WO2015080052A1

WO2015080052A1 - Copper foil with attached carrier foil and copper-clad laminate

Info

Publication number: WO2015080052A1
Application number: PCT/JP2014/080921
Authority: WO
Inventors: 哲広松永; 光由松田; 哲聡高梨; 信之河合
Original assignee: 三井金属鉱業株式会社
Priority date: 2013-11-27
Filing date: 2014-11-21
Publication date: 2015-06-04
Also published as: MY187285A; TW201536876A; KR102272762B1; JP2019178431A; JP6784806B2; JP6855164B2; KR102356179B1; KR20210037020A; CN105745360A; JPWO2015080052A1; KR20160090818A; CN105745360B; TWI644995B

Abstract

In order to provide a copper foil having an attached carrier foil, whereby the carrier foil can be easily peeled off a copper foil layer even when used during copper-clad laminate production using temperatures of at least 250°C, a copper foil having an attached carrier foil is provided that comprises a layer structure including a carrier foil, a bonded interface layer, and a copper foil layer. The copper foil having the attached carrier foil is characterized by using as the carrier foil an electrolytic copper foil that, after heat treatment for 60 minutes at 250°C, has a tensile strength of at least 40 kgf/mm².

Description

Copper foil with carrier foil and copper clad laminate

This application relates to copper foil with carrier foil. In particular, the present invention relates to a peelable copper foil with a carrier foil that can be easily peeled off even after being subjected to a high temperature load.

Conventionally, the present applicant has proposed a copper foil with a carrier foil disclosed in Patent Document 1 or the like as a raw material for producing a printed wiring board having a fine pitch circuit. The copper foil with a carrier foil disclosed in Patent Document 1 is a copper foil with a so-called peelable carrier foil, and a bonding interface layer formed using an organic agent is formed on the surface of the carrier foil. It is characterized in that an electrolytic copper foil layer is deposited on the interface layer. According to the copper foil with the carrier foil, the peeling strength of the bonding interface layer can be kept low and stabilized, so that the instability of the peeling strength of the carrier foil after press molding is eliminated and small It is possible to peel off the carrier foil stably with force.

However, in recent years, in the printed wiring board manufacturing process, the press temperature at the time of bonding the copper foil with carrier foil and the insulating layer constituting material tends to be higher. In particular, a temperature exceeding 300 ° C. may be applied. In such a case, in the copper foil with a carrier foil disclosed in Patent Document 1, the carrier foil and the electrolytic copper foil are connected to each other by the mutual diffusion of the metal of the carrier foil and the electrolytic copper foil due to a high temperature load. Thus, the carrier foil cannot be peeled off from the electrolytic copper foil.

Therefore, the present applicant has disclosed the carrier described in Patent Document 2 as a copper foil with a carrier foil that can be peeled off with a small force even when a temperature exceeding 300 ° C. is applied. We have proposed copper foil with foil. The copper foil with a carrier disclosed in Patent Document 2 is formed by forming a bonding interface layer using thiocyanuric acid so that the carrier foil and the electrolytic copper foil are heated before heating and after heating in the range of 225 to 360 ° C. The peel strength at the bonding interface has achieved a level of 200 gf / cm or less. According to the copper foil with a carrier foil, the carrier foil is extremely small compared to the conventional copper foil with a peelable carrier foil, and the carrier foil can be removed stably.

Further, in the case of Patent Document 3, the present applicant forms an organic bonding interface layer using an organic agent on the surface of the carrier foil, and nickel, nickel alloy, cobalt, or cobalt alloy is formed on the organic bonding interface layer. A method for producing a copper foil with a carrier foil has been proposed in which a dissimilar metal layer is formed using a copper and an electrolytic copper foil layer is provided on the dissimilar metal layer. The copper foil with carrier foil obtained by this production method has a layer configuration of “carrier foil / organic bonding interface layer / dissimilar metal layer such as nickel and cobalt / electrolytic copper foil layer”. By providing the dissimilar metal layer, the carrier foil-attached copper foil can more stably prevent the carrier foil and the electrolytic copper foil from being connected when a temperature exceeding 300 ° C. is applied.

JP 2000-309898 A JP 2001-068804 A JP 2003-328178 A

However, when a temperature of 250 ° C. or higher is applied, the carrier foil of the copper foil with carrier foil is peeled off from the electrolytic copper foil even if the copper foil with carrier foil disclosed in Patent Document 2 and Patent Document 3 is used. There was a large in-lot variation in peeling strength (hereinafter simply referred to as “carrier foil peeling strength”). When the carrier foil peel strength of the copper foil with carrier foil is increased as described above, the carrier foil and the electrolytic copper foil are connected as described above, and the carrier foil cannot be easily peeled off from the electrolytic copper foil. I was able to confirm the phenomenon.

This is shown in FIG. FIG. 2 shows a cross-section of a conventional copper foil with a carrier foil after heat treatment at 250 ° C. for 60 minutes. A relatively large interdiffusion site formed by a high temperature load can be confirmed in the enlarged bonding interface layer in the lower stage of FIG. FIG. 3 schematically shows the situation at this time in an easy-to-understand manner. In FIG. 3, an interdiffusion site (hereinafter simply referred to as “connecting portion 5”) formed by high-temperature loading through the bonding interface layer 4 between the carrier foil 2 and the copper foil 3. Is shown. It has been found that if the connecting portion 5 is large and increases, the carrier foil cannot be easily peeled off from the copper foil.

From the above, the present invention can easily peel off the carrier foil from the copper foil even when it is used for the production of a copper clad laminate in which a temperature of 250 ° C. or higher is loaded, and the carrier with less variation in the lot. The purpose is to provide copper foil with foil.

Therefore, as a result of intensive studies by the present inventors, in the copper foil with carrier foil after the heat treatment at a temperature of 250 ° C. or higher, the carrier foil and the copper are provided with certain conditions described below. It was conceived that the formation of the connecting portion in the bonding interface layer with the foil was suppressed, and the carrier foil could be easily peeled off from the copper foil. Hereinafter, this technical idea will be described.

Copper foil with carrier foil: The copper foil with carrier foil according to the present application has a layer configuration of carrier foil / bonding interface layer / copper foil layer, and after performing heat treatment at 250 ° C. for 60 minutes as the carrier foil. An electrolytic copper foil having a tensile strength of 40 kgf / mm ² or more is used.

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

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

The copper foil with carrier foil according to the present application can easily peel off the carrier foil from the electrolytic copper foil even when a temperature of 250 ° C. or higher is applied, and can reduce lot-to-lot variations. Therefore, it can be suitably used in the production of a copper clad laminate in which a temperature of 250 ° C. or higher is loaded.

In Example 2, 250 ° C. × 60 minutes of a copper foil with a carrier foil using an electrolytic copper foil having a tensile strength of “40 kgf / mm ² or more after performing a heat treatment at 250 ° C. for 60 minutes” as a carrier foil. It is a cross-sectional observation photograph after performing this heat processing. In a comparative example, 250 ° C. × 60 minutes of a copper foil with a carrier foil using an electrolytic copper foil having a tensile strength of “less than 40 kgf / mm ² after performing a heat treatment at 250 ° C. × 60 minutes” as a carrier foil. It is a cross-sectional observation photograph after heat-processing. It is a cross-sectional schematic diagram supposing the case where six connection parts exist in a predetermined joining interface, after performing heat processing with respect to copper foil with a carrier foil for 250 degreeC x 60 minutes.

Hereinafter, the forms of “copper foil with carrier foil” and “copper-clad laminate” according to the present application will be described.

Form of copper foil with carrier foil: The copper foil with carrier foil according to the present application has a layer configuration of carrier foil / bonding interface layer / copper foil layer. And as this carrier foil, after performing the heat processing for 250 degreeC x 60 minutes, the electrolytic copper foil provided with the tensile strength of 40 kgf / mm < ² > or more is used. The heating condition of “250 ° C. × 60 minutes” corresponds to the heating condition generally employed when a copper clad laminate is manufactured by laminating a copper foil for printed wiring boards and an insulating layer constituent material such as a prepreg. To do.

If an electrolytic copper foil having a tensile strength of 40 kgf / mm ² or more after being subjected to a heat treatment at 250 ° C. for 60 minutes is adopted as the carrier foil, heating is performed by inhibiting the crystal growth of the carrier foil in the heating process. The diffusion of copper on the carrier foil side in the process can be slowed, and the formation of a connecting portion can be prevented. As a result, the peeling strength when the carrier foil is peeled off from the copper foil layer after heating can be stably reduced to 200 gf / cm or less, preferably 50 gf / cm or less without variation within the lot. On the other hand, when an electrolytic copper foil having a tensile strength of less than 40 kgf / mm ² after performing a heat treatment at 250 ° C. for 60 minutes is used as the carrier foil, the connecting portion is formed depending on the lot, and the copper is heated after heating. The peeling strength when peeling the carrier foil from the foil layer may exceed 200 gf / cm. Moreover, in the location in which the connection part was formed, a copper foil layer may be torn and it may remain on the surface of carrier foil. For these reasons, it is not preferable to use an electrolytic copper foil having a tensile strength of less than 40 kgf / mm ² as the carrier foil after the heat treatment under the above heating conditions because the peeling work may be difficult. .

The carrier foil according to the present application only needs to have the tensile strength after heating under the above heating conditions in the above specific range, and the tensile strength before heating of the carrier foil is not particularly limited. As the carrier foil, an electrolytic copper foil coated with a metal component such as zinc or tin can be used before heating. If an electrolytic copper foil coated with a metal component such as zinc or tin is heated at about 250 to 400 ° C., the coated metal component diffuses into the electrolytic copper foil, and crystal growth of the carrier foil in the heating process is inhibited. The mechanical strength before heating can be maintained. Therefore, such an electrolytic copper foil is also suitable as a carrier foil for a copper foil with a carrier foil according to the present application.

Moreover, it is preferable that the said electrolytic copper foil is "the average crystal grain diameter after performing a heat processing for 250 degreeC x 60 minutes is less than 1.0 micrometer." There is a certain correlation between the crystal structure of the electrolytic copper foil and the tensile strength. When the crystal grains constituting the crystal structure are fine, the tensile strength of the electrolytic copper foil shows a relatively high value. . An electrolytic copper foil composed of fine crystal grains having an average crystal grain size of less than 1.0 μm generally exhibits a high tensile strength of 40 kgf / mm ² or more. The average crystal grain size in the present application is determined by EBSD analysis of image data representing the crystal state of the cross section of the electrolytic copper foil according to the EBSD method. In addition, an example of a specific measuring method is demonstrated in an Example.

The copper foil with carrier foil according to the present application preferably includes a connecting portion for connecting the carrier foil and the copper foil layer in the bonding interface layer, and the maximum connecting portion diameter is preferably 200 nm or less. If there is a portion where the maximum connecting portion diameter exceeds 200 nm, it may be difficult to peel off the carrier foil at that portion, and if the carrier foil is forcibly peeled off, the connecting portion exceeding 200 nm may cause a copper foil. There is a higher tendency for the layers to tear and remain on the surface of the carrier foil. However, in the copper foil with a carrier foil according to the present application, the connecting portion means that when the copper is diffused between the carrier foil and the copper foil layer when heated under the above heating conditions, the bonding interface. The interdiffusion site | part which penetrates the layer and connects the said carrier foil and the said copper foil layer is shown.

The copper foil with carrier foil according to the present application is present in the bonding interface layer corresponding to 2000 nm when the direction perpendicular to the thickness direction of the copper foil with carrier foil is the length direction as described above. It is preferable that the total length of the connecting portions to be performed is 500 nm or less. In addition, the total length of this connection part is corresponded to the total length of each connection part diameter of each connection part which exists in the joining interface layer of the width | variety of 2000 nm. When the total length of the connecting portion exceeds 500 nm, mutual diffusion due to heating occurs excessively, and it may be difficult to peel off the carrier foil.

And the copper foil with carrier foil which concerns on this application is the said junction interface equivalent to length 2000nm in the cross section of the said junction interface layer after performing the heat processing for 250 degreeC x 60 minutes to the said copper foil with carrier foil. It is preferable that the average connection part diameter which exists in a layer is 50 nm or less. If the average connecting portion diameter exceeds 50 nm, the peeling strength when peeling the carrier foil from the copper foil layer may exceed 200 gf / cm, and the copper foil layer may be broken and remain on the surface of the carrier foil. This is not preferable. Here, what is indicated by reference numeral 5 in FIG. 3 is a “connecting portion” formed by diffusion of copper that occurs between the carrier foil 2 and the copper foil layer 3 by heating. In FIG. What is indicated by “R2, R3, R4, R5, R6” is the “connecting portion diameter”. The “average connecting portion diameter” in the case of FIG. 3 is a value obtained by dividing the sum of the six connecting portion diameters R1, R2, R3, R4, R5, and R6 by 6.

The bonding interface layer of the copper foil with carrier foil according to the present application described above preferably has a thickness of 5 nm to 60 nm. If the thickness of the bonding interface layer is less than 5 nm, the distance between the carrier foil and the copper foil layer becomes too close, and copper diffusion occurring between the carrier foil and the copper foil layer becomes easy. On the other hand, when the thickness of the bonding interface layer exceeds 60 nm, it is not preferable because the carrier foil becomes unstable to hold the copper foil layer. The bonding interface layer is more preferably 5 nm to 30 nm in thickness. When the bonding interface layer has a thickness of 30 nm or less, variations in the thickness of the bonding interface layer are reduced, and the distribution of the connecting portions formed in the bonding interface by heating becomes extremely uniform. This is because the peeling strength at the time of peeling is stabilized.

The bonding interface layer of the copper foil with carrier foil according to the present application includes an “organic bonding interface layer” formed using an organic component and an “inorganic bonding interface layer” formed using an inorganic component.

And when employing the “organic bonding interface layer”, an organic component containing at least one compound selected from the group consisting of nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids should be used. Is preferred. The nitrogen-containing organic compound here includes a nitrogen-containing organic compound having a substituent. Specifically, examples of the nitrogen-containing organic compound include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, which are triazole compounds having a substituent, and 1H. It is preferable to use -1,2,4-triazole, 3-amino-1H-1,2,4-triazole and the like. As the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazolethiol, or the like. As the carboxylic acid, monocarboxylic acid is preferably used, and oleic acid, linoleic acid, linolenic acid, and the like are particularly preferable. This is because these organic components are excellent in heat resistance at high temperatures, and it is easy to form a bonding interface layer having a thickness of 5 nm to 60 nm on the surface of the carrier foil.

And, when adopting “inorganic bonding interface layer”, it is selected from the group consisting of Ni, Mo, Co, Cr, Fe, Ti, W, P as an inorganic component, or an alloy or compound mainly composed of these. It is possible to use at least one or more of them. These inorganic bonding interface layers can be formed by using a known method such as a wet film formation method such as an electrolytic plating method or an electroless plating method, or a dry film formation method such as a sputtering method or a vapor deposition method. is there.

The copper foil with carrier foil according to the present application described above has a layer structure of carrier foil / bonding interface layer / copper foil layer. In order to stably peel off the carrier foil from the copper foil layer after heating, it is necessary to suppress the diffusion of copper between the carrier foil and the copper foil layer via the bonding interface layer as described above. In order to more effectively suppress the copper diffusion behavior, the copper foil with carrier foil according to the present application is provided with a heat-resistant metal layer between the carrier foil and the copper foil layer in order to suppress copper diffusion due to heating. It is preferable. Specifically, the copper foil with carrier foil according to the present application includes “carrier foil / bonding interface layer / heat-resistant metal layer / copper foil layer”, “carrier foil / heat-resistant metal layer / bonding interface layer / copper foil layer”, etc. It is preferable to have the layer configuration of

This heat-resistant metal layer is made of nickel, nickel-phosphorus, nickel-chromium, nickel-molybdenum, nickel-molybdenum-cobalt, nickel-cobalt, nickel-tungsten, nickel-tin-phosphorus in consideration of heat stability. A nickel alloy such as cobalt, cobalt-phosphorus, cobalt-molybdenum, cobalt-tungsten, cobalt-copper, cobalt-nickel-phosphorus, cobalt-tin-phosphorus, etc. preferable. This heat-resistant metal layer can be formed using a known method such as a wet film formation method such as an electrolytic plating method or an electroless plating method, or a dry film formation method such as a sputtering method or a vapor deposition method. The thickness of the refractory metal layer is preferably 1 nm to 50 nm.

In the copper foil with carrier foil according to the present application, there is no particular limitation on the thickness of the carrier foil, and it is sufficient that the thickness is 9 μm to 200 μm that can function as the carrier foil. Also, the thickness of the copper foil layer is not particularly limited, but it can be considered as a thin copper foil that requires a carrier foil and a thickness of about 0.1 μm to 18 μm.

The copper foil with carrier foil described above uses “electrolytic copper foil with a tensile strength of 40 kgf / mm ² or more after heat treatment at 250 ° C. for 60 minutes” as the carrier foil. What is necessary is just to provide the layer structure of an interface layer / copper foil layer, and it does not specifically limit about the copper foil which comprises a copper foil layer, There is no limitation also about the manufacturing method. For example, the copper foil layer may be a copper layer formed by an electroplating method or a wet film forming method such as an electroless plating method, or may be formed by a dry film forming method such as a sputtering method or an evaporation method. A copper layer may be used, and these manufacturing methods may be used in combination, and the copper foil layer may be formed of a plurality of copper layers having different manufacturing methods. However, a copper layer formed by a wet film forming method is preferable because the manufacturing cost is low compared to the dry film forming method. In addition, compared to the electroless plating method, it is an electrolytic copper foil layer formed by an electrolytic plating method from the viewpoint that a copper layer having a predetermined thickness can be formed at a rate commensurate with the industrial production rate. Is preferred. The electrolytic copper foil has a crystal structure suitable for etching processing, and is suitable for use as a circuit forming layer such as a printed wiring board. When forming a copper foil layer by an electrolytic plating method, the copper foil with a carrier foil according to the present application can be manufactured by, for example, the manufacturing method disclosed in Patent Document 1 described above. That is, the surface of the carrier foil is cleaned by pickling or the like, a bonding interface layer is formed on the surface of the cleaned carrier foil, a copper foil layer is formed on the bonding interface layer, and if necessary, the copper foil It can be produced by subjecting the surface of the layer to a roughening treatment, an antirust treatment, a silane coupling agent treatment and the like, followed by a drying treatment.

The copper foil with carrier foil according to the present application can be used when manufacturing a copper-clad laminate and a printed wiring board described later. Moreover, when manufacturing a coreless buildup multilayer printed wiring board, the said copper foil with a carrier foil can be used as a support substrate. Specifically, a build-up layer having the required number of layers is formed on the surface of the support substrate obtained by laminating the copper foil with carrier foil and the prepreg. Thereafter, the carrier foil and the copper foil layer are peeled off at the bonding interface layer of the copper foil with carrier foil, and the buildup layer is separated. By such a process, a coreless build-up multilayer printed wiring board can be obtained. If the copper foil with a carrier foil is used as a support substrate, even when heated at a temperature of 250 ° C. or higher when laminating an insulating layer on the copper foil with a carrier foil, as described above, The diffusion of copper into the layer is slow, and the formation of the connecting portion can be suppressed. For this reason, when peeling carrier foil and a copper foil layer, carrier foil can be peeled stably. Therefore, after forming the build-up layer, when the carrier foil and the copper foil layer are peeled off, problems such as the copper foil layer remaining on the carrier foil side do not occur, and the yield reduction can be suppressed. Furthermore, as described above, the copper foil with a carrier foil according to the present application has high tensile strength of the carrier foil, so that it can satisfy the mechanical strength required for the support substrate and prevent warpage of the support substrate. Can be handled easily. Further, even if the thickness of the carrier foil of the copper foil with carrier foil is thin, the mechanical strength required for the support substrate can be satisfied, so that the thickness of the carrier foil is used to prevent warpage of the support substrate. It is not necessary to increase the thickness, and wasteful consumption of resources can be suppressed.

Copper-clad laminate: The copper-clad laminate according to the present application is a laminate of the copper foil with carrier foil and the insulating layer constituent material according to the present application, which is a rigid copper-clad laminate and a flexible copper-clad laminate. Including both. That is, there is no particular limitation on the type of insulating layer constituent material here. If the copper foil with carrier foil according to the present application is used, even when heated to a temperature of 250 ° C. or higher when laminated to the insulating layer constituting material, the connecting portion is difficult to be formed as described above. Can be peeled off. In addition, even if the thickness of the carrier foil is thin, it has sufficient mechanical strength, so when handling the copper-clad laminate, the copper-clad laminate is less likely to be warped and handling becomes easy. .

Printed wiring board: The printed wiring board according to the present application was obtained using the copper foil with carrier foil according to the present application described above. Both the rigid type printed wiring board and the flexible type printed wiring board Including. The printed wiring board according to the present application includes all printed wiring boards such as a single-sided printed wiring board, a double-sided printed wiring board, and a multilayer printed wiring board.

Production of carrier foil: Current density 60 A / dm ² using a sulfuric acid-based copper electrolyte having a copper concentration of 80 g / L, a free sulfuric acid concentration of 250 g / L, a chlorine concentration of 2 mg / L, a gelatin concentration of 2 mg / L, and a liquid temperature of 50 ° C. To produce an electrolytic copper foil having a thickness of 18 μm, which was used as a carrier foil. The normal tensile strength of the electrolytic copper foil at this time was 43.8 kgf / mm ² , and the tensile strength after the heat treatment at 250 ° C. for 60 minutes was 42.2 kgf / mm ² . The normal state of the carrier foil and the tensile strength after heating were measured according to IPC-TM-650. The same applies to the following examples and comparative examples.

Formation of bonding interface layer: A bonding interface layer was formed on the surface of the carrier foil as follows. The carrier foil is immersed for 30 seconds in an organic agent-containing dilute sulfuric acid aqueous solution of sulfuric acid 150 g / L, copper concentration 10 g / L, carboxybenzotriazole (CBTA) concentration 800 mg / L, and liquid temperature 30 ° C. While pickling and removing, CBTA was adsorbed on the surface of the carrier foil, and a bonding interface layer made of CBTA was formed on the surface of the carrier foil to obtain a “carrier foil having a bonding interface layer”.

Formation of the copper foil layer: Next, in the copper electrolyte, the “carrier foil having a bonding interface layer” is cathodically polarized, and a copper foil layer is formed on the surface of the bonding interface layer to obtain a copper foil with a carrier foil. It was. The copper foil layer is formed by electrolysis at a current density of 30 A / dm ² using a copper sulfate solution having a copper concentration of 70 g / L, a free sulfuric acid concentration of 150 g / L, and a liquid temperature of 45 ° C., and a thickness of 3 μm. Formed.

Surface treatment of copper foil layer: Zinc-nickel alloy rust preventive layer is formed on the surface of the copper foil layer of the copper foil with carrier foil obtained above without roughening, electrolytic chromate treatment, amino system A silane coupling agent treatment was performed to obtain a surface-treated copper foil with a carrier foil.

Average crystal grain measurement: For measuring the crystal grain diameter of the carrier foil, an FE gun type scanning electron microscope (SUPRA 55VP, manufactured by Carl Zeiss Co., Ltd.) equipped with an EBSD evaluation device (OIM Analysis, manufactured by TSL Solutions Co., Ltd.) ) And the attached EBSD analyzer. Using this apparatus, image data of the crystal state of the cross section of the copper foil was obtained according to the EBSD method for the sample that was appropriately cross-section processed, and this image data was obtained from the EBSD analysis program (OIM Analysis, Inc. The average crystal grain size was quantified in the analysis menu of TSL Solutions. In this evaluation, an orientation difference of 5 ° or more was regarded as a crystal grain boundary. The conditions of the scanning electron microscope during observation were as follows: acceleration voltage: 20 kV, aperture diameter: 60 mm, high current mode, sample angle: 70 °. The measurement results are summarized in Table 1.

Measurement of peel strength: The peel strength of the carrier foil after normal heating and heating was measured according to IPC-TM-650. In the measurement, a plate-shaped test piece prepared by the following method was used. First, an insulating resin layer constituent material was bonded to the surface of the copper foil layer of the copper foil with carrier foil described above using an adhesive to prepare a copper clad laminate. At this time, a cured prepreg having a thickness of 100 μm was used as the insulating layer constituent material. And the carrier foil in the surface of this copper clad laminated board was cut, and the plate-shaped test piece of width 10mm x length 10cm was produced. When preparing a sample for measuring the normal peel strength, a copper foil with a carrier foil before heat treatment is used, and when preparing a sample for measuring the peel strength after heating, 250 ° C. in advance. A copper foil with a carrier foil subjected to a heat treatment of × 60 minutes was used. In addition, about the peeling strength of the carrier foil after a heating, it sampled from five different places of copper foil with carrier foil, each measured, and the range of the measured value of 5 times was shown. The measurement results are summarized in Table 1.

Measurement of connecting part diameter: Based on the image data of the crystal state of the cross section of the copper foil used for the measurement of the average crystal grain, the copper foil with the carrier foil obtained above was subjected to a heat treatment at 250 ° C. for 60 minutes. In the cross section of the subsequent bonding interface layer, in the same manner as the method schematically shown in FIG. 3, the diameter of the connecting portion existing in the bonding interface layer corresponding to the length of 2000 nm is obtained. The total length and the maximum joint diameter were determined. The measurement results are summarized in Table 1.

Example 2 differs from Example 1 only in that a step of “formation of a refractory metal layer” is provided between “formation of a bonding interface layer” and “formation of a copper foil layer”. Therefore, only “formation of the refractory metal layer” will be described.

Formation of heat-resistant metal layer: Next, a nickel layer was formed as a heat-resistant metal layer on the surface of the bonding interface layer. This heat-resistant metal layer is formed by using nickel sulfate (NiSO ₄ .6H ₂ O) 330 g / L, nickel chloride (NiCl ₂ .6H ₂ O) 45 g / L, boric acid 35 g / L, and liquid temperature 45. Electrolysis was performed at a current density of 2.5 A / dm ² using a Watt bath at 0 ° C. and a pH of 3 to form a nickel layer having a converted thickness of 10 nm.

Hereinafter, as in Example 1, a copper foil layer is formed on the surface where the heat resistant metal layer and the bonding interface layer of the “carrier foil including the heat resistant metal layer and the bonding interface layer” are present, and the surface of the copper foil layer is the surface. The copper foil with carrier foil was obtained by processing. A cross-sectional observation photograph of the electrolytic copper foil with carrier foil obtained in Example 2 is shown in FIG.

Example 3 is different from Example 1 only in the carrier foil. Therefore, only the manufacture of a carrier foil different from that in Example 1 will be described.

Production of carrier foil: sulfuric acid system having a copper concentration of 80 g / L, a free sulfuric acid concentration of 140 g / L, a chlorine concentration of 0.25 mg / L, an iodine concentration of 5.0 mg / L using potassium iodide (KI), and a solution temperature of 50 ° C. Electrolysis was performed using a copper electrolyte at a current density of 75 A / dm ² to produce an electrolytic copper foil having a thickness of 18 μm, which was used as a carrier foil. Tensile strength of normal electrodeposited copper foil in this case the tensile strength after the heat treatment of ^{48.7kgf / mm 2, 250 ℃ ×} 60 minutes was 45.0kgf / mm ^2.

Example 4 is different from Example 1 only in the carrier foil. Therefore, only the manufacture of a carrier foil different from that in Example 1 will be described.

Production of carrier foil: Current density using a sulfuric acid-based copper electrolyte having a copper concentration of 80 g / L, a sulfuric acid concentration of 140 g / L, a molecular weight of polyethyleneimine of 53 mg / L, a chlorine concentration of 2.2 mg / L, and a liquid temperature of 50 ° C. Electrolysis was performed at 70 A / dm ² to produce an electrolytic copper foil having a thickness of 18 μm, which was used as a carrier foil. The normal tensile strength of the electrolytic copper foil at this time was 62.2 kgf / mm ² , and the tensile strength after the heat treatment at 250 ° C. for 60 minutes was 48.1 kgf / mm ² .

Example 5 is different from Example 1 only in the carrier foil. Therefore, only the manufacture of a carrier foil different from that in Example 1 will be described.

Production of carrier foil: In Example 5, an acidic copper electrolyte with a copper concentration of 80 g / L, a sulfuric acid concentration of 140 g / L, a molecular weight of 10000 polyethyleneimine, a chlorine concentration of 1.0 mg / L, and a liquid temperature of 50 ° C. Then, electrolysis was performed at a current density of 70 A / dm ² to produce an electrolytic copper foil having a thickness of 18 μm, which was used as a carrier foil. The normal tensile strength of the electrolytic copper foil at this time was 79.0 kgf / mm ² , and the tensile strength after the heat treatment at 250 ° C. for 60 minutes was 55.4 kgf / mm ² .

Comparative example

In the comparative example, instead of the electrolytic copper foil used as the carrier foil in Example 1, the tensile strength after carrying out the heat treatment at a normal tensile strength of 40.3 kgf / mm ² and 250 ° C. × 60 minutes is An electrolytic copper foil of 35.0 kgf / mm ² was used as a carrier foil. Regarding other processes, a copper foil with a carrier foil as a comparative example was obtained in the same manner as in Example 2. And the average crystal grain of the carrier foil, the peeling strength of the carrier foil, and the diameter of the connecting portion were measured in the same manner as in the examples. The measurement results are summarized in Table 1. Moreover, the cross-sectional observation photograph of the electrolytic copper foil with a carrier foil obtained by the comparative example is shown in FIG.

[Contrast between Example and Comparative Example]

As can be understood from Table 1, with respect to Examples 1 to 5, as the carrier foil, “electrolytic copper foil having a tensile strength of 40 kgf / mm ² or more after being subjected to a heat treatment at 250 ° C. × 60 minutes” Is used. On the other hand, the comparative example has only a tensile strength of 35.0 kgf / mm ² after the heat treatment at 250 ° C. for 60 minutes. As a result, with respect to Examples 1 to 5, “the maximum connecting portion diameter is 200 nm or less among the connecting portions existing in the bonding interface layer”, “the connection existing in the bonding interface layer corresponding to the length of 2000 nm. The total length of the part was 500 nm or less. However, in the case of the comparative example, the maximum connecting part diameter exceeds 200 nm, and the total length of the connecting part also exceeds 500 nm. Therefore, it can be understood that the peeling strength and variation of the carrier foil of the comparative example are extremely high values as compared with the example. In the case of the peeling strength of the carrier foil of this comparative example level, since these variations occur, it may be difficult to peel off the carrier foil.

The copper foil with carrier foil according to the present application is capable of easily peeling the carrier foil from the electrolytic copper foil even when a temperature of 250 ° C. or higher is applied. It can be suitably used in the production of tension laminates. Since the peeling strength when peeling the carrier foil from the copper foil layer is stable at a low level, the carrier foil can be easily peeled off.

DESCRIPTION OF SYMBOLS 1 Copper foil with carrier foil 2 Carrier foil 3 Copper foil layer 4 Bonding interface layer 5 Connection part

Claims

A copper foil with a carrier foil comprising a layer configuration of carrier foil / bonding interface layer / copper foil layer,
A copper foil with a carrier foil, characterized in that an electrolytic copper foil having a tensile strength of 40 kgf / mm 2 or more after heat treatment at 250 ° C. for 60 minutes is used as the carrier foil.
2. The copper foil with carrier foil according to claim 1, further comprising a connecting portion for connecting the carrier foil and the copper foil layer in the bonding interface layer, wherein the maximum connecting portion diameter is 200 nm or less.
The total length of the connecting portions existing in the bonding interface layer corresponding to a length of 2000 nm is 500 nm or less, where the length direction is a direction perpendicular to the thickness direction of the copper foil with carrier foil. Or the copper foil with a carrier foil of Claim 2.
The copper foil with a carrier foil according to any one of claims 1 to 3, wherein the bonding interface layer has a thickness of 5 nm to 60 nm.
The copper foil with a carrier foil according to any one of claims 1 to 4, wherein the bonding interface layer is formed using an organic component.
The copper foil with a carrier foil according to claim 5, wherein the organic component of the bonding interface layer includes at least one compound selected from the group consisting of a nitrogen-containing compound, a sulfur-containing compound, and a carboxylic acid.
The copper foil with a carrier foil according to any one of claims 1 to 4, wherein the bonding interface layer is formed using an inorganic component.
The inorganic component of the bonding interface layer includes at least one selected from the group consisting of Ni, Mo, Co, Cr, Fe, Ti, W, P, or an alloy or compound containing these as a main component. 8. Copper foil with carrier foil according to 7.
The copper foil with carrier foil according to any one of claims 1 to 8, further comprising a heat-resistant metal layer between the carrier foil and the copper foil layer constituting the copper foil with carrier foil.
A copper clad laminate obtained by using the copper foil with a carrier foil according to any one of claims 1 to 9.
A printed wiring board obtained by using the copper foil with a carrier foil according to any one of claims 1 to 9.