JP3466506B2 - Electrolytic copper foil with carrier foil, method for producing the electrolytic copper foil, and copper-clad laminate using the electrolytic copper foil - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 widely used as a basic material for manufacturing a printed wiring board widely used in the fields of electric and electronic industries. Generally, an electrolytic copper foil is laminated with a glass-epoxy base material, a phenol base material, a polymer insulating base material 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 on the B stage, and an end plate serving as a spacer are laminated in multiple stages, and a high pressure is applied in a high temperature atmosphere to form the copper foil and the prepreg. By thermocompression bonding (hereinafter, this step may be referred to as "press molding") to obtain a copper clad laminate. If wrinkles are present in the copper foil at this time, cracks will occur in the copper foil at the wrinkles, causing the resin to seep out from the prepreg and cause a disconnection of the formed circuit in the printed wiring board manufacturing process which is a later etching process. Sometimes.

The generation of wrinkles on the copper foil becomes a serious problem as the copper foil becomes thinner. The electrolytic copper foil with carrier foil has been attracting attention as an epoch-making copper foil which can solve such problems and prevent foreign matter from being mixed into the glossy surface of the copper foil during hot forming press. 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 press-molding with the carrier foil attached, just before forming a copper circuit by etching, the carrier foil Can be removed. This prevents wrinkles during handling and pressing of electrolytic copper foil,
It is possible to prevent surface contamination as a copper clad laminate.

In the present specification, the name "carrier foil" is used, but this carrier foil is used as if it were laminated in a plane with the electrolytic copper foil. The "carrier foil" in this specification has the following properties. Considering the method for producing an electrolytic copper foil with a carrier foil according to the present invention, since a copper component to be an electrolytic copper foil is electrodeposited on the surface of the carrier foil, at least the surface of the carrier foil needs to have conductivity. Becomes Then, this electrolytic copper foil with carrier foil flows through a continuous manufacturing process, at least until the end of the production of the copper-clad laminate, maintains a state of being bonded to the electrolytic copper foil layer, facilitating handling, and electrolytic copper foil. Since it has a role to reinforce and protect in any sense, the carrier foil needs to have a predetermined strength. If it satisfies these requirements, it can be used as a "carrier foil", and a metal foil is generally assumed, but the invention is not limited thereto.

[0006] Generally, electrolytic copper foil with carrier foil can be roughly classified into peelable type and etchable type. In a nutshell, the peelable type is a type that peels and removes the carrier foil after press molding, and the etchable type is a type that removes the carrier foil by an etching method after press molding. Is.

[0007]

However, in the conventional peelable type, the peel strength of the carrier foil after press molding is extremely unstable, and it is generally 50.
A range of up to 300 gf / cm has been regarded as a good range.
On the other hand, in an extreme case, the carrier foil may not be peeled off, and the desired peeling strength is difficult to obtain. This drawback has been the biggest obstacle when the electrolytic copper foil with carrier foil is widely used in general applications.

The cause of the unstable peeling strength of the carrier foil is considered as follows. The conventional electrolytic copper foil with carrier foil, regardless of whether it is a peelable type or an etchable type, has a metal-based bonding interface layer typified by zinc formed between the carrier foil and the electrolytic copper foil. is there. The peelable type and the etchable type are made differently by controlling the amount of metal present in the bonding interface layer, although there is a slight difference depending on the type of carrier foil.

The metal-based bonding interface layer is formed mainly by electrolysis of a solution containing a predetermined metal element and electrodeposition, and an electrochemical method has been adopted. However, the electrochemical method is difficult to control a very small amount of deposition, and is inferior in reproducibility to other technical methods. In addition, the boundary of the required precipitation amount of peelable type or etchable type is only a slight difference in the amount of metal present in the bonding interface layer, so it is difficult to derive stable performance. it is conceivable that. Further, the carrier foil is generally peeled off at a temperature of 180 ° C. or higher under a high pressure, and after the completion of pressing for 1 to 3 hours, the bonding interface layer causes mutual diffusion with the carrier foil or the electrolytic copper foil. It is possible to cause it. This rather acts in the direction of increasing the bonding strength, and is considered to be one of the reasons for the unstable peeling strength.

In recent years, the demand for downsizing of electronic and electric devices has not stopped, and the multilayered printed wiring board which is the basic component, the high density of the copper foil circuit, and the high density mounting of the mounted components are required. There is a growing demand for it. In such a case, the amount of heat radiated from the mounted components is increased, so that the printed wiring board as a built-in component is also required to have high heat resistance. Heat-resistant substrates have come to be used. The pressing temperature of the copper clad laminate, which is the material of the printed wiring board as a whole, tends to increase. Considering the above, it is expected that use of the conventional peelable type electrolytic copper foil with carrier foil will become more and more difficult.

On the other hand, in the etchable type,
Dedicated 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 total manufacturing cost, and has a drawback that it cannot be easily used in a very wide range of applications.

[0012]

Therefore, as a result of intensive research, the inventors of the present invention have decided to eliminate the drawbacks of the conventional peelable type electrolytic copper foil with carrier foil.
It can be used in the same way as when using a so-called normal electrolytic copper foil, and as a new technical idea, it can stabilize the peel strength of the interface between the carrier foil and the electrolytic copper foil at a low level. We have developed an electrolytic copper foil with a carrier foil based on it. The present invention will be described below.

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

The electrolytic copper foil with carrier foil according to the present invention is
As shown in the schematic cross-sectional view of FIG. 1, the carrier foil and the electrolytic copper foil are as if they were bonded together.
Electrolytic copper foil layer on the bonding interface layer formed on one side of
It is formed by precipitation . 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 respectively indicate the same part, and are appropriately used according to the contents of the description.

The electrolytic copper foil with 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, the peeling of the carrier foil as a peelable type is stable and easy with a very small force even after high-temperature press molding for producing a copper-clad laminate. It will be something that can be done.

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 producing a copper-clad laminate can be easily peeled by a human hand. It is possible to control the level. Moreover, it completely eliminates defects such as the state where peeling cannot be performed and the fragment of the carrier foil remaining on the copper foil surface after peeling, which is observed when a metal-based material is used for the conventional bonding interface layer. It becomes possible.

When an organic agent is used to form the bonding interface layer,
There is little possibility of mutual diffusion between carrier foil and electrolytic copper foil during press molding at high temperature, and it does not increase the bonding strength by heating, but rather functions as a barrier layer for mutual diffusion between carrier foil and electrolytic copper foil. It is possible to maintain the bonding strength between the carrier foil and the electrolytic copper foil at the time of manufacturing the electrolytic copper foil with the carrier foil at a substantially constant value until after the press molding.

As an example, in the case where a 35 μm carrier foil is formed with a bonding interface layer using an organic agent and a 9 μm electrolytic copper foil layer is formed, its peeling strength is examined. As a result, the best example is 3 gf / cm before heating and 3 gf / cm after heating at 180 ° C. for 1 hour, which is not changed at all.

As the organic agent used herein, it is preferable to use one or two or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids.

Among nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids, the nitrogen-containing organic compounds include nitrogen-containing organic compounds having a substituent. Specifically, the nitrogen-containing organic compound is a triazole compound having a substituent, 1,2,3-benzotriazole (hereinafter, referred to as "BTA"), 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 referred to as "AT").
A ". ) And the like are 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"). )
And the like are preferably used.

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

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

Further, the formation of the bonding interface layer with the organic agent can be carried out by appropriately combining the above-mentioned organic agents, and the above-mentioned forming method 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 metal carrier foil, the organic agent is adsorbed to a metal oxide layer which is a metal oxide film formed on the surface layer of the carrier foil. It is presumed that, from the state of being adsorbed on the metal oxide layer, the organic agent that binds to the bond such as oxygen existing in the surface layer and forms the bonding interface layer is stabilized. Therefore, it can be said that the higher the concentration of the organic agent is, the faster the speed at which the organic agent is adsorbed on the surface of the carrier foil, 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 the contact time is practically 5 to 60 seconds.

As a result of taking these matters into consideration, when the concentration is lower than the lower limit value of 0.01 g / l, the adsorption to the carrier foil surface in a short time is difficult,
Moreover, the thickness of the formed bonding interface layer varies,
Stabilization of product quality becomes impossible. On the other hand, even if the concentration exceeds the upper limit value of 10 g / l, the adsorption rate of the organic agent on the surface of the carrier foil does not increase with the addition amount, and it can be said that it is preferable from the viewpoint of production cost. Because there is no.

By using the above-mentioned organic agent,
It becomes possible to facilitate quantitative control when forming the bonding interface layer and keep the bonding strength between the carrier foil and the electrolytic copper foil within a certain range. Moreover, it is excellent in thermal stability, and it is possible to secure the stability of peeling strength after pressing.

When the carrier foil and the electrolytic copper foil are peeled off, the organic agent also transfers to the surface layer of the electrolytic copper foil as an organic film, and therefore also functions as a rust preventive layer for the electrolytic copper foil. It will be fulfilled. The organic coating can be easily removed by pickling with a solution of dilute sulfuric acid, dilute hydrochloric acid or the like, and does not adversely affect the manufacturing process of the printed wiring board.

More importantly, the organic agents described here are various resist coating and etching steps which are presently present as a manufacturing step of a printed wiring board after processing into a copper clad laminate. It has been confirmed that there is no adverse effect in various plating processes, surface mounting processes and the like.

In general, these organic agents are not electrically conductive materials but materials having an insulating property. Therefore, the electrolytic copper foil with a carrier foil according to claim 1 is one in which the carrier foil itself is polarized as a cathode, and copper is directly electrolytically deposited on a bonding interface layer formed of an organic agent on the carrier foil. Therefore, it is necessary to make it possible 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 enable stable electrolytic deposition of copper.

Therefore, it is not important that the concentration of the organic agent used in the solvent and the treatment time for forming the bonding interface layer are important, but the thickness of the bonding interface layer formed as a result, in other words, The amount of organic agent present at the bonding interface is important. Therefore, in claim 7,
The thickness of the bonding interface layer using an organic agent is preferably 1 n
It is clarified that it is in the range of m to 1 μm.

Within the thickness range specified here, proper peel strength can be ensured and stable electrolytic deposition of copper is possible. That is, when the amount (thickness) of the organic agent used for the bonding interface layer is less than the lower limit value 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 proper peeling strength after press molding cannot be obtained, and in some cases, the carrier foil cannot be peeled off.

When the upper limit value 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. Moreover, even if copper is deposited over a long period of time, the minimum required peeling strength at which press molding can be safely completed will not be satisfied. Then, when the thickness of the bonding interface layer is further increased, it becomes a state in which current cannot be supplied completely.

The thickness of the bonding interface layer is in the nm-μm level,
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 piece sample cut along AA ′ shown in FIG. Then, argon ions are simultaneously irradiated from the directions of arrows B and B ′ shown in FIG.
M Sputtering was performed until the thickness became observable.
As a result, it is possible to directly observe the junction interface layer sandwiched between the electrolytic copper foil layer and the carrier foil layer at the site C.

Then, the TEM image of the region C where the TEM can be observed is observed by using a TEM, the observed image is photographed, and the thickness of the bonding interface layer is measured as an actual measurement value from the photograph. did. An observation photograph at this time is shown in FIG. FIG. 3 shows a joint interface layer having a thickness of about 7 to 25 nm. By such a method, it was judged that it is practical for the electrolytic copper foil with a carrier foil having an appropriate peeling strength that the thickness of the bonding interface layer is 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 in consideration of the actual use of the conventional peelable type electrolytic copper foil with carrier foil, the peel strength (peeling strength) at the interface between the carrier foil and the electrolytic copper foil, which is considered to be appropriate obtained from experience, This range is in consideration of the ideal value required by the user of the electrolytic copper foil with carrier foil.
The lower the peel strength at the interface between the carrier foil and the electrolytic copper foil, the easier the peeling work. However, if the peeling strength is less than 1 gf / cm, the carrier foil and the electrolytic copper foil are naturally partially separated from each other when the electrolytic copper foil with a carrier foil is wound at the time of manufacturing or when the copper clad laminate is manufactured. It may peel off and cause defects such as blistering and displacement. On the other hand, when the peeling strength exceeds 300 gf / cm, it is not the characteristic of the patented invention that the carrier foil can be easily peeled off.
Therefore, a method such as using a special peeling device is required.

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

The chemical quantitative analysis method is a method in which an organic agent existing at the bonding interface is dissolved in a predetermined solvent selected according to the type of the organic agent, and the solvent is quantitatively analyzed using liquid chromatography. 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 method is 1 to 100 m.
It was in the range of g / m ² .

The surface resistance measurement method is intended to be measured using the Hiresta manufactured by Dia Instruments, teff
The surface resistance of the electrolytic copper foil with a carrier foil, which was cut into a predetermined size on a Ron (registered trademark) plate, was placed face down and a voltage of 10 V was applied to measure the surface resistance.
When this method is used, the measured value varies depending on the type of carrier foil, but in the case of an electrolytic copper foil with a carrier foil in which an electrolytic copper foil of 18 μm thickness is used as a carrier foil and an electrolytic copper foil layer of 9 μm is formed, the surface resistance is The resistance value measured by the method is 10
It can be said that those having a value of 5Ω order or less are appropriate.

The polarization potential was measured by using an Ag / AgCl electrode as a reference electrode under the 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. When it is 100 mV or more, it means that the bonding interface layer is formed using a proper organic agent.

The material of the carrier foil used in the electrolytic copper foil with carrier foil according to the present invention is not particularly limited. As a carrier foil, it is used as a concept including aluminum foil, copper foil, resin foil whose surface is metal-coated, and the like which can be used as a carrier. The thickness of the carrier foil is also not particularly limited. From an industrial viewpoint, the concept of a foil is generally called a foil having a thickness of 200 μm or less, and it is sufficient to use this concept.

Then, as if pasted on the carrier foil
The deposited electrolytic copper foil is 12μ
Not only electrolytic copper foil called ultra-thin copper foil of m or less, 12
This includes cases where the thickness is thicker than μm. The conventional electrolytic copper foil with carrier foil is used exclusively for the purpose of providing an ultrathin copper foil, and the electrolytic copper foil with carrier foil according to the present invention having an electrolytic copper foil layer of 12 μm or more is commercially available. Was not supplied to. In the background that could be such an electrolytic copper foil with a carrier foil, by using an organic agent in the bonding interface layer, the carrier foil and the electrolytic copper foil can be stably and easily peeled off. This is because a new method of using the electrolytic copper foil with a carrier foil to be described becomes possible.

[0043] Here, although previously described in confirmatory, apart from the case of special applications, use a copper-clad laminate and printed wiring board applications, put on an electrolytic copper foil with carrier foil of the present invention
The fine copper particles are uniformly attached to the outer surface of the copper foil layer. This is a fine copper particle similar to that formed on the surface of the electrolytic copper foil to be bonded, when bonding a general electrolytic copper foil and a resin substrate, to obtain an anchor effect for the bonded substrate, This is to prevent the electrolytic copper foil from easily peeling from the base material.

Further , an electrolytic copper foil with a carrier foil according to the present invention
As another form of the , on both sides of the carrier foil, a bonding interface layer is formed using an organic agent, copper is electrolytically deposited on each bonding interface layer, and the deposited copper layer is used as an electrolytic copper foil. It is an electrolytic copper foil with a carrier foil used. Book mentioned above
The electrolytic copper foil with a carrier foil according to the invention, as in the state where the electrolytic copper foil is attached to one surface of the carrier foil, the carrier foil
Electrolytic copper foil layer is deposited on the bonding interface layer formed on one side of
In contrast to the formed carrier , as shown in the schematic sectional view of FIG. 4, another form of carrier of the present invention is used.
Electrolytic copper foil with foil, as in the state in which both sides of the carrier foil by bonding electrodeposited copper foil, on each of the bonding interface layer formed on both surfaces of the career foil, deposited forming an electrolytic copper foil layer It was done.

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

At this time, electrolytic copper foil layers were formed on both sides of the carrier foil.
When an electrolytic copper foil with a carrier foil including is used, as shown in FIG. 6, the lowermost layer and the uppermost layer in the laid-up state are
Electrolytic copper foil layer on one side of normal electrolytic copper foil or carrier foil
Using an electrolytic copper foil with carrier foil with a, and electrolytic those located in the middle layer the other, on both sides of the carrier foil
By using a double-sided electrolytic copper foil with a carrier foil having a copper foil layer, it is possible to omit all the end plates located in the intermediate layer portion, and peel off from the carrier foil at the time of disassembly after press molding.

The fact that the mirror plate of the intermediate layer is unnecessary means that
It is possible to increase the number of steps of the copper foil and the prepreg that are housed between the daylights of the press plate by the thickness corresponding to the omitted end plate, and increase the number of copper-clad laminates manufactured by one press. You can Also, the heat transfer is improved,
It is possible to improve productivity. The thickness of the end 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 predicted that the productivity will be extremely large.

Further , electrolytic copper with carrier foil according to the present invention
As another form of the foil, with a carrier foil, 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. There is electrolytic copper foil . In addition, as an electrolytic copper foil layer of fine copper particles
For electrolytic copper foil with carrier foil, which only has a joint foil, a bonding interface layer is formed on both sides of the carrier foil using an organic agent, and fine copper particles are electrolytically deposited on each bonding interface layer, and the deposition is performed. There is an electrolytic copper foil with a carrier foil that uses a fine copper grain layer as an electrolytic copper foil .

When an ordinary electrolytic copper foil is observed from the cross section, as shown in FIG. 7, in general, a fine surface treatment layer for ensuring adhesion stability between the bulk copper layer and the insulating substrate for ensuring conductivity is provided. It is composed of copper grains and a rust preventive layer. With carrier foil with only fine copper grains as this electrolytic copper foil layer
Electrolytic copper foil is different from electrolytic copper foil layer, which is a bulk copper layer ,
As shown in FIGS. 8 and 9, it means an electrolytic copper foil with a carrier foil in which only fine copper particles are formed on a bonding interface layer made of an organic agent. Electrolysis with carrier foil shown in FIGS. 8 and 9.
The copper foil can be used in the same manner as the electrolytic copper foil with carrier foil shown in FIG. 1 or FIG. 4, 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 manufacturer removes the carrier and forms a bulk copper layer to be a conductor with a predetermined thickness by a timing according to the purpose and an arbitrary copper plating method. It is possible. 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. Can be formed by the method. According to this method, the thickness of the bulk copper layer can be arbitrarily adjusted according to the type of circuit to be formed, and an appropriate etching process according to the target circuit width can be performed. Therefore, such a printed wiring board manufacturing method is more effective as the size of the circuit to be formed becomes finer, and it is easy to increase the density of the circuit of the printed wiring board.

Next, a book using electrolytic copper foil as the carrier foil
The electrolytic copper foil with a carrier foil of the invention will be described. In order to make this description easier to understand, a brief explanation will be given here on the ordinary electrolytic copper foil used as the carrier foil.

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

Electrolytic copper foil, more precisely the bulk of electrolytic copper foil
The copper layer manufacturing apparatus is configured such that a copper sulfate solution is flown between a drum-shaped rotating cathode and a lead-based anode that is arranged to face the rotating cathode, and copper is rotated using the electrolytic reaction. The copper is deposited on the surface of the drum, and the deposited copper becomes a foil, which is continuously peeled off from the rotating cathode and wound up. The copper foil at this stage is hereinafter referred to as "separation foil". At this stage of the deposited foil, no surface treatment such as rust prevention is performed, and the copper immediately after electrodeposition is in an activated state and is in a state where it is easily oxidized by oxygen in the air. is there.

The surface of the separating foil peeled off from the state of contact with the rotating cathode is a mirror-finished surface of the rotating cathode, and is called a glossy surface because it is glossy and smooth. . On the other hand, the surface shape of the separation foil on the deposition side shows a mountain-shaped uneven shape because the crystal growth rate of the deposited copper is different for each crystal surface, and this is called a rough surface. This rough surface serves as a bonding surface with the insulating material when the copper clad laminate is manufactured. In the above and below, the term "rough surface" is used in the description when using the separation foil.

Next, the separated foil is subjected to surface roughening treatment and rustproofing treatment in the surface treatment step. Roughening treatment to a rough surface is performed by applying an electric current under the so-called burn plating condition in a copper sulfate solution to deposit and deposit fine copper particles on the uneven surface of the rough surface, and then immediately cover it in the current range under the smooth plating condition. By plating, it prevents the fine copper particles from falling off. Therefore, a rough surface on which fine copper particles are deposited and attached is referred to as a "roughening 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, the front and back of the copper foil are subjected to rust prevention treatment by plating with zinc, zinc alloy, chromium or the like, dried, and rolled up to form an electrolytic copper foil as a product. It is completed. This is generally referred to as "surface treated foil". In the present invention, the electrolytic copper foil as the carrier foil to be used is mainly used in the state of the above-mentioned deposition foil, but may be used in the state of surface-treated foil. Below, carrier foil using electrolytic copper foil for the carrier foil
The attached electrolytic copper foil will be specifically described.

In the drawings, some schematic cross-sectional views of an electrolytic copper foil with a carrier foil and a normal electrolytic copper foil are shown. However, in these schematic drawings, the description of the rustproofing layer is omitted. ing. Usually, the anticorrosion treatment layer is present in the outermost layer of the electrolytic copper foil after the surface treatment, since it prevents the copper foil from contacting air and oxidizing. That is, in the case of the electrolytic copper foil with a carrier foil, the rust-preventive treatment layer is present at least on the outermost surface of the roughening-treated surface of the electrolytic copper foil layer.

Odor of electrolytic copper foil with carrier foil according to the present invention
Then, as the carrier foil, 12 μm to 210 μm
It is preferable to use a copper foil . This is because by using an electrolytic copper foil as the carrier foil, various advantageous effects which are not present in the conventional electrolytic copper foil with a carrier foil can be obtained.

The following may be considered as advantageous effects of using an electrolytic copper foil as the carrier foil. When using a foil obtained by the rolling method as a carrier foil, as represented by rolled aluminum, it is unavoidable that rolling oil adheres to the foil, and oil components are taken into consideration in consideration of oxidation. May be applied. When these are used as a carrier foil, it becomes a hindrance when copper is deposited on the carrier, so that it is necessary to remove oil in the process. If it is an electro-deposited copper foil, its manufacturing method does not inevitably cause oil to adhere, and even if an oxide film is formed, it can be easily pickled and removed, reducing the number of steps or The process control can be facilitated.

When an electrolytic copper foil is used as the carrier foil,
The carrier foil and the electrolytic copper foil bonded to the carrier foil can be considered to be the same in terms of physical properties and components, and both etching treatments can be performed with the same type of etching solution. Therefore, it is also possible to peel off the carrier foil after processing it into a copper clad laminate, forming an etching resist layer on the carrier foil without peeling off the carrier foil, and etching the printed wiring circuit to create a printed wiring circuit. Become. By doing this, the surface of the copper foil circuit is protected from contamination and adhesion of foreign matter until the etching process is completed.
It is possible to significantly improve the work reliability of the plating process and the like performed thereafter.

The electrolytic copper foil used as the carrier foil has a purity of 99.99% or more. Further, the electrolytic copper foil with a carrier foil according to the present invention does not contain other metal element as an impurity in the bonding interface layer. Therefore, the carrier foil after being peeled off can be easily recycled and does not unnecessarily generate industrial waste from the viewpoint of environmental protection. For example, the carrier foil can be recovered and redissolved into a copper ingot, or 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 thickness of the electrolytic copper foil used as the carrier foil is set to 12 μm to 210 μm because it serves as a reinforcing material for preventing the generation of wrinkles in the ultrathin copper foil having a thickness of 9 μm or less as the carrier foil. Requires a minimum thickness of about 12 μm, and when the upper limit of the thickness is 210 μm or more, it exceeds the concept of foil and is rather close to a copper plate, and it is difficult to wind it into a rolled state. is there.

When an electrolytic copper foil is used as the carrier foil
The electrolytic copper foil with a carrier foil according to the present invention forms a bonding interface layer made of an organic agent on a glossy surface of an electrolytic copper foil which is a carrier foil, and deposits an electrolytic copper foil layer on the bonding interface layer. The electrolytic copper foil with carrier foil is shown. This electrolytic copper foil with 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 is a form in which the glossy surfaces of the ordinary electrolytic copper foil face each other,
It has a structure in which two electrolytic copper foils are bonded together with a joint interface layer sandwiched therebetween. However, fine copper as an electrolytic copper foil layer
The electrolytic copper foil layer in the electrolytic copper foil with a carrier foil provided with only grains is a concept including both the case where it is composed of a normal bulk copper layer and a fine copper grain layer, and the one constituted only by the fine copper grain layer. Used as.

The electrolytic copper foil used as the carrier foil at this time may be either a deposition foil or a surface-treated foil. This is because there is no difference in the roughness of the glossy surface between the deposition foil and the surface-treated foil. FIG. 10 (a) shows a schematic sectional view of the case where the separation foil is used as the carrier foil, and FIG. 10 (b) is a schematic 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, the use method at the time of producing a copper-clad laminate obtained using each of them is completely different depending on whether the carrier foil is a separation foil or a surface-treated foil. is there.

Here will be described the usage methods that can be used in the production of copper-clad laminates of electrolytic copper foils with carrier foils, in the case of using the separation foil as the carrier foil and the case of using the surface-treated foil. First, as a method for manufacturing the first copper-clad laminate, a case where a separation foil is used as the carrier foil 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 you can see from this figure, the surface that can be bonded to the prepreg is
As the surface roughening treatment, this is the surface of the electrolytic copper foil layer to which fine copper particles are attached.

Therefore, the electrolytic copper foil with the carrier foil and the prepreg (when the outer copper foil layer of the multilayer board is formed are laid up as shown in FIG. 5 and are processed in the same process as when the ordinary copper foil is used. Can be press-molded using a prepreg and an inner layer substrate) and a mirror plate to obtain a copper clad laminate. Further, by using the electrolytic copper foil with a carrier foil, press molding without the inner layer end plate is possible. That is, as shown in FIG. 11, the mirror plate is arranged only in the outermost layer that is in direct contact with the press plate, and the electrolytic copper foil with carrier foil and the prepreg are laminated between the two mirror plates to lay up. Of.

One electrolytic copper foil with a carrier foil is arranged on the uppermost layer and the lowermost layer when laid up. Then, the copper foil located in the other inner layer when laid up is, as shown in the enlarged view of FIG. 11, the carrier foil surface and the carrier foil surface of the two electrolytic copper foils with carrier foil are back to back, The electrolytic copper foil layer is arranged so that the roughened surface is in contact with the prepreg. Then, at the time of disassembling work after the completion of press molding, the carrier foil is peeled off from the bonding interface layer, whereby the outer copper foil layer of the double-sided board or the multilayer board can be formed.

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 cross-sectional shape shown in 0 (b). As can be seen from this figure, the surface that can be bonded to the prepreg is the surface that has been subjected to the roughening treatment and the fine copper particles have been adhered, so that it exists on the carrier foil side as well as the electrolytic copper foil side. Will be done.

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

The electrolytic copper foil with carrier foil, the prepreg (the prepreg and the inner layer substrate when the outer layer copper foil layer of the multilayer substrate is formed) and the end plate are press-molded to obtain a copper clad laminate. By using an electrolytic copper foil with a carrier foil, press molding can be performed without the inner layer end plate. That is, as shown in FIG. 12, the mirror plate is arranged only in the outermost layer that is in direct contact with the press plate, and the electrolytic copper foil with carrier foil and the prepreg are laid up between the two mirror plates.

As the uppermost layer and the lowermost layer when laid up, one sheet of electrolytic copper foil with carrier foil or normal copper foil is arranged. Then, for the copper foils positioned in the other inner layers when laid up, as shown in the enlarged view of FIG. 12, prepregs are arranged on both sides of the electrolytic copper foil with carrier foil. In this way, by press-molding, it becomes possible to mold without using an end plate. Then, at the time of dismantling work after the completion of press molding, the outer layer copper foil layer of the double-sided board or the multi-layer board can be formed by peeling it from the bonding interface layer of the electrolytic copper foil with carrier foil. This method also has the advantage that no scrap is generated.

The above-described method of using the electrolytic copper foil with carrier foil according to the present invention makes it possible to maintain the peel strength of the bonding interface layer of the electrolytic copper foil with carrier foil low and to stabilize it. This is the first press molding method that can be realized. Therefore, the useful effects brought about by the electrolytic copper foil with a carrier foil according to the present invention have a very large influence on the printed wiring board industry, and contribute greatly to the reduction of 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, which is the carrier foil, is extremely thin, a copper clad laminate to which the extremely thin copper foil is attached is formed. When using this to form a circuit having a pitch of about 50 μm, the etching time of the copper foil portion can be made extremely fast, and a fine circuit having an extremely good aspect ratio can be formed.

Then, an electrolytic copper foil was used as the carrier foil.
The electrolytic copper foil with a carrier foil of the present invention, on the rough surface of the electrolytic copper foil is a carrier foil, to form a bonding interface layer made of an organic agent, electrolytically depositing copper on the bonding interface layer, It is also possible to use the deposited copper layer as an electrolytic copper foil. The carrier foil used here uses the above-mentioned deposition foil, and there is little possibility of using the surface-treated foil as the carrier foil. This is because the rough surface of the surface-treated foil has fine copper particles attached thereto.

FIG. 13 shows an electrolytic copper foil which is a carrier foil .
A bonding interface layer made of an organic agent is formed on the rough surface,
The cross-sectional schematic diagram of the electrolytic copper foil with a carrier foil in which copper is electrolytically deposited on the bonding interface layer is shown. As can be seen from FIG. 13, the ultrathin electrolytic copper foil layer is formed along the uneven shape of the rough surface of the electrolytic copper foil which is 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 its wavy shape. This shape is very useful in forming a fine circuit. In addition, of the electrolytic copper foil which is the carrier foil
Form a bonding interface layer made of an organic agent on the rough surface, and
For use in producing a copper clad laminate of an electrolytic copper foil with a carrier foil in which copper is electrolytically deposited on the interfacial layer, see above.
Interface layer consisting of organic agent on glossy surface of electrolytic copper foil
Is formed and copper is electrolytically deposited on the bonding interface layer, and thus the duplicate description is omitted.

When the factors required for the electrolytic copper foil necessary for forming a fine circuit are roughly grasped, (1) ensuring good adhesion with an etching resist, (2) ensuring a good exposure state, (3) Fast etching time, (4) Other physical properties such as peeling strength (including chemical resistance) are considered. Most of the characteristics mentioned here are good, but among them, the electrolytic copper foil with a wavy shape is
It mainly contributes to ensuring good adhesion with an etching resist and ensuring a good exposure state.

By using an electrolytic copper foil having a wavy shape for a copper clad laminate, the adhesion between various resists and the electrolytic copper foil surface is improved. For example, if the adhesiveness with the etching resist is improved, it is possible to prevent the etching solution from entering the bonding interface between the copper foil and the etching resist, and it is possible to form a circuit cross section having a good aspect ratio. It becomes easy to form a fine circuit considering the above. In addition, by having a wavy surface shape, it has a gloss that is closer to matte than a normal flat glossy surface. As a result, it is possible to suppress excessive scattering of the exposure light at the time of exposure with respect to the etching resist of the etching pattern, and it is possible to reduce the influence of so-called exposure blur at the edge portion of the circuit pattern. .

Further, a copper clad laminate using an electro-deposited copper foil having a wavy shape was subjected to a plating treatment, and the result was obtained that the peel strength at the interface between the copper foil surface and the plating layer was improved. There is. Therefore, it can be said that the use of the carrier-coated electrolytic copper foil improves the adhesion of the plating layer. Moreover, the peeling strength between the electrolytic copper foil and the FR-4 substrate was also described above.
Form a bonding interface layer consisting of an organic agent on the glossy surface of electrolytic copper foil
And electrolytically depositing copper on the bonding interface layer of the present invention.
Compared with the electrolytic copper foil with carrier foil, it is improved by about 3 gf / cm.

As a result, 50
It is possible to prevent the deterioration of the aspect ratio of the circuit cross section, which occurs when a fine circuit having a μm pitch level is formed, and to form a circuit having an ideal aspect ratio. Moreover, since exposure blur of the etching resist is small, the linear stability of the edge portion of the forming circuit is improved, and the fine circuit can be easily formed.

The improvement of the linear stability of the edge portion of the forming circuit means that the upper edge portion and the lower edge portion of the circuit shown in FIG. 14 are excellent in linearity and that the component is mounted on the printed wiring board. This means that the edge portion of the entire formation circuit such as the edge shape of the circular circuit portion such as the land portion to be used is smooth. That is, the linear stability of the circuit is excellent, and the shape without rattling suppresses copper migration that may occur when it is used as a printed wiring board, and the circuit edge portion when a high frequency signal is used. It can be said that it is possible to eliminate the discharge phenomenon from the protruding portion of the.

Furthermore, a book using an electrolytic copper foil as the carrier foil
The electrolytic copper foil with a carrier foil of the present invention is a copper foil having the characteristics of the electrolytic copper foil with a carrier foil of the present invention shown in FIGS. 10 and 13, and has both glossy and rough surfaces of the electrolytic copper foil as a carrier foil. Forming a bonding interface layer made of an organic agent on the top,
It is possible to electrolytically deposit copper on each bonding interface layer and use each deposited copper layer as an electrolytic copper foil.

The electrolytic copper foil as the carrier foil used here is composed of an organic agent on the rough surface of the electrolytic copper foil which is the carrier foil.
A bonding interface layer made of copper, and copper is deposited on the bonding interface layer.
As in the case of the analyzed electrolytic copper foil with carrier foil of the present invention, it is necessary to form the electrolytic copper foil layer on the rough surface of the carrier foil, and therefore, the deposition 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 herein has an electrolytic copper foil as a carrier foil located inside and an electrolytic copper foil layer formed on both outer layer surfaces thereof. Is.

With such a structure, the carry
A. On both the glossy and rough surfaces of electrolytic copper foil, which is a foil,
A bonding interface layer made of a system agent is formed, and each bonding interface layer is formed.
Inventive carrier foil of the invention with copper electrolytically deposited on the layer
The electrolytic copper foil with a coating is one of those described above as the method for producing the copper clad laminate of the electrolytic copper foil with a carrier foil shown in FIG.
Press molding is performed as shown in FIG. 12, and it is possible to use the above-described second method of manufacturing a copper clad laminate. The method of use is substantially the same as the method of use described above.

FIG. 10 used in this manufacturing method .
Instead of the electrolytic copper foil with carrier foil shown in (b),
The electrolytic copper foil with carrier foil shown is used. That is, since the electrolytic copper foil with carrier foil, the prepreg (when forming the outer layer copper foil layer of the multilayer substrate, the prepreg and the inner layer substrate are used) and the end plate are press-molded to obtain a copper clad laminate. However, by using the electrolytic copper foil with a carrier foil, press molding without the inner layer end plate is possible. That is, similarly to the case shown in FIG. 12, the mirror plate is arranged only on the outermost layer that is in direct contact with the press plate, and the electrolytic copper foil with carrier foil and the prepreg are alternately laid up between the two mirror plates. Of.

As the uppermost layer and the lowermost layer in this laid-up, one sheet of electrolytic copper foil with carrier foil or normal copper foil is arranged. The electrolytic copper foil with carrier foil shown in FIG. 15 is added to the copper foil located in the other inner layer when laid up .
One piece is used and laminated alternately with the prepreg. In this way, by press-molding, it becomes possible to mold without using an end plate. Then, at the time of dismantling work after the completion of press molding, the outer layer copper foil layer of the double-sided board or the multi-layer board can be formed by peeling it from the bonding interface layer of the electrolytic copper foil with carrier foil.

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

The present invention according to the present invention described above
Of the electrolytic copper foil with carrier foil, bulk copper is used as the carrier foil.
-Sided electrolytic copper foil with carrier foil having electrolytic copper foil layer which is a layer
(FIG. 1, FIG. 4, FIG. 10, FIG. 13)
It is desirable to adopt the following manufacturing method. The manufacturing method
The carrier foil wound in a roll from one direction
Unwinding, the carrier foil is electrolyzed with a washing treatment tank.
As a copper foil layer forming process, a continuous pickling treatment tank,
Bonding interface forming tank by machine system agent, bulk that becomes electrolytic copper foil layer
Copper layer forming tank, fine copper particles to form on the surface of bulk copper layer
The roughening treatment tank, rust prevention treatment tank and drying treatment section to be formed
By passing through each, the organic agent on the carrier foil
To continuously form a joint interface layer and an electrolytic copper foil layer by
is there.

The carrier foil generally exists in a roll shape, and it is preferable from the viewpoint of production yield that the roll-shaped carrier foil is continuously processed without breaks. Therefore, the inventors of the present invention unwind the rolled-up carrier foil from one direction, and the carrier foil is pickled continuously as a step of forming an electrolytic copper foil layer provided with a water washing treatment tank. Treatment tank, joining interface forming tank using organic agent, tank for forming bulk copper layer to be an electrolytic copper foil layer, roughening treatment tank for forming fine copper particles to be formed on the surface of bulk copper layer, anticorrosion treatment tank, and By passing through each of the drying treatment section, a method for producing an electrolytic copper foil with a carrier foil, which is characterized by continuously forming a bonding interface layer and an electrolytic copper foil layer with an organic agent on a carrier foil, was adopted. .

Specifically, as a first method, a carrier foil unwound as shown in FIG. 16 meanders and runs in the process of forming an electrolytic copper foil layer while forming a bonding interface forming tank and a copper foil layer. Bulk copper layer forming tank, a roughening treatment tank for forming fine copper particles formed on the surface of the bulk copper layer, a rustproofing treatment tank, and a drying treatment section. Alternatively, as a second method, as shown in FIG. 17, the unwound carrier foil horizontally travels in a floating manner on each treatment tank to form a bonding interface layer, an electrolytic copper foil layer and a surface treatment tank. A method using a device for continuously performing the above can be considered.

The first method and the second method are used properly depending on the thickness of the carrier foil. In the first method, since the carrier foil is designed to meander using a tension roll, it is easy to adjust the tension (tension) of the carrier foil over a short distance, and an appropriate tension adjustment is performed. This makes it easy to prevent wrinkles from occurring on the carrier foil during running. If wrinkles are generated on the carrier foil during running, the distance between the wrinkles and the anode electrode becomes non-uniform, and the electrodeposition state varies, impairing the electrodeposition stability. Moreover, according to the first method, by disposing the anode electrodes on both sides of the carrier foil in the bath, electrolytic copper foil layers are formed on both sides of the carrier foil described in claim 2, claim 4 and claim 11. It is possible to manufacture the formed electrolytic copper foil with carrier foil.

At this time, in the bulk copper layer forming tank,
If the 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 the carrier foil can be easily obtained. In other words, with the electrolytic copper foil layer
And electrolytic copper with carrier foil of the present invention having only fine copper particles
It is possible to manufacture foils (FIGS. 8, 9). This also applies to the second method described below.

On the other hand, the second method is used exclusively for producing an electrolytic copper foil with a carrier foil in which an electrolytic copper foil layer is formed on one surface of the carrier foil. In this method, the solution in each tank runs horizontally from the gap of anode electrodes, etc. arranged in parallel facing the carrier foil so that the carrier foil floats on the various solutions and runs horizontally. Occasionally, a fluttering phenomenon (here, the vertical movement of the carrier foil during traveling) occurs, and the electrodeposition state may fluctuate. Moreover, in this method, it is more difficult to apply tension to the running carrier foil than in the first method, and the tension control becomes more difficult as the thinner carrier foil is used. Therefore, it can be said that this method can be used when a relatively thick carrier foil is used.

The pickling treatment tank is a step for carrying out so-called pickling treatment, and is performed for the purpose of degreasing treatment for completely removing oil and fat components attached to the carrier foil and removal of surface oxide film when a metal foil is used. It is a thing. By passing the carrier foil through this pickling treatment tank, the carrier foil is cleaned to ensure uniform electrodeposition in the following steps. For this pickling treatment, various solutions such as a hydrochloric acid-based solution, a sulfuric acid-based solution, a sulfuric acid-hydrogen peroxide-based solution can be used, and it is not particularly limited. 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 separation foil as a carrier foil, and is necessarily required when using a surface-treated foil having a rust preventive element on its surface layer as a carrier foil. is not.

The organic bonding interface forming tank is a process of forming a bonding interface layer on one surface or both surfaces of the carrier foil using the above-mentioned organic agent. The bonding interface layer is formed by (1) a method of filling the organic bonding interface forming tank with a solution containing an organic agent, and immersing the carrier foil in the solution.
(2) A method of showering or dropping a solution containing an organic agent onto the surface of the carrier foil forming the bonding interface in the organic bonding interface forming tank, (3) in the organic bonding interface forming tank It is possible to employ a method of electrodepositing the organic agent with.

After the formation of the organic bonding interface, the bulk copper layer of the electrolytic copper foil is subsequently 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, if it is a copper sulfate-based solution, the concentration is 30 to 100 g / l of copper and 50 to 50% of sulfuric acid.
200 g / l, liquid temperature 30-80 ° C, current density 1-100
A / dm ² condition, if the solution is a copper pyrophosphate solution, the concentration is 10 to 50 g / l of copper, and potassium pyrophosphate is 100 to 700.
g / l, liquid temperature 30 to 60 ° C., pH 8 to 12, current density 1
For example, the condition is 10 A / dm ² . Here, by immersing the carrier foil having the organic bonding interface formed therein in the solution, arranging the anode electrode in parallel with the surface of the carrier foil having the organic bonding interface, and performing the cathode polarization of the carrier foil itself. , A step of uniformly and smoothly depositing the copper component forming the bulk copper layer on the organic bonding interface. Hereinafter, the same anode electrode arrangement shall be adopted in the 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 the roughening treatment tank. The process performed in the surface-roughening treatment tank, if further subdivided, is composed of a step of depositing fine copper particles on the bulk copper layer and a covering plating step for preventing the fine copper particles from falling off. It

In the step of depositing and depositing fine copper particles on the bulk copper layer, the same solution as that used in the bulk copper forming bath is used as a copper ion supply source. However, the electroplating conditions used in the bulk copper forming bath are smooth plating conditions, while the electrolysis conditions used here are burnt plating conditions. Therefore, generally, the solution concentration used in the step of depositing and depositing fine copper particles on the bulk copper layer is lower than the solution concentration used in the formation layer of the bulk copper so as to easily create the burn plating condition. There is. 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 to 200 g / l, and other optional additives (α-naphthoquinoline, dextrin, glue, thiourea, etc.), liquid temperature 15 to 40 ° C., current density 10
For example, the condition is 50 A / dm ² .

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

In the anticorrosion treatment tank, this is a step for preventing the surface of the electrolytic copper foil layer from being oxidized and corroded so as not to hinder the manufacturing process of the copper clad laminate and the printed wiring board. As a method used for the rust prevention treatment, there is no problem even if any of organic rust prevention using benzotriazole, imidazole or the like or inorganic rust prevention using zinc, chromate, zinc alloy or the like is adopted. Corrosion prevention may be selected according to the intended use of the electrolytic copper foil with carrier foil. In the case of organic rust prevention, it is possible to adopt a technique such as dip coating, showering coating, electrodeposition method or the like with an organic rust inhibitor. In the case of inorganic rust prevention, it is possible to use a method of electrolytically precipitating a rust preventive element on the surface of the electrolytic copper foil layer, or other so-called substitutional precipitation method. For example, as the zinc anticorrosion 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 zinc 5 to 30 g / l, potassium pyrophosphate 50 to 500 g / l, the liquid temperature is 20 to 50 ° C,
The conditions are pH 9 to 12 and current density of 0.3 to 10 A / dm ² .

The dry treatment section is a final step for the carrier foil to pass through a tank filled with various solutions in the above-mentioned steps and to wind the completed electrolytic copper foil with carrier foil into a roll. It is something that will be done. That is, the completed electrolytic copper foil with carrier foil in a wet state is passed through a heating and drying furnace to be thermally dried.

The electrolytic copper foil with a carrier foil according to the present invention is manufactured through the steps described above . And these electrolytic copper foils with a carrier foil will be mainly used as a basic material of printed wiring board manufacture. Therefore, the book
Copper-clad using the electrolytic copper foil with carrier foil of the present invention according to the invention
Laminates can be manufactured using the copper clad laminate
It is possible to manufacture a printed wiring board .

The copper clad laminate or the printed wiring board as used herein includes the concept of all layer structures of a single-sided board, a double-sided board and a multilayer board, and the base material is not limited to a rigid board, but a so-called It includes all of flexible substrates including special substrates such as TAB and COB, hybrid substrates, and the like.

[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 the evaluation results thereof will be described. Will be described. Here, the case where an electrolytic copper foil is used as the carrier foil will be mainly described. In addition, about the code | symbol in drawing, the same code | symbol is used when pointing to the same thing as much as possible.

First Embodiment: In the present embodiment,
An electrolytic copper foil 1 with a carrier foil according to claim 9, comprising:
0 (a) will be described. The manufacturing apparatus 2 used here is the one shown in FIG. 18, in which the unwound carrier foil 3 meanders in the process of forming the electrolytic copper foil layer 5. Here, the separation foil classified into Grade 3 having a thickness of 18 μm was used as the carrier foil 3, and the electrolytic copper foil layer 5 having a thickness of 5 μ was formed on the glossy surface 4 side. The manufacturing conditions will be described below in the order in which various tanks are continuously arranged in series.

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

The carrier foil 3 that has left the pickling treatment tank 6 enters the joint interface forming tank 7. The joining interface forming tank 7 contains CBTA with a concentration of 5 g / l, a liquid temperature of 40 ° C., and a p
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.

When the bonding interface layer 8 is formed, the bulk copper layer 9 of the electrolytic copper foil is subsequently formed on the interface. In the bulk copper forming tank 10, the concentration of 150 g / l
It was filled with sulfuric acid, 65 g / l copper, and a copper sulfate solution having a liquid temperature of 45 ° C. 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 electrodeposited uniformly and smoothly on the bonding interface. As shown in FIG. 18, a flat plate anode electrode 11 was arranged in parallel to one surface of the carrier foil 3 on which No. 8 was formed, and electrolysis was performed for 60 seconds under a smooth plating condition with a current density of 15 A / dm ² . At this time, since the carrier foil 3 itself is cathode-polarized, at least one of the tension rolls 12 in contact with the meandering 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 is put into the surface treatment bath 14 as a step of forming the fine copper particles 13 on the surface of the bulk copper layer 9.
The treatment performed in the surface treatment bath 14 includes a step 14A for depositing and depositing the fine copper particles 13 on the bulk copper layer 9, and a cover plating step 14B for preventing the fine copper particles 13 from falling off. .

In the step 14A of depositing and depositing the fine copper particles 13 on the bulk copper layer 9, the bulk copper forming bath 10 described above is used.
Copper sulfate solution similar to that used in
/ L sulfuric acid, 18g / l copper, liquid temperature 25 ° C, current density 10A
Electrolysis was performed for 10 seconds under a burnt plating condition of / dm ² . At this time, the flat plate 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 overcoating step 14B for preventing the fine copper particles 13 from falling off, the same copper sulfate solution as that used in the bulk copper forming bath 10 was used, and the concentration was 150 g / l.
Sulfuric acid, 65g / l copper, liquid temperature 45 ° C, current density 15A / d
Electrolysis was performed for 20 seconds under smooth plating conditions of m ² . At this time,
The flat plate anode electrode 11 was arranged in parallel to the surface of the carrier foil 3 on which the fine copper particles 13 were adhered and formed, as shown in FIG.

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

When the anticorrosion treatment is completed, the carrier foil 3 is finally heated in the drying treatment section 17 by an electric heater at an ambient temperature of 11 ° C.
It passed through a furnace heated to 0 ° C. for 40 seconds, and was wound into a roll as the completed electrolytic copper foil 1 with a carrier foil.
The traveling speed of the carrier foil in the above process is 2.0 m / m.
In addition, a washing layer 18 which can be washed with water for about 15 seconds is provided between the steps of the respective tanks for washing, and the carry-in of the solution in the pretreatment step is prevented.

This electrolytic copper foil with carrier foil 1 and 150 μm
A double-sided copper clad laminate was manufactured using two m-thick FR-4 prepregs, 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 peeling strength was 4 gf / cm before heating and 4 gf / cm after heating at 180 ° C. for 1 hour.

Furthermore, the present inventors changed to CBTA used in the first embodiment and used it as the above-mentioned organic agent such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and mercaptobenzoic acid. Table 1 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, before and after heating. A circuit width of 25 μm is obtained by using the electrolytic copper foil with carrier foil shown in this embodiment.
A printed wiring board having a fine circuit portion with a gap of 25 μm was manufactured, but it was finished as a very good printed wiring board, and there were no problems in various characteristics as the printed wiring board.

[0115]

[Table 1]

Second Embodiment: In the present embodiment,
An electrolytic copper foil 1 with a carrier foil according to claim 9, comprising:
0 (a) will be described. The manufacturing apparatus 2 ′ used here is the one shown in FIG. 19, and the unwound carrier foil 3 is of a type that horizontally travels during the process of forming the electrolytic copper foil layer 5. This device
At least the bulk copper forming bath 10 and the surface treatment bath 14 are arranged such that a plurality of divided anode electrodes 11 ′ are arranged opposite to each other in parallel to the carrier foil 3.

The anode electrode 1 divided into a plurality of parts
The electrolytic solution is spouted from the gap 18 of 1 ′ so that the carrier foil 3 can be floated and uniformly contact with the surface of the carrier foil 3. In each of the other tanks, in order to enable the floating of the carrier foil 3,
It does not have a function as an anode electrode, but has the same structure. Here, a separation foil classified into Grade 3 having a thickness of 70 μm was used as the carrier foil 3, and an electrolytic copper foil layer 5 having a thickness of 5 μm was formed. The manufacturing conditions will be described below in the order in which various tanks are continuously arranged in series.

The unwound carrier foil 3 first enters the pickling treatment tank 6. Concentration 150g inside the pickling tank 6
/ L, a liquid temperature of 30 ℃ dilute sulfuric acid solution is filled, by contacting this with one side of the carrier foil 3 for about 25 seconds,
The pickled oil and fat components were removed by pickling, and the surface oxide film was removed.

The carrier foil 3 that has left the pickling treatment tank 6 enters the joint interface forming tank 7. The joint interface forming tank 7 contains CBTA with a concentration of 5 g / l, and the liquid temperature is 40 ° C., p
Filled with an aqueous solution of H5. Therefore, while the carrier foil 3 is running horizontally, the carrier foil 3 is in contact with the 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.

When the bonding interface layer 8 is formed, the bulk copper layer 9 of the electrolytic copper foil 5 is subsequently formed on the interface. In the bulk copper forming tank 6, the concentration of 150 g / l
Sulfuric acid, 65 g / l copper, and a copper sulfate solution having a liquid temperature of 45 ° C. were introduced. Then, the bonding interface layer 8 is formed in order to deposit the bulk copper layer 9 on the bonding interface layer 8 uniformly and smoothly while the carrier foil 3 on which the bonding interface layer 8 is formed passes through the solution. As shown in FIG. 19, a block-shaped anode electrode 11 ′ was arranged in parallel to the carrier foil 3 and was electrolyzed for 90 seconds under a smooth plating condition of a current density of 10 A / dm ² . At this time, since the carrier foil 3 itself is subjected to cathodic polarization, at least one of the drive rolls 19 in contact with the horizontally traveling 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 bath 14 in the next step of forming the fine copper particles 13 on the surface of the bulk copper layer 9. The processing performed in the surface treatment bath 14 is a step 14A of depositing and depositing the fine copper particles 13 on the bulk copper layer 9, and a covering plating step 14 for preventing the fine copper particles 13 from falling off.
Composed of B and.

In the step 14A of depositing and depositing the fine copper particles 13 on the bulk copper layer 9, the bulk copper forming bath 10 described above is used.
Copper sulfate solution similar to that used in
/ L sulfuric acid, 18g / l copper, liquid temperature 25 ° C, current density 10A
Electrolysis was performed for 15 seconds under a burnt plating condition of / dm ² . At this time, the block-shaped anode electrode 11 ′ is the bulk copper layer 9
As shown in FIG. 19, they were arranged in parallel with the surface of the carrier foil 3 on which was formed.

In the overcoating step 14B for preventing the fine copper particles 13 from falling off, the same copper sulfate solution as that used in the bulk copper forming bath 10 described above and having a concentration of 150 g /
l sulfuric acid, 65g / l zinc, liquid temperature 45 ° C, current density 15A
Electrolysis was performed for 20 seconds under the smooth plating condition of / dm ² . Also at this time, the block-shaped anode electrode 11 ′ has fine copper grains 13
19 was placed in parallel with the surface of the carrier foil 3 on which was adhered and formed.

In the rustproofing tank 15, rustproofing was carried out using a zinc sulfate bath as a rustproofing element. Here, as the soluble anode 16 ′ using a zinc plate as the anode electrode, the zinc concentration balance in the anticorrosion treatment tank 15 is maintained. The electrolysis conditions here are as follows: concentration 70 g / l sulfuric acid, 20 g / l zinc, liquid temperature 40 ° C., current density 0.3 A /
dm ² , electrolysis time was 20 seconds.

When the anticorrosion treatment is completed, the carrier foil 3 is finally dried in the drying treatment section 17 by an electric heater at an ambient temperature of 11 ° C.
It passed through a furnace heated to 0 ° C. for 40 seconds, and was wound into a roll as the completed electrolytic copper foil 1 with a carrier foil.
The traveling speed of the carrier foil 3 in the above process is 2.0 m /
It is set to min, and a washing tank 18 that can be washed with water for about 15 seconds is provided between the steps of each tank to prevent the solution from being brought in in the pretreatment step.

This electrolytic copper foil with carrier foil 1 and 150 μm
A double-sided copper-clad laminate was produced 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 peeling strength was 4 gf / cm before heating and 4 gf after heating at 180 ° C. for 1 hour.
Was / cm.

Furthermore, the present inventors changed the CBTA used in the second embodiment to the above-mentioned organic agents such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and mercaptobenzoic acid, and others. Table 2 collectively 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, before and after heating. A printed wiring board having a fine circuit portion having 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 it was finished as a very good printed wiring board. There were no problems in the characteristics of the printed wiring board.

[0128]

[Table 2]

Third Embodiment: In the present embodiment,
The electrolytic copper foil with carrier foil 1 according to claim 10 shown in FIG. 13 will be described. The manufacturing apparatus 2 used here is shown in FIG. 18, and is common to the first embodiment in this respect. The difference is that the carrier foil 3 is unwound so that the front and back sides 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 of a type that runs meandering in the process of forming 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 by using a separation foil classified into grade 3 having a thickness.

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

The electrolytic 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.
Of copper sulfate solution, the current density was 15 A / dm ² , and the electrolysis time was 10 seconds. In the step 14A of depositing and depositing the fine copper particles 13 on the bulk copper layer 9, the same copper sulfate solution as that used in the bulk copper forming tank 10 having a concentration of 1 is used.
Electrolysis was carried out under burnt plating conditions of 00 g / l sulfuric acid, 18 g / l copper, liquid temperature 25 ° C., current density 10 A / dm ² , and electrolysis time 10 seconds. In the cover plating step 14B for preventing the fine copper particles 13 from falling off, the bulk copper forming bath 10 described above is used.
The same copper sulphate solution as that used in
l sulfuric acid, 65 g / l copper, liquid temperature 45 ° C., current density 15 A /
Electrolysis was performed under smooth plating conditions of dm ² and electrolysis time of 20 seconds. The electrolytic conditions in the anticorrosion treatment tank 15 are: 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.

This electrolytic copper foil with carrier foil 1 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.
Was / cm.

Furthermore, the present inventors changed to CBTA used in the third embodiment and used palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, mercaptobenzoic acid and the like as organic agents, and Table 3 shows the peeling strength of the joint interface 8 between the carrier foil layer 3 and the electrolytic copper foil layer 5 under the same conditions, before and after heating. A circuit width of 25 μm is obtained by using the electrolytic copper foil with carrier foil shown in this embodiment.
Although a printed wiring board having a fine circuit portion with a m and a gap of 25 μm was manufactured, it was finished as a very good printed wiring board, and there were no problems in various characteristics as the printed wiring 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 shown in FIG. 20, and is a type in which the unwound carrier foil 3 meanders in the process of forming the electrolytic copper foil layer 5. Here, the separation foil classified into grade 3 having a thickness of 18 μm was used as the carrier foil 3, and the electrolytic copper foil layer 5 was formed on both the glossy surface 4 and the rough surface 20. The manufacturing conditions will be described below in 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, description of 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 bonding interface forming tank 7, and the heating / drying section 17. In the case of the first embodiment, the electrolytic copper foil layer 5 is formed on one surface of the carrier foil 3, but in the present embodiment, the electrolytic copper foil layer 5 is formed on both surfaces 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
It was filled with g / l sulfuric acid, 65 g / l copper, and a copper sulfate solution having a liquid temperature of 45 ° C. Then, as shown in FIG. 20, two flat plate 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 electrolysis at this time was electrolysis for 60 seconds under 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 bulk copper forming bath 10 described above is used.
Copper sulfate solution of the same type used in
/ L sulfuric acid, 65 g / l copper, liquid temperature 25 ° C., current density on both glossy surface 4 side and rough surface 20 side of carrier foil is 10 A /
Electrolysis was performed for 10 seconds under the dm ² burnt plating condition. The arrangement of the anode electrode 11 is the same as that for depositing bulk copper.

In the overcoating step 14B for preventing the fine copper particles 13 from falling off, the same copper sulfate solution as that used in the bulk copper forming bath 10 described above and having a concentration of 150 g /
l sulfuric acid, 65 g / l copper, liquid temperature 45 ° C., current density on the glossy surface 4 side and rough surface 20 side of the carrier foil are both 15 A
Electrolysis was performed for 20 seconds under the smooth plating condition of / dm ² .

In the anticorrosion treatment tank 15, anticorrosion treatment was performed using a zinc sulfate bath. Here, as the soluble anode 16 using a zinc plate as the anode electrode, the rust preventive treatment tank 15 is used.
There is no change in maintaining the zinc concentration balance in the inside. The electrolysis conditions here are concentration 70 g / l, 20 g / l.
1 zinc, the liquid temperature was 40 ° C., and the current density was 0.3 A / dm ² . The traveling speed of the carrier foil 3 in the above process is 2.0.
It was set to m / min.

This electrolytic copper foil with carrier foil 1 and 150 μm
A double-sided copper-clad laminate was produced using two m-thick FR-4 prepregs, and the peeling strength at 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 peeling strength at each interface between the carrier foil 3 and the electrolytic copper foil 5 was 4 gf / cm on the glossy surface 4 side before heating and 4 gf on the rough surface 20 side. / C
m, and 5 gf on the glossy surface 4 side after heating as described above
/ Cm, and the rough surface 20 side was 6 gf / cm.

Furthermore, the present inventors changed the CBTA used in the fourth embodiment to the above-mentioned organic agents such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and mercaptobenzoic acid, and others. Table 4 and Table 5 show 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, before and after heating. A circuit width of 25 μm is obtained by using the electrolytic copper foil with carrier foil shown in this embodiment.
Although a printed wiring board having a fine circuit portion with a m and a gap of 25 μm was manufactured, it was finished as a very good printed wiring board and there were no problems in various characteristics as the printed wiring board.

[0143]

[Table 4]

[0144]

[Table 5]

Fifth Embodiment: In the present embodiment,
An electrolytic copper foil 1 with a carrier foil according to claim 9, comprising:
0 (b) will be described. The manufacturing apparatus 2 used here is the one shown in FIG. 18, and the unwound carrier foil 3 is of a type that runs meandering in the process of forming an electrolytic copper foil layer. Here, a surface-treated foil classified into Grade 3 having a thickness of 18 μm was used as the carrier foil 3, and the electrolytic copper foil layer 5 was formed on the glossy surface 4 side.

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

This electrolytic copper foil with carrier foil 1 and 150 μm
It was possible to manufacture a double-sided copper-clad laminate by laying up and press-molding with a m-thick FR-4 prepreg as shown in FIG. 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 peeling strength measurement was manufactured and analyzed, and as a result, the thickness of the bonding interface layer 8 was measured. The average thickness 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.

Furthermore, the present inventors changed the CBTA used in the fifth embodiment to the above-mentioned organic agents such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and mercaptobenzoic acid, and Table 6 shows the peeling 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. A printed wiring board having a fine circuit portion having 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 it was finished as a very good printed wiring board. There were no problems in the characteristics of the printed wiring board.

[0149]

[Table 6]

Using the electrolytic copper foil with a carrier obtained in the above embodiment, the peeling strength at the bonding interface between the carrier foil and the electrolytic copper foil was measured. It was confirmed that it was extremely smaller than the electrolytic copper foil with foil and was stable. Therefore, as described above, it is possible to adopt a non-conventional method of using the electrolytic copper foil with a carrier foil. The inventors of the present invention investigated products of 30 lots or more with respect to each product described in the embodiment. The peel strength at the bonding interface between the carrier foil and the electrolytic copper foil was measured before and after heating and after heating. It was stable at a level of 50 gf / cm or less, did not change significantly, and there was no phenomenon that it could not be peeled off.

[0151]

The electrolytic copper foil with carrier foil according to the present invention is
Since peeling at the interface between the carrier foil layer and the electrolytic copper foil layer can be easily performed with a very small force, it is not possible with the conventional peelable type electrolytic copper foil with carrier foil. The peeling stability at the time of peeling can be maintained. By obtaining such characteristics, the copper clad laminate as described above can be manufactured for the first time, and the production yield can be greatly improved.
Therefore, the electrolytic copper foil with a carrier foil according to the present invention has a possibility of changing the conventional copper clad laminate manufacturing method and the manufacturing method of the printed wiring board from the basis, and the influence on the development of the industry is Considered to be very large.

[Brief description of drawings]

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

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

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

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

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

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

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

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

FIG. 17 is a schematic cross section of an apparatus for producing an electrolytic copper foil with a carrier foil.

FIG. 18 is a schematic cross section of an apparatus for producing an electrolytic copper foil with a carrier foil.

FIG. 19 is a schematic cross section of an apparatus for producing an electrolytic copper foil with a carrier foil.

FIG. 20 is a schematic cross section of an apparatus for producing an electrolytic copper foil with a carrier foil.

[Explanation of symbols] 1 Electrolytic copper foil with carrier foil Equipment for manufacturing electrolytic copper foil with 2,2 'carrier foil 3 carrier foil (carrier foil layer) 4 glossy surface 5 electrolytic copper foil (electrolytic copper foil layer) 6 pickling tank 7 junction interface forming tank 8 Bonding interface (bonding interface layer) 9 bulk copper (bulk copper layer) 10 bulk copper forming tank 11,11 'Anode electrode 12 tension rolls 13 Fine copper grains 14 surface treatment tank 15 Antirust treatment tank 16,16 'zinc soluble anode 17 Drying processing section 18 water washing tank 19 drive roll 20 rough surface

Front page continuation (72) Inventor Tsutomu Higuchi 1419-1 Hara-shi, Ageo-shi, Saitama Fujimi Dormitory (72) Inventor Akiko Sugioka 4-9-24 Suzuya, Yono-shi, Saitama Yono Park Square No. 212 (72) Inventor Atsushi Yoshioka 3-814 Kashiwaza, Ageo-shi, Saitama 2-814 Park Ageo 2-814 (72) Inventor Shinichi Kohata 862 Hanuki, Ina-cho, Kita Adachi-gun, Saitama Seiji Mansion 206 (72) Inventor Sakuko Tomonaga Kitabukuro-cho, Omiya-shi, Saitama 2-35-2 Kitabukuro Minami Condominium No. 302 (72) Inventor Makoto Dobashi 3233-91 Hara City, Ageo City, Saitama Prefecture (56) References JP 2000-196226 (JP, A) JP 2000-190420 (JP, A) ) JP 2000-151068 (JP, A) JP 2000-43188 (JP, A) JP 11-317574 (JP, A) JP 8-1859 (JP, A) Actual development Sho 61-42872 ( JP, U) Special Table 2001-525127 (JP, A) Patent 3370636 (JP, B2) Patent 3370624 (JP, B2) International Publication 98/051485 (WO, A1) (58) Field (Int.Cl. ⁷ , DB name) C25D 7/06 H05K 1/09 B32B 15/08

Claims (14)

(57) [Claims] 1. A bonding interface layer is formed by coating one surface of a carrier foil with an organic agent consisting of one or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids. In an electrolytic copper foil with a carrier foil formed by depositing an electrolytic copper foil layer on the bonding interface layer, repeatedly applying the bonding interface layer in combination with the same organic agent or different organic agents. An electrolytic copper foil with a carrier foil, which is formed by 2. A bonding interface layer is formed by coating one surface of a carrier foil with an organic agent consisting of one or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids. In the electrolytic copper foil with a carrier foil formed by depositing fine copper particles as an electrolytic copper foil layer on the bonding interface layer, the bonding interface layer is combined with the same kind of organic agent or different kinds of organic agents. An electrolytic copper foil with a carrier foil, which is formed by repeatedly applying the same. 3. 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. 4. The electrolytic copper foil with a carrier foil according to claim 1, wherein the carrier foil is an electrolytic copper foil having a thickness of 12 μm to 210 μm. 5. The carrier foil according to claim 4, wherein a bonding interface layer is formed on a glossy surface of an electrolytic copper foil which is a carrier foil, and an electrolytic copper foil layer is deposited and formed on the bonding interface layer. Attached electrolytic copper foil. 6. The carrier foil according to claim 4, wherein a bonding interface layer is formed on a rough surface of an electrolytic copper foil which is a carrier foil, and an electrolytic copper foil layer is deposited and formed on the bonding interface layer. Attached electrolytic copper foil. 7. A bonding interface layer is formed by applying an organic agent consisting of one or more selected from a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid on both surfaces of a carrier foil. In an electrolytic copper foil with a carrier foil formed by depositing and forming an electrolytic copper foil layer on each bonding interface layer, the bonding interface layer is repeatedly applied by combining the same kind of organic agent or different kinds of organic agents. An electrolytic copper foil with a carrier foil, which is formed by the above. 8. A bonding interface layer is formed by applying an organic agent comprising one or more selected from a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid on both sides of a carrier foil. In an electrolytic copper foil with a carrier foil, which is formed by depositing fine copper particles as an electrolytic copper foil layer on each bonding interface layer, the bonding interface layer may be formed of the same organic agent or different organic agents. An electrolytic copper foil with a carrier foil, which is formed by combining and repeatedly applying. 9. The electrolytic copper foil with a carrier foil according to claim 7, wherein the bonding interface layer is made of an organic agent having a thickness of 1 nm to 1 μm. 10. The carrier foil has a thickness of 12 μm to 210 μm.
The electrolytic copper foil with a carrier foil according to any one of claims 7 to 9, which is the electrolytic copper foil. 11. The electrolytic copper foil as a carrier foil is provided with a bonding interface layer on a glossy surface and a rough surface, and an electrolytic copper foil layer is deposited and formed on each bonding interface layer.
An electrolytic copper foil with a carrier foil as described in. 12. A copper clad laminate obtained by using the electrolytic copper foil with a carrier foil according to claim 1. 13. The method for producing an electrolytic copper foil with a carrier foil according to claim 1 or 7, wherein the carrier foil rolled into a roll is unwound from one direction, and the carrier foil is washed with water. As the process of forming the electrolytic copper foil layer with the treatment tank, a pickling treatment tank that is continuously arranged, a bonding interface forming tank with an organic agent, a bulk copper layer forming tank that becomes the electrolytic copper foil layer, and a surface of the bulk copper layer By passing through each of the roughening treatment tank that forms the fine copper particles to be formed, the rust-prevention treatment tank, and the drying treatment section, the bonding interface layer and the electrolytic copper foil layer with the organic agent are continuously formed on the carrier foil. A method for producing an electrolytic copper foil with a carrier foil, which comprises: 14. The method for producing an electrolytic copper foil with a carrier foil according to claim 2, wherein the carrier foil wound into a roll is unwound from one direction, and the carrier foil is washed with water. As the electrolytic copper foil layer forming process with the treatment tank, a pickling treatment tank continuously arranged, a bonding interface forming tank with an organic agent, a roughening treatment tank for forming fine copper particles to be an electrolytic copper foil layer, A method for producing an electrolytic copper foil with a carrier foil, which comprises continuously forming a bonding interface layer and an electrolytic copper foil layer with an organic agent on a carrier foil by passing through each of a rust treatment tank and a drying treatment section.