JP2012102407A - Ultra-thin copper foil with carrier and printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ultra-thin copper foil with a carrier which suppresses the generation of a blister at an interface of release layers, does not influence carrier peel, has a wide control range in the condition for producing the ultra-thin copper foil with the carrier, achieves stable production quality, is friendly to an environment, and enables the easy peeling of the ultra-thin copper foil from the carrier foil even in a high-temperature environment.SOLUTION: The ultra-thin copper foil with the carrier includes carrier foil, a diffusion prevention layer, a release layer, and ultra-thin copper foil. The release layer includes two layers each having a different composition ratio of metal A to metal B, the metal A selected from the group of Mo, Ta, V, Mn, and W, and the metal B selected from the group of Fe, Co, Ni, and Cr. Here, the following expression for percentage is satisfied: |(c/c+d)-(e/e+f)|*100≥3(%), wherein c and d represent the content of metal A and metal B which constitute the release layer at the side of the carrier foil, respectively, and e and f represent the content of metal A and metal B which constitute the release layer at the side of the ultra-thin copper foil, respectively.

Description

The present invention relates to an ultra-thin copper foil with a carrier and a printed wiring board using the ultra-thin copper foil with a carrier, and more particularly to a printed wiring board, a multilayer printed wiring board, a chip-on for high-density ultra-fine wiring (fine pattern). The present invention relates to an ultrathin copper foil with a carrier suitable for a film wiring board.

In general, copper foil used for printed wiring boards that are the basis of printed wiring boards, multilayer printed wiring boards, chip-on-film wiring boards, etc., has a roughened surface on the surface to be thermocompression bonded to a resin board. The anchor effect with respect to the board is exhibited on the surface, and the bonding strength between the board and the copper foil is increased to ensure the reliability as a printed wiring board.
More recently, a copper foil with resin, in which the roughened surface of the copper foil is previously coated with an adhesive resin such as an epoxy resin and the adhesive resin is used as an insulating resin layer in a semi-cured state (B stage), is used for circuit formation. As a copper foil, a printed wiring board is obtained by thermocompression bonding the insulating resin layer side to a substrate, and a build-up wiring board is manufactured by laminating the printed wiring board in multiple layers. A build-up wiring board is a type of multilayer printed wiring board, in which an insulating layer and a conductor pattern are formed in order on an insulating board in that order, and plating is performed on holes (vias) opened by the laser method or photo method. It is a wiring board which piled up wiring layers, making conduct.

In this wiring board, vias can be miniaturized in response to high integration of various electronic components, and therefore, there is an increasing demand for fine line widths and line pitches in wiring patterns. For example, these wiring boards are used in semiconductor packages. In the case of a printed wiring board, it is required to provide a printed wiring board having high-density ultrafine wiring with a line width and a line pitch of around 30 μm.
As a copper foil for such a fine pattern printed wiring board, if a thick copper foil is used, the etching time at the time of wiring circuit formation by etching becomes long, and as a result, the verticality of the side wall of the formed wiring pattern is disrupted, When the wiring line width of the wiring pattern to be formed is narrow, it may lead to disconnection. Therefore, a copper foil having a thickness of 9 μm or less is demanded as a copper foil used for fine pattern applications. At present, a copper foil having a thickness of about 5 μm is most frequently used, and further ultrathin copper foil is required. ing.

However, such a thin copper foil (hereinafter sometimes referred to as an ultrathin copper foil) has a low mechanical strength, is likely to cause wrinkles and creases during the production of a printed wiring board, and may cause the copper foil to break. Therefore, as an ultra-thin copper foil used for fine pattern applications, an electrode with a carrier in which an ultra-thin copper foil layer is directly electrodeposited via a release layer on one side of a metal foil (hereinafter referred to as carrier foil) as a carrier. Thin copper foil is used.
As described above, the copper foil having a thickness of 5 μm that is widely used at present is provided as an ultrathin copper foil with a carrier.
The ultrathin copper foil with a carrier is formed by forming a peeling layer and an ultrathin copper foil by electrolytic copper plating in this order on one side of the carrier foil, and the outermost surface of the ultrathin copper foil made of the electrolytic copper plating Has a roughened surface.
For the release layer formed on one side of the carrier foil, organic coating, Cr metal, Cr alloy, chromate, etc. are commonly used. However, in recent years, in a wiring board using a high temperature plastic such as polyimide as an insulating substrate, a copper foil and a substrate are used. Since the conditions such as the pressing temperature or the curing temperature are high, the organic release layer cannot be peeled off and the organic coating cannot be used, and a metal release layer is used.

As described above, Cr metal, Cr alloy, and chromate are the mainstreams for forming the release layer. However, when Cr is used for the release layer, blisters are generated in the wiring board manufacturing process at a high temperature, the peelability varies, and there is a slight problem in stable manufacturing of the wiring board.
In addition, some of these metals such as Cr are said to have an adverse effect on the human body, and the use of these metals is expected to be prohibited in the future. Therefore, the current situation is that the metal such as Cr should be used in the direction where it is not used as much as possible.

As described above, the release layer made of Cr lacks the manufacturing stability of the wiring board at high temperatures, and does not use or minimizes the use of Cr metal that may affect the human body, even at high temperatures. The appearance of an ultrathin copper foil with a carrier that can be easily peeled is desired.

In view of the present situation, the present invention suppresses the occurrence of swelling, does not affect the carrier peel, has a wide management range in the manufacturing conditions of the ultra-thin copper foil with a carrier, has stable manufacturing quality, is environmentally friendly, An object is to provide an ultra-thin copper foil with a carrier that can easily peel off the carrier foil and the ultra-thin copper foil even when placed in an environment.
Another object of the present invention is to provide a printed wiring board that serves as a base material for a fine pattern use printed wiring board, multilayer printed wiring board, chip-on-film wiring board, etc., using the ultrathin copper foil with carrier. To do.

The ultra-thin copper foil with a carrier of the present invention is an ultra-thin copper foil with a carrier comprising a carrier foil, a diffusion prevention layer, a release layer, and an ultra-thin copper foil, and the release layer includes Mo, Ta, V, Mn, and W. The metal A selected from the group consisting of 2 and the metal B selected from the group consisting of Fe, Co, Ni, and Cr are composed of two layers different from each other, and contains the metal A constituting the release layer on the carrier foil side. When the amount c, the content d of the metal B, the content e of the metal A constituting the peeling layer on the ultrathin copper foil side, and the content f of the metal B | (c / c + d) − (e / e + f) | * 100 ≧ 3 (%)
It is the ratio of these.

The ultra-thin copper foil with a carrier of the present invention is an ultra-thin copper foil with a carrier comprising a carrier foil, a diffusion preventing layer, a release layer, an antioxidant layer, and an ultra-thin copper foil, and the release layer retains peelability. A metal A selected from the group of Mo, Ta, V, Mn, and W having different composition ratios between the metal A and the metal B that facilitates plating of an ultrathin copper foil, and Fe, Co, Ni, and Cr. It consists of two layers having a composition ratio different from that of the metal B selected from the group. The content c of the metal A constituting the release layer on the carrier foil side, the content d of the metal B, and the release layer on the ultrathin copper foil side When the content e of the constituent metal A and the content f of the metal B are | (c / c + d) − (e / e + f) | * 100 ≧ 3 (%)
The ratio of
The anti-oxidation layer is a single metal layer having a melting point of 450 ° C. or lower, or a low melting point metal layer that is an alloy.

Adhesion amount of the release layer is preferably a total (Total) metal deposition amount is ^{0.05mg / dm 2 ~50mg / dm 2} .

The low melting point metal forming the antioxidant layer is preferably Zn, Sn, Bi, In, or an alloy containing as a main component one of Zn, Sn, Pb, Bi, and In.

The printed wiring board of the present invention is a printed wiring board for use in high-density ultrafine wiring obtained by laminating an ultrathin copper foil with a carrier of the present invention on a resin substrate.

The present invention suppresses the occurrence of blisters at the peeling layer interface, does not affect the carrier peel, stabilizes the production quality, is environmentally friendly, and makes it easy to make the carrier foil and ultrathin copper foil even when placed in a high temperature environment An ultrathin copper foil with a carrier that can be peeled off is provided.

Moreover, this invention can provide the printed wiring board used as base materials, such as a printed wiring board for a fine pattern using the said ultra-thin copper foil with a carrier, a multilayer printed wiring board, a wiring board for chip-on-film.

Generally, aluminum foil, aluminum alloy foil, stainless steel foil, titanium foil, titanium alloy foil, copper foil, copper alloy foil, etc. can be used as the metal carrier foil for ultrathin copper foil with carrier. As a carrier foil used for a foil or a copper alloy foil (hereinafter collectively referred to as an ultrathin copper foil when it is not necessary to distinguish between them), from the viewpoint of easy handling, an electrolytic copper foil, an electrolytic copper alloy foil, Rolled copper foil or rolled copper alloy foil is preferred. Moreover, it is preferable to use the foil whose thickness is 7 micrometers-200 micrometers.

If a thin copper foil with a thickness of 7 μm or less is used as the carrier foil, the mechanical strength of the carrier foil is weak, so that wrinkles and folds are likely to occur during the production of printed circuit boards, etc. There is. Further, when the thickness of the carrier foil is 200 μm or more, the weight per unit coil (coil single weight) increases, which greatly affects the productivity and requires a higher tension on the equipment, which is not preferable because the equipment becomes large. . Therefore, the thickness of the carrier foil is preferably 7 μm to 200 μm.

As the carrier foil, it is preferable to use a metal foil having a surface roughness of at least one surface of Rz: 0.01 μm to 5.0 μm, and particularly when visibility in a wiring board for chip-on-film is required. It is preferable that it is 0.01 micrometer-2.0 micrometers. Therefore, when using a carrier foil having a surface roughness range of Rz: 2 μm to 5.0 μm when visibility such as for a chip-on-film wiring board is required, mechanical polishing or electrolytic polishing is performed on the rough surface in advance. And the surface roughness is preferably smoothed to a range of Rz: 0.01 μm to 2 μm. Note that a carrier foil having a surface roughness Rz of 5 μm or more can be preliminarily mechanically polished and electrochemically dissolved and smoothed before use.

In the present invention, a diffusion preventing layer is provided between the release layer and the carrier foil in order to stabilize the heat resistance against the peelability of the release layer described later. The diffusion prevention layer is preferably formed of Ni or an alloy thereof. In addition, formation with Cr or Cr alloy is also effective.

In the present invention, the release layer provided on the diffusion prevention layer is composed of a mixture of a metal and a non-metal or metal oxide or alloy. In particular, the release layer of the present invention is composed of a metal A that maintains releasability and a metal B that facilitates plating of an ultrathin copper foil.
The metal A constituting the release layer is selected from the group of Mo, Ta, V, Mn, and W.
The metal B is selected from the group of Fe, Co, Ni, and Cr.
In addition, since Cr metal contains a problem to the environment, it is particularly preferable that it is not used as much as possible, or even if it is used, it is suppressed to a necessary minimum amount.

The release layer is composed of two layers having different composition ratios of the metal A that keeps peelability and the metal B that facilitates plating of an ultrathin copper foil, and the content of the metal A that constitutes the release layer on the diffusion layer side c, the content B of the metal B, the content e of the metal A constituting the peeling layer on the ultrathin copper foil side, and the content f of the metal B | (c / c + d) − (e / e + f ) | * 100 ≧ 3 (%)
The ratio of
Each layer is (a / a + b) * 100 = 10 to 70 (%)
(C / c + d) * 100 = 10 to 70 (%)
The effect is further improved by satisfying this ratio.

The above two layers or more layers may change the composition ratio on the carrier foil surface side and the ultrathin copper foil side depending on the plating conditions without intentionally changing the composition. If the difference between the upper and lower composition ratios is 3% or more at a thickness of 0.1% or more and 5% or less of the total adhesion amount from the carrier foil side and the ultra-thin copper foil side, it is equivalent to the case where two layers are consciously provided. Create an effect.
Even if the peeling layer is composed of two layers and the two layers are composed of different metals, the same effect can be produced if the metal species belonging to metal A and the metal species belonging to metal B are within the above composition ratio range. Can do.

In the present invention, the adhesion amount of the release layer to be adhered is
0.05 mg / dm ^{2 to} 50 mg / dm ²
It is preferable that
An adhesion amount of 0.05 mg / dm ² or less is unsuitable because it does not perform a sufficient function as a release layer, and even if it is 50 mg / dm ² or more, it can be peeled off. The metal species to be formed is a metal that is difficult to plate, and if it is thick, the smoothness is lost, the peel force varies, the stability is lost, and it may cause blistering, so it is preferably 50 mg / dm ² or less. It is preferable. Furthermore, in consideration of the smoothness of the surface of the ultrathin copper foil, it is preferably 20 mg / dm ² or less. The roughness of the release layer surface is preferably 1.5 times or less of the surface roughness of the carrier foil, and the surface area is preferably 1.5 times or less of the surface area of the carrier foil. This is because when the surface roughness and the surface area are increased, the carrier peel is increased as a whole and the variation is also increased.
In the present invention, when the release layer has two layers, the total adhesion amount of the two layers is 0.05 mg / dm ^{2 to} 50 m / dm ² as described above, and in particular, the adhesion amount of the first layer on the carrier foil side The smaller the amount of adhesion of the second layer on the ultrathin copper foil side, the better the peelability.

Moreover, it is good to provide the antioxidant layer which consists of a low melting metal from the reason for preventing the oxidation of the ultra-thin copper foil surface on a peeling layer. The low melting point metal is a single metal having a melting point of 450 ° C. or lower or an alloy thereof. Specifically, the effect of suppressing oxidation discoloration on the surface of an ultrathin copper foil by adhering an alloy mainly composed of one of Zn, Sn, Bi, In or Zn, Sn, Pb, Bi, In. Is preferable.
Further, as an effect of this low melting point metal, in order to make the release layer and the thin copper foil easily adhere to each other in a normal state, plating defects (pin holes) of the thin copper foil and blistering when heat treatment is performed are made difficult. Further, when pasted on polyimide, heat is applied and the low melting point metal diffuses on the surface of the thin copper foil, so that a space is formed between the release layer and the thin copper foil, and the carrier peel is also lowered. The amount of low melting point metal on the release layer is preferably 0.01 mg / dm ² or more, depending on the metal species. In particular, 0.05mg ^/ dm ² ~10mg ^/ dm 2 is optimal. A commercially available plating solution can be used without particularly specifying the plating bath to which each low melting point metal adheres.

The ultrathin copper foil is formed by electrolytic plating on the release layer using a copper sulfate bath, a copper pyrophosphate bath, a copper sulfamate bath, a copper cyanide bath, or the like. The plating bath is preferably a copper plating bath having a pH between 1 and 12.
Ultra-thin copper foil is formed when the release layer is made of a metal that is easily dissolved in a plating solution such as Zn, the dip time / current value in the plating solution, the plating solution draining / washing in the plating finish, metal Since the plating solution pH immediately after plating determines the remaining state of the release layer, the bath type must be selected in relation to the surface of the release layer and the metal formed thereon.

In addition, the formation of the ultrathin copper foil on the release layer is very difficult to perform uniform plating because of the peelability of the release layer, resulting in a large number of pinholes in the ultrathin copper foil. Sometimes. Under such plating conditions, strike copper plating is performed first, and then normal electrolytic plating is performed, so that uniform plating can be performed on the release layer, and the number of pinholes generated in the ultrathin copper foil is drastically reduced. be able to.

The thickness of the copper plating deposited by strike plating is preferably 0.01 μm to 1 μm, and the conditions vary depending on the type of bath. The current density is 0.1 A / dm ^{2 to} 20 A / dm ² , and the plating time is 0. One second or more is preferable. When the current density is 0.1 A / dm ² or less, it is difficult to uniformly deposit the plating on the release layer, and when the current density is 20 A / dm ² or more, the burn plating is generated in the strike plating in which the metal concentration of the plating solution is reduced. In addition, a uniform copper plating layer cannot be obtained, which is not preferable. Regarding the plating time, 0.1 seconds or less is not preferable because it is too short to obtain a sufficient plating layer.
After forming a copper plating layer having a thickness of 0.01 μm or more which does not impair the peelability of the release layer on the release layer by strike plating, copper plating is performed to a desired thickness to obtain an ultrathin copper foil.
Further, when P is contained on the surface of the ultrathin copper foil, the adhesive strength with the release layer is weakened, so that the peel strength is reduced. Therefore, in order to adjust the peel strength, it is effective to include P on the surface of the ultrathin copper foil.

In order to obtain stronger adhesion with the insulating substrate on the surface of the ultrathin copper foil, the surface of the ultrathin copper foil is subjected to a roughening treatment, and the roughness of the surface is Rz: 0.2 to 3.0 (μm ). As for the roughening treatment, if the roughness is 0.2 (μm) or less, there is no effect on the adhesion, so it is meaningless to roughen. If the roughness is 3 (μm), sufficient adhesion is achieved. This is because no further roughening is required.
Finally, Ni, Zn, or, in some cases, Cr, which has an effect on rust prevention and heat resistance, is deposited on the roughened surface. It is also effective to apply silane in order to improve the peel strength.

Hereinafter, the present invention will be specifically described by way of examples.
The plating conditions in each example are as follows.
(1) Copper plating conditions <Copper plating conditions 1>
Cu ₂ P ₂ O ₇ 3H ₂ O: 3 to 50 g / l
_{K 4 P 2 O 7: 50~350g} / l
pH: 8-11
Current density: 0.1 to 5 A / dm ²

<Copper plating condition 2>
_{Cu 2 P 2 O 7 · 3H} 2 O: 10~150g / l
_{K 4 P 2 O 7: 50~400g} / l
NH ₃ OH (28%): 1 to 10 ml / l
pH: 8-12
Bath temperature: 20-60 ° C

<Copper plating condition 3>
Copper sulfate (as Cu metal): 10-70 g / dm ³
Sulfuric acid: 30-120 g / dm ³
Current density: 1 to 60 A / dm ²
Energizing time: 1 second-2 minutes Bath temperature: 10-70 ° C

(2) Nickel plating conditions Nickel sulfate (as Ni): 1-120 g / dm ³
Boric acid: 10-50 g / dm ³
Current density: 1 to 60 A / dm ²
Energizing time: 1 second-2 minutes Bath temperature: 10-70 ° C

(3) Ni-Co plating conditions Nickel sulfate (as Ni): 5 to 120 g / dm ³
Cobalt sulfate (as Co metal): 0.5 to 40 g / dm ³
pH: 2-4
Current density: 0.5 to 10 A / dm ²
Time: 1 second to 2 minutes

(4) Mo—Co plating condition Co amount: 0.1 to 20 g / dm ³
Mo amount: 0.05 to 20 g / dm ³
Citric acid: 5-240 g / dm ³
Current density: 0.1 to 60 A / dm ²
Energizing time: 1 second to 5 minutes Bath temperature: 10 ° C to 70 ° C

(5) Mo—Ni plating condition Ni sulfate sulfate: 10 to 100 g / dm ³
Sodium molybdate dihydrate: 10 to 100 g / dm ³
Sodium citrate: 30 to 200 g / dm ³
Bath temperature: 10-50 ° C
Current density: 0.5 to 15 A / dm ²

(6) W-Ni plating conditions Ni sulfate sulfate: 10 to 100 g / dm ³
Sodium tungstate dihydrate: 10 to 100 g / dm ³
Sodium citrate: 30 to 200 g / dm ³
Bath temperature: 30-90 ° C
Current density: 0.5 to 15 A / dm ²

<Example 1>
Carrier foil-> Ni (diffusion prevention layer)-> Mo-Co (peeling layer)-> copper plating (ultra-thin copper foil) with a carrier made of ultra-thin copper foil with a Rz: 0.8 μm copper foil (thickness: 31 μm) ) Was used as a carrier foil, a diffusion prevention layer was applied on the carrier foil under the Ni plating conditions, and then a release layer was formed by Mo-Co plating under the following conditions.
Co amount: 4.0 g / dm ³
Mo amount: 2.0 g / dm ³
Citric acid: 80 g / dm ³
Current density: 2 A / dm ²
Energizing time: 15 seconds Bath temperature: 50 ° C
The adhesion amount of the formed release layer was 1.5 mg / dm ² and Mo / (Mo + Co) * 100 = 31 (%).
On the formed release layer, copper plating is performed to a thickness of 0.2 μm under the above <copper plating condition 1>, and then copper plating is performed according to the above <copper plating condition 3> at a current density of 4.5 A / dm ² . An ultrathin copper foil having a thickness of 3 μm was formed to obtain an ultrathin copper foil with a carrier.
Next, after surface treatment of Ni: 0.5 mg / dm ² , Zn: 0.05 mg / dm ² , Cr: 0.3 mg / dm ² , silane coupling agent treatment (post treatment) is performed, and ultrathin copper with a carrier A foil was obtained.

<Example 2>
Carrier foil → Ni (diffusion prevention layer) → Mo—Ni (peeling layer) → Manufacture of ultra-thin copper foil with carrier by copper plating (thin copper foil) Copper foil (thickness: 31 μm) on one side Rz: 0.85 μm Was used as a carrier copper foil and plated under the Ni plating conditions, and then a Mo-Ni plating layer was formed thereon under the following conditions.
Sulfuric acid Ni hexahydrate: 50 g / dm ³
Sodium molybdate dihydrate: 60 g / dm ³
Sodium citrate: 90 g / dm ³
Bath temperature: 30 ° C
Current density: 3 A / dm ²
Energizing time: adhesion amount of 20 seconds fabricated release layer: 2.4 mg / ^dm 2,
Mo / (Mo + Ni) * 100 = 29 (%).
After forming a copper plating layer having a thickness of 0.2 μm on the release layer under <copper plating condition 1>, further using <copper plating condition 3>, the copper plating layer is plated with a current density of 4.5 A / dm ² Then, an ultrathin copper foil having a thickness of 3 μm was formed to obtain an ultrathin copper foil with a carrier.
Next, after surface treatment of Ni: 0.5 mg / dm ² , Zn: 0.05 mg / dm ² , Cr: 0.3 mg / dm ² , silane coupling agent treatment (post treatment) is performed, and ultrathin copper with a carrier A foil was obtained.

<Example 3> Carrier foil-> Ni (diffusion prevention layer)-> W-Ni (peeling layer)-> copper plating (ultra-thin copper foil) with a carrier made of ultra-thin copper foil with carrier Rz: 0.82 μm copper foil (Thickness: 31 μm) was used as a carrier copper foil, and after plating was performed under Ni plating conditions, a W—Ni layer was formed under the following plating conditions.
Sulfuric acid Ni hexahydrate: 50 g / dm ³
Sodium tungstate dihydrate: 60 g / dm ³
Sodium citrate: 90 g / dm ³
Bath temperature: 70 ° C
Current density: 2.5 A / dm ²
Energizing time: 18 seconds Amount of adhesion of release layer: 2. 1 mg / dm ² ,
W * 100 / W + Ni = 20%
Formed.
After the copper plating is formed to a thickness of 0.2 μm according to the above <copper plating condition 1>, further plating is performed at a current density of 3.5 A / dm ^{2 according} to the copper plating condition <copper plating condition 3>. A thin copper foil was formed into an ultrathin copper foil with a carrier.
Then, after surface treatment of Ni 0.5 mg / dm ² , Zn: 0.05 mg / dm ² , Cr: 0.3 mg / dm ² , silane coupling agent treatment (post treatment) is performed, and an ultrathin copper foil with a carrier is obtained. Obtained.

<Example 4> Carrier foil → Ni (diffusion prevention layer) → Mo—Co (first layer) → Mo—Co (second layer) (peeling layer) → copper plating (ultra thin copper foil) with carrier ultra thin copper One side of the foil was a copper foil (thickness: 22 μm) having a Rz: 0.74 μm carrier copper foil, plated with <Ni plating conditions>, and then a Mo—Co plated layer was prepared under the following conditions.
<First-layer plating conditions>
Co amount: 4.0 g / dm ³
Mo amount: 3.0 g / dm ³
Citric acid: 80 g / dm ³
Current density: 2 A / dm ²
Energizing time: 10 seconds Bath temperature: 50 ° C
<Second layer plating conditions>
Co amount: 4.0 g / dm ³
Mo amount: 1.5 g / dm ³
Citric acid: 80 g / dm ³
Current density: 2 A / dm ²
Energizing time: 5 seconds Bath temperature: 50 ° C
Adhesion amount of release layer (first layer + second layer): 2.3 mg / dm ²
1st layer Mo * 100 / Mo + Co = 56%
Second layer Mo * 100 / Mo + Co = 23%
Formed.
After copper plating is formed to a thickness of 0.2 μm under <Copper Plating Conditions 1>, it is further plated with a current density of 3.5 A / dm ² using <Copper Plating Conditions 3>, and an ultrathin copper with a thickness of 3 μm. A foil was formed into an ultrathin copper foil with a carrier.
Next, Ni 0.5 mg / dm ² , Zn: 0.05 mg / dm ² , Cr: 0.3 mg / dm ² after surface treatment, silane coupling agent treatment (post treatment) is performed, and an ultrathin copper foil with a carrier is obtained. Obtained.

<Example 5>
An ultrathin copper foil with a carrier was obtained in the same manner as in Example 1 except that the diffusion preventing layer was Ni-Co.

<Example 6>
An ultrathin copper foil with a carrier was obtained in the same manner as in Example 2 except that the diffusion prevention layer was Ni-Co.

<Example 7>
An ultrathin copper foil with a carrier was obtained in the same manner as in Example 3 except that the diffusion preventing layer was Ni-Co.

<Example 8>
An ultrathin copper foil with a carrier was obtained in the same manner as in Example 4 except that the diffusion prevention layer was Ni-Co.

<Example 9>
After forming the release layer (Mo—Co) as in Example 1, 0.3 mg / dm ² of zinc, which is a low melting point metal, was applied on the release layer under the following plating conditions to obtain an ultrathin copper foil with a carrier. .
Zinc plating on the release layer
Zn metal concentration: 1 to 40 g / dm ³
NaOH: ^{3 to} 100 g / dm ³
Temperature 10-60 ° C
Current density: 0.1 to 10 A / dm ²

<Comparative Example 1>
1. Carrier foil Surface roughness Rz of carrier foil: A copper foil having a thickness of 1.2 μm was used as a carrier foil.
2. Formation of release layer Cr metal was attached to the carrier copper foil to form a release layer.
3. Formation of ultrathin copper foil Cu ₂ P ₂ O ₇ · 3H ₂ O: 30 g / l
K ₄ P ₂ O ₇ : 300 g / l
pH: 8
Current density: 4 A / dm ²
After plating with a thickness of 1 μm under the conditions of: Cu concentration: 50 g / l
H ₂ SO ₄ : 100 g / l
Current density: 20 A / dm ²
Then, electroplating was performed so as to obtain an ultrathin copper foil having a thickness of 3 μm, and further, a roughening treatment for attaching copper particles was performed by a known method.
As a rust prevention treatment and a surface treatment, a galvanizing and chromate treatment was performed on the ultrathin copper layer subjected to the roughening treatment by a known method to obtain an ultrathin copper foil with a carrier.

<Comparative example 2>
1. Carrier foil Surface roughness Rz of carrier foil: A copper foil having a thickness of 1.2 μm was used as a carrier foil.
2. To form the carrier copper foil of the release layer continuously performs electroplating Cr, to form a Cr plating peeling layer of the deposited amount 1.5 mg / dm ^2. A hydrated oxide is formed on the surface layer.
3. Formation of ultrathin copper foil On this Cr plating release layer,
_{Cu 2 P 2 O 7 · 3H} 2 O: 30g / l
K ₄ P ₂ O ₇ : 300 g / l
pH: 8
Current density: 1.5 A / dm ²
Strike copper plating for 60 seconds under the conditions of
_{Cu 2 P 2 O 7 · 3H} 2 O: 30g / l
K ₄ P ₂ O ₇ : 300 g / l
pH: 8
Current density: 4 A / dm ²
Cu concentration after plating with a thickness of 1 μm under the conditions of: 50 g / l
H ₂ SO ₄ : 100 g / l
Current density: 20 A / dm ²
Then, electroplating was performed so as to obtain an ultrathin copper foil having a thickness of 3 μm, and further, a roughening treatment for attaching copper particles was performed by a known method.
As a rust prevention treatment and a surface treatment, a galvanizing and chromate treatment was performed on the ultrathin copper layer subjected to the roughening treatment by a known method to obtain an ultrathin copper foil with a carrier.

<Evaluation>
Samples for evaluation of carrier peel of the ultrathin copper foil with carrier prepared in the above Examples and Comparative Examples were prepared and evaluated as follows.
(1) Measurement of carrier peel and ultrathin copper foil with sample carrier for swelling check (Examples 1 to 4, Comparative Examples 1 and 2) were cut into 250 mm length and 250 mm width, and then heated at 350 ° C. for 10 minutes. A sample for confirmation of blisters was created.
Moreover, the resin substrate was affixed with the double-sided tape on the ultra-thin copper foil side of the heat-treated sample, and a single-sided copper-clad laminate for measuring a polyimide carrier peel with a carrier foil was obtained.

(2) Ultra-thin copper foil with pinhole confirmation sample carrier (Examples 1 to 4, Comparative Examples 1 and 2) was cut into a length of 250 mm and a width of 250 mm, and a transparent tape was attached to the ultra-thin copper foil side. The thin copper foil was peeled from the carrier foil to obtain a sample for pinhole confirmation.

<Characteristic evaluation of ultrathin copper foil>
(1) Carrier peel measurement method and check of blisters (a) Check of blisters Whether or not the ultra-thin copper foil on the carrier foil is swollen was visually observed, and the number of blisters was counted. The results are shown in Table 1.
(B) Measurement of carrier peel In accordance with the method specified in JIS C6511, the sample prepared by the method of (1) above is peeled off from the carrier foil with a measurement sample width of 10 mm, and the carrier peel (peel strength) ) Was measured by n number 3. The evaluation results are shown in Table 1.

(C) Pinhole confirmation The above (2) pinhole measurement sample was irradiated with light from below, and the number of visible light was counted as the number of pinholes.

<Evaluation results>
The ultra-thin copper foil with a carrier of Comparative Example 1 has a high carrier peel and little swelling. On the other hand, the ultrathin copper foil with a carrier of Comparative Example 2 has a low carrier peel and a lot of swelling. Thus, according to the comparative example, when the carrier peel is low, the swelling tends to increase, and when the number of swelling is small, the carrier peel tends to increase.
On the other hand, the ultra-thin copper foil with a carrier of the present invention has a low carrier peel and little swelling.
In comparison with the presence or absence of the diffusion prevention layer, the carrier peel tends to be higher than that of the case where there is no diffusion prevention layer, but the level is practically acceptable.

As shown in a comparative example, the ultrathin copper foil with a carrier of the present invention has a stable bulge and carrier peel as compared with a conventional ultrathin copper foil with a carrier whose main component of the release layer is Cr.
In addition, the two layers constituting the release layer have two different metal composition ratios, and by changing the composition ratio between the portion in contact with the carrier foil side and the portion in contact with the ultrathin copper foil, It becomes a very thin copper foil with a stable carrier.

In the above examples, Mo—Co, Mo—Ni, W—Ni layers were used as the release layer, but in addition to this, Mo—Fe, V—Fe, V—Co, V—Ni, Mn—Fe, The same effect can be obtained by a combination of Mn—Co, Mn—Ni, W—Fe, and W—Co.
Further, since Cr is not used at all or in a very small amount in the present day when environmental problems are becoming important, the ultrathin copper foil with a carrier of the present invention can be provided as an environmentally friendly material.

As described above, the present invention suppresses the occurrence of swelling at the peeling layer interface without affecting the carrier peel, and is easy on the carrier foil and the ultrathin copper foil even in an environment that is environmentally friendly and high temperature. An ultrathin copper foil with a carrier that can be peeled off can be provided.
In addition, the present invention provides a printed wiring board having a stable production quality as a substrate for a fine pattern use printed wiring board, multilayer printed wiring board, chip-on-film wiring board, etc., using the ultra-thin copper foil with carrier. It has an excellent effect.

Claims (5)

In the ultra-thin copper foil with a carrier comprising a carrier foil, a diffusion prevention layer, a release layer, and an ultra-thin copper foil, the release layer comprises a metal A selected from the group consisting of Mo, Ta, V, Mn, and W, Fe, It consists of two layers having different composition ratios with the metal B selected from the group of Co, Ni, and Cr, the content c of the metal A constituting the release layer on the carrier foil side, the content d of the metal B, ultrathin copper When the content e of the metal A constituting the release layer on the foil side and the content f of the metal B are defined as | (c / c + d) − (e / e + f) | * 100 ≧ 3 (%)
An ultrathin copper foil with a carrier, characterized in that In an ultra-thin copper foil with a carrier comprising a carrier foil, a diffusion prevention layer, a release layer, an anti-oxidation layer, and an ultra-thin copper foil, the release layer facilitates plating of the metal A holding the peelability and the ultra-thin copper foil. The composition ratio of the metal A selected from the group of Mo, Ta, V, Mn, and W, which is different from the composition ratio of the metal B to be performed, and the metal B selected from the group of Fe, Co, Ni, and Cr is different. It consists of two layers, the content c of the metal A constituting the release layer on the carrier foil side, the content d of the metal B, the content e of the metal A constituting the release layer on the ultrathin copper foil side, and the content of the metal B When the amount is f | (c / c + d) − (e / e + f) | * 100 ≧ 3 (%)
The ratio of
The antioxidant layer is a single layer of a metal having a melting point of 450 ° C. or lower, or a low melting point metal that is an alloy.
An ultra-thin copper foil with a carrier. The adhesion amount of the release layer, the total (Total) with a carrier electrode thin copper foil according to claim 1 or 2, wherein the metal coating weight is ^{0.05mg / dm 2 ~50mg / dm 2} .   3. The carrier according to claim 2, wherein the low melting point metal forming the antioxidant layer is Zn, Sn, Bi, In, or an alloy mainly containing one of Zn, Sn, Pb, Bi, and In. With ultra-thin copper foil. A printed wiring board for high-density ultrafine wiring, wherein the ultrathin copper foil with a carrier according to any one of claims 1 to 4 is laminated on a resin substrate.