JP2005288856A - Electrolytic copper foil with carrier foil and method for manufacturing the same and copper-clad laminated sheet using electrolytic copper foil with carrier foil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolytic copper foil with a carrier foil which can be used in a press molding temperature region at 230°C or lower and uses an organic agent in a bonding interface layer. <P>SOLUTION: The electrolytic copper foil 1a with the carrier foil is equipped with the bonding interface layer 2 on one face of the carrier foil C, and is equipped with an electrolytic copper foil layer CF on the bonding interface layer 2. The bonding interface layer 2 is formed by using a solution containing triazine thiols. The triazine thiols here is especially preferably 2-anilino-4,6-dimercapto-s-triazine. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrolytic copper foil with a carrier foil, a method for producing the electrolytic copper foil with a carrier foil, and a copper-clad laminate using them.

  Conventionally, an electrolytic copper foil with a carrier foil has been widely used as a basic material for producing printed wiring boards widely used in the fields of the electric and electronic industries. This electrolytic copper foil with carrier foil is bonded to a polymer insulating substrate such as glass-epoxy substrate, phenol substrate, polyimide, etc. by hot press forming into a copper-clad laminate, and used for printed wiring board production It is.

  This electrolytic copper foil with carrier foil is subjected to thermocompression bonding with a prepreg cured on a B stage under a high temperature atmosphere (hereinafter, this process is referred to as “press molding”) to produce a copper clad laminate. This prevents wrinkles of the copper foil layer that occur at the time, and causes cracks in the copper foil at the ridges to prevent the resin from exuding from the prepreg. And it makes it easy to form a thin copper foil layer on the surface of a copper clad laminated board.

  This electrolytic copper foil with carrier foil can be roughly divided into a peelable type and an etchable type. In short, the peelable type is a type that peels and removes the carrier foil after press molding, and the etchable type is a type that removes the carrier foil by etching after press molding. It is.

  Among these, peelable type has extremely unstable peeling strength value of the carrier foil after press molding. In extreme cases, the carrier foil may not be peeled off, and the desired peeling will occur. It had a drawback that it was difficult to obtain strength. In order to solve this problem, the present inventors have solved the disadvantages of the conventional peelable type electrolytic copper foil with carrier foil and stabilize the peel strength at the interface between the carrier foil and the electrolytic copper foil at a low level. In an electrolytic copper foil with a carrier foil, a bonding interface layer is formed on the surface of the carrier foil, copper is electrolytically deposited on the bonding interface layer, and the deposited copper layer is used as an electrolytic copper foil. Patent Document 1 has proposed an electrolytic copper foil with a carrier foil characterized by using various organic agents in the bonding interface layer.

  The joint interface layer of the electrolytic copper foil with carrier foil that has been proposed by the present inventors is formed by adsorbing an organic agent on the surface of the carrier foil using an aqueous solution containing an organic agent constituting the joint interface layer. Met. This electrolytic copper foil with carrier foil is around 180 ° C. when using a normal FR-4 prepreg, compared with conventional electrolytic copper foil with carrier foil using a metal material such as chromium as the bonding interface layer. Even after pressing, the carrier foil showed very good performance and the carrier foil could be peeled off very easily, but it was difficult to form at a pressing temperature exceeding 200 ° C.

  Therefore, the present inventors, in Patent Document 2, provided with a carrier foil having a bonding interface layer formed using thiocyanuric acid on a carrier foil and having an electrolytic copper foil layer deposited on the bonding interface layer. The use of electrolytic copper foil has been advocated. This electrolytic copper foil with carrier foil has a feature that the carrier foil can be stably peeled off even when heated at around 300 ° C.

JP 2000-309898 A JP 2001-68804 A

  However, although the electrolytic copper foil with carrier foil disclosed in Patent Document 2 is excellent in high temperature heat resistance, the cost of the organic agent constituting the bonding interface is high, so the manufacturing cost is high, and the manufacturing stability during mass production tends to be lacking. Therefore, the peel strength value of the carrier foil after press molding tended to be more unstable than originally planned. Further, there was a defect in appearance that the surface of the copper foil layer in contact with the bonding interface formed using thiocyanuric acid turned black.

  In addition, printed wiring materials in recent years have been diversified, such as the use of a substrate using BT resin and a high heat-resistant substrate such as a polyimide substrate. Electrolytic copper foil with carrier foil in a press molding temperature range of 170 ° C. to 230 ° C. Higher demands have been made regarding the quality stability of Moreover, in order to survive the international price competition, cheaper products have been demanded.

  Therefore, although the quality superiority of the electrolytic copper foil with carrier foil using an organic agent in the bonding interface layer has been recognized in the market, the demand for products with more stable quality has increased.

  Thus, as a result of earnest research, the inventors have been able to stabilize the peeling strength of the interface between the carrier foil and the electrolytic copper foil at a low level even when a press molding temperature of 170 ° C. to 230 ° C. is added. Triazine thiols (triazine derivatives) were used to form the bonding interface. Hereinafter, the present invention will be described by dividing it into an electrolytic copper foil with a carrier foil and a manufacturing method thereof.

<Electrolytic copper foil with carrier foil according to the present invention>
The electrolytic copper foil with carrier foil according to the present invention has a layer structure as classified as the following electrolytic copper foil with first carrier foil to sixth electrolytic copper foil with carrier foil. However, since the basic configuration is the electrolytic copper foil with the first carrier foil, the main features of the invention of the electrolytic copper foil with the carrier foil according to the present invention are described in detail in the section of the electrolytic copper foil with the first carrier foil. To do.

(Electrolytic copper foil with first carrier foil)
The first electrolytic copper foil with a carrier foil according to the present invention is “in an electrolytic copper foil with a carrier foil comprising a bonding interface layer on one side of the carrier foil and an electrolytic copper foil layer on the bonding interface layer. The bonding interface layer is formed by using triazine thiols, and can be expressed as an electrolytic copper foil with a carrier foil. FIG. 1 schematically shows a cross section of the electrolytic copper foil 1a with carrier foil.

  As is apparent from FIG. 1, the carrier foil-attached electrolytic copper foil 1a is a product in which the carrier foil C and the electrolytic copper foil CF are bonded together. And this electrolytic copper foil 1a with a carrier foil is in the state with carrier foil C attached, and after attaching the electrolytic copper foil layer CF to the resin base material, the carrier foil C is peeled off to obtain a copper clad laminate. Used. In the above and the following, the electrolytic copper foil and the electrolytic copper foil layer, the carrier foil and the carrier foil layer, the bonding interface and the bonding interface layer indicate the same portions, and are appropriately used according to the description.

  The electrolytic copper foil 1a with carrier foil according to the present invention is characterized in that triazine thiols are used for the bonding interface 2 located between the carrier foil C and the electrolytic copper foil CF. By forming the bonding interface layer 2 using these triazine thiols, the accuracy of peeling of the carrier foil after press molding in a range of 230 ° C. or lower compared to the case where the bonding interface layer 2 is formed by conventional CBTA or the like Is dramatically improved.

  Thus, the joint interface layer formed using triazine thiols exhibits very excellent stability in a press molding temperature region of 230 ° C. or lower, and stabilizes the peel strength of the carrier foil after press working at a low level. By using triazine thiols, the bonding interface layer is formed as a dense and uniform film on the surface of the carrier foil, so that the carrier foil is not partially exposed and the bonding interface layer is not partially lost. . In addition, the joint interface layer with uniform thickness formed using triazine thiols is very good as the electrodeposited surface of copper, and can increase the film thickness uniformity of the electrolytic copper foil layer formed by electrolysis. It can be done.

  That is, by using triazine thiols for the bonding interface layer, the peel strength of the carrier foil after the press molding in the temperature range of 170 ° C. to 230 ° C. for the production of copper-clad laminate can be easily performed by human manual work. It becomes possible to control to a level that can be peeled off. The state in which the carrier foil cannot be peeled off after press molding in the temperature range of 170 ° C. to 230 ° C., and defects such that the pieces of the carrier foil remain on the copper foil surface after peeling can be completely eliminated. it can. Speaking only when press molding is performed at a temperature range of 170 ° C. to 230 ° C., it is very difficult to form a bonding interface layer at a temperature of 200 ° C. or lower such as benzotriazole or carboxybenzotriazole, which are other organic agents. Performance higher than that of an organic agent that exhibits stable performance is obtained, and performance equivalent to that of thiocyanuric acid that is particularly excellent in high-temperature heat resistance is obtained.

  The triazine thiols here refer to triazine thiol derivatives excluding 2,4,6-trimercapto-s-triazine. Among them, the use of 2-anilino-4,6-dimercapto-s-triazine, whose structural formula is shown in FIG. 2, is good stability of the peeling strength of the carrier foil and discoloration of the surface layer of the electrolytic copper foil layer. It is particularly preferable from the viewpoint of not inviting. Such triazine thiols have been used for applications such as mold release agents, recovery of valuable metals, and immobilization of harmful metals. However, as will be apparent from the method for producing an electrolytic copper foil with a carrier foil according to the present invention, which will be described later, the triazine thiols constituting the bonding interface layer in the present invention are not merely for obtaining a releasing action. That is, it serves as an adhesive layer between the carrier foil layer and the electrolytic copper foil layer, and the bonding interface layer composed of triazine thiols serves as an electrodeposition surface of the electrolytic copper foil layer. Furthermore, it functions as a peeling surface between the carrier foil layer and the electrolytic copper foil layer after pressing.

  Organic agents such as triazine thiols are generally not conductive materials. Accordingly, the electrolytic copper foil with a carrier foil according to the present invention is polarized by using the carrier foil itself as a cathode and directly depositing copper on the organic bonding interface layer formed on the carrier foil. It is necessary to be able to conduct electricity through the interface layer. That is, the thickness of the bonding interface layer composed of the organic agent naturally has a limit, and it is necessary to ensure an appropriate peeling strength and enable stable electrolytic deposition of copper.

  Therefore, the thickness of the bonding interface layer of the electrolytic foil with carrier foil according to the present invention is preferably 0.5 nm to 1 μm. In the thickness range specified here, it is possible to ensure an appropriate peeling strength of the carrier foil after press molding, and to allow stable electrolytic deposition of copper. That is, when the thickness of the bonding interface layer formed using triazine thiols is less than the lower limit of 0.5 nm, the thickness of the bonding interface layer varies, and the carrier foil cannot be uniformly coated, A stable and appropriate peeling strength after press molding cannot be obtained, and in some cases, the carrier foil cannot be peeled off.

  If the upper limit of 1 μm is exceeded, the energized state becomes unstable when attempting to form the electrolytic copper foil layer, the copper deposition state is unstable, and it is difficult to form an electrolytic copper foil layer with a uniform thickness. It becomes. When the thickness of the bonding interface layer is further increased, the energization is completely impossible.

  Since the thickness of the bonding interface layer is very thin, on the order of nm to μm, the thin sample is processed by focused ion beam processing (FIB), and this sample is processed by a transmission electron microscope (TEM). It is desirable to observe directly using. Therefore, also in this invention, the TEM image was observed, and the thickness of the bonding interface layer was measured as an actual measurement value of the bonding interface layer from the observed image.

  The “appropriate peel strength” here is considered to have a value measured in accordance with JIS C 6481 in the range of 1 gf / cm to 100 gf / cm. This is due to the peeling strength (peeling strength) at the interface between the carrier foil and the electrolytic copper foil, which is considered appropriate, based on the experience of using the conventional peelable type electrolytic copper foil with carrier foil. It is the range as what considered the ideal request | requirement value of the user of the said electrolytic copper foil with a carrier foil. The lower the peel strength at the interface between the carrier foil and the electrolytic copper foil, the easier the peeling operation.

  However, if the peel strength is less than 1 gf / cm, the carrier foil and the electrolytic copper foil may be naturally peeled off during roll forming during the production of the electrolytic copper foil with a carrier foil, This may cause defects such as partial blistering and misalignment. On the other hand, if the peel strength exceeds 100 gf / cm, the load of the manual peel work increases, and if it exceeds 200 gf / cm, the carrier foil is easily peeled off, which is a feature of the patented invention. It is not an image of an image to be used, and a method such as using a special peeling device is required for peeling.

  Even if triazine thiols constituting the bonding interface layer located between the carrier foil layer and the electrolytic copper foil layer remain on the surface layer of the electrolytic copper foil after the carrier foil is peeled off, dilute sulfuric acid, dilute hydrochloric acid, etc. It can be easily removed by pickling with this solution, and does not adversely affect the production process of the printed wiring board. That is, even if triazine thiols remain on the surface of the electrolytic copper foil layer, various resist coating, etching processes, and various plating existing as a printed wiring board manufacturing process after processing into a copper-clad laminate. There is no adverse effect in processes such as processing and surface mounting.

  The carrier foil used here is not particularly limited in material. The carrier foil is used as a concept including everything that can be used as a carrier, such as an aluminum foil, a copper foil, and a resin film whose surface is metal-coated. However, it is necessary for the triazine thiols to form a good film, and if it cannot be energized, it is impossible to form an electrolytic copper foil layer, so the metal component must be present on the surface. Moreover, there is no limitation in particular also about the thickness as carrier foil. From an industrial point of view, the concept as a foil is generally referred to as a foil having a thickness of 210 μm or less, and it is sufficient to use this concept.

  Here, the advantage of using the electrolytic copper foil for the carrier foil C will be described. Usually, an electrolytic copper foil is manufactured through an electrolysis process and a surface treatment process, and is mainly used as a basic material for manufacturing a printed wiring board used in the fields of the electric and electronic industries. And as for the electrolytic copper foil used for carrier foil C, it is preferable to use the thing of thickness of 12 micrometers-210 micrometers. By using the electrolytic copper foil having such a thickness as the carrier foil, various advantageous effects not obtained in the conventional electrolytic copper foil with carrier foil can be obtained. Here, the thickness of the electrolytic copper foil used as the carrier foil is set to 12 μm to 210 μm in order to serve as a reinforcing material for preventing generation of wrinkles of the ultrathin copper foil of 9 μm or less as the carrier foil. This is because when a thickness of at least about 12 μm is required and the thickness exceeds the upper limit of 210 μm, it exceeds the concept of foil and is rather close to a copper plate, making it difficult to wind up and form a roll.

  The advantageous effect of using an electrolytic copper foil as the carrier foil C is as follows. As represented by the rolled aluminum material, when the foil obtained by the rolling method is used as a carrier foil, it is inevitable that the rolling oil adheres to the foil, and the oil component is taken into consideration for the prevention of oxidation. May be applied. When these are used as a carrier foil, it becomes an obstacle when copper is deposited on the carrier, and therefore it is necessary to remove oil in the process. If it is an electrolytic copper foil, from its manufacturing method, oil will inevitably adhere, and even if an oxide film is formed, it can be easily pickled and removed, reducing the number of steps or Process management can be facilitated.

  In addition, when an electrolytic copper foil is used as the carrier foil C of the electrolytic copper foil 1a with a carrier foil, the carrier foil C and the electrolytic copper foil CF in a form bonded to the carrier foil C are structurally component. Can be considered as the same, and both etching processes can be performed with the same kind of etching solution. Therefore, after processing into a copper-clad laminate, without peeling off the carrier foil C, an etching resist layer is formed on the carrier foil C, and after etching processing to create a printed wiring circuit, the carrier foil C is peeled off. Is also possible. In this way, the surface of the copper foil circuit is protected from contamination and foreign matter adhesion until the etching process is completed, and it is possible to greatly improve the work reliability of the subsequent plating process and the like.

  The electrolytic copper foil layer includes not only an electrolytic copper foil called an ultrathin copper foil of 12 μm or less, but also a case where it is thicker than 12 μm. Conventional electrolytic copper foil with carrier foil is used exclusively for the purpose of providing ultra-thin copper foil, and those having an electrolytic copper foil layer of 12 μm or more like the electrolytic copper foil with carrier foil according to the present invention are marketed. Was not supplied to. The advantage of the electrolytic copper foil with carrier foil having such a thick electrolytic copper foil layer is that the organic foil interface layer using triazine thiols makes the carrier foil layer and the electrolytic copper foil layer stable after high-temperature pressing. This is because the method of using a new electrolytic copper foil with a carrier foil, which will be described later, becomes possible by peeling easily.

  Here, although it is described for confirmation, the electrolytic copper foil 1a with carrier foil shown in FIG. 1 is electrolyzed when used for copper-clad laminates and printed wiring boards, apart from special applications. The fine copper particles 4 are uniformly attached to the outer surface of the copper foil layer CF. This is the same fine copper particles as those formed on the bonding surface of a general electrolytic copper foil to a resin base material, and an anchor effect for the bonded base material is obtained. It is intended not to peel off.

(Electrolytic copper foil with second carrier foil)
Moreover, the electrolytic copper foil with the second carrier foil is “in the electrolytic copper foil with a carrier foil that includes a bonding interface layer on both surfaces of the carrier foil and an electrolytic copper foil layer on each of the bonding interface layers. The interface layer is an electrolytic copper foil with a carrier foil, which is formed using triazine thiols, and the cross section of this electrolytic copper foil with carrier foil 1b is schematically shown in FIG. The above-described electrolytic copper foil with carrier foil 1a has a shape in which electrolytic copper foil CF is bonded to one side of carrier foil C as shown in FIG. As apparent from the schematic cross-sectional view of FIG. 3, the foil 1 b has a shape such that the electrolytic copper foil CF is bonded to both surfaces of the carrier foil C.

  For example, if the copper foil 1a with carrier foil shown in FIG. 1 is used for laying up and pressing as shown in FIG. 4, the intermediate layer end plate M can be certainly omitted. However, by using this electrolytic copper foil 1b with carrier foil, it is possible to more easily omit the end plate during the production of the copper clad laminate, and to completely prevent foreign matter from being mixed into the copper foil surface during press molding. It is possible to prevent it. As shown in FIG. 5, a typical double-sided copper-clad laminate is generally manufactured by mirror plate M made of a heat-resistant material such as stainless steel between upper and lower press plates P, copper foil CF, one sheet or a plurality of sheets. A sheet of prepreg PP, copper foil CF, and end plate M is repeatedly laminated (commonly referred to as lay-up), and the press plate P is heated at high temperature and sandwiched to melt the resin component of the prepreg PP. CF and prepreg PP are bonded at high temperature and pressure.

  When the above-mentioned double-sided electrolytic copper foil 1b with carrier foil is used, as shown in FIG. 6, a normal electrolytic copper foil or a single-sided electrolytic copper foil with carrier foil is used for the lowermost layer and the uppermost layer OF in the laid-up state. By using the double-sided electrolytic copper foil 1b with carrier foil as the one located in the other intermediate layer, all of the end plate M located in the intermediate layer portion can be omitted, and the carrier foil C at the time of disassembly after press molding It can be peeled off from the bonding interface 2 between the copper foil layer and the electrolytic copper foil layer CF.

  The fact that the intermediate layer end plate M becomes unnecessary means that the number of steps of the copper foil CF and the prepreg PP accommodated between the daylights of the press plate P can be increased by the thickness corresponding to the omitted end plate M, The number of copper-clad laminates produced by a single press can be increased. In addition, heat conductivity is improved, and productivity can be improved. Considering that the thickness of the end plate M is usually 0.8 mm to 3.0 mm, the copper foil CF is 3 to 50 μm thick, and one prepreg PP is 30 to 180 μm thick. It can be predicted that this will have a significant productivity improvement effect.

(Electrolytic copper foil with third carrier foil)
In general, the electrolytic copper foil layer CF includes (1) a bulk copper layer 3 for forming a conductor circuit, and (2) a roughening treatment for improving the adhesion of the copper-clad laminate to the base resin. Although it is comprised from a layer (fine copper grain 4), in this invention, it is set as the concept containing the electrolytic copper foil layer comprised only by the roughening process 4 of (2). Therefore, the “electrolytic copper foil layer” of the above-described two types of electrolytic copper foil with carrier foil is composed of only the fine copper particles 4 deposited and adhered by the electrolytic method.

  7 and 8 schematically show cross-sectional forms of carrier-foil-attached electrolytic copper foils 1c and 1d in which this electrolytic copper foil layer is composed of only fine copper grains 4. FIG. At the time of manufacturing a copper clad laminate using these carrier foil surface electrolytic copper foils, only the fine copper particles 4 are bonded to the prepreg, and there is no bulk copper layer. However, since the bulk copper layer is indispensable for forming the conductor circuit, the carrier foil C is removed in the printed wiring board manufacturing process, and the fine copper particles are obtained by the timing and an arbitrary copper plating method according to the purpose. A bulk copper layer having a predetermined thickness can be formed on 4. For example, a bulk copper layer can be formed on the surface of the fine copper particles 4 as the electrolytic copper foil layer by a panel plating method, or an electroless copper plating method can be used. According to such a method, the thickness of the bulk copper layer can be arbitrarily adjusted according to the type of the formed circuit, and a bulk copper layer having a thickness capable of performing an appropriate etching process according to the target circuit width can be obtained. It is. Therefore, such a printed wiring board manufacturing method is more effective as the created circuit becomes finer, and the density of the printed wiring board circuit can be easily increased.

(4th electrolytic copper foil with carrier foil to 6th electrolytic copper foil with carrier foil)
The fourth electrolytic copper foil with carrier foil referred to in the present invention is one in which the refractory metal layer 5 is provided between the joining interface layer of the first electrolytic copper foil with carrier foil and the electrolytic copper foil layer. It is electrolytic copper foil 1a 'with a carrier foil which has a schematic cross-section layer structure shown in FIG. Providing a refractory metal layer in this way is considered to be a drawback in that it does not contain foreign elements. However, this refractory metal layer remains attached to the surface of the bulk copper layer even after the carrier foil is peeled off, and is very useful in recent laser drilling. Such nickel, cobalt, or these nickel-based alloys and cobalt-based alloys are known as elements having high laser light absorption efficiency, and improve the laser drilling workability of the electrolytic copper foil layer.

  The electrolytic copper foil with the fifth carrier foil referred to in the present invention is a refractory metal layer provided between the joining interface layer of the electrolytic copper foil with the second carrier foil and the electrolytic copper foil layer. It is electrolytic copper foil 1b 'with a carrier foil which has the schematic cross-section layer structure shown.

  The sixth electrolytic copper foil with carrier foil referred to in the present invention is one in which a refractory metal layer is provided between the joining interface layer of the third electrolytic copper foil with carrier foil and the electrolytic copper foil layer. Electrolytic copper foils 1c ′ and 1d ′ with carrier foil having the schematic cross-sectional layer configuration shown in FIG.

  Therefore, only the refractory metal layer provided between each bonding interface layer and the electrolytic copper foil layer will be described here. Other explanations are the same as the above explanations, and will be omitted. This refractory metal layer has an electrolytic copper foil layer that is heated to a high temperature by press molding to prevent direct contact with a bonding interface layer composed of triazine thiols, which are organic agents. It functions as a barrier that prevents it from diffusing. In addition, by providing the refractory metal layer on the bonding interface layer, even if a pit-like defect exists in the bonding interface layer, the refractory metal fills the defect, and the electrolytic copper foil layer and the carrier In order to prevent direct contact with the foil, partial seizure between the electrolytic copper foil layer and the carrier foil is prevented in press molding at about 230 ° C. Therefore, the peeling property of the carrier foil after press molding in a temperature range of 230 ° C. or lower is further improved.

  In order to constitute the refractory metal layer 5 referred to herein, it is preferable to use nickel or a nickel-based alloy. Nickel is widely known as a metal excellent in high-temperature heat resistance, and it is possible to form a refractory metal layer having excellent formation characteristics as a thin film and excellent film thickness uniformity. The nickel-based alloy includes other alloy elements such as cobalt and platinum on the basis of the nickel component. The nickel-cobalt alloy exhibits particularly excellent characteristics when it comes to the peeling characteristics of the carrier foil after press molding in a temperature range of 230 ° C. or lower.

  The refractory metal layer 5 only needs to function as a barrier for preventing thermal diffusion of copper, and the thickness of the refractory metal layer 5 may be selectively set to a minimum thickness that fulfills the barrier function. Therefore, the upper limit of the thickness of the refractory metal layer is not particularly limited. However, it is considered that a thickness of 20 nm or more is necessary. If the refractory metal layer 5 becomes too thick, the load caused by etching increases, so that it is desirable that the thickness be as thin as possible. Is preferred.

<Advantage of electrolytic copper foil with carrier foil according to the present invention>
Assuming that an electrolytic copper foil is used for the carrier foil, the following method of use will be described. The purity of the electrolytic copper foil is 99.99% or more. And the electrolytic copper foils 1a-1d with carrier foil which concern on this invention do not contain the other metal element used as the impurity in the joining interface layer 2. As shown in FIG. Accordingly, the carrier foil after being peeled off can be easily recycled, and from the viewpoint of environmental protection, industrial waste is not generated unnecessarily. For example, the carrier foil can be recovered and redissolved to obtain a copper ingot, or it can be dissolved again with sulfuric acid as a raw material for producing the electrolytic copper foil to obtain a copper sulfate solution.

  As the electrolytic copper foil as the carrier foil C at this time, either an untreated foil that has not been roughened or a surface-treated foil that has been roughened may be used. There is no difference in the roughness of the glossy surface between the untreated foil and the surface-treated foil, and if the copper foil layer is formed on the glossy surface, there is no difference in the copper foil layer itself. FIG. 13A shows a schematic cross-sectional view when an untreated electrolytic copper foil is used as a carrier foil, and FIG. 13B shows a cross-sectional schematic view when a surface-treated electrolytic copper foil is used as a carrier foil. In these electrolytic copper foils 1e and 1f with carrier foil, the usage method at the time of manufacture of the copper clad laminated board obtained using each differs by whether untreated foil is used for carrier foil C or surface-treated foil is used. It comes.

  Here, the usage method which can be employ | adopted in manufacture of the copper clad laminated board of each electrolysis copper foil 1e, 1f with a carrier foil when the case where an untreated foil is used for a carrier foil and the case where a surface treatment foil is used is demonstrated. Initially, the case where an untreated foil is used for the carrier foil C is demonstrated as a manufacturing method of a 1st copper clad laminated board. The electrolytic copper foil 1e with carrier foil in such a case has a cross-sectional shape shown in FIG. As can be seen from this figure, the surface that can be bonded to the prepreg is only the surface of the electrolytic copper foil layer CF to which the fine copper particles 4 are adhered as the roughening treatment.

  Therefore, the electrolytic copper foil 1e with carrier foil and the prepreg PP (when forming the outer layer copper foil layer of the multilayer substrate) in the same process as when laying up and using a normal copper foil as shown in FIG. It is possible to obtain a copper-clad laminate by press molding using the prepreg and inner layer substrate) and the end plate M. Further, by using the electrolytic copper foil with carrier foil, press molding without the inner layer end plate is also possible. That is, as described in FIG. 14, the mirror plate M is disposed only on the outermost layer that is in direct contact with the press plate P, and the electrolytic copper foil 1e with carrier foil and the prepreg PP are placed between the two mirror plates M. They are stacked and laid up.

  One electrolytic copper foil with carrier foil or ordinary copper foil OF is disposed on the uppermost layer and the lowermost layer when the layers are laid up. And as shown in the enlarged view of FIG. 14, the copper foil located in the other inner layer at the time of laying up has the carrier foil C surface and the carrier foil C surface of the electrolytic copper foil 1e with two carrier foils on the back. In addition, the surface of the electrolytic copper foil layer CF that has been subjected to the roughening treatment is disposed so as to be in contact with the prepreg PP. Then, at the time of dismantling work after the press molding, the carrier foil C is peeled off from the bonding interface layer 2 so that the outer layer copper foil layer of the double-sided board or the multilayer board can be formed.

  On the other hand, the usage method in manufacture of a copper clad laminated board of the electrolytic copper foil 1f with a carrier foil which used surface treatment foil for the carrier foil C as a manufacturing method of a 2nd copper clad laminated board is demonstrated. In such a case, the electrolytic copper foil with carrier foil 1f has a cross-sectional shape shown in FIG. As can be seen from this figure, the surface that can be bonded to the prepreg PP is a surface to which fine copper particles 4 are adhered by roughening treatment, so that not only the electrolytic copper foil CF side but also the carrier foil C It will also exist on the side.

  That is, the electrolytic copper foil 1f with carrier foil is finished in a shape as if the glossy surfaces of the two ordinary surface treated copper foils are bonded together. Therefore, the carrier foil can also be used as the electrolytic copper foil of the copper clad laminate. Since it has such a structure, it can be used as follows.

  The electrolytic copper foil with carrier foil 1f, prepreg PP (in the case of forming the outer layer copper foil layer of the multilayer substrate, prepreg and inner layer substrate) and the end plate M are press-molded to obtain a copper clad laminate, By using the electrolytic copper foil with carrier foil 1f, press molding without the inner layer end plate is possible. That is, as described in FIG. 15, the mirror plate M is disposed only on the outermost layer that is in direct contact with the press plate P, and the electrolytic copper foil 1f with carrier foil and the prepreg PP are placed between the two mirror plates M. Lay up.

  One electrolytic copper foil with carrier foil or ordinary copper foil OF is disposed on the uppermost layer and the lowermost layer when the layers are laid up. And the copper foil located in the other inner layer at the time of laying up arrange | positions the prepreg PP on both surfaces of the said electrolytic copper foil 1f with a carrier foil, as shown in the enlarged view of FIG. In this manner, press molding can be performed without using the end plate M. And at the time of the dismantling operation after the press molding is completed, the outer layer copper foil layer of the double-sided board or the multilayer board can be formed by peeling from the bonding interface layer 2 of the electrolytic copper foil with carrier foil 1f. According to this method, there is an advantage that no scrap is generated.

  The usage method of the electrolytic copper foils 1a to 1f with carrier foil according to the present invention described above is such that the peel strength of the bonding interface layer 2 of the electrolytic copper foil with carrier foil can be kept low and stabilized. This is the first press forming method that can be realized. Therefore, the useful effect brought about by the electrolytic copper foils 1a to 1f with carrier foil according to the present invention has a great influence on the printed wiring board industry, and greatly contributes to the reduction of the manufacturing cost of the copper clad laminate. I can say that.

  At this time, if the thickness of the electrolytic copper foil layer deposited on the glossy surface of the electrolytic copper foil as the carrier foil C is extremely thin, a copper-clad laminate with the ultrathin copper foil attached is used. When a circuit having a pitch of about 50 μm is formed, the etching time of the copper foil portion can be made extremely fast, and a fine circuit with a very good aspect ratio can be formed.

  And on the rough surface of the electrolytic copper foil used as carrier foil C, the joining interface layer 2 is formed using triazine thiols, and copper is electrolytically deposited on the joining interface layer 2, and the deposited copper layer is electrolyzed. It can also be set as the electrolytic copper foil with a carrier foil used as copper foil. The carrier foil used here is the aforementioned untreated foil. In FIG. 16, the cross-sectional schematic diagram of this electrolytic copper foil 1g with carrier foil is shown. As can be seen from FIG. 16, the ultrathin electrolytic copper foil layer is formed along the rough surface of the electrolytic copper foil that is the carrier foil C. That is, the electrolytic copper foil layer CF has a wavy shape.

  Therefore, when a copper-clad laminate is produced using 1 g of the electrolytic copper foil with carrier foil, it is press-molded while maintaining the wavy shape. This shape is very useful in forming a fine circuit. In addition, about the lay-up method at the time of manufacturing a copper clad laminated board using this electrolytic copper foil 1g with carrier foil, since it is the same by the method similar to having described in FIG. 5, the overlapping description is abbreviate | omitted And

  Roughly grasping the factors required for the electrolytic copper foil necessary for forming a fine circuit, (1) ensuring adhesion with a good etching resist, (2) securing a good exposure state, (3) It is considered to be physical characteristics such as fast etching time, (4) other peeling strength (including chemical resistance, etc.). Most of the properties mentioned here are good, but the electrolytic copper foil with a wavy shape is the main contributor to ensuring good adhesion to the etching resist and ensuring good exposure. To do.

  Adhesiveness between various resists and the surface of the electrolytic copper foil is improved by using the electrolytic copper foil having a corrugated shape for the copper-clad laminate. For example, if the adhesion to the etching resist is improved, the etching solution can be prevented from entering the bonding interface between the copper foil and the etching resist, and a circuit cross section having a good aspect ratio can be formed. It becomes easy to form a fine circuit in consideration of the above. In addition, by having a wavy surface shape, the gloss is close to matte compared to a normal flat glossy surface. As a result, it is possible to suppress the excessive scattering of the exposure light at the time of exposure with respect to the etching resist of the etching pattern, and the influence of so-called exposure blur at the edge portion of the circuit pattern can be reduced. . Furthermore, it is possible to improve the laser drilling workability.

  Moreover, the result that the peel strength at the interface between the copper foil surface and the plating layer is improved when copper plating treatment is applied to a copper clad laminate having an electrolytic copper foil layer having a wavy shape is obtained. Yes. Therefore, it can be said that the adhesion of the plating layer is improved by using the electrolytic copper foil with carrier foil.

  As a result, it is possible to prevent the deterioration of the aspect ratio of the circuit cross section seen when a fine circuit having a pitch level of 50 μm is formed using a normal electrolytic copper foil, and a circuit having an ideal aspect ratio can be formed. In addition, since the exposure blur of the etching resist is small, the linear stability of the edge portion of the formed circuit is improved, and the formation of a fine circuit can be facilitated. The improvement of the linear stability of the edge part of the formed circuit means that the linearity of the upper edge part and the lower edge part of the circuit formed by etching is excellent, and the land part used for component mounting on the printed wiring board. This means that the edge part of the entire forming circuit such as the edge shape of the circular circuit part is smooth. In other words, because of the excellent linear stability of the circuit, suppression of copper migration that may occur when used as a printed wiring board, elimination of discharge phenomenon from protrusions at the circuit edge when using high-frequency signals, etc. Can also be said.

  As described above, the method for using the electrolytic copper foils 1a to 1g with carrier foil according to the present invention described above maintains the peel strength of the bonding interface layer 2 of the electrolytic copper foils 1a to 1g with carrier foil, Moreover, this is a press molding method that can be stabilized for the first time.

<Method for producing electrolytic copper foil with carrier foil according to the present invention>
As described above, the method for producing an electrolytic copper foil with a carrier foil is characterized in that a solution containing 1 ppm to 500 ppm of a triazine thiol is used to form a bonding interface on the surface of the carrier foil. The manufacturing flow of the electrolytic copper foil with carrier foil according to the present invention will describe only the concept necessary for each step with reference to FIG.

Pickling treatment: The first pickling treatment of the carrier foil is performed for the purpose of degreasing treatment for completely removing the oil and fat components attached to the carrier foil and removal of the surface oxide film when the metal foil is used. By passing the carrier foil through the acid solution, the carrier foil is cleaned, and uniform adhesion and electrodeposition in the following steps are ensured. In this pickling treatment, various solutions such as a hydrochloric acid solution, a sulfuric acid solution, and a sulfuric acid-hydrogen peroxide solution can be used, and there is no particular limitation. And it is sufficient to adjust the solution concentration, the liquid temperature, etc. according to the characteristics of the production line.

Formation of bonding interface layer: The formation of the bonding interface layer performed after the pickling treatment is a step of performing a process of forming the bonding interface layer on one side or both sides of the carrier foil using the above-described solution containing triazine thiols. That is. The bonding interface layer is formed by (1) a method of immersing the carrier foil in a solution containing triazine thiols, and (2) a solution containing triazine thiols on the surface of the carrier foil forming the bonding interface layer. On the other hand, a method of showering or dropping, (3) a method of electrodepositing on the surface of the carrier foil forming the bonding interface layer using a solution containing triazine thiols can be employed.

  When the formation of the bonding interface layer is completed, when producing any one of the electrolytic copper foil with the first carrier foil to the electrolytic copper foil with the second carrier foil, the electrolytic copper foil layer is directly formed on the bonding interface. . However, in the case of producing any one of the above-described fourth electrolytic copper foil with carrier foil to sixth electrolytic copper foil with carrier foil, a refractory metal layer is formed on the bonding interface layer as necessary. .

Formation of refractory metal layer: The case where the refractory metal layer is formed first will be described. For the formation of the refractory metal layer, it is preferable to adopt the following method. This refractory metal layer is formed by performing smooth and short-time plating of nickel, cobalt or the like on the carrier foil in which the bonding interface layer has been formed, or adopts a dry method such as sputtering deposition. The dry method is not particularly required to be explained, and may be performed according to a conventional method. Even when the plating method is adopted, electroless plating or electrolytic plating may be used. The plating conditions when employing electrolytic plating will be described below.

When a nickel thin film layer is formed, a solution used as a nickel plating solution can be widely used. For example, i) nickel sulfate is used and the nickel concentration is 5 to 30 g / l, the liquid temperature is 20 to 50 ° C., the pH is ^{2 to} 4, the current density is 0.3 to 10 A / dm ² , and the nickel concentration is nickel sulfate. 5 to 30 g / l, potassium pyrophosphate 50 to 500 g / l, liquid temperature 20 to 50 ° C., pH 8 to 11, current density 0.3 to 10 A / dm ² , iii) nickel concentration of 10 to 10 using nickel sulfate 70 g / l, boric acid 20 to 60 g / l, liquid temperature 20 to 50 ° C., pH ^{2 to} 4, current density 1 to 50 A / dm ² , and other general Watt bath conditions.

When a cobalt thin film layer is formed, a solution used as a cobalt plating solution can be used. For example, i) Conditions using cobalt sulfate and a cobalt concentration of 5-30 g / l, trisodium citrate 50-500 g / l, liquid temperature 20-50 ° C., pH 2-4, current density 0.3-10 A / dm ² Ii) Using cobalt sulfate, the cobalt concentration is 5-30 g / l, potassium pyrophosphate 50-500 g / l, liquid temperature 20-50 ° C., pH 8-11, current density 0.3-10 A / dm ² , iii ) Using cobalt sulfate, the cobalt concentration is 10 to 70 g / l, boric acid 20 to 60 g / l, liquid temperature 20 to 50 ° C., pH ^{2 to} 4 and current density 1 to 50 A / dm ² .

In the case of forming a nickel-zinc alloy thin film layer, for example, nickel sulfate is used and the nickel concentration is 1 to 2.5 g / l, and zinc pyrophosphate is used and the zinc concentration is 0.1 to 1 g / l. The conditions are 50 to 500 g / l, the liquid temperature is 20 to 50 ° C., the pH is 8 to 11, and the current density is 0.3 to 10 A / dm ² .

When forming a nickel-cobalt alloy thin film layer, for example, cobalt sulfate 80-180 g / l, nickel sulfate 80-120 g / l, boric acid 20-40 g / l, potassium chloride 10-15 g / l, phosphoric acid 2 The conditions are sodium hydride 0.1 to 15 g / l, liquid temperature 30 to 50 ° C., pH 3.5 to 4.5, and current density 1 to 10 A / dm ² .

In the case of nickel, nickel-phosphorus alloy plating can be obtained by using a phosphoric acid solution. In this case, nickel sulfate 120-180 g / l, nickel chloride 35-55 g / l, H ₃ PO ₄ 30-50 g / l, H ₃ PO ₃ 20-40 g / l, liquid temperature 70-95 ° C., pH 0.5- The conditions are 1.5, the current density is 5 to 50 A / dm ² , and the like.

Formation of electrolytic copper foil layer: Next , formation of the electrolytic copper foil layer will be described. Except for the electrolytic copper foil with carrier foil in which the electrolytic copper foil layer is composed only of fine copper grains, the bulk copper layer is first formed. The copper electrolyte used for forming this bulk copper layer is not particularly limited, and a solution that can be used as a copper ion source such as a copper sulfate-based solution or a copper pyrophosphate-based solution is used. For example, in the case of a copper sulfate-based solution, the concentration is copper 30-100 g / l, sulfuric acid 50-200 g / l, liquid temperature 30-80 ° C., current density 1-100 A / dm ² , copper pyrophosphate-based solution. If present, the conditions are such that the concentration is copper 10-50 g / l, potassium pyrophosphate 100-700 g / l, liquid temperature 30-60 ° C., pH 8-12, current density 1-10 A / dm ² .

  Then, when the formation of the bulk copper layer is completed, next, fine copper grains are formed on the surface of the bulk copper layer. When depositing fine copper particles, it is common to deposit fine copper particles on the bulk copper layer, and then perform overplating to prevent the fine copper particles from falling off. In addition, when an electrolytic copper foil layer is comprised only with a fine copper particle, formation of an electrolytic copper foil layer abbreviate | omits formation of a bulk copper layer, and starts from this process.

In order to deposit and deposit fine copper particles on the bulk copper layer, the same kind of copper electrolyte as that used in the above-described bulk copper forming tank is used, and the condition of burnt plating is adopted. Therefore, the solution concentration used in the process of depositing and adhering fine copper particles on the bulk copper layer is generally lower than the solution concentration used in the bulk copper formation layer so that burn plating conditions can be easily created. Yes. This burn plating condition is not particularly limited, and is determined in consideration of the characteristics of the production line. For example, if a copper sulfate-based solution is used, the concentration is 5 to 20 g / l copper, 50 to 200 g / l sulfuric acid, and other additives (α-naphthoquinoline, dextrin, glue, thiourea, etc.), liquid For example, the temperature is 15 to 40 ° C. and the current density is 10 to 50 A / dm ² .

In addition, in the covering plating for preventing the fine copper particles from falling off, the copper is uniformly deposited so as to cover the fine copper particles under the smooth plating condition in order to prevent the fine copper particles deposited and adhered from falling off. is there. Therefore, here, the same solution as that used in the above-described bulk copper forming tank can be used as the copper ion supply source. The smooth plating conditions are not particularly limited and are determined in consideration of the characteristics of the production line. For example, if a copper sulfate-based solution is used, the conditions are copper 50 to 80 g / l, sulfuric acid 50 to 150 g / l, liquid temperature 40 to 50 ° C., and current density 10 to 50 A / dm ^2. .

  When the basic structure of the electrolytic copper foil with carrier foil is completed as described above, the rust prevention treatment is usually performed next. This antirust treatment is for preventing the surface of the electrolytic copper foil layer from being oxidatively corroded so as not to hinder the manufacturing process of the copper clad laminate and the printed wiring board. As the rust prevention treatment, there is no problem even if either organic rust prevention using benzotriazole, imidazole or the like, or inorganic rust prevention using zinc, chromate, zinc alloy or the like is adopted. What is necessary is just to select the rust prevention according to the intended purpose of the electrolytic copper foil with carrier foil. In the case of organic rust prevention, it is possible to employ techniques such as dip coating, shower ring coating, and electrodeposition method with an organic rust preventive.

In the case of inorganic rust prevention, it is possible to use a method of depositing a rust-preventive element on the surface of the electrolytic copper foil layer by electrolysis or other so-called substitution deposition method. For example, a zinc pyrophosphate plating bath, a zinc cyanide plating bath, a zinc sulfate plating bath, or the like can be used for the zinc rust prevention treatment. For example, in the case of a zinc pyrophosphate plating bath, the concentration is 5 to 30 g / l of zinc, 50 to 500 g / l of potassium pyrophosphate, the liquid temperature is 20 to 50 ° C., the pH is 9 to 12, and the current density is 0.3 to 10 A / dm ^2. And so on.

  When the rust prevention treatment is completed, it is washed with water and dried to obtain a finished electrolytic copper foil with a carrier foil. In addition, since the operation of preventing the carry-in of the solution of the previous process to the subsequent process by providing means that can be appropriately washed between each process is natural, the description of the manufacturing flow is dare Not specified.

(Copper-clad laminate using electrolytic copper foil with carrier foil according to the present invention)
The above-described electrolytic copper foil with carrier foil is processed into a copper-clad laminate mainly used as a basic material for the production of printed wiring boards. The term “copper-clad laminate” as used herein includes the concept of all layer structures of single-sided boards, double-sided boards, and multilayer boards, and the base material is not limited to rigid-type boards, but also special boards such as TAB and COF. Including all of flexible substrates, hybrid substrates and the like.

  The electrolytic copper foil with a carrier foil according to the present invention uses a triazine thiol to form a bonding interface layer, so that peeling at the interface between the carrier foil layer and the electrolytic copper foil layer at a temperature range of 230 ° C. or less is extremely It can be done easily with a small force. Moreover, in the production of the electrolytic copper foil with carrier foil according to the present case, an organic coating having a uniform thickness can be obtained by using triazine thiols for the formation of the bonding interface layer. It is considered that the stability of the thickness of the electrolytic copper foil layer is also improved because it shows very good film thickness uniformity as a precipitation surface when forming the foil. In addition, since the production method using the triazine thiols adopted in the present invention is less likely to cause process variations and is a very stable production process, the production yield is dramatically improved.

  Hereinafter, the electrolytic copper foil with carrier foil was manufactured using the manufacturing method of the electrolytic copper foil with carrier foil according to the present invention. And in order to confirm the peeling strength of the carrier foil after being press-molded into a copper clad laminate and its stability, the obtained electrolytic copper foil with carrier foil is subjected to a heat treatment equivalent to press molding, The peel strength of the carrier foil was measured. In the following examples, the description will be focused on the case where an electrolytic copper foil is used as the carrier foil.

  In this example, an electrolytic copper foil that was not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 18 μm was used for the carrier foil C. Hereinafter, description will be given in the order of each step.

  First, pickling treatment of the carrier foil C was performed. Fill the inside of the pickling bath with a dilute sulfuric acid solution having a concentration of 150 g / l and a liquid temperature of 30 ° C., so that the carrier foil C is immersed in this for 30 seconds. The surface oxide film was removed.

A bonding interface layer 2 was formed on one surface of the carrier foil C after the pickling treatment. The bonding interface layer 2 is formed by anodic polarization in an aqueous solution of carrier foil C that has been pickled and washed with water in an aqueous solution having a concentration of 200 ppm of 2-anilino-4,6-dimercapto-s-triazine and a liquid temperature of 35 ° C. Then, electrolysis was performed at a current density of 1.7 mA / dm ² , the bonding interface layer 2 was formed on one side of the carrier foil C, and washed with water. The thickness of the bonding interface layer 2 obtained here was 10 nm on average.

When the formation of the bonding interface layer 2 was completed, the bulk copper layer 3 constituting the electrolytic copper foil layer CF was formed on the bonding interface layer 2 formed on one side of the carrier foil C. The formation of the bulk copper layer 3 was performed by filling a copper electrolytic bath with a copper sulfate solution having a sulfuric acid concentration of 150 g / l, a copper concentration of 65 g / l, and a liquid temperature of 45 ° C. In order to cathode polarize the carrier foil itself, the one side of the carrier foil C after forming the bonding interface layer 2 immersed in this solution and the stainless steel plate serving as the anode electrode are spaced apart so as to be parallel. did. Hereinafter, when the electrolysis method was employed, the same method was employed. Electrolysis was then performed under smooth plating conditions with a current density of 5 A / dm ² , and a bulk copper layer 3 having a thickness of 5 μm was formed on the bonding interface layer on one side of the carrier foil C.

  After the formation of the bulk copper layer 3, the surface of the bulk copper layer 3 was subjected to a roughening process. In the roughening treatment, first, fine copper particles 4 were formed on the electrolytic copper foil layer CF, and further, overplating was performed to prevent the fine copper particles 4 from falling off.

The formation of fine copper particles 4 is a copper sulfate solution, using a copper electrolyte solution having a sulfuric acid concentration of 100 g / l, a copper concentration of 18 g / l, and a liquid temperature of 25 ° C., and a current density of 10 A / dm ² For 10 seconds.

The overplating is a copper sulfate solution, which uses a copper electrolyte solution having a sulfuric acid concentration of 150 g / l, a copper concentration of 65 g / l, and a liquid temperature of 45 ° C., and is electrolyzed for 20 seconds under a smooth plating condition with a current density of 15 A / dm ^2. It was done by doing.

When the roughening treatment is completed, the rust prevention treatment is performed by depositing zinc on both surfaces by the electrolytic method in the rust prevention treatment step for the purpose of preventing the corrosion of the carrier foil C and the electrolytic copper foil surface after the roughening treatment. It was. The conditions for electrodeposition of zinc here were a zinc sulfate bath, a sulfuric acid concentration of 70 g / l, a zinc concentration of 20 g / l, a liquid temperature of 40 ° C., and a current density of 15 A / dm ² . Through the steps so far, an electrolytic copper foil 1a with a carrier foil was produced.

  When the rust prevention treatment was finally completed, the electrolytic copper foil 1a with carrier foil was obtained by washing with water and finally drying.

  The peel strength between the carrier foil layer C and the electrolytic copper foil layer CF of the electrolytic copper foil 1a with carrier foil was measured. In measurement, the electrolytic copper foil 1a with carrier foil is heated at a predetermined temperature, and the strength when peeling the 10 mm-wide linear circuit-shaped electrolytic copper foil layer side is measured. did. Further, the peel strength values of the embodiments in the present specification shown below are all average values for 30 lots, and at a predetermined temperature when 30 lots are measured as an index for comparing the stability of the peel strength. The standard deviation of the peel strength after heating for 1 hour was shown. As a result, the peel strength between the carrier foil layer C and the electrolytic copper foil layer CF of the electrolytic copper foil 1a with carrier foil was measured. As a result, the peel strength was 2.4 gf / cm before heating, 2.7 gf / cm after heating at 180 ° C. for 1 hour (standard deviation 1.0 gf / cm), and 5.8 gf after heating at 230 ° C. for 1 hour. / Cm (standard deviation 4.5 gf / cm).

  In the present embodiment, an untreated rolled copper foil having a thickness of 90 μm was used for the carrier foil C. Hereinafter, description will be given in the order of each step.

  First, the rolled foil as the carrier foil C was subjected to alkali degreasing treatment and pickling treatment, and the joining interface layer 2 was formed on both surfaces thereof with 2-anilino-4,6-dimercapto-s-triazine. However, the alkaline degreasing process itself was performed according to a conventional method, and is basically the same as in Example 1. Therefore, these duplicate descriptions are omitted. In addition, the thickness of the joining interface layer 2 obtained here was 11 nm on average.

When the formation of the bonding interface layer 2 on both sides of the carrier foil is completed, the bonding interface formed on both sides of the carrier foil C is produced in order to produce the copper foil 1c with carrier foil provided with the electrolytic copper foil layer CF on both sides of the carrier foil C. A bulk copper layer 3 constituting the electrolytic copper foil layer CF was formed on each surface of the layer 2. The formation of the bulk copper layer 3 was performed by filling a copper electrolytic bath with a copper sulfate solution having a sulfuric acid concentration of 150 g / l, a copper concentration of 65 g / l, and a liquid temperature of 45 ° C. Then, in order to cathodically polarize the carrier foil C itself, the stainless steel plates to be the anode electrodes are arranged in parallel so as to be parallel to both surfaces of the carrier foil C after the bonding interface layer 2 immersed in the solution is formed. And electrolyzed. Hereinafter, when the electrolysis method was employed, the same method was employed. Electrolysis was then performed under smooth plating conditions with a current density of 5 A / dm ² , and a bulk copper layer 3 having a thickness of 5 μm was formed on each bonding interface layer 2 on both sides of the carrier foil C.

  When the formation of the bulk copper layer 3 on both sides was completed, the surface of each bulk copper layer 3 on both sides was then subjected to a roughening treatment. In the roughening treatment, first, fine copper particles 4 were formed on the bulk copper layer 3 and then plated to prevent the fine copper particles 4 from falling off.

  The same method as in Example 1 was adopted for the formation of fine copper particles 4 and the covering plating. Therefore, the description here is omitted to avoid redundant description. When the formation of the electrolytic copper foil layer CF is completed as described above, the carrier foil electrolysis completed by performing rust prevention treatment on both surfaces, washing with water and finally drying in the same manner as in Example 1. Copper foil 1b was obtained.

  The peel strength between the carrier foil layer C and the electrolytic copper foil layer CF of the electrolytic copper foil 1b with carrier foil was measured. As a result, the peel strength of the carrier foil C on one side was 3.4 gf / cm before heating, 3.7 gf / cm (standard deviation 1.5 gf / cm) after heating at 180 ° C. for 1 hour, and 1 at 230 ° C. After heating for a while, it was 4.5 gf / cm (standard deviation 1.9 gf / cm).

  The peel strength of the carrier foil C on the other side is 3.7 gf / cm before heating, 4.2 gf / cm (standard deviation 1.6 gf / cm) after heating at 180 ° C. for 1 hour, and 1 at 230 ° C. It was 4.8 gf / cm (standard deviation 2.3 gf / cm) after the time heating.

  In this example, an electrolytic copper foil not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 18 μm is used for carrier foil C, pickling treatment, 2-anilino-4,6-dimercapto- The same method as in Example 1 was performed until the bonding interface layer 2 was formed with s-triazine. Therefore, these descriptions are omitted here to avoid redundant description.

  When the formation of the bonding interface layer 2 is completed, the electrolytic copper foil layer CF is formed. The electrolytic copper foil layer CF here is a type of only the fine copper particles 4. Therefore, after the formation of the bonding interface layer 2 is completed, the surface of the bonding interface layer 2 is subjected to a burn copper plating process. In the roughening treatment, first, fine copper particles 4 were formed on the electrolytic copper foil layer CF, and further, overplating was performed to prevent the fine copper particles 4 from falling off. At this time, the same method as in Example 1 was adopted for the formation of the fine copper grains 4 and the covering plating. However, the formation of the fine copper particles 4 is different in that the electrolysis is performed for 20 seconds under the same burn plating conditions, and a sufficient amount of the fine copper particles 4 is attached by extending the electrolysis time.

  When the formation of the electrolytic copper foil layer CF is completed as described above, the electrolytic copper foil with carrier foil is completed by performing the rust prevention treatment, washing with water and finally drying in the same manner as in Example 1. 1c was obtained.

  And the peeling strength of carrier foil layer C and electrolytic copper foil layer CF of this electrolytic copper foil 1c with carrier foil was measured. As a result, the peel strength was 2.7 gf / cm before heating, 3.2 gf / cm after heating at 180 ° C. for 1 hour (standard deviation 1.4 gf / cm), and 5.8 gf after heating at 230 ° C. for 1 hour. / Cm (standard deviation 2.2 gf / cm).

  In this example, a rolled copper foil having a thickness of 18 μm which has not been subjected to a roughening treatment and a rust prevention treatment is used for the carrier foil C, and pickling treatment, bonding interface with 2-anilino-4,6-dimercapto-s-triazine The same method as in Example 2 was performed until the layer 2 was formed. Therefore, these descriptions are omitted here to avoid redundant description.

  When the formation of the bonding interface layer 2 was completed, the electrolytic copper foil layer CF was formed on both surfaces of the bonding interface layer 2 formed on both surfaces of the carrier foil C. The electrolytic copper foil layer CF here is composed of fine copper particles 4 Only type. Accordingly, when the formation of the bonding interface layer 2 is completed, the surface of the bonding interface layer 2 is then subjected to a roughening treatment. In the roughening treatment, first, the fine copper particles 4 were formed on the bonding interface layer 2 and then overplating was performed to prevent the fine copper particles 4 from falling off. At this time, the same method as in Example 2 was used for the formation of the fine copper grains 4 and the covering plating. However, the formation of the fine copper particles 4 is different in that the electrolysis is performed for 20 seconds under the same burn plating conditions, and a sufficient amount of the fine copper particles 4 is attached by extending the electrolysis time.

  When the formation of the electrolytic copper foil layer CF is completed as described above, the electrolytic copper foil with carrier foil is completed by performing the rust prevention treatment, washing with water and finally drying in the same manner as in Example 1. 1d was obtained.

  And the peeling strength of carrier foil layer C and electrolytic copper foil layer CF of this electrolytic copper foil 1d with carrier foil was measured. As a result, the peel strength of the carrier foil C on one side was 3.5 gf / cm before heating, 4.1 gf / cm after heating for 1 hour at 180 ° C. (standard deviation 2.1 gf / cm), and 1 at 230 ° C. After the time heating, it was 5.0 gf / cm (standard deviation 2.4 gf / cm).

  The peel strength of the carrier foil C on the other side is 3.1 gf / cm before heating, 4.5 gf / cm (standard deviation 1.8 gf / cm) after heating for 1 hour at 180 ° C., and 1 at 230 ° C. After the time heating, it was 4.9 gf / cm (standard deviation 2.0 gf / cm).

  In this example, a refractory metal layer was provided after the bonding interface layer 2 was formed with 2-anilino-4,6-dimercapto-s-triazine of Example 1, and then an electrolytic copper foil was formed in the same manner as in Example 1. The layer was formed and the electrolytic copper foil 1e with carrier foil was manufactured. Therefore, description of the part which becomes the description which overlaps with Example 1 is abbreviate | omitted, and it demonstrates about formation of a refractory metal layer. In this example, nickel, cobalt, nickel-zinc alloy, nickel-cobalt alloy, nickel-phosphorus alloy, and nickel-iron-cobalt alloy were used as the high melting point metal.

When the refractory metal layer is a nickel layer, nickel sulfate is used as the nickel plating solution, the nickel concentration is 60 g / l, the boric acid concentration is 30 g / l, the liquid temperature is 30 ° C., the pH is 3, and the current density is 5 A / dm ^2. The film was formed as a thin film layer having a thickness of 22 nm.

When the refractory metal layer is a cobalt layer, cobalt sulfate is used, and the cobalt concentration is 15 g / l, trisodium citrate 200 g / l, liquid temperature 35 ° C., pH 3, and current density 5 A / dm ² are employed. The thin film layer was converted to a film thickness of 22 nm.

When the refractory metal layer is a nickel-zinc alloy layer, nickel sulfate is used, the nickel concentration is 2.0 g / l, zinc pyrophosphate is used, the zinc concentration is 0.5 g / l, and potassium pyrophosphate 250 g / l. The conditions of a liquid temperature of 35 ° C., pH of 10, and a current density of 5 A / dm ² were adopted to form a thin film layer having a thickness of 22 nm.

When the refractory metal layer is a nickel-cobalt alloy layer, cobalt sulfate 130 g / l, nickel sulfate 100 g / l, boric acid 30 g / l, potassium chloride 12.5 g / l, sodium dihydrogen phosphate 8 g / l The conditions of a liquid temperature of 40 ° C., pH 4.0, and a current density of 5 A / dm ² were adopted to form a thin film layer having a thickness of 22 nm.

When the refractory metal layer is a nickel-iron-cobalt alloy layer, cobalt sulfate 150 g / l, nickel sulfate 150 g / l, ferrous sulfate 150 g / l, boric acid 40 g / l, liquid temperature 50 ° C., pH 4 .5, adopts a current density of 5A / dm ^2, was formed as a thin layer having a thickness of 22nm conversion.

  The peel strength of the carrier foil of the electrolytic copper foil with carrier foil obtained as described above was measured in the same manner as in Example 1. The results are shown in Table 1.

  In this example, a refractory metal layer was provided after the formation of the bonding interface layer 2 with 2-anilino-4,6-dimercapto-s-triazine in Example 2, and then the electrolytic copper foil was formed in the same manner as in Example 1. A layer was formed to produce an electrolytic copper foil 1f with a carrier foil. Therefore, the description of the part which overlaps with Example 1 is abbreviate | omitted. And since formation of a refractory metal layer is the same as that of Example 5, it abbreviate | omits in order to avoid the duplicate description. In this embodiment, nickel, cobalt, nickel-zinc alloy, nickel-cobalt alloy, nickel-phosphorus alloy, and nickel-iron-cobalt alloy were used as the refractory metal.

  The peel strength of the carrier foil of the electrolytic copper foil with carrier foil obtained as described above was measured in the same manner as in Example 1. The results are shown in Table 2. In addition, since the measurement surface in a present Example is on both surfaces, in Table 2, the measurement of one side is classified as 1, and the measurement of the other surface is classified as 2.

  In this example, a refractory metal layer was provided after the bonding interface layer 2 was formed with 2-anilino-4,6-dimercapto-s-triazine of Example 3, and then the electrolytic copper foil was formed in the same manner as in Example 1. A layer was formed to produce 1 g of electrolytic copper foil with carrier foil. Therefore, the description of the part which becomes description overlapping with Example 3 is abbreviate | omitted. And since formation of a refractory metal layer is the same as that of Example 5, it abbreviate | omits in order to avoid the duplicate description. In this embodiment, nickel, cobalt, nickel-zinc alloy, nickel-cobalt alloy, nickel-phosphorus alloy, and nickel-iron-cobalt alloy were used as the refractory metal.

  The peel strength of the carrier foil of the electrolytic copper foil with carrier foil obtained as described above was measured in the same manner as in Example 1. The results are shown in Table 3.

  In this example, a refractory metal layer was provided after forming the bonding interface layer 2 with 2-anilino-4,6-dimercapto-s-triazine of Example 4, and then an electrolytic copper foil in the same manner as in Example 1. The layer was formed and the electrolytic copper foil 1h with carrier foil was manufactured. Therefore, the description of the part which becomes description overlapping with Example 4 is abbreviate | omitted. And since formation of a refractory metal layer is the same as that of Example 5, it abbreviate | omits in order to avoid the duplicate description. In this embodiment, nickel, cobalt, nickel-zinc alloy, nickel-cobalt alloy, nickel-phosphorus alloy, and nickel-iron-cobalt alloy were used as the refractory metal.

  The peel strength of the carrier foil of the electrolytic copper foil with carrier foil obtained as described above was measured in the same manner as in Example 1. The results are shown in Table 4. In addition, since the measurement surface in a present Example is on both surfaces, in Table 2, the measurement of one side is classified as 1, and the measurement of the other surface is classified as 2.

Comparative Example 1

  In this comparative example, an electrolytic copper foil not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 18 μm is used for the carrier foil, and basically the same production flow as in Example 1 is adopted. Thus, carboxybenzotriazole (hereinafter referred to as CBTA) was used to form the bonding interface layer. Therefore, only the formation of the bonding interface layer will be described.

  First, the pickling treatment of the carrier foil was performed in the same manner as in Example 1. And the joining interface layer was formed in the surface of the carrier foil 3 which the pickling process was complete | finished. This bonding interface layer is formed by immersing the carrier foil, which has been pickled and washed with water, soaked in an aqueous solution containing CBTA at a concentration of 5 g / l, a liquid temperature of 40 ° C. and a pH of 5 for 30 seconds. A bonding interface layer was formed on the surface of 3 and washed with water. The thickness of the bonding interface layer formed with CBTA obtained here was 11 nm on average. However, the bonding interface layer composed of CBTA varies between 2 nm and 25 nm depending on the location observed by TEM, and the film thickness is not uniform.

  When the formation of the bonding interface layer is completed, the bulk copper layer forming the bulk copper layer constituting the electrolytic copper foil layer is formed on one side of the bonding interface layer formed on both sides of the carrier foil, and the fine copper particles are adhered and plated A roughening treatment, an antirust treatment, and a drying treatment were performed to produce an electrolytic copper foil with a carrier foil for comparison. Since each of these manufacturing conditions is the same as that of Example 1, detailed description here is abbreviate | omitted in order to avoid the duplicate description.

  The peel strength between the carrier foil layer and the electrolytic copper foil layer of this electrolytic copper foil with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength was 18 gf / cm before heating, 25 gf / cm after heating for 1 hour at 180 ° C. (standard deviation 2.73 gf / cm), and could not be peeled after heating for 1 hour at 230 ° C.

Comparative Example 2

  In this comparative example, an electrolytic copper foil not subjected to roughening treatment and rust prevention treatment classified as grade 3 having a thickness of 18 μm is used for the carrier foil, and basically the same production flow as in Example 1 is adopted. The commercially available thiocyanuric acid was used to form the bonding interface layer. Therefore, only the formation of the bonding interface layer will be described.

  First, the pickling treatment of the carrier foil was performed in the same manner as in Example 1. And the joining interface layer was formed in the surface of the carrier foil 3 which the pickling process was complete | finished. The bonding interface layer was formed by using an aqueous solution containing thiocyanuric acid at a concentration of 5 g / l and having a liquid temperature of 40 ° C. and a pH of 5 and immersing the carrier foil in this for 30 seconds. The bonding interface layer composed of thiocyanuric acid varied between 2 nm and 25 nm depending on the location observed with TEM, and lacked uniformity in film thickness.

  When the formation of the bonding interface layer is completed, the bulk copper layer forming the bulk copper layer constituting the electrolytic copper foil layer is formed on one side of the bonding interface layer formed on both sides of the carrier foil, and the fine copper particles are adhered and plated A roughening treatment, an antirust treatment, and a drying treatment were performed to produce an electrolytic copper foil with a carrier foil for comparison. Since each of these manufacturing conditions is the same as that of Example 1, detailed description here is abbreviate | omitted in order to avoid the duplicate description.

  The peel strength between the carrier foil layer and the electrolytic copper foil layer of this electrolytic copper foil with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength was 5.4 gf / cm before heating, 5.5 gf / cm after heating at 180 ° C. for 1 hour (standard deviation 4.65 gf / cm), and 5.8 gf after heating at 230 ° C. for 1 hour. / Cm (standard deviation 4.88 gf / cm).

<Contrast between Example and Comparative Example>
Judging from the comparison between the above example and the comparative example, the following can be understood. First, the comparative example 2 and each example are compared. Among the electrolytic copper foils with a carrier foil according to the present invention, those not provided with a refractory metal layer have the same average peel strength of the carrier foil as compared with the case of using the thiocyanuric acid of Comparative Example 2. ing. On the other hand, among the electrolytic copper foils with a carrier foil according to the present invention, those provided with a refractory metal layer have a small peel strength as compared with the case of using the thiocyanuric acid of Comparative Example 2. Furthermore, when the magnitude of the peel strength variation is viewed from the standard deviation, the peel strength variation of the carrier foil of the electrolytic copper foil with carrier foil according to the present invention is equal to or smaller than that of Comparative Example 2. In particular, among the electrolytic copper foils with carrier foil according to the present invention, those provided with a refractory metal layer have almost no change in the peel strength of the carrier foil even when heated in a temperature range of 230 ° C. or lower. Is understood. Here, it is clearly stated that even if the electrolytic copper foil with a carrier foil according to the present invention does not have a refractory metal layer, the reliability can sufficiently prevent the natural peeling of the carrier foil C due to handling during pressing. And the carrier foil C can be removed by hand very easily after heating.

  Accordingly, when the press molding temperature is 230 ° C. or lower, the electrolytic copper foil with carrier foil according to the present invention shows the same heat resistance as that of the electrolytic copper foil with carrier foil using the thiocyanuric acid of Comparative Example 2 as the bonding interface layer. Moreover, regarding the stability of the peeling strength of the carrier foil, it can be said that it shows better quality stability. Further, the electrolytic copper foil with carrier foil using CBTA of Comparative Example 1 does not need to be compared with the above examples, and cannot be peeled off at a press molding temperature of 230 ° C., and with the carrier foil according to the present invention. The difference in quality from the electrolytic copper foil is clear.

  The electrolytic copper foil with carrier foil according to the present invention is a carrier foil using a conventional thiocyanuric acid at the bonding interface in a use environment having a press molding temperature of 230 ° C. or lower by using triazine thiols for forming the bonding interface layer. Since it exhibits the same performance as an electro-deposited copper foil and the material cost can be reduced, it can be supplied to the market as an inexpensive product. In addition, the heat resistance in a temperature range of 200 ° C. or higher, which cannot be achieved by an electrolytic copper foil with a carrier foil using CBTA, which has been widely used in the past, is significantly improved. Therefore, it becomes easy to expand the range of applications other than the FR-4 base material of the electrolytic copper foil with carrier foil. Moreover, since the manufacturing method of the electrolytic copper foil with a carrier foil which concerns on this case is excellent in mass production stability, the market supply on the mass production basis of the electrolytic copper foil with a high quality carrier foil becomes easy.

The cross-sectional schematic diagram of the electrolytic copper foil with a carrier foil which concerns on this invention. Structural formula of triazine thiols used in the present invention. The schematic diagram which showed the lay-up structure at the time of press molding using the electrolytic copper foil with a carrier foil which concerns on this invention. The schematic diagram which showed the lay-up structure at the time of press molding using the electrolytic copper foil with a carrier foil which concerns on this invention. The schematic diagram which showed the normal layup structure at the time of press molding. The schematic diagram which showed the lay-up structure at the time of press molding using the electrolytic copper foil with a carrier foil which concerns on this invention. The cross-sectional schematic diagram of the electrolytic copper foil with a carrier foil which concerns on this invention. The cross-sectional schematic diagram of the electrolytic copper foil with a carrier foil which concerns on this invention. The cross-sectional schematic diagram of the electrolytic copper foil with a carrier foil which concerns on this invention. The cross-sectional schematic diagram of the electrolytic copper foil with a carrier foil which concerns on this invention. The cross-sectional schematic diagram of the electrolytic copper foil with a carrier foil which concerns on this invention. The cross-sectional schematic diagram of the electrolytic copper foil with a carrier foil which concerns on this invention. The cross-sectional schematic diagram of the electrolytic copper foil with carrier foil which concerns on this invention at the time of using electrolytic copper foil for carrier foil. The schematic diagram which showed the lay-up structure at the time of press molding using the electrolytic copper foil with a carrier foil which concerns on this invention. The schematic diagram which showed the lay-up structure at the time of press molding using the electrolytic copper foil with a carrier foil which concerns on this invention. The cross-sectional schematic diagram of the electrolytic copper foil with carrier foil which concerns on this invention at the time of using electrolytic copper foil for carrier foil. The schematic diagram showing the manufacture flow of electrolytic copper foil with carrier foil.

Explanation of symbols

1a to 1g Electrolytic copper foil with carrier foil 2 Bonding interface layer 3 Bulk copper layer 4 Fine copper grains (roughening treatment layer)
5 High melting point metal layer C Carrier foil CF Electrolytic copper foil layer

Claims (10)

In the electrolytic copper foil with a carrier foil provided with a bonding interface layer on one side of the carrier foil, and provided with an electrolytic copper foil layer on the bonding interface layer,
The bonding interface layer is formed using a solution containing triazine thiols, and is an electrolytic copper foil with a carrier foil. Electrolytic copper foil with carrier foil provided with a bonding interface layer on both sides of the carrier foil, and with an electrolytic copper foil layer on each of the bonding interface layers,
The said joining interface layer is formed using triazine thiols, Electrolytic copper foil with carrier foil characterized by the above-mentioned. The electrolytic copper foil with carrier foil according to claim 1 or 2, wherein the electrolytic copper foil layer is composed only of fine copper particles deposited and adhered by an electrolytic method. 4. The electrolytic copper foil with a carrier foil according to claim 1, wherein the triazine thiols contain 2-anilino-4,6-dimercapto-s-triazine. 5. 5. The electrolytic copper foil with carrier foil according to claim 1, wherein the bonding interface layer has a thickness of 0.5 nm to 1 μm. The carrier foil is an electrolytic copper foil. The electrolytic copper foil with a carrier foil according to any one of claims 1 to 5. The electrolytic copper foil with a carrier foil according to any one of claims 1 to 6, wherein a refractory metal layer is provided between the bonding interface layer and the electrolytic copper foil layer. The electrolytic copper foil with a carrier foil according to claim 7, wherein the refractory metal layer is made of nickel or a nickel-based alloy. In the manufacturing method of the electrolytic copper foil with a carrier foil in any one of Claims 1-8,
The formation of the bonding interface layer on the surface of the carrier foil is carried out by using a solution containing 1 ppm to 500 ppm of triazine thiols and adsorbing the organic agent to form an organic coating. Foil manufacturing method. The copper clad laminated board obtained using the electrolytic copper foil with a carrier foil in any one of Claims 1-8.

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