JP2000309898A - Electrolytic copper foil with carrier foil, production of the electrolytic copper foil and copper laminated sheet using the electrolytic copper foil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stabilize the peeling strength of the boundary between carrier foil and electrolytic copper foil at a low degree by forming a joint boundary layer on one side of carrier foil and forming the joint boundary layer by using an organic agent. SOLUTION: A joint boundary layer 8 is formed on one side of carrier foil 3 by using an organic agent, copper is electrolytically precipitated on the joint boundary layer 8, and electyrolytic copper foil with the carrier foil in which the precipitated copper layer is used as an electrolytic copper foil layer 5 is produced. As the organic agent, the one composed of one or >= two kinds selected from a nitrogen-contg. organic compd., a sulfur-contg. organic compd. and carboxyic acid is preferably used. As the nitrogen-contg. organic compd., 1,2,3,-benzotriazole, carboxybenzotriazole, N',N'-bis(benzotriazolyl methyl) urea, or the like, as triazole compds. having substituting groups is used, and, as the sulfur-contg. organic compd., mercaptobenzotiazole, thiocyaniric acid, or the like, is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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, a laminate using the electrolytic copper foil with a carrier foil, and the like.

[0002]

2. Description of the Related Art Conventionally, an electrolytic copper foil with a carrier foil has been used as a basic material for manufacturing a printed wiring board widely used in the fields of the electric and electronic industries. Generally, an electrolytic copper foil is laminated with a glass-epoxy substrate, a phenol substrate, or a polymer insulating substrate such as polyimide by hot press molding to form a copper-clad laminate, which is used for manufacturing a printed wiring board.

In this hot forming press, a copper foil, a prepreg (base material) cured to a B stage, and other end plates serving as spacers are laminated in multiple stages, and a high pressure is applied in a high temperature atmosphere to form the copper foil and the prepreg together. (Hereinafter, this step may be referred to as “press forming”) to obtain a copper-clad laminate. At this time, if wrinkles are present in the copper foil, cracks occur in the copper foil at the wrinkles, and the resin exudes from the prepreg or causes disconnection of a formed circuit in a printed wiring board manufacturing process which is an etching process later. Sometimes.

[0004] Wrinkling of the copper foil becomes a serious problem as the copper foil becomes thinner. Electrolytic copper foil with a carrier foil has attracted attention as an epoch-making copper foil capable of solving such a problem and preventing foreign substances from being mixed into the glossy surface of the copper foil during hot pressing. That is, the electrolytic copper foil with a carrier foil has a configuration in which a carrier foil and an electrolytic copper foil are laminated in a plane, and is pressed with the carrier foil attached, and immediately before forming a copper circuit by etching, the carrier foil is formed. Can be eliminated. This prevents wrinkles during handling and pressing of electrolytic copper foil,
This makes it possible to prevent surface contamination as a copper-clad laminate.

[0005] In the present specification, the name "carrier foil" is used, but this carrier foil is used in a form as if it were bonded to an electrolytic copper foil in a planar manner. The “carrier foil” in the present specification has the following properties. Considering the method for producing an electrolytic copper foil with a carrier foil according to the present invention, it is necessary that at least the surface of the carrier foil has conductivity since at least the surface of the carrier foil is electrodeposited with a copper component to be an electrolytic copper foil on the surface of the carrier foil. Becomes Then, the electrolytic copper foil with a carrier foil flows through a continuous manufacturing process, maintains a state of being bonded to the electrolytic copper foil layer at least until the end of the production of the copper-clad laminate, facilitates handling, and improves the electrolytic copper foil. Since the carrier foil has a role of reinforcing and protecting in every sense, the carrier foil needs to have a predetermined strength. If it satisfies these requirements, it can be used as a “carrier foil”, and generally a metal foil is assumed, but is not limited thereto.

[0006] Electrolytic copper foil with a carrier foil can be generally classified into a peelable type and an etchable type. In a nutshell, the peelable type is a type in which the carrier foil is peeled off and removed after press molding, and the etchable type is a type in which the carrier foil is removed by an etching method after press molding. It is.

[0007]

However, in the conventional peelable type, the value of the peeling strength of the carrier foil after press molding is extremely unstable.
A range of up to 300 gf / cm has been considered a good range.
On the other hand, in an extreme case, a situation occurs in which the carrier foil cannot be peeled off, and it has a disadvantage that it is difficult to obtain the desired peeling strength. This drawback has been the greatest obstacle to widespread use of electrolytic copper foil with a carrier foil for general applications.

The reason why the peel strength of the carrier foil becomes unstable is considered as follows. Conventional electrolytic copper foil with carrier foil, regardless of peelable type and etchable type, between the carrier foil and electrolytic copper foil, formed a metal-based bonding interface layer represented by zinc. is there. Whether to use the peelable type or the etchable type is slightly different depending on the type of the carrier foil, but has been performed by controlling the amount of metal present in the bonding interface layer.

The formation of a metal-based bonding interface layer is mainly performed by electrolysis of a solution containing a predetermined metal element and electrodeposition, and an electrochemical method has been employed. However, it is difficult to control an extremely small amount of deposition by the electrochemical method, and the electrochemical method is inferior in reproducibility as compared with other technical methods. Moreover, since the boundary of the required amount of deposition between the peelable type and the etchable type is only a slight difference in the amount of metal present in the bonding interface layer, it is difficult to obtain stable performance. it is conceivable that. Furthermore, since the carrier foil is generally peeled off at a temperature of 180 ° C. or higher at a high pressure and after the completion of pressing for 1 to 3 hours, the bonding interface layer interdiffuses with the carrier foil and the electrolytic copper foil. It is possible to wake up. This rather acts in the direction of increasing the bonding strength, and is considered to be a cause of the peel strength becoming unstable.

In recent years, the demand for downsizing of electronic and electrical equipment has never stopped, and the basic components such as multilayer printed wiring boards, high-density copper foil circuits, and high-density mounting of mounting components have been increasing. It is becoming more demanding. In such a case, since the amount of heat radiation from the mounted components increases, high heat resistance is also required for the printed wiring board as a built-in component. Heat resistant substrates have been used. The press temperature of the copper-clad laminate, which is a material of the printed wiring board, generally tends to increase. In view of the above, it is expected that the use of the conventional peelable type electrolytic copper foil with carrier foil will become increasingly difficult.

On the other hand, in the case of the etchable type,
Special etching equipment is required, and the time cost required for etching tends to be high. As a result, the use of the conventional etchable type electrolytic copper foil with a carrier foil increases the overall manufacturing cost, and has a drawback that it cannot be easily used for an extremely wide range of applications.

[0012]

The inventors of the present invention have conducted intensive studies and, as a result, have resolved the disadvantages of the conventional peelable type electrolytic copper foil with a carrier foil.
It is possible to use it as much as the case of using so-called normal electrolytic copper foil, and it is possible to stabilize the peeling strength of the interface between the carrier foil and the electrolytic copper foil at a low level. This led to the development of an electrolytic copper foil with a carrier foil. Hereinafter, the present invention will be described.

According to a first aspect of the present invention, a bonding interface layer is formed on one surface of a carrier foil, copper is electrolytically deposited on the bonding interface layer, and the deposited copper layer is used as an electrolytic copper foil. In the copper foil, the bonding interface layer is an electrolytic copper foil with a carrier foil, which is formed using an organic agent.

The electro-deposited copper foil with a carrier foil referred to in claim 1 is an electro-deposited copper foil in a state where the carrier foil and the electro-deposited copper foil are bonded together, as shown in the schematic sectional view of FIG. . In the above and below, 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, respectively, and are appropriately used according to the description.

The electrolytic copper foil with a carrier foil according to the present invention is characterized in that an organic agent is used at the bonding interface between the carrier foil and the electrolytic copper foil. By using this organic agent at the bonding interface, even after high-temperature press molding of copper-clad laminate production, peeling of the carrier foil as a peelable type is stable and easy with very small force. You can do it.

That is, by using an organic agent for the bonding interface layer, the peeling strength of the carrier foil after high-temperature press molding for the production of a copper-clad laminate can be easily peeled off manually by a human. It is possible to control to the level. In addition, defects such as a state in which a metal-based material is used for a conventional bonding interface layer and a state in which peeling is impossible or a fragment of a carrier foil remaining on the copper foil surface after peeling are completely eliminated. It becomes possible.

When an organic agent is used for forming the bonding interface layer,
During press forming at high temperatures, there is little possibility of interdiffusion between the carrier foil and the electrolytic copper foil, and it does not increase the bonding strength by heating, but rather functions as a barrier layer for the interdiffusion between the carrier foil and the electrolytic copper foil. In addition, the bonding strength between the carrier foil and the electrolytic copper foil at the time of producing the electrolytic copper foil with the carrier foil can be maintained at a substantially constant value until after the press molding.

Here, as an example, when a bonding interface layer using an organic agent is formed on a 35 μm carrier foil, and a 9 μm electrolytic copper foil layer is formed, the peel strength is examined. As a result, the best example is 3 gf / cm before heating and 3 gf / cm even after heating at 180 ° C. for 1 hour, which is not changed at all.

As used herein, the organic agent used is one or more selected from a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid. Is preferred.

Among the nitrogen-containing organic compound, the sulfur-containing organic compound and the carboxylic acid, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. Specifically, as the nitrogen-containing organic compound, 1,2,3-benzotriazole (hereinafter, referred to as “BTA”), which is a triazole compound having a substituent, and carboxybenzotriazole (hereinafter, referred to as “CBTA”). .), N ',
N'-bis (benzotriazolylmethyl) urea (hereinafter referred to as "BTD-U"), 1H-1,2,4-
Triazole (hereinafter, referred to as “TA”) and 3-amino-1H-1,2,4-triazole (hereinafter, “AT”)
A ". ) Is preferably used.

The sulfur-containing organic compounds include mercaptobenzothiazole (hereinafter, referred to as "MBT"), thiocyanuric acid (hereinafter, referred to as "TCA"), and 2-benzimidazole thiol (hereinafter, referred to as "BIT"). )
It is preferable to use such as.

As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linoleic acid and the like.

The method of using the above-mentioned organic agent will be described while describing a method of forming a bonding interface layer on a carrier foil. The formation of the bonding interface layer on the carrier foil is performed by dissolving the above-described organic agent in a solvent and immersing the carrier foil in the solvent, or showering the surface on which the bonding interface layer is to be formed, spraying, It can be performed using a dropping method, an electrodeposition method, or the like, and there is no need to employ a particularly limited method. At this time, the concentration of the organic agent in the solvent is preferably in the range of 0.01 g / l to 10 g / l and the liquid temperature in the range of 20 to 60 ° C. in all of the organic agents described above. The concentration of the organic agent is not particularly limited, and there is no problem whether the concentration is originally high or low.

Further, the formation of the bonding interface layer with an organic agent can be carried out by appropriately combining the above-mentioned organic agents described in claim 5 as described in claim 6. Can be repeated. As a result, it is possible to control the thickness of the bonding interface layer with higher accuracy.

From the principle of forming the bonding interface layer, it is considered that the above-mentioned organic agent is stably present on the carrier foil surface for the following reason. For example, when a bonding interface layer of an organic agent is formed on a carrier foil that is a metal, the organic agent is adsorbed on a metal oxide layer that is a metal oxide film formed on a surface layer of the carrier foil. From the state of being adsorbed on the metal oxide layer, it is presumed that the organic agent that forms a bonding interface layer by bonding to a bond such as oxygen existing in the surface layer is stabilized. Therefore, it can be said that the higher the concentration of the organic agent, the higher the speed at which the organic agent is adsorbed on the carrier foil surface, and the concentration of the organic agent is basically determined according to the speed of the production line. The time for contacting the carrier foil with the organic agent dissolved in the solvent is also determined by the speed of the production line, and is practically 5 to 60 seconds.

As a result of considering these facts, when the concentration of the organic agent is lower than 0.01 g / l, which is the lower limit, it is difficult to adsorb onto the carrier foil surface in a short time,
Moreover, the thickness of the bonding interface layer formed varies,
It is impossible to stabilize product quality. On the other hand, even when the concentration exceeds the upper limit of 10 g / l, the rate of adsorption of the organic agent on the surface of the carrier foil does not increase in accordance with the amount added, which is preferable from the viewpoint of production cost. Because there is no.

By using the above-mentioned organic agent,
Quantitative control when forming the bonding interface layer is facilitated, and the bonding strength between the carrier foil and the electrolytic copper foil can be kept within a certain range. In addition, the thermal stability is excellent, and the stability of the peeling strength after pressing can be secured.

When the carrier foil and the electrolytic copper foil are peeled off, the organic agent is also transferred to the surface layer of the electrolytic copper foil as an organic film, so that it also plays a role as a rust preventive layer of the electrolytic copper foil. Will fulfill. The organic film can be easily removed by pickling with a solution of diluted sulfuric acid, diluted hydrochloric acid, or the like, and does not adversely affect the manufacturing process of the printed wiring board.

More importantly, the organic-based agent described here is processed into a copper-clad laminate at the present stage, and is present in various resist coating and etching processes which are present in the manufacturing process of a printed wiring board. It was confirmed that there was no adverse effect in the steps of various plating processes, surface mounting, and the like.

In general, these organic agents are not conductive materials but are insulating materials. Therefore, the electrolytic copper foil with a carrier foil according to the first aspect is characterized in that the carrier foil itself is polarized as a cathode, and copper is electrolytically deposited directly on a bonding interface layer made of an organic agent formed on the carrier foil. Therefore, it is necessary to be able to conduct electricity through the bonding interface layer. That is, the thickness of the bonding interface layer made of an organic agent naturally has a limit, and it is necessary to ensure a proper peeling strength and to have a thickness that enables stable electrolytic deposition of copper.

Therefore, it is not important what kind of concentration of the organic agent is used and what kind of processing time is used to form the bonding interface layer, but the thickness of the resulting bonding interface layer, in other words, That is, the amount of the organic agent present at the bonding interface is important. From this, in claim 7,
The thickness of the bonding interface layer using an organic agent is preferably 1 n
It is clear that the range is from m to 1 μm.

In the thickness range specified here, appropriate peel strength can be ensured, and stable electrolytic deposition of copper becomes possible. That is, when the amount (thickness) of the organic agent used for the bonding interface layer is less than the lower limit of 1 nm,
The thickness of the bonding interface layer made of an organic agent varies,
A uniform bonding interface layer cannot be formed. As a result, stable and appropriate peel strength after press molding cannot be obtained, and in some cases, the carrier foil cannot be peeled.

If the upper limit of 1 μm is exceeded, the energized state becomes unstable, the copper deposition state becomes unstable, and it becomes difficult to form an electrolytic copper foil layer having a uniform thickness. In addition, even if copper is deposited for a long time, the minimum required peeling strength that does not end the press forming safely can not be satisfied. Then, when the thickness of the bonding interface layer is further increased, it becomes impossible to conduct electricity completely.

The thickness of the bonding interface layer is on the order of nm to μm.
Since it was very thin, a transmission electron microscope (TEM) was used for the measurement. Here, this analysis method will be described with reference to FIG. First, the electrolytic copper foil with a carrier foil according to the present invention is used as a small sample cut along AA ′ shown in FIG. Then, argon ions were simultaneously irradiated from the directions of arrows B and B ′ shown in FIG.
Sputtering was performed until the thickness became M observable.
As a result, in part C, direct observation of the bonding interface layer sandwiched between the electrolytic copper foil layer and the carrier foil layer becomes possible.

Then, a TEM image of the portion C where the TEM observation becomes possible is observed using a TEM, the observed image is photographed, and as a measured value from the photograph, the thickness of the bonding interface layer is measured. did. The observation photograph at this time is shown in FIG. FIG. 3 shows the case where the thickness of the bonding interface layer is about 7 to 25 nm. By such a method, it was determined that it is practical that the electrolytic copper foil with a carrier foil having an appropriate peel strength has a thickness of the bonding interface layer in the range of 1 nm to 1 μm.

The term "appropriate peel strength" as used herein means that the value measured in accordance with JIS-C-6481 is in the range of 1 to 300 gf / cm.
This is based on the experience of using a conventional peelable type electrolytic copper foil with a carrier foil, and the peel strength (peel strength) at the interface between the carrier foil and the electrolytic copper foil, which is considered appropriate based on experience, This is a range in which an ideal demand value of a user of the electrolytic copper foil with a carrier foil is taken into consideration.
The lower the peel strength at the interface between the carrier foil and the electrolytic copper foil, the easier the peeling operation. However, when the peeling strength is less than 1 gf / cm, the carrier foil and the electrolytic copper foil are partially spliced naturally during the production of the electrolytic copper foil with the carrier foil and the production of the copper-clad laminate. It causes peeling, blistering and misalignment. On the other hand, when the peel strength exceeds 300 gf / cm, the carrier foil is not an image that the carrier foil can be easily peeled, which is a feature of the present invention.
Techniques such as using a special peeling device are required.

As a method for examining the thickness of the bonding interface layer described above, in addition to the above-described method using the TEM, it is also possible to use alternative characteristics based on other analysis methods. Strictly speaking, it is considered desirable to select and use an appropriate analytical method depending on the type of organic agent used. As other analysis methods, a method by a chemical quantitative analysis method, a method by a surface resistance measurement method, a method by a polarization potential measurement method, and the like can be applied.

The chemical quantitative analysis method involves dissolving an organic agent present at a bonding interface in a predetermined solvent selected according to the type of the organic agent, and quantitatively analyzing the solvent using liquid chromatography. It is. Depending on the type of organic agent, for example, when the organic agent is BTA, T
When the thickness by EM observation is in the range of 1 nm to 20 nm, the value detected by the chemical quantitative analysis is 1 to 100 m
g / m ² .

The surface resistance is measured using a high resta manufactured by Dia Instruments, and the electrolytic copper foil with the carrier foil cut into a predetermined size on a Teflon plate with the electrolytic copper foil side down. The surface resistance was measured by applying a voltage of 10 volts. When this method is used, the measured value differs depending on the type of the carrier foil.
In the case of an electrolytic copper foil with a carrier foil having a μm electrolytic copper foil layer formed thereon, it is appropriate that the resistance value measured by the surface resistance method is less than or equal to 10 ⁵ Ω.

The polarization potential was measured by using an Ag / AgCl electrode as a reference electrode and measuring a potential of −100 mV when measured under conditions of 70 g / l sulfuric acid, 250 g / l copper sulfate, a liquid temperature of 40 ° C., and a current density of 5 A / dm 2. This indicates that a bonding interface layer using an appropriate organic agent has been formed.

The material of the carrier foil used in the first aspect is not particularly limited. Aluminum foil, copper foil, resin foil with metal coating on the surface as carrier foil, etc.
It is used as a concept that includes everything that can be used as a carrier. There is no particular limitation on the thickness of the carrier foil. From an industrial point of view, the concept of a foil is generally referred to as a foil having a thickness of 200 μm or less, and it is sufficient to use this concept.

The electro-deposited copper foil to be bonded to the carrier foil includes not only an electro-deposited copper foil called an ultra-thin copper foil of 12 μm or less, but also a case where it is thicker than 12 μm. The conventional electrolytic copper foil with a carrier foil is used exclusively for the purpose of providing an ultra-thin copper foil, and the electrolytic copper foil with a carrier foil of 12 μm or more such as the electrolytic copper foil with a carrier foil according to the present invention is commercially available. Had not been supplied to. Behind the fact that such an electrolytic copper foil with a carrier foil was able to be used, the carrier foil and the electrolytic copper foil were stably and easily peeled off by using an organic agent for the bonding interface layer. This is because a new method of using an electrolytic copper foil with a carrier foil to be described can be used.

Here, the copper foil of the electrolytic copper foil with a carrier foil according to claim 1, which is used for a copper-clad laminate and a printed wiring board, except for special uses. Fine copper particles are uniformly adhered to the outer surface of the foil layer for use. This is the same fine copper particles as those formed on the surface of the electrolytic copper foil to be bonded when bonding the general electrolytic copper foil and the resin base material, and obtains an anchor effect on the bonded base material, The purpose is to prevent the electrolytic copper foil from easily peeling off from the substrate.

According to a second aspect of the present invention, a bonding interface layer is formed on both surfaces of the carrier foil using an organic agent, and copper is electrolytically deposited on each of the bonding interface layers. It is an electrolytic copper foil with a carrier foil used as a foil. Claim 1
Has a shape in which an electrolytic copper foil is adhered to one side of a carrier foil, whereas, as shown in a schematic cross-sectional view in FIG. It has a shape as if a copper foil was attached.

By using an electrolytic copper foil with a carrier foil having such a structure, it is possible to omit a mirror plate at the time of manufacturing a copper-clad laminate, and to prevent foreign matter from entering the glossy surface of the copper foil at the time of press molding. It is possible to completely prevent it. Generally, as shown in FIG. 5, a double-sided copper-clad laminate is manufactured by forming a mirror-finished heat-resistant material such as stainless steel between one upper and lower press plates, a copper foil, one or more prepregs, a copper foil, The order of the end plates is repeatedly laminated (commonly referred to as lay-up), the press plate is heated at a high temperature, the resin component of the prepreg is melted by sandwiching the press plate, and the copper foil and the prepreg are bonded at high temperature and pressure. .

At this time, when the electrolytic copper foil with a carrier foil according to the second aspect is used, as shown in FIG. By using the electrodeposited copper foil with a carrier foil described in 1 and the other one located in the intermediate layer as the double-sided electrolytic copper foil with a carrier foil according to claim 2, all the end plates located in the intermediate layer portion are formed. It can be omitted, and it is only necessary to peel it off from the carrier foil at the time of disassembly after press molding.

The fact that the end plate of the intermediate layer becomes unnecessary is as follows.
By increasing the number of copper-clad laminates produced by one press, it is possible to increase the number of stages of copper foil and prepreg to be accommodated between daylights in the press plate by the thickness equivalent to the omitted end plate. Can be. Also, the heat transfer is improved,
It is possible to improve productivity. The thickness of the head plate is usually 0.8 mm to 3.0 mm, the copper foil is 3 to 50 μm thick, and one prepreg is 30 to 180 μm.
Considering that the thickness is m, it can be expected that an extremely large productivity improvement effect will be obtained.

According to a third aspect of the present invention, a bonding interface layer made of an organic agent is formed on one surface of the carrier foil, and only fine copper particles are electrolytically deposited on the bonding interface layer. In claim 4, a bonding interface layer is formed using an organic agent on both surfaces of the carrier foil, and fine copper particles are electrolytically deposited on each bonding interface layer. An electrolytic copper foil with a carrier foil using the deposited fine copper particle layer as an electrolytic copper foil.

When a normal electrolytic copper foil is observed from a cross section, as shown in FIG. 7, a fine surface treatment layer, which is generally a surface treatment layer for securing adhesion stability between the bulk copper layer and the insulating substrate for securing conductivity, is generally obtained. It consists of copper grains and a rust-preventive layer. Here, the bulk copper layer of the electro-deposited copper foil layer of the first and second aspects is omitted, and only fine copper particles are formed on the bonding interface layer made of an organic agent as shown in FIGS. Means an electrolytic copper foil with a carrier foil. These copper foils can be used in the same manner as the copper foils according to claims 1 and 2, but only fine copper particles are bonded to the prepreg during the production of the copper-clad laminate. become.

Then, in the printed wiring board manufacturing process, the printed wiring board maker removes the carrier and forms a bulk copper layer having a predetermined thickness to be a conductor by a suitable timing and an arbitrary copper plating method. You can do it. For example, such an electrolytic copper foil with a carrier foil is a copper-clad laminate with only the fine copper particles as the electrolytic copper foil, and a bulk copper layer is panel-plated on the fine copper particles on the substrate surface. It can be formed by a method. According to this method, the thickness of the bulk copper layer can be arbitrarily adjusted according to the type of a circuit to be formed, and an appropriate etching process can be performed according to a target circuit width. Therefore, such a method of manufacturing a printed wiring board is more effective as the circuit to be formed becomes finer, and the density of the circuit of the printed wiring board can be easily increased.

Next, an electrolytic copper foil with a carrier foil according to the present invention will be described in which an electrolytic copper foil is used as the carrier foil. This description, to make it easier to understand, for the normal electrolytic copper foil used as a carrier foil,
Here, a brief description will be given.

Usually, an electrolytic copper foil is produced through an electrolytic process and a surface treatment process, and is mainly used as a basic material for producing a printed wiring board used in the fields of the electric and electronic industries. .

An apparatus for producing an electrolytic copper foil, or more precisely, a bulk layer of an electrolytic copper foil, comprises a rotating cathode in the form of a drum and a lead-based anode opposed to the rotating cathode.
A copper sulfate solution is allowed to flow, and copper is deposited on the drum surface of the rotating cathode using an electrolytic reaction, and the deposited copper becomes a foil state, which is continuously peeled off from the rotating cathode and wound up. The copper foil at this stage is hereinafter referred to as “deposition foil”. At the stage of the deposition foil, no surface treatment such as rust prevention treatment has been performed, and the copper immediately after electrodeposition is in an activated state and becomes very easily oxidized by oxygen in the air. is there.

The surface of the deposited foil peeled off from the state in contact with the rotating cathode is a transfer of the mirror-finished surface of the rotating cathode, and is called a glossy surface because it is a glossy and smooth surface. . On the other hand, the surface shape of the deposited foil on the deposition side shows a mountain-shaped uneven shape because the crystal growth rate of the deposited copper differs for each crystal plane, and this is called a rough surface. This rough surface becomes the surface to be bonded to the insulating material when the copper-clad laminate is manufactured. Above and below, the term “rough surface” is used in the description of the case of using the deposition foil.

Next, the deposited foil is subjected to a surface roughening treatment and a rust prevention treatment in a surface treatment step. Roughening treatment on a rough surface is a process in which a current under so-called burn plating conditions is applied in a copper sulfate solution to deposit and attach fine copper particles to the uneven surface of the rough surface, and immediately cover the surface in the current range under the smooth plating conditions. The plating prevents the fine copper particles from falling off. Therefore, the rough surface on which fine copper particles are deposited and attached is referred to as "roughened surface". In this specification, the term "roughened surface" is also used for the surface of the electrolytic copper foil with carrier foil on which fine copper particles are deposited.

Subsequently, in the surface treatment step, rust prevention treatment is performed on the front and back of the copper foil by zinc, zinc alloy, chromium-based plating, etc., and the electrodeposited copper foil as a product is dried and wound up. It is completed. This is generally referred to as "surface treated foil". In the present invention, the electrolytic copper foil as a carrier foil to be used is mainly used in the state of the above-mentioned deposited foil, but may be used in the state of a surface-treated foil. Hereinafter, the electrolytic copper foil with a carrier foil described in claims 8 to 11 will be described.

In the drawings, cross-sectional schematic views of some electrolytic copper foils with a carrier foil and normal electrolytic copper foils are shown, but in these schematic views, the description of the rustproofing layer is omitted. ing. Usually, the rustproofing layer is provided on the outermost layer of the electrolytic copper foil after the surface treatment because the rustproofing layer prevents the copper foil from being oxidized by contact with air. That is, in the case of an electrolytic copper foil with a carrier foil, a rust-preventive treatment layer exists at least on the outermost surface of the roughened surface of the electrolytic copper foil layer.

According to claim 8, the carrier foil has a thickness of 12 μm.
An electrolytic copper foil with a carrier foil according to any one of claims 1 to 7, wherein an electrolytic copper foil having a thickness of up to 210 µm is used. This is because various advantageous effects not obtained in the conventional electrolytic copper foil with a carrier foil can be obtained by using the electrolytic copper foil as the carrier foil.

Advantageous effects of using an electrolytic copper foil as the carrier foil include the following. When a foil obtained by a rolling method is used as a carrier foil, as represented by a rolled aluminum material, it is inevitable that rolling oil adheres to the foil, and an oil component is taken into consideration in order to prevent oxidation. May be applied. When these are used as a carrier foil, they become obstacles when depositing copper on the carrier, and therefore, it is necessary to remove oil in the process. If it is an electrolytic copper foil, it cannot be inevitably adhered to oil from the manufacturing method, and even if an oxide film is formed, it can be easily pickled and removed, thereby reducing the number of steps or Process control can be facilitated.

When an electrolytic copper foil is used for the carrier foil,
The carrier foil and the electrolytic copper foil bonded to the carrier foil can be considered to be the same in both physical properties and components, and both etching processes can be performed with the same type of etching solution. Therefore, it is also possible to form a printed wiring circuit by forming an etching resist layer on the carrier foil, etching the carrier foil without peeling off the carrier foil, and peeling off the carrier foil without peeling off the carrier foil. Become. By doing so, the surface of the copper foil circuit is protected from contamination and foreign matter adhesion until the etching process is completed,
It is possible to greatly improve the work reliability of the subsequent plating process and the like.

Further, the purity of the electrolytic copper foil used as the carrier foil is 99.99% or more. In addition, the electrolytic copper foil with a carrier foil according to the present invention does not include another metal element serving as an impurity in the bonding interface layer. Therefore, the carrier foil after being peeled can be easily recycled, and does not unnecessarily generate industrial waste from the viewpoint of environmental protection. For example, the carrier foil can be collected and redissolved to form a copper ingot, or it can be dissolved again with sulfuric acid as a raw material for producing an electrolytic copper foil to form a copper sulfate solution.

Here, the reason why the thickness of the electrolytic copper foil used as the carrier foil is set to 12 μm to 210 μm is to serve as a reinforcing material for preventing the generation of wrinkles of the ultra-thin copper foil of 9 μm or less as the carrier foil. Requires a thickness of at least about 12 μm, and when the thickness exceeds the upper limit of 210 μm, it exceeds the concept of foil and is rather close to a copper plate, and it is difficult to wind and roll it. is there.

According to a ninth aspect, a bonding interface layer made of an organic agent is formed on a glossy surface of an electrolytic copper foil as a carrier foil,
It describes an electrolytic copper foil with a carrier foil in which an electrolytic copper foil layer is deposited and formed on the bonding interface layer. This electrolytic copper foil with a carrier foil has a sectional structure shown in FIG. 10 as a schematic sectional view. That is, the electrolytic copper foil with a carrier foil referred to here has a structure such that two electrolytic copper foils are bonded to each other with a bonding interface layer interposed therebetween, in such a manner that the glossy surfaces of the electrolytic copper foil face each other. . However, the electro-deposited copper foil layer in claims 8 to 11 is a concept that includes both a case where the copper foil layer is composed of a normal bulk copper layer and a fine copper grain layer, and a case where only the fine copper grain layer is formed. Used.

As the electrolytic copper foil as the carrier foil at this time, any of an electrodeposition foil and a surface-treated foil may be used. This is because there is no difference in the roughness of the glossy surface between the separated foil and the surface-treated foil. FIG. 10A is a schematic cross-sectional view of the case where the deposited foil is used as the carrier foil, and FIG. 10B is a schematic cross-sectional view of the case where the surface-treated foil is used as the carrier foil.
In these electrolytic copper foils with a carrier foil, whether to use a deposition foil for the carrier foil or to use a surface-treated foil, since the method of use at the time of producing a copper-clad laminate obtained using each of them is completely different, is there.

Here, a description will be given of a method of using an electrolytic copper foil with a carrier foil, which can be used in the production of a copper-clad laminate, in the case of using a deposition foil as the carrier foil and the case of using a surface-treated foil. First, as a method of manufacturing the first copper-clad laminate, a case in which a deposition foil is used as a carrier foil will be described. The electrolytic copper foil with carrier foil in such a case is shown in FIG.
It has the cross-sectional shape shown in FIG. As can be seen from this figure, the surface that can be bonded to the prepreg is
This is a surface of the electrolytic copper foil layer to which fine copper particles are adhered as a roughening treatment.

Therefore, as shown in FIG. 5, the lay-up is performed, and the electrolytic copper foil with the carrier foil and the prepreg (in the case where the outer copper foil layer of the multilayer substrate is formed) are formed in the same process as when the normal copper foil is used. Is press-formed using a prepreg and an inner layer substrate) and a head plate to obtain a copper-clad laminate. Further, by using the electrolytic copper foil with the carrier foil, press molding without the inner-layer end plate becomes possible. That is, as shown in FIG. 11, a mirror plate is arranged only on the outermost layer which is in direct contact with the press plate, and between the two mirror plates, the electrolytic copper foil with carrier foil and the prepreg are laminated and laid up. It is.

One electrolytic copper foil with a carrier foil is disposed on the uppermost layer and the lowermost layer when laid up. And, as shown in the enlarged view of FIG. 11, the copper foil located in the other inner layers when laid up is made such that the carrier foil surface and the carrier foil surface of the two electroplated copper foils with a carrier foil are back to back, The electrodeposited copper foil layer is arranged so that the roughened surface thereof comes into contact with the prepreg. Then, at the time of the disassembly operation after the completion of the press molding, the outer copper foil layer of the double-sided board or the multilayer board can be formed by peeling the carrier foil from the bonding interface layer.

On the other hand, as a second method for producing a copper-clad laminate, a method of using an electrolytic copper foil with a carrier foil using a surface-treated foil as a carrier foil in producing a copper-clad laminate will be described. The electrolytic copper foil with carrier foil in such a case is shown in FIG.
It has a sectional shape shown in FIG. As can be seen from this figure, the surface that can be bonded to the prepreg is the surface to which the fine copper particles are adhered by roughening treatment, so it exists not only on the electrolytic copper foil side but also on the carrier foil side. Will do.

That is, an electrolytic copper foil with a carrier foil is finished in such a shape that the glossy surfaces of two surface-treated normal electrolytic copper foils are bonded to each other. 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 copper clad laminate is obtained by press molding using the electrolytic copper foil with carrier foil, prepreg (prepreg and inner layer substrate in the case of forming an outer copper foil layer of a multilayer substrate) and a mirror plate. By using the electrolytic copper foil with a carrier foil, press molding without the inner layer end plate becomes possible. That is, as shown in FIG. 12, a mirror plate is arranged only on the outermost layer which is in direct contact with the press plate, and between the two mirror plates, the electrolytic copper foil with carrier foil and the prepreg are laid up.

A single electrolytic copper foil with a carrier foil or a normal copper foil is disposed on the uppermost layer and the lowermost layer when laid up. Then, as shown in the enlarged view of FIG. 12, prepregs are arranged on both sides of the electrolytic copper foil with the carrier foil, as shown in the enlarged view of FIG. Press molding in this way enables molding without using a head plate. Then, at the time of the disassembly work after the completion of the press molding, the outer copper foil layer of the double-sided board or the multilayer board can be formed by peeling off the bonding interface layer of the electrolytic copper foil with the carrier foil. According to this method, there is also an advantage that no scrap is generated at all.

The method of using the electrolytic copper foil with a carrier foil according to the present invention described above makes it possible to keep the peel strength of the bonding interface layer of the electrolytic copper foil with a carrier foil low and to stabilize it. This is the first press forming method that can be realized. Therefore, the useful effect provided by the electrolytic copper foil with a carrier foil according to the present invention has a very large effect on the printed wiring board industry, and greatly contributes to a reduction in the manufacturing cost of the copper-clad laminate. I can say.

At this time, if the thickness of the electrolytic copper foil layer deposited and formed on the glossy surface of the electrolytic copper foil as the carrier foil is extremely thin, the copper-clad laminate to which the ultra-thin copper foil is adhered is used. When a circuit having a pitch of about 50 μm is formed by using this method, the etching time of the copper foil portion can be extremely shortened, and a fine circuit having an extremely good aspect ratio can be formed.

According to a tenth aspect, a bonding interface layer made of an organic agent is formed on a roughened surface of an electrolytic copper foil as a carrier foil, and copper is electrolytically deposited on the bonding interface layer. The deposited copper layer is an electrolytic copper foil with a carrier foil used as the electrolytic copper foil. As the carrier foil used here, the above-mentioned deposited foil is used, and there is little possibility that the surface-treated foil is used as the carrier foil. This is because the fine particles of copper adhere to the rough surface of the surface-treated foil.

FIG. 13 is a schematic sectional view of an electrolytic copper foil with a carrier foil according to the tenth aspect. As can be seen from FIG. 13, the ultra-thin electrolytic copper foil layer is formed along the uneven shape of the rough surface of the electrolytic copper foil as the carrier foil. That is, the electrolytic copper foil layer has a wavy shape. Therefore, when a copper-clad laminate is manufactured using this copper foil, the copper-clad laminate is press-formed while maintaining the wavy shape as it is. This shape is very useful in forming a fine circuit. The method of manufacturing the copper clad laminate of the electrolytic copper foil with a carrier foil according to claim 10 is the same as that described in claim 9, and thus redundant description is omitted. I do.

The factors required for an electrolytic copper foil required for forming a fine circuit can be roughly understood to secure good adhesion with an etching resist, secure a good exposure state, fast etching time, and other factors. It is considered physical properties such as peel strength (including chemical resistance and the like). Most of the characteristics mentioned here are good, but among them, the corrugated electrolytic copper foil mainly contributes to securing good adhesion to the etching resist and securing good exposure state Is what you do.

By using an electrolytic copper foil having a wavy shape for a copper-clad laminate, the adhesion between various resists and the surface of the electrolytic copper foil is improved. For example, if the adhesion to the etching resist is improved, the intrusion of the etching solution into the bonding interface between the copper foil and the etching resist can be prevented, and a circuit cross section having a good aspect ratio can be formed. The formation of a fine circuit in consideration of the above is facilitated. In addition, by having a wavy surface shape, the gloss becomes almost matte as compared with a normal flat glossy surface. As a result, it is possible to suppress extra scattering of exposure light at the time of exposure to the etching resist of the etching pattern, and to reduce the influence of so-called exposure blur at the edge of the circuit pattern. .

Further, a result was obtained that plating treatment was performed on a copper-clad laminate using an electrolytic copper foil having a wavy shape to improve the peel strength at the interface between the copper foil surface and the plating layer. I have. Therefore, it can be said that the use of the electrolytic copper foil with a carrier foil improves the adhesion of the plating layer. In addition, the peel strength between the electrolytic copper foil and the FR-4 substrate is also set to claim 9.
Is improved by about 3 gf / cm as compared with the copper foil described in (1).

As a result, 50%
It is possible to prevent the aspect ratio of the circuit cross section from deteriorating when a fine circuit of a μm pitch level is formed, and to form a circuit having an ideal aspect ratio. In addition, since 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 in the linear stability of the edge portion of the formed circuit means that the linearity of the upper edge portion and the lower edge portion of the circuit shown in FIG. 14 is excellent, and that the components are mounted on a printed wiring board. This means that the edge portion of the entire formed circuit such as the edge shape of the circular circuit portion such as the land portion used is smooth. In other words, the linear stability of the circuit is excellent, and the shape without rattling suppresses copper migration that may occur when used as a printed wiring board, and the circuit edge when using a high-frequency signal It can be said that the discharge phenomenon from the projections can be eliminated.

Further, the present invention provides a copper foil having the features of the copper foil according to the ninth and tenth aspects of the present invention, wherein the copper foil has both the glossy surface and the rough surface of an electrolytic copper foil as a carrier foil.
A bonding interface layer made of an organic agent is formed, copper is electrolytically deposited on each bonding interface layer, and each deposited copper layer is used as a double-sided electrolytic copper foil with a carrier foil used as an electrolytic copper foil.

In the electrolytic copper foil used as the carrier foil used here, it is necessary to form an electrolytic copper foil layer on the rough surface of the carrier foil as in the case of the electrolytic copper foil with a carrier foil according to claim 10. Therefore, the use of an exfoliated foil is exclusively used. As is clear from the schematic cross-sectional view shown in FIG. 15, the electrolytic copper foil with a carrier foil referred to here has an electrolytic copper foil as a carrier foil positioned inside, and an electrolytic copper foil layer formed on both outer layer surfaces. It is.

With such a structure, the copper foil according to the eleventh aspect is the same as the method for producing a copper-clad laminate of an electrolytic copper foil with a carrier foil according to the eighth aspect described above with reference to FIG. Press molding as shown in
It is possible to use the above-described second method for producing a copper-clad laminate. This method of use is substantially the same as the above-mentioned method of use.

An electrolytic copper foil with a carrier foil according to claim 11 is used in place of the electrolytic copper foil with a carrier foil according to claim 9 used in this manufacturing method. That is, a copper clad laminate is obtained by press-forming using the electrolytic copper foil with a carrier foil, a prepreg (when forming an outer copper foil layer of a multilayer substrate, the prepreg and the inner layer substrate are used) and a mirror plate. However, by using the electrolytic copper foil with the carrier foil, it is possible to perform press forming without the inner layer end plate. That is, in the same manner as described in FIG. 12, a mirror plate is arranged only on the outermost layer which is in direct contact with the press plate, and between the two mirror plates, the electrolytic copper foil with a carrier foil and the prepreg are alternately laid up. It is.

A single electrolytic copper foil with a carrier foil or a normal copper foil is disposed on the uppermost layer and the lowermost layer when laid up. Then, one piece of the electrolytic copper foil with a carrier foil according to claim 11 is alternately laminated and arranged with the prepreg on the copper foil located on the other inner layer when laid up. Press molding in this way enables molding without using a head plate. Then, at the time of the disassembly work after the completion of the press molding, the outer copper foil layer of the double-sided board or the multilayer board can be formed by peeling off the bonding interface layer of the electrolytic copper foil with the carrier foil.

In the above-described method using the electrolytic copper foil with a carrier foil according to the present invention, the peel strength of the bonding interface layer of the electrolytic copper foil with a carrier foil is kept low and stabilized, as described above. This is the first press forming method that can be realized.

The above-described claims 1 to 1
As a method for producing an electrolytic copper foil with a carrier foil according to 1,
It is desirable to adopt the manufacturing method described in claim 12. The carrier foil is generally present in the form of a roll, and it is preferable to continuously process the roll-shaped carrier foil without a break from the viewpoint of production yield.

Therefore, the present inventors unwound the carrier foil wound in a roll shape from one direction, and the carrier foil was continuously arranged as a step of forming an electrolytic copper foil layer provided with a washing tank. Pickling tank, bonded interface formation tank with organic agent, tank for forming bulk copper layer to be electrolytic copper foil layer, roughening tank for forming fine copper particles formed on the surface of bulk copper layer, rust prevention Adopting a method for producing an electrolytic copper foil with a carrier foil, characterized by continuously forming a bonding interface layer and an electrolytic copper foil layer with an organic agent on the carrier foil by passing through each of a treatment tank and a drying treatment section. It was done.

More specifically, as a first method, as shown in FIG. 16, the carrier foil unwound from the joining interface forming tank and the copper foil layer while meandering through the step of forming the electrolytic copper foil layer. Using a device that continuously passes through a formation tank for forming a bulk copper layer, a roughening treatment tank for forming fine copper particles formed on the surface of the bulk copper layer, a rust prevention treatment tank, and a drying treatment section. Alternatively, as a second method, the carrier foil unwound as shown in FIG. 17 travels horizontally in a floating manner on each processing tank to form a bonding interface layer, an electrolytic copper foil layer, and a surface processing tank. Can be considered using a device that continuously performs the above.

The first method and the second method are selectively used in consideration of the thickness of the carrier foil. In the first method, since the carrier foil is designed to meander using a tension roll, the tension (tension) of the carrier foil over a short distance can be easily adjusted, and a proper tension adjustment is performed. This makes it easy to prevent wrinkles generated on the carrier foil during traveling. If wrinkles are generated in the carrier foil during running, the distance from the anode electrode to the wrinkles becomes uneven, which causes variations in the electrodeposition state and impairs the electrodeposition stability. Moreover, in the case of the first method, by arranging the anode electrodes on both sides of the carrier foil in the tank, the electrolytic copper foil layers can be formed on both sides of the carrier foil according to claims 2, 4 and 11. It is possible to manufacture the formed electrolytic copper foil with a carrier foil.

At this time, in the bulk copper layer forming tank,
If bulk copper is not formed, an electrolytic copper foil with a carrier foil in which only fine copper particles as an electrolytic copper foil are formed on a carrier foil can be easily obtained. This is the same in the second method described below.

On the other hand, the second method is exclusively used for producing an electrolytic copper foil with a carrier foil in which an electrolytic copper foil layer is formed on one side of the carrier foil. In this method, the solution in each tank travels horizontally with a variety of solutions spouted from gaps of an anode electrode or the like arranged parallel to the carrier foil so that the carrier foil floats on the various solutions. Occasionally, a fluttering phenomenon (here, up and down movement of the carrier foil during traveling) occurs, and the state of electrodeposition varies. Moreover, in this method, it is difficult to apply tension to the running carrier foil as compared with the first method, and the tension control becomes more difficult as a thinner carrier foil is used. Therefore, it can be said that this method can be used when a relatively thick carrier foil is used.

[0093] The pickling tank is a step of performing a so-called pickling treatment, which is performed for the purpose of degreasing treatment for completely removing the oil and fat components attached to the carrier foil and removing the surface oxide film when a metal foil is used. Things. By passing the carrier foil through this pickling tank, the carrier foil is cleaned, and uniform electrodeposition and the like in the following steps are ensured. Various solutions such as a hydrochloric acid-based solution, a sulfuric acid-based solution, and a sulfuric acid-hydrogen peroxide-based solution can be used for this pickling treatment, and there is no particular limitation. Then, it is sufficient to adjust the solution concentration, the liquid temperature, and the like according to the characteristics of the production line. Moreover, the pickling treatment is generally required when using the deposited foil as a carrier foil, and is necessarily required when using a surface-treated foil having a rust-preventive element in its surface layer as the carrier foil. is not.

The organic bonding interface forming tank is a step of performing a process of forming a bonding interface layer on one or both surfaces of the carrier foil using the organic agent according to the fifth aspect. The formation of the bonding interface layer is performed by filling the organic bonding interface forming tank with a solution containing an organic agent, and immersing the carrier foil in the solution, and forming the bonding interface in the organic bonding interface forming tank. A method of showering or dropping a solution containing an organic agent on the surface of the foil, a method of electrodepositing the organic agent in an organic bonding interface forming tank, or the like can be employed.

After the formation of the organic bonding interface, a bulk copper layer of an electrolytic copper foil is formed on the interface. In the bulk copper forming tank, a solution that can be used as a copper ion supply source such as a copper sulfate-based solution and a copper pyrophosphate-based solution is used, and is not particularly limited. For example, in the case of a copper sulfate solution, the concentration of copper is 30 to 100 g / l, and the concentration of sulfuric acid is 50 to 100 g / l.
200g / l, liquid temperature 30-80 ° C, current density 1-100
A / dm ^2, a copper pyrophosphate-based solution having a concentration of copper of 10 to 50 g / l and potassium pyrophosphate of 100 to 700
g / l, liquid temperature 30-60 ° C, pH 8-12, current density 1
And 10 A / dm ² . Here, the carrier foil having the organic bonding interface formed therein is immersed in the solution, the anode electrode is arranged in parallel with the surface of the carrier foil having the organic bonding interface formed, and the carrier foil itself is cathode-polarized. And a step of uniformly and smoothly depositing a copper component forming a bulk copper layer on an organic bonding interface. Hereinafter, the same anode electrode arrangement is adopted in a corresponding tank using the electrolysis method.

When the formation of the bulk copper layer is completed,
Next, as a step of forming fine copper particles on the surface of the bulk copper layer, the carrier foil is put into a roughening treatment tank. The processing performed in the surface roughening treatment tank, when further subdivided, is composed of a step of depositing and attaching fine copper particles on the bulk copper layer, and a covering plating step for preventing the fine copper particles from falling off. You.

In the step of depositing and depositing fine copper particles on the bulk copper layer, the same solution as used in the above-described bulk copper forming tank is used as a supply source of copper ions. However, while the electrolysis conditions used in the bulk copper forming tank are smooth plating conditions, the electrolysis conditions here are burnt plating conditions. Therefore, the solution concentration used in the step of depositing and depositing fine copper particles on the bulk copper layer is generally lower than the solution concentration used in the bulk copper formation layer, so as to easily create burn plating conditions. I have. The burn 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 concentration of copper is 5 to 2%.
0 g / l, sulfuric acid 50-200 g / l, other additives as required (α-naphthoquinoline, dextrin, glue, thiourea, etc.), liquid temperature 15-40 ° C., current density 10-10
For example, a condition of 50 A / dm ² is set.

In the cover plating step for preventing the fine copper particles from falling off, copper is uniformly deposited so as to cover the fine copper particles under smooth plating conditions in order to prevent the fine copper particles deposited and deposited from falling off. It is a process for. Therefore, here, the same solution as that used in the above-described bulk copper forming tank can be used as a supply source of copper ions. The conditions for the smooth plating 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 concentration of copper is 50 to 80 g / l,
For example, sulfuric acid 50 to 150 g / l, liquid temperature 40 to 50 ° C., current density 10 to 50 A / dm ² are set.

The rust prevention treatment tank is a step for preventing the surface of the electrolytic copper foil layer from being oxidized and corroded so as not to hinder the production process of the copper-clad laminate and the printed wiring board. Regarding the method used for the rust prevention treatment, there is no problem even if any of organic rust prevention using benzotriazole, imidazole or the like and inorganic rust prevention using zinc, chromate, zinc alloy or the like is used. Rust prevention may be selected according to the intended use of the electrolytic copper foil with carrier foil. In the case of organic rust prevention, techniques such as dip coating, showering coating, and electrodeposition of an organic rust preventive can be adopted. 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 a so-called substitution deposition method. For example, as the zinc rust preventive treatment, a zinc pyrophosphate plating bath, a zinc cyanide plating bath, a zinc sulfate plating bath, or the like can be used. 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, and the liquid temperature is 20 to 50 ° C.
pH 9-12, current density 0.3-10 A / dm ² , etc.

The drying section is a final step in which the carrier foil passes through the tanks filled with the various solutions in the above-described steps, and the completed electrolytic copper foil with the carrier foil is wound into a roll. It is something to be done. That is, the completed electrolytic copper foil with carrier foil in a wet state passes through a heating and drying furnace and is thermally dried.

Through these steps, claims 1 to 11
The production of an electrolytic copper foil with a carrier foil described in (1) is performed. These electrolytic copper foils with a carrier foil are mainly used as a basic material for manufacturing a printed wiring board. Therefore, claim 13 includes claims 1 to 11
And a copper-clad laminate or printed wiring board obtained using the electrolytic copper foil with a carrier foil described in (1).

The term “copper-clad laminate” or “printed wiring board” as used herein includes the concept of all the layer constitutions of a single-sided substrate, a double-sided substrate and a multilayer substrate. It includes all flexible substrates and hybrid substrates including special substrates such as TAB and COB.

[0103]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing an electrolytic copper foil with a carrier foil according to the present invention, a copper-clad laminate using the copper foil, and evaluation results thereof will be described. Will be described. Here, description will be made mainly on the case where an electrolytic copper foil is used as the carrier foil. In the drawings, the same reference numerals are used to refer to the same items whenever possible.

First Embodiment: In the present embodiment,
It is an electrolytic copper foil 1 with a carrier foil according to claim 9, wherein FIG.
A description will be given of what is shown in FIG. The manufacturing apparatus 2 used here is shown in FIG. 18, in which the unwound carrier foil 3 travels in a meandering manner in the step of forming the electrolytic copper foil layer 5. Here, an electrolytic copper foil layer 5 having a thickness of 5 μm was formed on the glossy surface 4 side by using an 18 μm-thick deposited foil classified as grade 3 for the carrier foil 3. Hereinafter, the production conditions will be described in accordance with the order in which various tanks are continuously arranged in series.

The unwound carrier foil 3 first enters the pickling tank 6. The concentration in the pickling tank 6 is 150 g.
/ L, a dilute sulfuric acid solution at a liquid temperature of 30 ° C was filled, and the immersion time was 30 seconds to remove the oil and fat component attached to the carrier foil 3 and remove the surface oxide film.

The carrier foil 3 that has left the pickling tank 6 enters the joint interface forming tank 7. The bonding interface forming tank 7 contains CBTA at a concentration of 5 g / l and has a liquid temperature of 40 ° C.
Filled with an aqueous solution of H5. Therefore, the carrier foil 3 was immersed in the solution for 30 seconds while running, and the bonding interface layer 8 was formed on the surface of the carrier foil 3.

After the formation of the bonding interface layer 8, a bulk copper layer 9 of electrolytic copper foil is formed on the interface. In the bulk copper forming tank 10, the concentration is 150 g / l.
A copper sulfate solution having a sulfuric acid of 65 g / l copper and a liquid temperature of 45 ° C. was filled. Then, while the carrier foil 3 on which the bonding interface layer 8 is formed passes through the solution, the copper component forming the bulk copper layer 9 is uniformly and smoothly deposited on the bonding interface. As shown in FIG. 18, a flat anode electrode 11 was arranged in parallel with one surface of the carrier foil 3 on which 8 was formed, and electrolysis was performed for 60 seconds under a smooth plating condition of a current density of 15 A / dm ² . At this time, at least one of the tension rolls 12 contacting the meandering carrier foil 3 was used as a current supply roll to cathodic polarize the carrier foil 3 itself.

When the formation of the bulk copper layer 9 is completed, the carrier foil 3 is put into the surface treatment tank 14 as a step of forming fine copper particles 13 on the surface of the bulk copper layer 9.
The treatment performed in the surface treatment tank 14 includes a step 14A of depositing and depositing the fine copper particles 13 on the bulk copper layer 9 and a covering plating step 14B for preventing the fine copper particles 13 from falling off. .

In the step 14A of depositing and depositing the fine copper grains 13 on the bulk copper layer 9, the above-described bulk copper forming tank 10 is formed.
The same copper sulfate solution as used in the above, with a concentration of 100 g
/ L sulfuric acid, 18g / l copper, liquid temperature 25 ° C, current density 10A
/ Dm ² for 10 seconds under the burn plating conditions. At this time, the flat anode electrode 11 was arranged in parallel to the surface of the carrier foil 3 on which the bulk copper layer 9 was formed, as shown in FIG.

In the cover plating step 14B for preventing the fine copper particles 13 from falling off, the same copper sulfate solution as used in the above-mentioned bulk copper forming tank 10 was used, and the concentration was 150 g / l.
Sulfuric acid, 65g / l copper, liquid temperature 45 ° C, current density 15A / d
and electrolysis for 20 seconds at a smooth plating conditions of m ^2. At this time,
The flat anode electrode 11 was arranged in parallel with the surface of the carrier foil 3 on which the fine copper particles 13 were formed as shown in FIG.

In the rust preventive treatment tank 15, rust preventive treatment was performed using zinc as a rust preventive element. Here, as the soluble anode 16 using a zinc plate as the anode electrode, the concentration balance of zinc in the rust prevention treatment tank 15 was maintained. The electrolysis conditions here were such that a zinc sulfate bath was used, and 70 g /
The concentration was 1 sulfuric acid and 20 g / l zinc, the liquid temperature was 40 ° C., and the current density was 15 A / dm ² .

When the rust prevention treatment is completed, finally, the carrier foil 3 is heated in the drying unit 17 by an electric heater at an ambient temperature of 11 ° C.
After passing through a furnace heated to 0 ° C. for 40 seconds, it was wound into a roll as a completed electrolytic copper foil 1 with a carrier foil.
The traveling speed of the carrier foil in the above steps is 2.0 m / m
The washing is performed by providing a water-washing layer 18 that can be washed for about 15 seconds between steps in each tank to prevent carry-in of the solution in the pretreatment step.

This electrolytic copper foil 1 with a carrier foil and 150 μm
A double-sided copper-clad laminate was produced using two FR-4 prepregs having a thickness of m, and the peel strength at the bonding interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5 was measured. as a result,
The thickness of the bonding interface layer 8 was 10 nm on average, and the peel strength was 4 gf / cm before heating and 4 gf / cm after heating at 180 ° C. for 1 hour.

Further, the present inventors changed the CBTA used in the first embodiment to the above-mentioned organic agents such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and mercaptobenzoic acid. Table 1 shows the peel strength of the bonding interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5 before and after heating under the same conditions. Note that, using the electrolytic copper foil with a carrier foil shown in this embodiment, a circuit width of 25 μm,
A printed wiring board having a fine circuit portion with a gap of 25 μm was manufactured. However, the printed wiring board was finished as a very good printed wiring board, and there was no problem in various characteristics as the printed wiring board.

[0115]

[Table 1]

Second Embodiment: In the present embodiment,
It is an electrolytic copper foil 1 with a carrier foil according to claim 9, wherein FIG.
A description will be given of what is shown in FIG. The manufacturing apparatus 2 ′ used here is shown in FIG. 19, in which the unwound carrier foil 3 travels horizontally in the step of forming the electrolytic copper foil layer 5. This device is
At least in the bulk copper forming bath 10 and the surface treatment bath 14, a plurality of divided anode electrodes 11 ′ are arranged so as to face the carrier foil 3 in parallel.

The anode electrode 1 divided into a plurality
From the gap 18 of 1 ', the electrolytic solution is spouted so that the carrier foil 3 can float and contact the surface of the carrier foil 3 uniformly. In each of the other tanks, in order to allow the carrier foil 3 to float,
Although the function as an anode electrode was not provided, the structure was the same. Here, an electrolytic copper foil layer 5 having a thickness of 5 μm was formed using a 70 μm-thick deposited foil classified as grade 3 as the carrier foil 3. Hereinafter, the production conditions will be described in accordance with the order in which various tanks are continuously arranged in series.

The unwound carrier foil 3 first enters the pickling tank 6. The concentration in the pickling tank 6 is 150 g.
/ L, a dilute sulfuric acid solution at a liquid temperature of 30 ° C is filled, and this is brought into contact with one side of the carrier foil 3 for about 25 seconds,
Oil and fat components attached by pickling were removed, and a surface oxide film was removed.

The carrier foil 3 leaving the pickling tank 6 enters the joint interface forming tank 7. The bonding interface formation tank 7 contains CBTA at a concentration of 5 g / l,
Filled with an aqueous solution of H5. Accordingly, while the carrier foil 3 travels horizontally, the carrier foil 3 comes into contact with an aqueous solution containing the organic agent blown upward from below in the joining interface forming tank 40 for 40 seconds, and the joining interface layer 8 is formed on one surface of the carrier foil 3. Formed.

After the formation of the bonding interface layer 8, a bulk copper layer 9 of the electrolytic copper foil 5 is formed on the interface. The concentration of 150 g / l in the bulk copper forming tank 6
Sulfuric acid, 65 g / l copper, and a copper sulfate solution at a liquid temperature of 45 ° C. were introduced. Then, while the carrier foil 3 on which the bonding interface layer 8 is formed passes through the solution, the bonding interface layer 8 is formed in order to uniformly and smoothly deposit the bulk copper layer 9 on the bonding interface layer 8. As shown in FIG. 19, a block-shaped anode electrode 11 ′ was arranged in parallel to the carrier foil 3, and electrolyzed for 90 seconds under a smooth plating condition of a current density of 10 A / dm ² . At this time, in order to polarize the carrier foil 3 itself, at least one of the drive rolls 19 that is in contact with the horizontally running carrier foil 3 was used as a current supply roll.

When the formation of the bulk copper layer 9 is completed, the carrier foil 3 passes through the surface treatment tank 14 as a step of forming fine copper grains 13 on the surface of the bulk copper layer 9. The treatment performed in the surface treatment tank 14 includes a step 14A of depositing and attaching fine copper grains 13 on the bulk copper layer 9 and a covering plating step 14 for preventing the fine copper grains 13 from falling off.
B.

In the step 14A of depositing and depositing the fine copper particles 13 on the bulk copper layer 9, the above-described bulk copper forming tank 10 is formed.
The same copper sulfate solution as used in the above, with a concentration of 100 g
/ L sulfuric acid, 18g / l copper, liquid temperature 25 ° C, current density 10A
/ M ² for 15 seconds under the burn plating conditions. At this time, the block-shaped anode electrode 11 ′ is
19 was arranged in parallel to the surface of the carrier foil 3 on which the was formed.

In the cover plating step 14B for preventing the fine copper particles 13 from falling off, the same copper sulfate solution as that used in the above-mentioned bulk copper forming tank 10 was used, and the concentration was 150 g / g.
1 sulfuric acid, 65 g / l zinc, liquid temperature 45 ° C, current density 15A
/ Dm ² for 20 seconds under a smooth plating condition. Also in this case, the block-shaped anode electrode 11 ′
19 was arranged in parallel to the surface of the carrier foil 3 on which was adhered.

In the rust preventive treatment tank 15, rust preventive treatment was performed using a zinc sulfate bath as a rust preventive element. Here, as the soluble anode 16 'using a zinc plate as the anode electrode, the zinc concentration balance in the rust prevention treatment tank 15 was maintained. The electrolysis conditions here were as follows: a concentration of 70 g / l sulfuric acid, 20 g / l zinc, a liquid temperature of 40 ° C., and a current density of 0.3 A /
dm ² , and the electrolysis time was 20 seconds.

When the rust prevention treatment is completed, finally, the carrier foil 3 is dried in the drying unit 17 at an atmospheric temperature of 11 ° C. by an electric heater.
After passing through a furnace heated to 0 ° C. for 40 seconds, it was wound into a roll as a completed electrolytic copper foil 1 with a carrier foil.
The traveling speed of the carrier foil 3 in the above steps is 2.0 m /
min, and a washing tank 18 capable of washing for about 15 seconds is provided between the steps in each tank to prevent the solution in the pretreatment step from being brought in.

This electrolytic copper foil 1 with a carrier foil and 150 μm
A double-sided copper-clad laminate was manufactured using two m-thick FR-4 prepregs, and the peeling strength of the bonding interface 8 between the carrier foil layer 4 and the electrolytic copper foil layer 5 was measured. As a result, the thickness of the bonding interface layer 8 was 8 nm on average, and the peel strength was 4 gf / cm before heating and 4 gf after heating at 180 ° C. for 1 hour.
/ Cm.

Further, the present inventors changed the CBTA used in the second embodiment and used the above-mentioned organic agents such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and mercaptobenzoic acid. Table 2 shows the peel strength of the bonding interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5 under the same conditions, and the measured values before and after heating. The printed wiring board having a fine circuit portion with a circuit width of 25 μm and a gap of 25 μm was manufactured using the electrolytic copper foil with a carrier foil shown in this embodiment, but was finished as a very good printed wiring board. There were no problems in various characteristics as a printed wiring board.

[0128]

[Table 2]

Third Embodiment: In the present embodiment,
The electrolytic copper foil 1 with a carrier foil according to claim 10 will be described with reference to FIG. The manufacturing apparatus 2 used here is shown in FIG. 18 and is common in this point to the first embodiment. The difference is that the carrier foil 3 is unwound so that the front and back are reversed from the case of the first embodiment, and the electrolytic copper foil layer 5 is formed on the rough surface 20 side. And it is a type of meandering traveling in the forming process of the electrolytic copper foil layer 5. Here, the carrier foil 3 has a thickness of 18 μm.
An electrolytic copper foil layer 5 having a thickness of 5 μm was formed using a deposition foil classified as a thick grade 3.

The manufacturing conditions in this case are basically the same as those in the first embodiment. Therefore, the description of the duplicated description will be omitted as much as possible, and only the basic and important portions will be described below. That is, there is no change in the conditions in the pickling tank 6, the bonding interface forming tank 7, and the heating / drying unit 17. However, since the surface on which the electrolytic copper foil layer 5 is formed is different from that of the first embodiment, a difference occurs in the surface roughness.
In some cases, it is necessary to finely adjust the electrolysis conditions when performing electrodeposition.

Electrolysis conditions in the bulk copper forming tank 10 are as follows: concentration 150 g / l sulfuric acid, 65 g / l copper, liquid temperature 45 ° C.
, A current density of 15 A / dm ² and an electrolysis time of 10 seconds. In the step 14A of depositing and attaching the fine copper particles 13 on the bulk copper layer 9, the same copper sulfate solution as used in the above-described bulk copper forming tank 10 having a concentration of 1
Electrolysis was performed under burn-out plating conditions of 00 g / l sulfuric acid, 18 g / l copper, a liquid temperature of 25 ° C., a current density of 10 A / dm ² , and an electrolysis time of 10 seconds. In the overplating step 14B for preventing the fine copper particles 13 from falling off, the bulk copper forming tank 10
The same copper sulfate solution as used in the above was used, and the concentration was 150 g /
1 sulfuric acid, 65 g / l copper, liquid temperature 45 ° C, current density 15 A /
Electrolysis was performed under the smooth plating conditions of dm ² and electrolysis time of 20 seconds. Electrolysis conditions in the rust prevention treatment tank 15 were as follows: a zinc sulfate bath, a concentration of 70 g / l sulfuric acid, 20 g / l zinc, a liquid temperature of 40 ° C.,
The current density was 0.3 A / dm ² and the electrolysis time was 20 seconds.

The electrolytic copper foil 1 with a carrier foil and 150 μm
A double-sided copper-clad laminate was manufactured using two m-thick FR-4 prepregs, and the peeling strength of the bonding interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5 was measured. As a result, the thickness of the bonding interface layer 8 was 8 nm on average, and the peel strength was 5 gf / cm before heating and 6 gf after heating at 180 ° C. for 1 hour.
/ Cm.

Further, the present inventors changed the CBTA used in the third embodiment, and used palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, mercaptobenzoic acid, etc. as organic agents. Table 3 shows the peeling strength of the bonding interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5 under the same conditions, and the measured values before and after heating. In addition, using the electrolytic copper foil with a carrier foil shown in this embodiment, a circuit width of 25 μm was used.
A printed circuit board having a fine circuit part having a gap of 25 μm and a gap of 25 μm was manufactured. However, the printed circuit board was finished as a very good printed circuit board, and there were no problems in various characteristics as the printed circuit board.

[0134]

[Table 3]

Fourth Embodiment: In the present embodiment,
The electrolytic copper foil 1 with a carrier foil according to claim 11, which is shown in FIG. 15, will be described. The manufacturing apparatus 2 used here is the one shown in FIG. 20, in which the unwound carrier foil 3 travels in a meandering manner in the step of forming the electrolytic copper foil layer 5. Here, an electrolytic copper foil layer 5 was formed on both surfaces of the glossy surface 4 and the rough surface 20 by using an 18 μm-thick deposited foil classified as grade 3 for the carrier foil 3. Hereinafter, the production conditions will be described in accordance with the order in which various tanks are continuously arranged in series.

The manufacturing conditions in this case are basically the same as those in the first embodiment. Therefore, the description of the duplicated portions will be omitted, and only different portions will be described below. That is, there is no change in the processing conditions of the pickling treatment tank 6, the joining interface forming tank 7, and the heating / drying unit 17. In the case of the first embodiment, the electrolytic copper foil layer 5 is formed on one side of the carrier foil 3, but in the present embodiment, the electrolytic copper foil layer 5 is formed on both sides of the carrier foil 3. Therefore, it is necessary to change the arrangement of the anode electrode 11 when performing electrodeposition.

In the bulk copper forming tank 10, a concentration of 150
g / l sulfuric acid, 65 g / l copper, and a copper sulfate solution at a liquid temperature of 45 ° C were filled. Then, as shown in FIG. 20, two flat anode electrodes 11 were arranged in parallel so as to sandwich the traveling carrier foil 3, and a bulk copper layer 9 was simultaneously deposited on both surfaces of the carrier foil 3. The current density used for the electrolysis at this time was such that electrolysis was performed for 60 seconds under the smooth plating conditions of 15 A / dm ² on both the glossy surface 4 and the rough surface 20 side.

In the step 14A of depositing and depositing the fine copper particles 13 on the bulk copper layer 9, the above-described bulk copper forming tank 10 is formed.
The same type of copper sulfate solution as used in the above, with a concentration of 100 g
/ L sulfuric acid, 65 g / l copper, liquid temperature 25 ° C, and the current density on both the glossy side 4 side and the rough side 20 side of the carrier foil is 10 A /
Electrolysis was performed for 10 seconds under dm ² burn plating conditions. The arrangement of the anode electrode 11 is the same as that for depositing bulk copper.

In the cover plating step 14B for preventing the fine copper particles 13 from falling off, the same type of copper sulfate solution as used in the above-mentioned bulk copper forming tank 10 was used, and the concentration was 150 g / g.
1 sulfuric acid, 65 g / l copper, liquid temperature 45 ° C., and the current density on both the glossy side 4 side and the rough side 20 side of the carrier foil is 15 A
/ Dm ² for 20 seconds under a smooth plating condition.

In the rust prevention treatment tank 15, rust prevention treatment was performed using a zinc sulfate bath. Here, as a soluble anode 16 using a zinc plate as an anode electrode, a rust prevention treatment tank 15 was used.
It does not change in maintaining the zinc concentration balance in the interior. The electrolysis conditions here were as follows: concentration 70 g / l, 20 g / l
1 zinc, liquid temperature 40 ° C., current density 0.3 A / dm ² . The traveling speed of the carrier foil 3 in the above steps is 2.0
m / min.

[0141] The electrolytic copper foil 1 with a carrier foil was
A double-sided copper-clad laminate was manufactured using two m-thick FR-4 prepregs, and the peeling strength of the bonding interface between the carrier foil layer 3 and the electrolytic copper foil layer 5 was measured. As a result, the thickness of the bonding interface layer 8 was 10 nm on average, and the peel strength at the interface between the carrier foil 3 and the electrolytic copper foil 5 was 4 gf / cm on the glossy side 4 before heating and 4 gf on the rough side 20 before heating. / C
m, and 5 gf on the glossy side 4 side after heating in the same manner as described above.
/ Cm, and 6 gf / cm on the rough surface 20 side.

Further, the present inventors changed the CBTA used in the fourth embodiment and used the above-mentioned organic agents such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and mercaptobenzoic acid. Tables 4 and 5 show the peel strength of the bonding interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5 under the same conditions, and the measured values before and after heating. In addition, using the electrolytic copper foil with a carrier foil shown in this embodiment, a circuit width of 25 μm was used.
A printed circuit board having a fine circuit part having a gap of 25 μm and a gap of 25 μm was manufactured. However, the printed circuit board was finished as a very good printed circuit board, and there were no problems in various characteristics as the printed circuit board.

[0143]

[Table 4]

[0144]

[Table 5]

Fifth Embodiment: In the present embodiment,
It is an electrolytic copper foil 1 with a carrier foil according to claim 9, wherein FIG.
A description will be given of what is shown in FIG. The manufacturing apparatus 2 used here is the one shown in FIG. 18, in which the unwound carrier foil 3 travels in a meandering manner in the step of forming the electrolytic copper foil layer. Here, an electrolytic copper foil layer 5 was formed on the glossy surface 4 side using a surface-treated foil classified as grade 3 having a thickness of 18 μm as the carrier foil 3.

The manufacturing conditions in this case are basically the same as those in the first embodiment. Therefore, since the description is duplicated, detailed description of the manufacturing conditions is omitted.

The electrolytic copper foil 1 with a carrier foil and 150 μm
As shown in FIG. 6, a double-sided copper-clad laminate was manufactured by lay-up and press molding using an FR-4 prepreg having a thickness of m. Then, in order to measure the peeling strength of the bonding interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5, a copper-clad laminate for measuring the peeling strength was manufactured and analyzed. As a result, the thickness of the bonding interface layer 8 was measured. The average was 11 nm, and the peeling strength at the bonding interface 8 between the carrier foil 3 and the electrolytic copper foil 5 was 5 gf / cm before heating and 5 gf / cm after heating as described above.

Further, the present inventors changed the CBTA used in the fifth embodiment, and used the above-mentioned organic agents such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and mercaptobenzoic acid. Table 6 shows the peel strength of the bonding interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5 under the same conditions, and the measured values before and after heating. The printed wiring board having a fine circuit portion with a circuit width of 25 μm and a gap of 25 μm was manufactured using the electrolytic copper foil with a carrier foil shown in this embodiment, but was finished as a very good printed wiring board. There were no problems in various characteristics as a printed wiring board.

[0149]

[Table 6]

Using the carrier-coated electrolytic copper foil obtained in the above embodiment and measuring the peel strength at the bonding interface between the carrier foil and the electrolytic copper foil, the conventional peelable type carrier is considered. It was confirmed that it was extremely small and stable compared to the electrolytic copper foil with foil. Therefore, as described above, it is possible to adopt a method of using an electrolytic copper foil with a carrier foil, which has not existed before. In addition, the present inventors investigated products of 30 lots or more for each product described in the embodiment, but before and after heating and after heating, the peeling strength at the joining interface between the carrier foil and the electrolytic copper foil was At a level of 50 gf / cm or less, there was no significant change, and there was no phenomenon that the film could not be peeled off.

[0151]

The electrolytic copper foil with a carrier foil according to the present invention comprises:
Since the peeling at the interface between the carrier foil layer and the electrolytic copper foil layer can be easily performed with a very small force, the carrier foil at the interface was not possible with the conventional peelable type electrolytic copper foil with a carrier foil. Peeling stability at the time of peeling can be maintained. By obtaining such characteristics, it is possible to manufacture the above-described copper-clad laminate for the first time, and it is possible to greatly improve the production yield.
Therefore, the electrolytic copper foil with a carrier foil according to the present invention is likely to change the conventional method of manufacturing a copper-clad laminate and a method of manufacturing a printed wiring board from the ground up, and has no influence on the development of industry. It is considered very large.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an electrolytic copper foil with a carrier foil.

FIG. 2 is a schematic diagram illustrating a method for preparing a TEM observation sample.

FIG. 3 is a bonding interface layer obtained by TEM observation.

FIG. 4 is a schematic cross-sectional view of an electrolytic copper foil with a carrier foil.

FIG. 5 is a schematic diagram showing a lay-up configuration during press molding.

FIG. 6 is a schematic diagram showing a lay-up configuration during press molding.

FIG. 7 is a schematic cross-sectional view of a normal electrolytic copper foil.

FIG. 8 is a schematic sectional view of an electrolytic copper foil with a carrier foil.

FIG. 9 is a schematic cross-sectional view of an electrolytic copper foil with a carrier foil.

FIG. 10 is a schematic cross-sectional view of an electrolytic copper foil with a carrier foil.

FIG. 11 is a schematic diagram showing a lay-up configuration during press molding.

FIG. 12 is a schematic diagram showing a lay-up configuration during press molding.

FIG. 13 is a schematic cross-sectional view of an electrolytic copper foil with a carrier foil.

FIG. 14 is a schematic view showing a copper foil circuit after etching.

FIG. 15 is a schematic cross-sectional view of an electrolytic copper foil with a carrier foil.

FIG. 16 is a schematic cross section of an apparatus for manufacturing an electrolytic copper foil with a carrier foil.

FIG. 17 is a schematic cross-sectional view of an apparatus for manufacturing an electrolytic copper foil with a carrier foil.

FIG. 18 is a schematic cross-sectional view of an apparatus for manufacturing an electrolytic copper foil with a carrier foil.

FIG. 19 is a schematic cross-sectional view of an apparatus for manufacturing an electrolytic copper foil with a carrier foil.

FIG. 20 is a schematic cross-sectional view of an apparatus for manufacturing an electrolytic copper foil with a carrier foil.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrolytic copper foil with a carrier foil 2, 2 'Manufacturing apparatus of electrolytic copper foil with a carrier foil 3 Carrier foil (carrier foil layer) 4 Glossy surface 5 Electrolytic copper foil (electrolytic copper foil layer) 6 Pickling treatment tank 7 Joining interface formation Tank 8 Joining interface (joining interface layer) 9 Bulk copper (bulk copper layer) 10 Bulk copper forming tank 11, 11 'Anode electrode 12 Tension roll 13 Fine copper particles 14 Surface treatment tank 15 Rust prevention treatment tank 16, 16' Zinc Soluble anode 17 Drying section 18 Rinse tank 19 Drive roll 20 Rough surface

Continued on the front page (72) Kenichiro Iwakiri, 1419-1 Fujimi Ryo, Hara-shi, Ageo-shi, Saitama (72) Inventor Tsutomu Higuchi 1419-1, Hara-shi, Ageo-shi, Saitama Fujimi-doryo (72) Inventor, Akiko Sugioka, Suzuya, Yono, Saitama 4-9-24 Yono Park Square 212 (72) Inventor Atsushi Yoshioka 3-1-48 Kashiwaza, Ageo-shi, Saitama 2-814 Park Ageo 2-72 (72) Inventor Shinichi Kobata 862 Hanuki Inamachi, Kita-Adachi-gun, Saitama Apartment No. 206 (72) Inventor Sakiko Asanaga 2-35-2 Kitabukurocho, Omiya City, Saitama Prefecture Kitabukuro Minami Mansion No. 302 (72) Inventor Makoto Dobashi 3233-91 Hara-shi, Ageo-shi, Saitama F-term (reference) 4E351 AA01 AA06 BB01 BB33 CC05 DD04 GG11 4K024 AA05 AA09 AB01 AB02 AB03 AB06 AB09 AB19 BA09 BB11 BC02 CB13 DA03 DA10 EA02 EA03 EA06 GA16

Claims (13)

[Claims] 1. An electrolytic copper foil with a carrier foil, wherein a bonding interface layer is formed on one surface of a carrier foil, and an electrolytic copper foil layer is formed on the bonding interface layer by deposition. An electrolytic copper foil with a carrier foil, wherein the electrolytic copper foil is formed by using: 2. An electrolytic copper foil with a carrier foil, wherein a bonding interface layer is formed on both surfaces of a carrier foil using an organic agent, and an electrolytic copper foil layer is deposited and formed on each bonding interface layer. 3. A bonding interface layer is formed on one surface of a carrier foil using an organic agent, and only fine copper particles are deposited and deposited as an electrolytic copper foil layer on the bonding interface layer. Electrolytic copper foil with carrier foil. 4. A bonding interface layer is formed on both surfaces of a carrier foil using an organic agent, and only fine copper particles are deposited and adhered as an electrolytic copper foil layer on each bonding interface layer. Electrolytic copper foil with carrier foil. 5. The organic agent used for the bonding interface layer comprises one or more selected from a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid. An electrolytic copper foil with a carrier foil according to claim 4. 6. The bonding interface layer is formed by repeatedly applying a combination of the same or different organic agents selected from the organic agents according to claim 5. An electrolytic copper foil with a carrier foil according to claim 5. 7. The electrolytic copper foil with a carrier foil according to claim 1, wherein the bonding interface layer is made of an organic agent having a thickness of 1 nm to 1 μm. 8. The electrolytic copper foil with a carrier foil according to claim 1, wherein the carrier foil is an electrolytic copper foil of 12 μm to 210 μm. 9. A method in which a bonding interface layer made of an organic agent is formed on a glossy surface of an electrolytic copper foil as a carrier foil, and an electrolytic copper foil layer is deposited and formed on the bonding interface layer. 9. The electrolytic copper foil with a carrier foil according to 8. 10. On a roughened surface of an electrolytic copper foil as a carrier foil,
The electrolytic copper foil with a carrier foil according to claim 8, wherein a bonding interface layer made of an organic agent is formed, and an electrolytic copper foil layer is deposited and formed on the bonding interface layer. 11. An electrolytic copper foil as a carrier foil, wherein a bonding interface layer made of an organic agent is formed on a glossy surface and a rough surface of the electrolytic copper foil, and an electrolytic copper foil layer is deposited and formed on each of the bonding interface layers. The electrolytic copper foil with a carrier foil according to claim 8, which is: 12. The method for producing an electrolytic copper foil with a carrier foil according to claim 1, wherein the carrier foil wound up in a roll is wound from one direction, and the carrier foil is appropriately wound. As a process of forming an electrolytic copper foil layer provided with a water washing treatment tank, a pickling treatment tank arranged continuously, a joining interface forming tank using an organic agent, a forming tank of a bulk copper layer to be an electrolytic copper foil layer, a surface of the bulk copper layer Continuously forms a bonding interface layer and an electrolytic copper foil layer with an organic agent on the carrier foil by passing through each of a roughening treatment tank, rust prevention treatment tank, and a drying treatment part that forms fine copper particles formed on the carrier foil A method for producing an electrolytic copper foil with a carrier foil. 13. A copper-clad laminate or printed wiring board obtained by using the electrolytic copper foil with a carrier foil according to claim 1.