JPWO2015170715A1 - Copper foil with carrier, method for producing copper foil with carrier, copper-clad laminate obtained using copper foil with carrier, and method for producing printed wiring board - Google Patents

Abstract

It is an object of the present invention to provide a carrier-attached copper foil that can perform a stable peeling operation by reducing variation in peel strength at the interface between the carrier and the copper foil layer. In order to achieve this object, in a copper foil with a carrier provided with a copper foil layer on the surface of the carrier via a bonding interface layer, the coefficient of variation (CV) in peel strength between the carrier and the copper foil layer is 0.2 or less. Adopting the carrier-provided copper foil or the like, the variation in the peeling strength in the width direction of the carrier is small, and stable carrier peeling is realized.

Description

  The invention which concerns on this application is related with the copper clad laminated board and printed wiring board which are obtained using the copper foil with a carrier, the manufacturing method of the copper foil with a carrier, the copper foil with a carrier. In particular, it relates to a peelable copper foil with a carrier.

  Conventionally, a copper foil with a carrier has been used as a material for manufacturing a printed wiring board used in the fields of the electric and electronic industries. Usually, this copper foil with a carrier is laminated with an insulating layer constituting material such as a prepreg by hot press forming to form a copper-clad laminate, and is used for manufacturing a printed wiring board.

  In particular, recent electronic devices are required to be downsized and reduced in power consumption due to the reduction in size, thickness, and size, and printed wiring boards incorporated in these electronic devices also meet the requirements for downsizing and the like. It is necessary to design a printed wiring board in which the thickness is reduced and a fine pitch wiring circuit is provided. Therefore, in order to realize such a demand from the market, a copper foil with a carrier is widely used when manufacturing the printed wiring board.

  The copper foil with a carrier is a peelable copper foil with a carrier that is laminated with an insulating layer constituent material by hot press forming to form a copper clad laminate, and then peeled off and removed from the copper clad laminate. . As for this peelable type copper foil with carrier, copper foil with carrier having various peeling layers is supplied to the market.

  For example, the copper foil with a carrier disclosed in Patent Document 1 is a copper foil with a carrier provided with a copper foil carrier, an intermediate layer laminated on the copper foil carrier, and an ultrathin copper layer formed on the intermediate layer. In the intermediate layer, nickel and molybdenum or cobalt or a molybdenum-cobalt alloy are laminated in this order on a copper foil carrier. That is, in the copper foil with a carrier of Patent Document 1, a release layer using nickel and an inorganic material such as molybdenum or cobalt is formed between the copper foil carrier and the ultrathin copper layer.

  Moreover, the electrolytic copper foil with a carrier disclosed in Patent Document 2 includes a bonding interface layer on the surface of the carrier, and an auxiliary metal layer and an electrolytic copper foil layer on the bonding interface layer. Is provided with a bonding interface layer formed using an organic agent or metal material on the smooth surface side of the carrier using a film or metal material having a smooth surface with a roughness (Rz) of 0.05 μm to 4.0 μm, A surface layer of the joining interface layer is provided with a nickel layer having a thickness of 0.08 μm to 2.0 μm or a cobalt layer having a thickness of 0.05 μm to 3.0 μm as an auxiliary metal layer, and a bulk layer and fine copper grains are formed on the surface layer of the auxiliary metal layer. And an electrolytic copper foil layer. That is, in the electrolytic copper foil with a carrier of Patent Document 2, 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 are provided between the carrier and the electrolytic copper foil layer. Is formed.

Patent No. 5228130 JP 2001-308477 A

  However, in Patent Document 1, when an intermediate layer made of nickel, molybdenum, cobalt, or the like is formed on the surface of the carrier by electrolytic treatment, the adhesion amount of nickel, molybdenum, or cobalt constituting the intermediate layer is such that the carrier and the ultrathin copper layer Affects the peel strength. If the adhesion amount of nickel is insufficient and the adhesion amount of molybdenum or cobalt is too large, the adhesive force between the copper foil carrier and the intermediate layer is reduced, and unintentional peeling of the carrier may occur during handling. In addition, the intermediate layer may remain in the ultrathin copper layer when the carrier is peeled off. Moreover, when the adhesion amount of nickel increases, pinholes increase on the surface on the ultrathin copper layer side, resulting in poor performance of the printed wiring board.

  Furthermore, during the electrolytic treatment for forming the intermediate layer, current tends to be concentrated at the electrode end compared to the center of the electrode, and the current density tends to be high, so the current density is not uniform across the entire copper foil carrier. . In particular, when the electrolytic treatment is performed using a wide electrolytic apparatus, the current density non-uniformity becomes remarkable. Therefore, it becomes difficult to uniformly form a layer made of nickel layer, molybdenum, cobalt, or the like on the surface of the copper foil carrier, and in particular, the peel strength varies in the width direction of the copper foil carrier.

  If the peel strength varies in the width direction of the copper foil carrier between the copper foil carrier and the ultrathin copper foil, the carrier may be partially peeled during handling or laminated with the insulating layer constituent material, and then the carrier is pulled. When peeling off, the carrier may be difficult to peel off partially. In particular, if the carrier is difficult to partially peel after the pressing step with the insulating layer constituent material, the ultrathin copper layer may be broken. In addition, if the peel strength of the carrier is partially high, an excessive load is applied to the substrate, causing the substrate to warp or twist.

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

  From the above, the present invention is to provide a copper foil with a carrier in which the peel strength at the interface between the carrier and the copper foil layer is stabilized.

  The present inventors have solved the above-mentioned problems by adopting the carrier-attached copper foil described below.

Copper foil with carrier: The copper foil with carrier according to the present invention is provided with a copper foil layer on the surface of the carrier via a bonding interface layer, and the coefficient of variation in peel strength between the carrier and the copper foil layer ( CV) is 0.2 or less.

Manufacturing method of copper foil with carrier: The manufacturing method of copper foil with carrier according to the present invention is a manufacturing method of the above-described copper foil with carrier, and includes steps A, B, and C described below. It is characterized by that.
Step A: A step of forming a release layer as a bonding interface layer on the surface of the carrier.
Step B: Using an organic component-containing solution containing sulfate as a metal component source and having a chloride ion concentration of 1 g / L or less, a metal component as a part of the bonding interface layer is formed on the surface of the release layer. Forming an organic layer containing.
Process C: The process of forming a copper foil layer on the surface of the organic layer containing the said metal component.

Copper-clad laminate: The copper-clad laminate according to the present invention is obtained using the above-described copper foil with a carrier.

Printed wiring board: The printed wiring board according to the present invention is obtained using the above-described copper foil with a carrier.

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

  Further, according to the method for manufacturing a copper foil with a carrier according to the present invention, the metal component does not react with the chloride ion by suppressing the mixing of the chloride ion into the organic layer containing the metal component. Can be combined efficiently. Therefore, the organic layer containing a metal component can be stably formed on the surface of the release layer.

It is a cross-sectional schematic diagram which shows the layer structure of the copper foil with a carrier which concerns on this invention. It is a schematic diagram of sample preparation used for evaluation of variation in peel strength. It is a figure which shows the measurement result of the peeling strength of each sample of Example 2. FIG.

  Below, the copper foil with a carrier which concerns on this invention, the manufacturing method of the copper foil with a carrier, the copper clad laminated board obtained using a copper foil with a carrier, and embodiment of a printed wiring board are demonstrated.

<Copper foil with carrier>
The copper foil with a carrier according to the present invention is a copper foil with a carrier having a copper foil layer on the surface of the carrier via a bonding interface layer, and a coefficient of variation (CV) in peel strength between the carrier and the copper foil layer. Is 0.2 or less. FIG. 1 shows a schematic cross-sectional view of a basic layer configuration of a carrier-attached copper foil according to the present invention. In addition, FIG. 1 is described so that the lamination state of each layer can be grasped, and does not reflect the actual thickness of each layer. As shown in FIG. 1, the copper foil 1 with a carrier according to the present invention has a layer configuration of carrier 2 / bonding interface layer 6 / copper foil layer 5. Hereinafter, “coefficient of variation (CV) in peel strength between carrier and copper foil layer”, “carrier”, “bonding interface layer”, and “copper foil layer” will be described in this order.

Coefficient of variation (CV) in peel strength between carrier and copper foil layer: In the copper foil with carrier according to the present invention, the coefficient of variation (CV) in peel strength between the carrier and the copper foil layer is 0.2 or less. A more preferable coefficient of variation (CV) in peel strength between the carrier and the copper foil layer is 0.15 or less. This peel strength is a value measured according to JIS C 6481-1996. 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 at each location in the width direction and the length direction of the copper foil with carrier. Yes, it becomes an index of variation in the peel strength of the carrier. Specifically, the coefficient of variation (CV) is obtained by the following equation.
Coefficient of variation (CV) = standard deviation (stdev) / average value (ave) (formula)

  In the present invention, since the coefficient of variation (CV) is 0.2 or less, there is little variation in peel strength in the width direction between the carrier and the copper foil layer. Therefore, it is possible to avoid the deterioration of the peeling workability caused by an increase in the peel strength variation, and the carrier can be peeled stably. Therefore, no carrier fragments remain on the surface of the copper foil layer when the carrier is peeled off. Here, the lower limit value of the coefficient of variation (CV) of the peel strength is not defined, but as the coefficient of variation (CV) is smaller, the uniformity of the peel strength in the entire region of the carrier-attached copper foil is increased and the product quality is improved. Can be made.

  In the copper foil with a carrier according to the present invention, the peel strength between the carrier and the copper foil layer is preferably 3 g / cm to 50 g / cm, more preferably 5 g / cm to 30 g / cm, and 7 g. More preferably, it is / cm-20 g / cm. In general, the smaller the peel strength at the interface between the carrier and the copper foil layer, the easier the peel work. However, if the peel strength is less than 3 g / cm, the carrier and the copper foil layer may be partially peeled unintentionally during winding of the copper foil with a carrier or the production of a copper clad laminate. Defects such as blistering and slippage are likely to occur. On the other hand, if the peel strength exceeds 50 g / cm, it is difficult to peel off the carrier from the copper foil layer.

Carrier: In the present invention, the carrier is a material having a predetermined thickness in order to improve the handleability of the thin copper foil layer, and the material is not particularly limited. However, when the copper foil layer is formed by electrolysis, it is preferable to use, as a carrier, an energizable material such as an aluminum foil, a copper foil, or a resin film whose surface is metal-coated. Further, the thickness of the carrier is not particularly limited, but when copper foil is used as the carrier, it is preferably 7 μm to 210 μm in consideration of handling properties. In the case where a copper foil as a carrier is expected to serve as a reinforcing material for preventing wrinkles, a thickness of at least 7 μm is required.

Bonding interface layer: In the present invention, the bonding interface layer is a layer that is sandwiched between the carrier and the copper foil layer and allows the carrier to be peeled off from the copper foil layer. In the copper foil with a carrier according to the present invention, the bonding interface layer is preferably composed of a “peeling layer” provided on the surface of the carrier and an “organic layer containing a metal component” provided on the surface of the peeling layer. In FIG. 1 mentioned above, the joining interface layer 6 consists of the peeling layer 3 and the organic layer 4 containing a metal component. In the present invention, the release layer 3 is preferably an “organic release layer” or an “inorganic release layer”.

  The “organic peeling layer” is preferably composed of one or more selected from a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid as an organic component. Specifically, examples of the nitrogen-containing organic compound include 1,2,3-benzotriazole, carboxybenzotriazole (hereinafter referred to as “CBTA”), N ′, N′-bis, which are triazole compounds having a substituent. (Benzotriazolylmethyl) urea, 1H-1,2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used. And as a sulfur containing organic compound, it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazole thiol, etc. As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like. And it is preferable that the thickness of this organic peeling layer is 1 nm-10 nm.

  On the other hand, the “inorganic release layer” includes, as an inorganic component, metals such as chromium, nickel, molybdenum, iron, titanium, tungsten, phosphorus, zinc, tantalum, vanadium, alloys of these enumerated metals, or these enumerated Metal oxides or oxides of these listed metal alloys can be used. For example, as the binary alloy, nickel-chromium, cobalt-chromium, chromium-tungsten, chromium-copper, chromium-iron, chromium-titanium, or the like can be used. Ternary alloys include nickel-iron-chromium, nickel-chromium-molybdenum, nickel-chromium-tungsten, nickel-chromium-copper, nickel-chromium-phosphorus, cobalt-iron-chromium, cobalt-chromium-molybdenum. Cobalt-chromium-tungsten, cobalt-chromium-copper, cobalt-chromium-phosphorus, or the like can be used. And the thickness of this inorganic peeling layer is preferably 1 nm to 300 nm, and more preferably 2 nm to 50 nm.

  Next, it is preferable that the organic layer 4 containing a metal component constitutes a bonding interface layer together with the release layer described above. The organic layer containing a metal component is a layer containing a metal component and an organic component, and is preferably provided on the surface of the release layer after providing the release layer on the surface of the carrier. By adopting the organic layer containing this metal component, the surface of the release layer is in a state where the organic component and the inorganic component coexist. The organic layer containing the metal component is obtained by an electrolytic method using an organic component-containing solution in which the organic component coexists at 0.5 mg / L to 10 mg / L with respect to the metal component concentration of 10 g / L to 50 g / L. It is preferable to form. Therefore, even if the electrolytic treatment is performed using a wide electrolysis apparatus, not only the metal component but also the organic component adheres to the electrode end portion where the current is concentrated as compared with the center portion of the electrode. Concentration can be avoided. Therefore, the organic component is formed on the surface of the release layer in a state of being uniformly dispersed in the metal component. Therefore, variation in the peel strength in the width direction can be effectively reduced, and the carrier can be peeled stably after press molding without causing partial peeling failure.

  Moreover, it is preferable to use the organic component enumerated as an organic component of the above-mentioned "organic peeling layer" for the organic component contained in the organic layer containing a metal component. The organic component described above is less likely to cause interdiffusion between the carrier and the copper foil layer during press molding at a high temperature. Therefore, since the organic layer containing the metal component exists in a state where the organic component is uniformly dispersed in the metal component on the surface of the release layer, it is possible to effectively reduce the variation in the peel strength in the width direction. . It is preferable to use a metal component containing nickel and / or cobalt as a main component. This is because it has excellent heat stability when processed into a copper-clad laminate and does not change the carrier peeling characteristics. Moreover, it is preferable that the thickness of the organic layer containing a metal component is 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: Although there is no limitation in the formation method in particular, a copper foil layer is preferably an electrolytic method. The copper foil layer is laminated with an insulating layer constituting material to form a copper clad laminate, and is used for circuit formation. The thickness of the copper foil layer is not particularly limited, but is preferably 12 μm or less. This is because when the thickness is larger than 12 μm, the significance of the copper foil with carrier is lost. Further, the surface of the copper foil layer can be subjected to a surface treatment such as a rust prevention treatment or a silane coupling agent treatment depending on the application. For example, when the roughening treatment is performed to obtain the anchor effect, the adhesion strength, heat resistance, and the like are improved as compared with the case where the roughening treatment is not performed.

<Method for producing copper foil with carrier>
The manufacturing method of the copper foil with a carrier which concerns on this invention is a manufacturing method of the copper foil with a carrier mentioned above, Comprising: Each process of the process A, the process B, and the process C which are described below is provided. Hereinafter, each step will be described.

Step A: Step A is a step of forming a release layer as a bonding interface layer on the surface of the carrier. In step A, a solution in which an organic component or an inorganic component for forming an organic release layer or an inorganic release layer is dissolved is used, a dipping method in which a carrier is immersed in the solution, a showering method for a surface on which a release layer is formed, and a spray method The release layer is preferably formed using a dropping method, an electrodeposition method, or the like. However, the method for forming the release layer in the present invention is not limited to the methods listed here.

  When forming an organic peeling layer, as described above, a mixture of one or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids is preferably used as the organic component. be able to. On the other hand, when forming an inorganic release layer, as described above, as an inorganic component, a metal such as chromium, nickel, molybdenum, iron, titanium, tungsten, phosphorus, zinc, tantalum, vanadium, or any of these listed metals. An alloy, an oxide of these enumerated metals, an oxide of an alloy of these enumerated metals, or the like can be used. What is necessary is just to set suitably regarding the density | concentration, liquid temperature, processing time, etc. of the organic component or inorganic component in the solution after melt | dissolving an organic component or an inorganic component.

Step B: In Step B, an organic component-containing solution containing sulfate as a metal component source and having a chloride ion concentration of 1 g / L or less is bonded to the surface of the release layer obtained in Step A. This is a step of forming an organic layer containing a metal component as part of the interface layer. In step B, the surface of the release layer is obtained by immersing the carrier in which the release layer is formed in an organic component-containing solution in which a metal component is allowed to coexist, placing an anode electrode on the surface of the release layer, and electrolyzing the solution. An organic layer containing a metal component can be formed.

  As an organic component used for formation of the organic layer containing a metal component, the organic components enumerated in the formation of the organic peeling layer described above can be used. In particular, when an organic release layer is formed as the release layer, it is preferable to use the same organic component used for forming the organic release layer as the organic component of the organic layer containing the metal component. On the other hand, as described above, nickel and / or cobalt can be suitably used as the metal component used for forming the organic layer containing the metal component.

  The organic component-containing solution is a solution containing sulfate as a metal component source and having a chloride ion concentration of 1 g / L or less. When the concentration of chloride ions in the organic component-containing solution exceeds 1 g / L, the chloride ions and the metal component react chemically, and the chemical bond between the metal component and the organic component is likely to be hindered. However, by suppressing the mixing of chloride ions, chemical bonding between the metal component and the organic component can be promoted, and the organic layer containing the metal component can be stably formed on the surface of the release layer.

  In addition, the content ratio of the organic component and the metal component in the organic component-containing solution preferably includes 0.5 mg / L to 10 mg / L of the organic component with respect to the metal component concentration of 10 g / L to 50 g / L. Within this range, the uniformity when electrodepositing the metal component can be sufficiently improved.

Furthermore, the electrolysis conditions of the organic component containing solution preferably current density of ^{0.01A / dm 2 ~10A / 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. In step C, the method for forming the copper foil layer is not particularly limited, but an electrolytic method is preferably employed. When the electrolytic method is employed, an electrolytic solution such as a copper sulfate-based solution, a copper pyrophosphate-based solution, a copper sulfamate solution, or a copper cyanide-based solution can be used. In step C, the carrier in which the organic layer containing the metal component is formed is immersed in the electrolytic solution, the anode electrode is disposed on the surface of the organic layer containing the metal component, and the electrolytic solution is electrolyzed, thereby A copper foil layer can be formed on the surface of the organic layer containing. In addition, the surface of the copper foil layer may be subjected to rust prevention treatment in consideration of long-term storage.

<Copper-clad laminate configuration>
The copper clad laminated board which concerns on this invention is obtained using the above-mentioned copper foil with a carrier, It is characterized by the above-mentioned. The concept of the copper clad laminate referred to in the present invention includes both a rigid copper clad laminate and a flexible copper clad laminate. If it is a rigid copper clad laminated board, it can be manufactured using a hot press system or a continuous laminating system. And if it is a flexible copper clad laminated board, it is possible to use a roll laminating system and a casting system.

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

<Form of printed wiring board>
The printed wiring board which concerns on this invention is obtained using the above-mentioned copper foil with a carrier, It is characterized by the above-mentioned. There is no special limitation regarding the manufacturing method of the printed wiring board which concerns on this invention. For example, if a circuit is formed by etching the above-described rigid copper-clad laminate, a rigid printed wiring board can be obtained. Moreover, if a circuit is formed by etching a flexible copper-clad laminate, a flexible printed wiring board having good bending performance can be obtained. In the copper foil with a carrier according to the present invention, the coefficient of variation (CV) of the peel strength between the laminated carrier and the copper foil layer is 0.2 or less, so the carrier of the laminated carrier and the copper foil layer The variation in peel strength in the width direction is small, and the carrier can be peeled stably from the copper foil layer.

  Next, examples of the copper foil with a carrier according to the present invention will be described. Examples 1 to 3 differ only in the organic component content of the solution forming the organic layer, and the other production conditions are the same. Therefore, after describing the first embodiment, the differences between the second embodiment and the third embodiment from the first embodiment will be described.

  In Example 1, an electrolytic copper foil having a width of 1350 mm and a thickness of 18 μm was used as a carrier, and the pickling treatment was performed by immersing 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. The oil and fat component and the surface oxide film were removed.

  Next, the carrier 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. .

Then, the carrier on which the organic release layer has been formed is 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 electrolyzed under a current density of 8 A / dm ² . The organic layer containing the metal component was formed on the surface of the organic release layer so that the total thickness of the bonding interface layer including the organic release layer and the organic layer containing the metal component was 15 nm. In this example, the solution used for forming the organic layer containing the metal component did not use nickel chloride as the metal component source, so the concentration of chloride ions was 1 g / L or less.

Thereafter, the carrier on which the organic layer containing the metal component is formed is immersed in a copper electrolyte solution having a copper concentration of 65 g / L, a sulfuric acid concentration of 150 g / L, and a liquid temperature of 45 ° C., and electrolyzed under the condition 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 containing the metal component. And after washing the carrier which formed the copper foil layer with water, a rust prevention process is performed and the copper foil with a carrier laminated | stacked in order of the carrier / joining interface layer (organic peeling layer / organic layer containing a metal component) / copper foil layer. Got.

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

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

[Comparative Example 1]
In Comparative Example 1, the carrier of Comparative Example 1 under the same conditions as in Example 1 except that a solution having a nickel sulfate concentration of 240 g / L that does not contain an organic component was used as a solution for forming an organic layer containing a metal component. An attached copper foil was produced.

[Comparative Example 2]
In Comparative Example 2, 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 as a solution for forming an organic layer containing a metal component. The chloride ion concentration of the solution was 15 g / L. Other than that, the copper foil with a carrier of the comparative example 2 was produced on the conditions similar to Example 1. FIG.

[Evaluation]
Each of the copper foils with carriers of Examples 1 to 3 and Comparative Examples 1 and 2 described above was brought into contact with a prepreg (manufactured by Mitsubishi Gas Chemical Company, Inc .: GHPL-830MBT), and a vacuum press was used. A copper-clad laminate was produced by laminating under conditions of a pressing pressure of 25 kg / cm ² , a temperature of 220 ° C., and a pressing time of 90 minutes. And as shown in the schematic diagram of FIG. 2, the width | variety of copper foil with a carrier is shown for the copper clad laminated board produced using the copper foil with a carrier of each Example 1- Example 3, Comparative Example 1, and Comparative Example 2. It was divided into 13 places in the direction and 5 places in the length direction, and a total of 65 100 mm × 70 mm samples were measured, and the peel strength was measured for each sample. The peel strength of each sample was measured according to JIS C6481-1996.

  In FIG. 3, the result when peeling strength is measured about each sample of the copper foil with a carrier of Example 2 is shown. FIG. 3 shows the peel strength of each sample corresponding to the position before the width direction and the length direction of the copper foil with carrier are cut.

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

  As shown in Table 1, the copper foil with a carrier of each Example provided with an organic layer in which a metal component and an organic component coexist had a variation coefficient (CV) of peel strength of 0.17 or less. Moreover, the average of the peeling strength of the copper foil with a carrier of each Example was 20 g / cm or less. On the other hand, instead of the organic layer containing the metal component, the carrier-attached copper foil of Comparative Example 1 provided with the metal layer composed only of the metal component not containing the organic component has an average peel strength of 24.6 g / cm. However, the coefficient of variation (CV) in peel strength was 0.276, which was higher than 0.2. Moreover, the copper foil with a carrier of the comparative example 2 using the solution whose chloride ion concentration of the solution which forms the organic layer containing a metal component is 15 g / L has an average peel strength of 7.3 g / cm, Although the CBTA concentration conditions were the same as in Example 2, the peel strength variation coefficient (CV) was 0.222, which was higher than 0.2 as in Comparative Example 1.

  From the above results, it is possible to reduce the variation coefficient (CV) of the peel strength of the copper foil with carrier, that is, the degree of variation in the peel strength, by forming the organic layer containing the metal component constituting the bonding interface layer. It turns out that. In addition, the coefficient of variation (CV) of the peel strength of the carrier-attached copper foil could be further reduced by forming an organic layer containing a metal component using a solution having a chloride ion concentration of 1 g / L or less. Was confirmed.

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

DESCRIPTION OF SYMBOLS 1 Copper foil with a carrier 2 Carrier 3 Peeling layer 4 Organic layer containing a metal component 5 Copper foil layer 6 Bonding interface layer

Copper foil with carrier: The copper foil with carrier according to the present invention comprises a copper foil layer on the surface of the carrier via a bonding interface layer, and the bonding interface layer is 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 , the copper foil with a carrier is laminated on a prepreg under the conditions of a press pressure of 25 kg / cm ² , a temperature of 220 ° C., and a press time of 90 minutes, The coefficient of variation (CV) in peel strength between the carrier and the copper foil layer measured in accordance with JIS C6481-1996 for each sample cut into 13 places in the direction and 5 places in the length direction is 0.2 or less. It is characterized by being.

Copper-clad laminates: copper-clad laminate according to the present invention is characterized by comprising the above-described copper foil with carrier.

Manufacturing method of a printed wiring board: The manufacturing method of the printed wiring board which concerns on this invention manufactures a printed wiring board using the copper foil with a carrier mentioned above.

According to the copper foil with a carrier according to the present invention, the copper foil with a carrier is laminated on a prepreg under the conditions of a pressing pressure of 25 kg / cm ² , a temperature of 220 ° C., and a pressing time of 90 minutes, and 13 places in the width direction, the length direction. Since the coefficient of variation (CV) of the peel strength between the carrier and the copper foil layer measured in accordance with JIS C6481-1996 for each sample cut into 5 locations is 0.2 or less, the peel strength in the width direction of the carrier Variation is small and the carrier can be peeled stably.

<Copper foil with carrier>
The copper foil with a carrier according to the present invention is a copper foil with a carrier provided with a copper foil layer on the surface of the carrier via a bonding interface layer, and the bonding interface layer is a release layer provided on the surface of the carrier, It consists of an organic layer containing a metal component provided on the surface of the release layer, and the copper foil with carrier is laminated on the prepreg under the conditions of a press pressure of 25 kg / cm ² , a temperature of 220 ° C., and a press time of 90 minutes, The coefficient of variation (CV) in peel strength between the carrier and the copper foil layer measured in accordance with JIS C6481-1996 for each sample cut into 13 places and 5 places in the length direction is 0.2 or less. It is characterized by that. FIG. 1 shows a schematic cross-sectional view of a basic layer configuration of a carrier-attached copper foil according to the present invention. In addition, FIG. 1 is described so that the lamination state of each layer can be grasped, and does not reflect the actual thickness of each layer. As shown in FIG. 1, the copper foil 1 with a carrier according to the present invention has a layer configuration of carrier 2 / bonding interface layer 6 / copper foil layer 5. Hereinafter, “coefficient of variation (CV) in peel strength between carrier and copper foil layer”, “carrier”, “bonding interface layer”, and “copper foil layer” will be described in this order.

Coefficient of variation (CV) in peel strength between carrier and copper foil layer: In the copper foil with carrier according to the present invention, the coefficient of variation (CV) in peel strength between the carrier and the copper foil layer is 0.2 or less. A more preferable coefficient of variation (CV) in peel strength between the carrier and the copper foil layer is 0.15 or less. This peel strength is a value when the copper foil with a carrier is laminated on a prepreg under conditions of a press pressure of 25 kg / cm ² , a temperature of 220 ° C., and a press time of 90 minutes, and measured in accordance with JIS C 6481-1996. . Then, the coefficient of variation (CV) of the peel strength is the standard deviation (stdev) and average value (ave) of the peel strength of each sample cut into 13 places in the width direction and 5 places in the length direction of the copper foil with carrier. Is a value calculated based on the above and serves as an index of variation in the peel strength of the carrier. Specifically, the coefficient of variation (CV) is obtained by the following equation.
Coefficient of variation (CV) = standard deviation (stdev) / average value (ave) (formula)

Bonding interface layer: In the present invention, the bonding interface layer is a layer that is sandwiched between the carrier and the copper foil layer and allows the carrier to be peeled off from the copper foil layer. In the copper foil with a carrier according to the present invention, the bonding interface layer is composed of a “peeling layer” provided on the surface of the carrier and an “organic layer containing a metal component” provided on the surface of the peeling layer . In FIG. 1 mentioned above, the joining interface layer 6 consists of the peeling layer 3 and the organic layer 4 containing a metal component. In the present invention, the release layer 3 is preferably an “organic release layer” or an “inorganic release layer”.

<Copper-clad laminate configuration>
Copper-clad laminate according to the present invention is characterized by having a copper foil with carrier described above. The concept of the copper clad laminate referred to in the present invention includes both a rigid copper clad laminate and a flexible copper clad laminate. If it is a rigid copper clad laminated board, it can be manufactured using a hot press system or a continuous laminating system. And if it is a flexible copper clad laminated board, it is possible to use a roll laminating system and a casting system.

<Mode of manufacturing printed wiring board>
The printed wiring board manufacturing method according to the present invention is characterized by manufacturing a printed wiring board using the above-described copper foil with a carrier. There is no special limitation regarding the manufacturing method of the printed wiring board which concerns on this invention. For example, if a circuit is formed by etching the above-described rigid copper-clad laminate, a rigid printed wiring board can be obtained. Moreover, if a circuit is formed by etching a flexible copper-clad laminate, a flexible printed wiring board having good bending performance can be obtained. In the copper foil with a carrier according to the present invention, the coefficient of variation (CV) of the peel strength between the laminated carrier and the copper foil layer is 0.2 or less, so the carrier of the laminated carrier and the copper foil layer The variation in peel strength in the width direction is small, and the carrier can be peeled stably from the copper foil layer.

Claims (9)

A copper foil with a carrier comprising a copper foil layer on the surface of the carrier via a bonding interface layer,
The carrier-attached copper foil, wherein a coefficient of variation (CV) in peel strength between the carrier and the copper foil layer is 0.2 or less.   2. The copper foil with a carrier according to claim 1, wherein the bonding interface layer includes a release layer provided on a surface of the carrier and an organic layer containing a metal component provided on the surface of the release layer.   The copper foil with a carrier according to claim 1, wherein the metal component contains nickel and / or cobalt.   The copper foil with a carrier according to claim 2 or 3, wherein the release layer comprises an organic component.   The said organic layer is copper foil with a carrier of Claim 4 containing the organic component used by the said peeling layer.   The copper foil with a carrier according to claim 2 or 3, wherein the release layer comprises an inorganic component. It is a manufacturing method of the copper foil with a carrier of Claims 1-6,
The manufacturing method of the copper foil with a carrier characterized by including each process of the process A, the process B, and the process C which are described below.
Step A: A step of forming a release layer as a bonding interface layer on the surface of the carrier.
Step B: Using an organic component-containing solution containing sulfate as a metal component source and having a chloride ion concentration of 1 g / L or less, a metal component as a part of the bonding interface layer is formed on the surface of the release layer. Forming an organic layer containing.
Process C: The process of forming a copper foil layer on the surface of the organic layer containing the said metal component.   A copper clad laminate obtained by using the copper foil with a carrier according to any one of claims 1 to 6.   A printed wiring board obtained by using the carrier-attached copper foil according to any one of claims 1 to 6.

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