that in the plating for forming the particle layer of the present invention, the content of copper is an effective means for preventing peeling and falling off of the plating layer.

In the second embodiment, as in the first embodiment, both the condition 1 and the condition 2 show a hole punching rate of 100%.
It showed a very good drilling rate. In this case, there was no powder dropping (peeling off or falling off of the plating layer) due to rubbing. This is because after forming the particle layer of the present invention, the cobalt-
Although the case was covered with nickel, it was confirmed that this plating was an effective means for preventing peeling and falling off of the plating layer.

In Comparative Example 1, the case where the copper foil itself was used was used.
Under condition 1, the laser drilling rate is 0, that is, drilling is practically impossible. In addition, the drilling rate is only 9% even under condition 2.
The result was extremely bad.

In Comparative Example 2, both the condition 1 and the condition 2 showed a 100% drilling rate, showing an extremely excellent drilling rate. However, powder rubbing (peeling off and falling off of the plating layer) due to rubbing was observed, and the powder was not endurable for actual use.

From the above, it can be seen that drilling of a copper foil itself with a carbon dioxide gas laser is practically impossible.
In the present invention, by forming a particle layer of 0.01 to 3 μm, drilling by a carbon dioxide gas laser was improved as shown in the above example. Further, the phenomenon of powder falling can be effectively prevented by adding copper to the plating composition when these particles are formed. In addition, the overcoating can be more firmly prevented, and such means can be employed if necessary.

[0026]

According to the present invention, when manufacturing a printed circuit board, direct opening of copper foil and easy formation of interlayer connection holes can be performed with a low energy laser such as a carbon dioxide gas laser, and peeling or falling off of a plating layer due to rubbing or the like can be prevented. It has a remarkable effect.

[Brief description of the drawings]

FIG. 1 is a micrograph of a roughened surface on which a particle layer of Example 1 is formed.

FIG. 2 is a micrograph of the surface of the electrolytic copper foil of Comparative Example 1.

FIG. 3 is a micrograph of a roughened surface on which a particle layer of Comparative Example 2 is formed.

Continuation of the front page (56) References JP-A-7-231152 (JP, A) JP-A-6-169169 (JP, A) JP-A-6-169168 (JP, A) JP-A-2000-190420 (JP, A) A) JP-A-2000-43188 (JP, A) JP-A-2000-228582 (JP, A) JP-A-8-174263 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C25D 7/06 C25D 5/10 H05K 3/46 B23K 26/00

Claims (2)

(57) [Claims] 1. A copper foil to be drilled by using a laser, wherein at least a laser incident surface of the copper foil contains Cu, Ni, Co, Sn, Zn, In, and copper containing copper.
A copper foil for laser drilling, characterized in that a metal layer of at least one kind of the alloy of ( 1) is applied and a particle layer of 0.01 to 3 μm is formed on said surface. 2. The copper foil for laser drilling according to claim 1, wherein a covering film is formed on the surface on which the particle layer has been formed by the metal plating without changing the surface shape.