TW201544636A - Copper foil having carrier, manufacturing method for producing the copper foil having carrier, copper clad laminate and printed wiring board using the copper foil having carrier - Google Patents

Abstract

The purpose of the present invention is to provide a copper foil having carrier which would be peeled stably with decreasing bias of the peel strength between the interface of the copper foil layer and the carrier. To achieve the purpose, a CV of the peel strength between the carrier and the copper foil of the copper foil having carrier lower than 0.2 is used through the medium of the interface layer on carrier surface of the copper foil having carrier which has copper layer. Therefore, a copper foil having stable-peeling carrier in width direction of the carrier with a lower bias of peel strength is obtained.

Description

Copper foil with carrier, method for producing copper foil with carrier, paste obtained by using copper foil with carrier Copper laminate and printed wiring board

The invention of the present application relates to a copper foil having a carrier, a method for producing a copper foil having a carrier, a copper-clad laminate obtained by using a copper foil having a carrier, and a printed wiring board.

In the past, a copper foil having a carrier has been used as a material for manufacturing a printed wiring board used in the electrical and electronic industries. Usually, the copper foil with a carrier is formed by heat-pressing, and an insulating layer such as a prepreg or the like is formed into a copper-clad laminate to be used for the production of a printed wiring board.

In particular, in recent years, electronic devices have been required to be thinner and lighter, and accordingly, reduction in size and power consumption have been demanded, and printed wiring boards incorporated in such electronic devices have been required to be shrunk according to the size reduction. The thickness of the conductor is reduced, and the design of a printed wiring board in which a fine pitch wiring circuit is provided becomes necessary. Therefore, in order to achieve the requirements of these markets, a copper foil having a carrier has been widely used in the production of the printed wiring board.

The copper foil with a carrier is formed by hot-pressing, and the copper-clad laminate is formed by laminating the insulating layer with a layer of the insulating layer, and then peeled off from the copper-clad laminate to be peeled off. A copper foil with a carrier. The peelable type copper foil with a carrier has been supplied with various kinds of copper foils having a release layer and having a carrier.

For example, the copper foil with a carrier disclosed in Patent Document 1 has a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and a copper foil with a carrier formed on the intermediate layer, wherein the intermediate layer It is formed by sequentially laminating nickel and molybdenum or cobalt or molybdenum-cobalt alloy on a copper foil carrier. In other words, the copper foil with a carrier of Patent Document 1 is formed between a copper foil carrier and an ultra-thin copper layer, and a release layer using an inorganic material such as nickel and molybdenum or cobalt is formed.

Further, the electrodeposited copper foil having a carrier disclosed in Patent Document 2 is provided with a joint interface layer on the surface of the carrier, and an auxiliary metal layer and an electrolytic copper foil layer are provided on the joint interface layer, and the carrier has roughness (Rz). a film or a metal material having a smooth surface of 0.05 μm to 4.0 μm, having a bonding interface layer formed of an organic agent or a metal material on the smooth surface side of the carrier, and 0.08 as an auxiliary metal layer on the surface layer of the bonding interface layer A nickel layer of μm~2.0 μm thick or a cobalt layer of 0.05 μm~3.0 μm thick has an electrolytic copper foil layer formed of a bulk layer and fine copper particles on the surface layer of the auxiliary metal layer. That is, the electrodeposited copper foil of the patent document 2 is formed between the carrier and the electrodeposited copper foil layer, and is formed with a bonding interface layer using an organic agent or a metal material, and an auxiliary metal layer using an inorganic material such as nickel or cobalt. .

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 5228130

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-308477

However, in Patent Document 1, when an intermediate layer made of nickel, molybdenum or cobalt is formed on the surface of the carrier by electrolytic treatment, the adhesion amount of nickel and molybdenum or cobalt constituting the intermediate layer is obtained. This will affect the peel strength of the carrier and the ultra-thin copper layer. When the amount of adhesion of nickel is insufficient and the amount of adhesion of molybdenum or cobalt is too large, the adhesion between the copper foil carrier and the intermediate layer becomes small, and undesired carrier peeling may occur during handling. In addition to this, when the carrier is peeled off, there is a case where the intermediate layer remains in the extremely thin copper layer. Further, when the amount of adhesion of nickel is too large, pinholes are formed on the surface of the ultra-thin copper layer side, resulting in poor performance of the printed wiring board.

Further, in the electrolytic treatment for forming the intermediate layer, the electrode end portion is more likely to concentrate than the current at the center of the electrode, and the current density tends to increase, so that the current density of the entire copper foil carrier becomes uneven. In particular, when electrolytic treatment is performed using a wide electrolytic apparatus, the unevenness of current density becomes remarkable. Therefore, it is difficult to uniformly form a nickel layer and a layer made of molybdenum or cobalt on the surface of the copper foil carrier, and in particular, the peel strength varies in the width direction of the copper foil carrier.

When the peel strength between the copper foil carrier and the ultra-thin copper foil varies in the width direction of the copper foil carrier, the carrier is partially peeled off during the treatment, and when the carrier layer is laminated with the insulating layer, the carrier may be partially removed. The case where the carrier is difficult to peel off. In particular, there is a case where the carrier of the insulating layer is hardly peeled off after the pressing step, and cracking occurs on the extremely thin copper layer. Further, when the peel strength of the carrier is large, a load of more than necessary is applied to the substrate, which causes the substrate to warp or twist.

On the other hand, in the case of the electrodeposited copper foil having a carrier of Patent Document 2, an auxiliary metal layer is formed by electrolytic treatment using an inorganic material such as nickel or cobalt on the surface layer of the joint interface layer using the organic agent. Therefore, the electrolytic copper foil having a carrier of Patent Document 2 is also similar to the copper foil having a carrier of Patent Document 1, and the electrode end portion is more likely to concentrate than the current at the center of the electrode during the electrolytic treatment, and the current density is changed. Since the tendency is high, it is difficult to form the auxiliary metal layer uniformly, and it is difficult to sufficiently reduce the deviation of the peel strength of the electrodeposited copper foil having the carrier in the width direction.

Based on the above, it is an object of the present invention to provide a copper foil having a carrier which stabilizes the peel strength of the interface between the carrier and the copper foil layer.

The present inventors have finally solved the above problems by using the following copper foil having a carrier.

Copper foil with carrier: The copper foil with carrier of the present invention is characterized in that a copper foil layer is interposed on the surface of the carrier by interposing the interface layer, wherein the variation coefficient of the peel strength of the carrier and the copper foil layer ( CV) is 0.2 or less.

A method for producing a copper foil having a carrier: a method for producing a copper foil having a carrier according to the present invention is a method for producing a copper foil having a carrier as described above, and the method includes the following steps A, B, and C.

Step A: a step of forming a peeling layer on the surface of the carrier as a bonding interface layer; and step B: using a solution containing an organic component as a source of a metal component and having a chloride ion concentration of 1 g/L or less, in the peeling layer a step of forming an organic layer containing a metal component as a part of the bonding interface layer; and a step of forming a copper foil layer on the surface of the organic component containing the metal component.

Copper-clad laminate: The copper-clad laminate of the present invention is characterized by using a copper foil having a carrier as described above.

Printed wiring board: The printed wiring board of the present invention is characterized by using a copper foil having a carrier as described above.

According to the copper foil with a carrier of the present invention, since the coefficient of variation (CV) of the peel strength of the carrier and the copper foil layer is 0.2 or less, the variation in peel strength in the width direction of the carrier is small, and the carrier can be stably peeled off.

Further, according to the method for producing a copper foil with a carrier of the present invention, by inhibiting the incorporation of chloride ions into the organic layer containing the metal component, the metal component does not react with the chloride ion, and can be efficiently combined with the organic component. . Therefore, an organic layer containing a metal component can be stably formed on the surface of the release layer.

1‧‧‧ copper foil with carrier

2‧‧‧ Carrier

3‧‧‧ peeling layer

4‧‧‧Organic layer containing metal components

5‧‧‧copper layer

6‧‧‧ joint interface layer

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the constitution of a copper foil having a carrier of the present invention.

Fig. 2 is a schematic view showing the preparation of a sample used for the evaluation of the deviation of the peel strength.

Fig. 3 is a graph showing the results of measurement of the peel strength of each sample of Example 2, and the numerical unit in the table is g/cm.

Hereinafter, an embodiment of a copper foil having a carrier, a method for producing a copper foil having a carrier, a copper-clad laminate obtained by using a copper foil having a carrier, and a printed wiring board will be described.

<copper foil with carrier>

The copper foil with a carrier of the present invention is characterized in that the copper foil with a carrier having a copper foil layer interposed on the surface of the carrier and interposing the interface layer, wherein the carrier and the copper foil layer have a coefficient of variation of the peel strength (CV) ) is 0.2 or less. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the constitution of a base layer of a copper foil having a carrier of the present invention. In addition, FIG. 1 is described as being able to grasp the state of the layers of each layer, and does not reflect the thickness of each layer in reality. As shown in Fig. 1, the copper foil 1 having a carrier of the present invention comprises a layer structure of a carrier 2/joining interface layer 6/copper foil layer 5. Hereinafter, the "coefficient of variation (CV)" of the peel strength of the carrier and the copper foil layer, the "carrier", the "joint interface layer", and the "copper foil layer" will be described in order.

Coefficient of variation (CV) of the peel strength of the carrier and the copper foil layer: The copper foil with a carrier of the present invention has a coefficient of variation (CV) of the peel strength of the carrier and the copper foil layer of 0.2 or less. The variation coefficient (CV) of the peel strength of the carrier and the copper foil layer is 0.15 or less. The peel strength is a value measured in accordance with JIS C 6481-1996. Further, the coefficient of variation (CV) of the peel strength is a value calculated based on the standard deviation (stdev) and the average value (ave) of the peel strength of each portion of the copper foil having the carrier in the width direction and the longitudinal direction, and is a peeling of the carrier. Indicator of intensity deviation. Specifically, the coefficient of variation (CV) is based on the following formula. Find: coefficient of variation (CV) = standard deviation (stdev) / average (ave) ... (form)

In the present invention, since the coefficient of variation (CV) is 0.2 or less, the variation in the peel strength in the width direction between the carrier and the copper foil layer is small. Therefore, it is possible to avoid the deterioration of the peeling workability due to the large deviation of the peel strength, and it is possible to stably peel off the carrier. Therefore, when the carrier is peeled off, the carrier fragments are not left on the surface of the copper foil layer. Here, although the lower limit of the coefficient of variation (CV) of the peel strength is not determined, the smaller the coefficient of variation (CV), the higher the uniformity of the peel strength in the entire region of the copper foil having the carrier, and the higher the Product quality.

Further, the copper foil with a carrier of the present invention preferably has a peel strength of the carrier and the copper foil layer of from 3 g/cm to 50 g/cm, more preferably from 5 g/cm to 30 g/cm, and even more preferably from 7 g/cm to 20 g/ Cm. Generally, the smaller the peel strength in the interface between the carrier and the copper foil layer, the easier the peeling operation. However, when the peeling strength is less than 3 g/cm, the carrier and the copper foil are undesirably partially separated and swelled during the production of the copper foil having the carrier, or the like, and the copper foil is likely to be staggered. Waiting for the bad. On the other hand, when the peel strength exceeds 50 g/cm, it is difficult to remove the carrier from the copper foil layer.

Carrier: In the present invention, the carrier is a material having a specific thickness for improving the copper foil layer having a thin copper foil thickness, and the material is not particularly limited. However, when the copper foil layer is formed by electrolysis, an energizable material such as an aluminum foil, a copper foil, or a metal-coated resin film is preferably used as the carrier. Further, the thickness of the carrier is not particularly limited, and when a copper foil is used as the carrier, the handleability is preferably from 7 μm to 210 μm. The copper foil as a carrier is required to have a thickness of at least 7 μm when it is expected to function as a reinforcing material for preventing wrinkles from occurring.

Bonding Interface Layer: In the present invention, the bonding interface layer is present in a state of being sandwiched between the carrier and the copper foil layer, and is a layer which allows the carrier to be peeled off from the copper foil layer. In the copper foil having a carrier in the present invention, it is preferred that the bonding interface layer be formed of a "peeling layer" provided on the surface of the carrier and a "metal component-containing organic layer" provided on the surface of the release layer. Above In Fig. 1, the joint interface layer 6 is formed of a peeling layer 3 and an organic layer 4 containing a metal component. In the present invention, the release layer 3 preferably uses either an "organic release layer" or an "inorganic release layer".

In the "organic release layer", one or two or more selected from the group consisting of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid are preferably used as the organic component. Specifically, as the nitrogen-containing organic compound, 1,2,3-benzotriazole having a substituent of a triazole compound, carboxybenzotriazole (hereinafter referred to as "CBTA"), N', N is preferably used. '-Bis(benzotriazolylmethyl)urea, 1H-1,2,4-triazole and 3-amino-1,2,4-triazole and the like. Further, as the sulfur-containing organic compound, hydrazine basic thiazole, trithiocyanuric acid, 2-benzimidazole thiol or the like is preferably used. Further, as the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid and linolenic acid are preferably used. Further, the thickness of the organic release layer is preferably from 1 nm to 10 nm.

On the other hand, in the "inorganic release layer", as the inorganic component, a metal such as chromium, nickel, molybdenum, iron, titanium, tungsten, phosphorus, zinc, antimony or vanadium, or an alloy of the metals listed therein, or The oxides of the metals listed, or the oxides of the alloys of the metals listed therein. For example, as the binary alloy, nickel-chromium, cobalt-chromium, chromium-tungsten, chromium-copper, chromium-iron, chromium-titanium or the like can be used. Further, as the ternary alloy, nickel-iron-chromium, nickel-chromium-molybdenum, nickel-chromium-tungsten, nickel-chromium-copper, nickel-chromium-phosphorus, cobalt-iron-chromium, cobalt-chromium- can be used. Molybdenum, cobalt-chromium-tungsten, cobalt-chromium-copper, cobalt-chromium-phosphorus, and the like. Further, the thickness of the inorganic release layer is preferably from 1 nm to 300 nm, more preferably from 2 nm to 50 nm.

Next, the organic layer 4 containing a metal component preferably forms a joint interface layer together with the above-mentioned release layer. The organic layer containing a metal component contains a layer of a metal component and an organic component, and is preferably provided on the surface of the release layer after the release layer is provided on the surface of the carrier. By using the organic layer containing the metal component, the surface of the release layer is in a state in which the organic component and the inorganic component coexist. The organic component-containing organic layer is preferably formed by an electrolytic method using a solution containing an organic component having an organic component content of 0.5 mg/L to 10 mg/L in a concentration of 10 g/L to 50 g/L. Therefore, use a wide-width electrolysis device for electricity At the end of the electrode where the current is more concentrated than the current at the center of the electrode, not only the metal component adheres but also the organic component adheres, and local concentration of the metal component can be avoided. Therefore, a state in which the organic component is uniformly dispersed in the metal component is formed on the surface of the release layer. Therefore, it is possible to effectively reduce the deviation of the peel strength in the width direction, and after the press molding, the partial peeling failure is not caused, and the carrier can be stably peeled off.

Further, as the organic component contained in the organic layer containing the metal component, the organic component exemplified as the organic component of the above-mentioned "organic release layer" is preferably used. When the organic component is press-formed at a high temperature, mutual diffusion of the carrier and the copper foil layer is less likely to occur. Therefore, the organic layer containing the metal component exists in the state in which the organic component is uniformly dispersed in the metal component on the surface of the release layer, so that the variation in the peel strength in the width direction can be effectively reduced. As the metal component described above, it is preferred to use nickel and/or cobalt as a main component. It is excellent in heat stability when processed into a copper-clad laminate, and does not change the peeling characteristics of the carrier. Further, the thickness of the organic layer containing a metal component is preferably from 5 nm to 100 nm. If it is in this range, the organic layer containing a metal component can be formed more uniformly.

Copper foil layer: The copper foil layer is not particularly limited in the formation method, but an electrolytic method is preferably used. The copper foil layer and the insulating layer constitute a material layer to form a copper laminated board for circuit formation. The thickness of the copper foil layer is not particularly limited, but is preferably 12 μm or less. Since it is thicker than 12 μm, the meaning as a copper foil having a carrier will be ignored. Further, the surface of the copper foil layer may be subjected to a surface treatment such as rustproof treatment or decane coupling agent treatment depending on the application. For example, in order to obtain an anchoring effect, a roughening treatment is applied, whereby adhesion strength, heat resistance, and the like can be improved as compared with the case where the roughening treatment is not applied.

<Method for Producing Copper Foil with Carrier>

The method for producing a copper foil with a carrier according to the present invention is a method for producing a copper foil having a carrier as described above, and the method includes the following steps A, B, and C. The following is a description of each step.

Step A: Step A is a step of forming a release layer on the surface of the carrier as a bonding interface layer. Step A is preferably a solution obtained by dissolving an organic component or an inorganic component which forms an organic release layer or an inorganic release layer, by a dipping method in which a carrier is immersed in the solution; a rinsing method and a spray for forming a surface of the release layer A peeling layer is formed by a method, a dropping method, an electroplating method, or the like. However, the method of forming the release layer of the present invention is not limited to the methods enumerated herein.

When the organic layer is formed, as the organic component, as described above, one or a mixture of two or more selected from the group consisting of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid can be preferably used. On the other hand, when the inorganic release layer is formed, as the inorganic component, as described above, a metal such as chromium, nickel, molybdenum, iron, titanium, tungsten, phosphorus, zinc, antimony or vanadium, or the like An alloy, or an oxide of the metal as exemplified, or an oxide of an alloy of the above-mentioned metals. The concentration of the organic component or the inorganic component in the solution in which the organic component or the inorganic component is dissolved, the liquid temperature, the treatment time, and the like may be appropriately set.

Step B: In step B, a solution containing an organic component containing a sulfate as a source of a metal component and having a chloride ion concentration of 1 g/L or less is used, and an organic layer containing a metal component is formed on the surface of the release layer obtained in the step A. The aforementioned step of joining a portion of the interface layer. In the step B, the carrier in which the release layer is formed is immersed in a solution containing an organic component in which a metal component is present, and a cathode electrode is disposed on the surface of the release layer, and by electrolyzing the solution, a metal component can be formed on the surface of the release layer. Organic layer.

As the organic component used for forming the organic layer containing the metal component, the organic component exemplified in the formation of the above organic release layer can be used. In particular, when the organic release layer is formed as the release layer, the organic component used as the organic layer containing the metal component is preferably the same as the organic component used in the formation of the organic release layer. On the other hand, as the metal component for forming the organic layer containing the metal component, as described above, nickel and/or cobalt can be preferably used.

Further, the solution containing the organic component is a solution containing a sulfate as a source of a metal component and having a chloride ion concentration of 1 g/L or less. When the chloride ion concentration of the solution containing the organic component exceeds 1 g/L, the chloride ion chemically reacts with the metal component, and it is easy to hinder the chemical combination of the metal component and the organic component, but by inhibiting the incorporation of chloride ions, The chemical combination of the metal component and the organic component is promoted, and the organic layer containing the metal component can be stably formed on the surface of the release layer.

Further, the content ratio of the organic component to the metal component in the solution containing the organic component is preferably from 0.5 m/L to 10 mg/L with respect to the metal component concentration of 10 g/L to 50 g/L. If it is in this range, the uniformity at the time of electroplating of a metal component can fully be improved.

Further, the electrolytic condition of the solution containing the organic component is preferably a current density of 0.01 A/dm ² to 10 A/dm ² .

Step C: Step C is a step of forming a copper foil layer on the surface of the organic layer containing the metal component obtained in Step B. The method of forming the copper foil layer in the step C is not particularly limited, but an electrolytic method is preferably employed. When the electrolysis method is used, an electrolyte solution such as a copper sulfate-based solution, a copper pyrophosphate-based solution, an ammonium sulfonate-based solution, or a copper cyanide-based solution can be used. Step C: immersing a carrier in which an organic layer containing a metal component is formed in the electrolytic solution, and disposing a cathode on a surface of the organic layer containing the metal component, and electrolyzing the electrolyte solution to form an organic layer containing a metal component A copper foil layer is formed on the surface. Further, in consideration of long-term storage properties and the like, rust-preventing treatment may be applied to the surface of the copper foil layer.

<Form of copper laminated board>

The copper-clad laminate of the present invention is characterized by using the above-described copper foil having a carrier. The concept of the copper-clad laminate in the present invention includes both a hard copper-clad laminate and a flexible copper-clad laminate. In the case of a hard copper-clad laminate, it can be produced by a hot press method or a continuous lamination method. Further, in the case of a flexible copper-clad laminate, a roll lamination method or a casting method can be used.

In the copper-clad laminate of the present invention, the coefficient of variation (CV) of the peel strength of the carrier and the copper foil layer to be laminated is 0.2 or less. Therefore, since the copper-clad laminate has a small deviation from the peel strength of the laminated carrier and the copper foil layer in the width direction of the carrier, the carrier can be stably peeled off from the copper foil layer.

<Form of printed wiring board>

The printed wiring board of the present invention is characterized by using the above-described copper foil having a carrier. The method for producing the printed wiring board of the present invention is not particularly limited. For example, when the hard copper-clad laminate is etched or the like to form an electric circuit, a hard printed wiring board can be obtained. In addition, when the flexible copper-clad laminate is etched or the like to form an electric circuit, a flexible printed wiring board having good bending performance can be obtained. In the copper foil with a carrier of the present invention, the coefficient of variation (CV) of the peel strength of the layered carrier and the copper foil layer is 0.2 or less, so that the deviation of the peel strength between the carrier of the layer and the copper foil layer in the width direction of the carrier Smaller, the carrier can be stably stripped from the copper foil layer.

Next, an embodiment of the copper foil with a carrier of the present invention will be described. In Examples 1 to 3, the content of the organic component in the solution in which only the organic layer was formed was different, and the other production conditions were the same. Therefore, with reference to the first embodiment, the second embodiment and the third embodiment will be described with respect to differences from the first embodiment.

[Example 1]

In the first embodiment, an electrolytic copper foil having a width of 1350 mm and a thickness of 18 μm was used as a carrier, and it was immersed in a dilute sulfuric acid solution having a sulfuric acid concentration of 150 g/L and a liquid temperature of 30 ° C for 30 seconds to carry out pickling treatment, and the oil component adhered to the surface was applied. Or the surface oxide film is removed.

Next, the carrier which had been subjected to the pickling treatment was washed with water, and then immersed in a solution having a CBTA concentration of 5 g/L, a liquid temperature of 40 ° C, and a pH of 5 for 30 seconds to form an organic peeling layer having a thickness of 5 nm on the surface of the carrier.

Next, the carrier on which the organic release layer was formed was immersed in a solution having a nickel sulfate concentration of 240 g/L, a CBTA concentration of 0.5 mg/L, a liquid temperature of 40 ° C, and a pH of 3, and electrolysis was carried out under the conditions of a current density of 8 A/dm ² . The thickness of the joint interface layer having the organic release layer and the organic layer containing the metal component was 15 nm, and an organic layer containing a metal component was formed on the surface of the organic release layer. In the present embodiment, since the solution for forming the organic layer containing the metal component is not used as the metal component source, the chloride ion concentration is 1 g/L or less.

Subsequently, the carrier in which the organic layer containing the metal component is formed is immersed in a copper electrolytic solution having a copper concentration of 65 g/L, a sulfuric acid concentration of 50 g/L, and a liquid temperature of 45 ° C, and is electrolyzed under the conditions of a current density of 15 A/dm ² . A copper foil layer having a thickness of 3 μm was formed on the surface of the organic layer of the metal component. Next, the carrier on which the copper foil layer was formed was washed with water, and then subjected to rust-preventing treatment to obtain a copper having a carrier laminated in the order of the carrier/bonding interface layer (organic release layer/organic component containing metal component)/copper foil layer. Foil.

[Example 2]

In Example 2, the CBTA concentration of the solution forming the organic layer containing the metal component was set to 2 mg/L.

[Example 3]

In Example 3, the CBTA concentration of the solution forming the organic layer containing the metal component was set to 5 mg/L.

[Comparative Example 1]

In Comparative Example 1, a copper having a carrier of Comparative Example 1 was produced under the same conditions as in Example 1 except that a solution containing no organic component and a nickel sulfate concentration of 240 g/L was used as a solution for forming an organic layer containing a metal component. Foil.

[Comparative Example 2]

In Comparative Example 2, as a solution for forming an organic layer containing a metal component, a solution having a nickel sulfate concentration of 240 g/L, a nickel chloride concentration of 50 g/L, and a CBTA concentration of 2 mg/L was used. The solution had a chloride ion concentration of 15 g/L. A copper foil having a carrier of Comparative Example 2 was produced under the same conditions as in Example 1 except for the above.

[Evaluation]

The copper foils having the carriers of the above-mentioned Examples 1 to 3 and Comparative Examples 1 and 2 were respectively brought into contact with a prepreg (manufactured by Mitsubishi Gas Chemical Co., Ltd.: GHPL-830MBT), and a vacuum presser was used. The laminate was laminated under the conditions of a pressure of 25 kg/cm ² , a temperature of 220 ° C, and a pressurization time of 90 minutes to prepare a copper-clad laminate. Next, a copper-clad laminate produced by using the copper foil of the carrier of each of Examples 1 to 3 and Comparative Example 1 and Comparative Example 2, as shown in the schematic view of FIG. 2, is used for the width of the copper foil having the carrier. Thirteen sites were cut out in the direction, and five sites were cut out in the longitudinal direction to prepare a total of 65 samples of 100 mm × 70 mm, and the peel strength was measured for each sample. Further, the measurement of the peel strength of each sample was carried out in accordance with JIS C6481-1996.

Fig. 3 shows the results of measuring the peel strength for each of the samples of the copper foil with a carrier of Example 2. Fig. 3 shows the peel strength of each sample corresponding to the width direction of the copper foil having the carrier and the position before the slit in the longitudinal direction.

Next, for each of the examples and the comparative examples, the average value and the standard deviation of the peel strengths of the 65 samples were calculated, and the coefficient of variation (CV) calculated from the average value of the peel strength and the standard deviation was calculated. The calculation results are shown in Table 1.

As shown in Table 1, the copper foil having a carrier of each of the examples in which the organic layer of the metal component and the organic component are present has a peeling strength coefficient of variation (CV) of 0.17 or less. Further, the peeling strength of the copper foil with a carrier of each of the examples was 20 g/cm or less on average. On the other hand, a metal layer which does not contain an organic component and consists only of a metal component is provided instead of The copper foil with a carrier of Comparative Example 1 having an organic layer of a metal component had an average peel strength of 24.6 g/cm, but the coefficient of variation (CV) of the peel strength was 0.276, which was higher than 0.2. Further, the solution containing the organic layer containing the metal component was a copper foil with a carrier of Comparative Example 2 using a solution having a chloride ion concentration of 15 g/L, and the peel strength was 7.3 g/cm on average, although the conditions were the same as those of the CBTA concentration. In the case of Example 2, the coefficient of variation (CV) of the peel strength was 0.222, which was more than 0.2 as in Comparative Example 1.

From the above results, it is understood that the degree of variation in the coefficient of variation (CV) of the peel strength of the copper foil having the carrier, that is, the peel strength, can be reduced by forming the organic layer containing the metal component constituting the joint interface layer. Further, it was confirmed that the organic layer containing the metal component was formed by using a solution having a chloride ion concentration of 1 g/L or less, and the coefficient of variation (CV) of the peel strength of the copper foil having the carrier was further reduced.

[Industrial Availability]

According to the copper foil with a carrier of the present invention, since the coefficient of variation (CV) of the peel strength of the carrier and the copper foil layer is 0.2 or less, the deviation of the peel strength of the carrier in the width direction is small, and it can be stably peeled off from the copper foil layer. Carrier.

1‧‧‧ copper foil with carrier

2‧‧‧ Carrier

3‧‧‧ peeling layer

4‧‧‧Organic layer containing metal components

5‧‧‧copper layer

6‧‧‧ joint interface layer

Claims (9)

A copper foil having a carrier characterized by a copper foil having a carrier with a copper foil layer interposed on the surface of the carrier and interposing the interface layer, wherein a coefficient of variation (CV) of the peel strength of the carrier and the copper foil layer is 0.2 or less. The copper foil with a carrier according to claim 1, wherein the bonding interface layer is formed of a release layer provided on the surface of the carrier and an organic layer containing a metal component provided on the surface of the release layer. A copper foil having a carrier according to claim 1, wherein the aforementioned metal component is nickel and/or cobalt. A copper foil having a carrier according to claim 2 or 3, wherein the peeling layer is formed of an organic component. The copper foil having a carrier according to claim 4, wherein the organic layer comprises an organic component used in the peeling layer. A copper foil having a carrier according to claim 2 or 3, wherein the peeling layer is made of an inorganic component. A method for producing a copper foil with a carrier according to any one of claims 1 to 6, characterized in that it comprises the following steps A, B, and C: Step A: forming a release layer on the surface of the carrier as an interface bonding a step of layering; step B: using a solution containing an organic component containing a sulfate as a source of a metal component and having a chloride ion concentration of 1 g/L or less, and forming an organic layer containing a metal component on the surface of the release layer as the bonding interface Step of one part of the layer; Step C: a step of forming a copper foil layer on the surface of the organic layer containing the metal component. A copper-clad laminate, which is characterized by using a copper foil having a carrier according to any one of claims 1 to 6. A printed wiring board characterized by using a copper foil having a carrier according to any one of claims 1 to 6.