JP2005307270A - Carrier foil-fitted electrolytic copper foil and method for producing the carrier foil-fitted electrolytic copper foil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an more inexpensive product as peelable type carrier foil-fitted electrolytic copper foil. <P>SOLUTION: Regarding the carrier foil-fitted electrolytic copper foil in which the surface of carrier foil is provided with a circuit formation layer, either the circuit formation layer or carrier foil is an organic agent-containing precipitated copper layer formed by electrolysis, also, the precipitated crystals in the precipitated copper layer have a fine and continuous crystal shape and are columnar, and the other is a pure copper layer having a purity of ≥99.9 wt.%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrolytic copper foil with a carrier foil and a method for producing the electrolytic copper foil with a carrier foil. In particular, the electrolytic copper foil with a carrier foil according to the present invention provides a peelable type electrolytic copper foil with a carrier foil that enables the carrier foil to be peeled off even without a bonding interface.

  In recent years, downsizing of printed wiring boards mounted on them has been performed at the same time due to the demand for light and thin electronic and electrical equipment, and there are remarkable increases in the printed circuit board wiring circuit density, mounting density, and multi-layering. . Conventionally, an electrolytic copper foil with a carrier foil has been widely used as a basic material for producing a printed wiring board having a fine pitch circuit in the fields of the electric and electronic industries. This electrolytic copper foil with carrier foil is bonded to a polymer insulating substrate such as glass-epoxy substrate, phenol substrate, polyimide, etc. by hot press forming into a copper-clad laminate, and used for printed wiring board production It is.

  For example, this electrolytic copper foil with carrier foil is thermocompression-bonded with a prepreg cured on a B stage under high pressure in a high temperature atmosphere (hereinafter, this process is referred to as “press molding”) to form a copper clad laminate. It is possible to prevent wrinkles of the thin copper foil layer generated during production, and to crack the copper foil at the heel portion, thereby preventing the resin from exuding from the prepreg. And it makes it easy to provide a thin copper foil layer on the surface of a copper clad laminated board.

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

  As shown in FIG. 13, in a general peelable type electrolytic copper foil 8 with a carrier foil, either an inorganic or organic bonding interface layer 7 is provided between the carrier foil 2 and the circuit forming layer 3. It was a configuration that existed. Among these, the electrolytic copper foil with a carrier foil provided with an inorganic joint interface such as chromium disclosed in Patent Document 1 has a peel strength value of the carrier foil after press molding with a base resin. It is extremely unstable, and in extreme cases, the carrier foil cannot be peeled off, resulting in the disadvantage that it is difficult to obtain the desired peel strength. From the viewpoint of solving this problem, the present inventors have proposed an electrolytic copper foil with a carrier foil provided with an organic bonding interface layer in place of the inorganic bonding interface as disclosed in Patent Document 2. The electrolytic copper foil with a carrier foil provided with this organic bonding interface is 185 in the case of using a normal FR-4 prepreg as compared with a conventional electrolytic copper foil with a carrier foil using a metallic bonding interface layer. Even after pressing at around 0 ° C., it shows very good performance and the carrier foil can be peeled off very easily.

Japanese Patent Laid-Open No. 2001-301087 JP 2000-309898 A

  However, when an inorganic material or an organic agent is used for the bonding interface layer, there are merits and demerits.

When an inorganic material is used for the bonding interface layer: When an inorganic material is used for the bonding interface, zinc, chromium, nickel, an alloy system, a mixture of a metal and a metal compound, or the like is used. This inorganic bonding interface layer has the advantages of excellent high-temperature heat resistance and the ability to easily peel off the carrier foil even after high-temperature heating, but it is difficult to build a stable bonding interface on a mass-production basis. There is a drawback of being. As a result, after peeling off the carrier foil, the metal component constituting the bonding interface may remain on the surface of the copper foil layer and cause etching failure. In addition, the carrier foil may be removed from the carrier foil so easily that the surface of the copper foil cannot be protected from contamination until after press molding, because the amount of the inorganic material constituting the bonding interface is slightly changed. One of the significance was the result of the retreat.

When an organic agent is used for the bonding interface layer: When an organic agent such as carboxybenzotriazole is used for the bonding interface, the peeling strength of the carrier foil is stable and the carrier foil is easily peeled off. Moreover, there is a merit that the metal component does not remain on the surface of the copper foil layer after the carrier foil is peeled off, which is a drawback when an inorganic material is used. However, since it is an organic agent that constitutes the bonding interface, after press molding in a range exceeding 200 ° C., the bonding interface constituted by the organic agent is damaged by heat and the organic agent is altered, and the carrier foil layer There was a phenomenon that the carrier foil was seized and the carrier foil could not be peeled off.

  As described above, there are advantages and disadvantages when an inorganic material is used for the bonding interface layer and when an organic agent is used for the bonding interface layer. The demerit common to these conventional electrolytic copper foils with carrier foil is that it is necessary to form a bonding interface, and the manufacturing process becomes complicated compared to ordinary electrolytic copper foils, resulting in high manufacturing costs. Met. Therefore, the supply of cheaper electrolytic copper foil with carrier foil has been demanded in the market.

  Therefore, as a result of earnest research, the present inventors have carried out electrolysis with a carrier foil that allows the carrier foil to be peeled off after press working even if the joining interface layer that is essential for the conventional electrolytic copper foil with a carrier foil is omitted. I came up with a copper foil. Since the electrolytic copper foil with carrier foil according to the present invention does not require a bonding interface layer, the manufacturing process and the manufacturing cost can be reduced. Hereinafter, the present invention will be described.

<Electrolytic copper foil with carrier foil>
The copper foil with the first carrier foil according to the present invention is “an electrolytic copper foil with a carrier foil provided with a circuit forming layer on the surface of the carrier foil, wherein the circuit forming layer is a precipitate containing an organic agent formed by electrolysis. The deposited crystal of the deposited copper layer is a continuous columnar crystal having a fine crystal shape, and the carrier foil is a pure copper layer having a purity of 99.9 wt% or more. Electrolytic copper foil with carrier foil. "

  Further, the second copper foil with a carrier foil according to the present invention is “an electrolytic copper foil with a carrier foil provided with a circuit forming layer on the surface of the carrier foil, the circuit forming layer having a purity of 99.9 wt% or more. It is a pure copper layer, the carrier foil is a deposited copper layer containing an organic agent formed by electrolysis, and the deposited crystal of the deposited copper layer is a carrier having a fine crystal shape and a continuous columnar crystal Electrolytic copper foil with foil. "

  FIG. 1 shows a schematic cross section of the first carrier foil-attached electrolytic copper foil 1a. And the schematic cross section of the electrolytic copper foil 1b with 2nd carrier foil is shown in FIG. As apparent from FIGS. 1 and 2, the two-layer structure of the carrier foil layer 2 and the circuit forming layer 3 is very simple. The relationship between FIG. 1 and FIG. 2 is that the composition constituting the carrier foil and the composition constituting the circuit forming layer are interchanged. Therefore, it is arbitrary which surface is used as the carrier foil or the circuit forming layer. What is common is that the carrier foil layer and the circuit forming layer are joined with an electrodeposition boundary. In the drawings, the description of the roughening treatment (fine copper grains, uneven shape, etc.) used for laminating the base material, the anticorrosive treatment layer, etc. is omitted when the copper clad laminate is manufactured. Therefore, this roughening treatment, rust prevention treatment and the like may be performed as necessary. Hereinafter, the description will be divided into an electrolytic copper foil with a first carrier foil and an electrolytic copper foil with a second carrier foil.

(Electrolytic copper foil with first carrier foil)
The circuit forming layer of the electrolytic copper foil with the first carrier foil is a deposited copper layer containing an organic agent formed by electrolysis, and the deposited crystal of the deposited copper layer has a fine crystal shape and a continuous columnar shape. It must be crystalline. The carrier foil is characterized in that a pure copper layer having a purity of 99.9 wt% or more is combined. If the combination of the composition of the circuit forming layer and the composition of the carrier foil is not adopted in this way, the carrier foil can be easily peeled off after the amount of heat at the press working level is applied with the bonding interface layer omitted. Will not be possible. Hereinafter, it demonstrates for every specific element of electrolytic copper foil with a carrier foil.

Circuit forming layer: First, the circuit forming layer is a deposited copper layer containing an organic agent formed by electrolysis (hereinafter referred to as “high carbon-containing copper layer”). That is, this circuit forming layer is obtained by depositing the surface of the carrier foil by electrodeposition using a copper electrolyte containing an organic agent. For example, a glue or the like in a copper sulfate solution or a copper pyrophosphate solution The organic agent is included in the crystal grains to be electrodeposited by adding the organic agent. This manufacturing method will be described in detail below.

  And the crystal structure which comprises this circuit formation layer (high carbon content copper layer) can be classified into the following two types. That is, one is a needle-like structure (referred to as a columnar structure in the present specification) that grows substantially continuously from the deposition start position DS to the deposition end position DF as shown in FIG. As shown in FIG. 4, “there is a very fine crystal structure, but the crystal has grown discontinuously from the precipitation start position DS to the precipitation end position DF. "It is a structure (it seems that dendritic crystals are deposited vertically)." Of these, the former crystal structure is used. When the latter crystal structure is used, the carrier foil cannot be easily peeled off after the amount of heat at the press working level is applied.

It is possible to separate the crystal structures of the two high carbon-containing coppers described above. Strictly speaking, since there is a relationship with the concentration of organic agent such as glue in the electrolyte, it is difficult to describe it as a clear current value. For example, when the former crystal structure is obtained, 10 A / dm Adopting a low current density of ² or less, and obtaining the latter crystal structure, a high current density of 20 A / dm ² or more is adopted.

  And in order to monitor content of the organic substance in a crystal | crystallization, it decided to use the carbon content of the precipitation copper layer which comprises a circuit formation layer as a parameter | index. As a result, the deposited copper layer constituting the circuit forming layer preferably contains 0.1 wt% to 0.4 wt% as the carbon content. When the carbon content is less than 0.1 wt%, even if the crystal structure shows a columnar structure, a good electrode boundary between the carrier foil and the circuit forming layer cannot be obtained, It is difficult to easily peel off the carrier foil after the amount of heat is applied. On the other hand, the upper limit of 0.4 wt% is a so-called saturation amount, and a carbon content higher than this cannot be achieved. As the carbon concentration in the circuit forming layer is higher, the peeling strength between the carrier foil layer and the circuit forming layer tends to be stabilized at a lower level. However, if the carbon content increases too much, the high carbon content copper tends to become brittle, and more preferably about 0.3 wt% is considered as the upper limit. When the carbon content exceeds 0.3 wt%, the structure of the high carbon content copper suddenly becomes brittle, and at the same time, the electrical resistance increases remarkably.

  And the circuit forming layer described here is a printed wiring such as roughening treatment, silane coupling agent treatment, and long-term storage stability, chemical resistance and moisture absorption resistance to obtain adhesion to the substrates to be bonded. In general, various surface treatments are performed to satisfy the required characteristics required for the plate. Therefore, the electrolytic copper foil with a carrier foil according to the present invention is also required to be provided on the market with a roughened layer on the surface of the circuit forming layer and a necessary surface-treated layer. There is no limitation on the roughening treatment here, and various methods such as a method of adhering and forming fine copper grains and a method of roughening by etching the copper foil surface can be adopted. Similarly, there is no particular limitation on the surface treatment such as rust prevention. Organic rust prevention using benzotriazole, imidazole, or the like, or inorganic rust prevention represented by zinc or brass can be used. In other words, it can be used appropriately and selectively according to the use environment and use conditions of the copper foil. However, in recent years, for the purpose of forming finer circuits, the roughening treatment is omitted, and there is a movement to obtain adhesion between the copper foil layer and the base material layer only by chemical bonding force. It can not be said that is more essential than rust prevention treatment.

Carrier foil layer: This carrier foil is combined with a pure copper layer having a purity of 99.9 wt% or more. Therefore, as long as the purity is 99.9 wt% or more, it may be an electrolytic copper foil or a rolled copper foil. In relation to the carbon content of the high carbon content copper used in the configuration of the circuit forming layer, it is preferable to use a copper foil having a purity of 99.9 wt% or more for the carrier foil of the electrolytic copper foil with a carrier foil. . If the difference between the composition of the carrier foil and the composition of the high-carbon copper layer of the circuit-forming layer that is electrodeposited on the surface is not more than a certain level, the carrier foil can be easily peeled off after the amount of heat at the press working level is applied. Will not be possible.

  In the high carbon content copper layer, the organic agent is dispersed in the grains of the precipitated crystals. That is, even if it is high carbon content copper, there exists a difference in the presence state of the organic substance in the crystal structure. The transmission electron microscope images in FIGS. Electrochem. Soc. 131 (10) 2246 (1984) was used to confirm the presence of organic substances in the crystal, which was observed by cutting perpendicularly to the crystal growth direction.

  Here, the presence of the organic agent in a dispersed manner is used as a general term indicating all the states shown in FIGS. Hereinafter, the dispersion mode of the organic agent will be described. As can be seen from the transmission electron microscope images shown in FIG. 5 and FIG. 6, a state that looks like a worm-like shape or a spherical shape that appears in the crystal grains is indicated, and some points are indicated by arrows. Here, FIG. 5 is a crystal structure in a normal state where no heat treatment is performed immediately after electrolysis, and FIG. 6 is a heat treatment of about 185 ° C. × 60 minutes using the electrolytic copper foil according to the present invention. It is the crystal structure after. As can be seen from these figures, halation occurred at the grain boundaries before heating by the press, and it was confirmed by the analysis with a transmission electron microscope that the organic matter was segregated here. However, depending on whether the organic substance at the grain boundaries has diffused or decomposed and disappeared by the press, halation of the crystal grain boundaries disappears, making it difficult to confirm the grain boundaries.

  On the other hand, even in the case of an electrolytic copper foil that can be recognized as the same high carbon-containing copper as the carbon content, as shown in FIGS. 7 and 8, organic substances are dispersed in the crystal grains before and after heating. There may be cases where no such state exists. In FIG. 7, it can be seen that the organic matter is segregated in a lump shape along the crystal grain boundary. In addition, even in the crystal structure after the heating shown in FIG. 8, there is no presence of organic substances dispersed in the crystal grains confirmed in FIGS. 5 and 6 in the crystal grains. The presence of organic matter in the world is confirmed.

  In addition, the presence state of the organic agent in the crystal of the high carbon content copper is related to the etching rate. In the case of the electrolytic copper foil corresponding to FIGS. 7 and 8, the etching rate is about 1.0 μm / min, whereas in the case of the electrolytic copper foil corresponding to FIGS. The etching rate exceeds 2.0 μm / min. The copper etching rate was measured by peeling off the carrier foil from a 5 cm square sample obtained by pressing an electrolytic copper foil with a carrier foil at 185 ° C. × 60 minutes on an FR-4 base material. It was immersed in sulfuric acid 40 ml / L, hydrogen peroxide water 32 ml / L, liquid temperature 30 ° C.), washed with water, dried, and weighed four times, and etched for a total of 80 seconds to convert the etching rate from the reduction of the copper foil.

Peeling state of carrier foil layer and circuit forming layer: The operation of peeling the carrier foil from the circuit forming layer of the electrolytic copper foil with carrier foil according to the present invention is rather difficult to peel off in the normal state before being heated, The carrier foil tends to be more easily peeled off after a heat amount of about 170 ° C. × 1 hour is applied. On the other hand, normal peelable type electrolytic copper foil with carrier foil is most easily peeled off in a normal state, and the peeling strength tends to increase after heating. Therefore, the behavior related to the peel strength of the carrier foil is completely different from that of the conventional electrolytic copper foil with carrier foil.

  The surface shape of the carrier foil and the circuit forming layer after the electrolytic copper foil with carrier foil according to the present invention is heated at 185 ° C. for 1 hour as the amount of heat received during standard press forming of a normal FR-4 substrate Will be shown. FIG. 9 shows a scanning ion microscope image of the peeled surface of the circuit forming layer, and FIG. 10 shows a scanning ion microscope image of the peeled surface of the carrier foil. Comparing FIG. 9 and FIG. 10, each peeled surface shows a replica shape of both, and because it has been physically peeled off, it is torn microscopically and has microscopic irregularities. A certain state can be confirmed. The fine uneven shape where the circuit forming layer does not exist on the surface of the normal electrolytic copper foil omits physical polishing such as buff polishing to increase the contact interface area with the chemical polishing liquid when surface conditioning. Even so, the reaction rate becomes faster. In addition, it improves resist adhesion when an etching resist layer such as a dry film is formed on the surface, eliminates exposure blur when exposing and developing the etching pattern, and improves the etching factor of the circuit. .

(Electrolytic copper foil with second carrier foil)
The circuit forming layer of the electrolytic copper foil with the second carrier foil is a pure copper layer having a purity of 99.9 wt% or more, a deposited copper layer containing an organic agent formed by electrolysis on the carrier foil, and the deposited The deposited crystal of the copper layer uses a continuous columnar crystal having a fine crystal shape. Therefore, the composition of the circuit forming layer and the carrier foil layer of the electrolytic copper foil with the first carrier foil is reversed. Although it can be clearly understood when compared with the electrolytic copper foil with the first carrier foil, the layer on which the circuit is to be formed is called a circuit forming layer, and the other is called a carrier foil. The reason why the carrier foil can be peeled and removed without the bonding interface layer is that a combination of the composition of the circuit forming layer and the composition of the carrier foil is adopted, and the electrolytic copper with the first carrier foil. The same as in the case of foil.

  Therefore, what is necessary is just to apply the concept regarding the carrier foil of the electrolytic copper foil with 1st carrier foil to the circuit formation layer of the electrolytic copper foil with 2nd carrier foil. However, in such a case, the concept of using a rolled copper foil as the carrier foil of the electrolytic copper foil with the first carrier foil is not applicable, and the circuit forming layer must have a purity of 99.9 wt% or more as the electrolytic copper foil. . And what is necessary is just to apply the concept regarding the circuit formation layer of the electrolytic copper foil with a 1st carrier foil to the carrier foil of the electrolytic copper foil with a 2nd carrier foil. However, since the electrolytic copper foil with the second carrier foil uses high carbon-containing copper as the carrier foil, the etching rate differs from the high carbon-containing copper layer as the circuit forming layer of the electrolytic copper foil with the first carrier foil. There is no need to consider these. From the above, in order to avoid redundant descriptions, descriptions on the circuit forming layer and the carrier foil of the electrolytic copper foil with the second carrier foil are omitted.

<Method for producing electrolytic copper foil with carrier foil>
(Method for producing electrolytic copper foil with first carrier foil)
In the method for producing an electrolytic copper foil with a carrier foil according to the present invention, on the surface of a pure copper layer having a purity of 99.9 wt% or more as a carrier foil, any one kind or two kinds or more of glue, gelatin and collagen peptide are 300 ppm to It is characterized by electrolysis at a current density of 1 A / dm ^{2 to} 10 A / dm ² using a copper sulfate solution containing 3000 ppm and having a liquid temperature of 20 ° C. to 52 ° C.

  In the method for producing an electrolytic copper foil with a carrier foil according to the present invention, a circuit forming layer is directly formed on the surface of the carrier foil using the carrier foil as a starting material. And surface treatments, such as a roughening process and a rust prevention process, are further given as needed.

  In the present invention, a method is adopted in which the carrier foil is cathodically polarized in a copper electrolyte containing an organic agent, and a circuit forming layer is directly deposited on the surface of the carrier foil by an electrolytic method. Also in the case of a normal electrolytic copper foil with a carrier foil, a technique of adding a glue at a level of 20 ppm or less is used in order to improve the elongation rate of the electrolytic copper foil, which is a copper sulfate solution. On the other hand, in the manufacturing method according to the present invention, a concentration of glue of 300 ppm or more is adopted. By setting the concentration to 300 ppm or more, the carbon content concentration (0.1 wt% or more) in the electrolytic copper foil that allows the carrier foil to be peeled off without providing the bonding interface layer can be achieved.

  And, when the organic matter concentration in the copper electrolyte is around 3000 ppm, the amount of organic matter that can be contained in the deposited copper is saturated and the carbon content becomes about 0.4 wt%, and the carbon amount does not increase any more. It becomes. In order to set the carbon content to 0.3 wt% which is the most preferable upper limit value, it is necessary to set the organic substance concentration in the copper electrolyte to about 800 ppm.

In the method for producing a circuit forming layer in the present invention, the liquid temperature is 20 ° C. to 52 ° C., and electrolytic conditions of a current density of 1 A / dm ^{2 to} 10 A / dm ² are used. Simply, in order to obtain high carbon-containing copper in which organic agents are dispersed in the crystal grains, electrolytic conditions in a wider range than those listed here can be employed. However, by performing electrolysis that satisfies this condition, it is a high carbon-containing copper in which the organic agent is dispersed in the grains of the precipitated crystals, and the crystal shape is fine and continuous columnar when observed in cross section. It becomes a crystal. If this condition is not met, even if high-carbon copper is present in which the organic agent is dispersed in the grains of the precipitated crystals, the crystal shape when viewed in cross-section is no longer fine and continuous columnar crystals, and the press It is impossible to easily peel off the carrier foil after the same amount of heat as in the molding is applied. In order to obtain a columnar crystal structure more stably, the current density is preferably 1 A / dm ^{2 to} 7.5 A / dm ^2, and more preferably the current density is 1 A / dm ^{2 to} 5 A / dm ^2. Use conditions.

  And it is preferable to use the organic substance glue, gelatin and collagen peptide having a number average molecular weight of 3500 or more. When the number average molecular weight is less than 3500, electrodeposition itself in the state of containing an organic substance tends to be difficult, and there is a large variation in the peeling strength of the carrier foil after press molding, and the peeling of the carrier foil itself May not be possible. More preferably, glue, gelatin or collagen peptide having a number average molecular weight of 4500 or more is used. The usable current density range is wide, and the stability of the peeling strength of the carrier foil is dramatically increased.

  Here, a method for measuring the number average molecular weight of the organic substance will be described. The number average molecular weight referred to in the present invention is measured using a gel permeation chromatography (GPC) method of a sample solution having a concentration of 3 ppm to 5 ppm in which the above organic substance is dissolved in water. In the present invention, a mixed solution of 20% by volume of acetonitrile and 80% by volume of dilute sulfuric acid having a concentration of 5 mM is used as the mobile phase, and this mobile phase is pumped out by a liquid feed pump. Three columns were passed. The first column is a PEEK column with an inner diameter of 7.5 mm and a length of 250 mm containing a filler having a particle size of 66 μm or less of Sephadex G-15 (exclusion limit molecular weight 1500) manufactured by Amsham Pharmacia Biotech. The second and third columns are Asahipak GS-320HQ (exclusion limit molecular weight 40000) manufactured by Showa Denko KK, an inner diameter of 7.6 mm, and a length of 300 mm. The molecular weight distribution of the organic agent was measured using an absorbance detector (UV210 nm) after passing through the first column to the third column, and the number average molecular weight was calculated.

In the measurement of the number average molecular weight of the organic agent, the reagents used for preparing the calibration curve are as follows. Moreover, the density | concentration of the organic agent was measured by creating a calibration curve using the aqueous solution with the known concentration of the same kind of organic agent.
(reagent)
・ ALBUMIN, BOVINE SERUM (Sigma Aldrich Japan Co., Ltd., molecular weight 66000)
CYTOCHROME C (Sigma Aldrich Japan Co., Ltd., molecular weight 12400)
・ APROTININ (Sigma Aldrich Japan Co., Ltd., molecular weight 6500)
INSULIN (Sigma Aldrich Japan Co., Ltd., molecular weight 5734)
INSULIN CHAIN B, OXIDIZED (Sigma Aldrich Japan Co., Ltd., molecular weight 3496)
・ NEUROTENSIN (manufactured by Sigma Aldrich Japan Co., Ltd., molecular weight 1673)
・ ANGIOTENSIN II (Sigma Aldrich Japan Co., Ltd., molecular weight 1046)
VAL-GLU-GLU-ALA-GLU (Sigma Aldrich Japan, molecular weight 576)

Hereinafter, the roughening treatment and the rust prevention treatment that can be arbitrarily used will be mentioned. In the case where the surface of the circuit forming layer is subjected to a roughening treatment, a method of depositing and adhering fine copper particles, a method of chemically treating the surface of the circuit forming layer, and the like to form an uneven shape. As the roughening treatment, a method of depositing fine copper particles is generally employed. In the case where fine copper particles are deposited using a copper sulfate-based solution, for example, the concentration is 5 to 20 g / l copper, 50 to 200 g / l sulfuric acid, and other additives (α-naphthoquinoline, dextrin, nickel , Thiourea, etc.), liquid temperature of 15 to 40 ° C., current density of 10 to 50 A / dm ² and so on. In order to prevent the fine copper particles deposited and deposited from falling off, it is also preferable to perform a process of uniformly depositing copper so as to cover the fine copper particles under smooth plating conditions. For example, if a copper sulfate-based solution is used, the smooth plating conditions include a copper concentration of 50 to 80 g / l, sulfuric acid 50 to 150 g / l, a liquid temperature of 40 to 50 ° C., and a current density of 10 to 50 A / dm ^2. It is.

Furthermore, a rust preventive treatment is performed as necessary to prevent the surface of the circuit forming layer from being oxidatively corroded so as not to hinder the manufacturing process of the copper clad laminate and the printed wiring board. The method used for the rust prevention treatment may be any of organic rust prevention using benzotriazole, imidazole or the like, or inorganic rust prevention using zinc, chromate, zinc alloy or the like. What is necessary is just to select the rust prevention according to the intended purpose of the electrolytic copper foil with carrier foil. When the zinc rust prevention treatment is performed, the zinc concentration is 5 to 30 g / l, the potassium pyrophosphate concentration is 50 to 500 g / l, the liquid temperature is 20 to 50 ° C., the pH is 9 to 12, and the current density is 0.3 to 10 A / dm ² . And so on.

  Furthermore, it is also preferable to provide a silane coupling agent treatment layer using a silane coupling agent on the surface of the circuit forming layer in order to enhance the adhesion to the base resin. Various silane coupling agents include the most common epoxy functional silane coupling agents, olefin functional silanes, acrylic functional silanes, amino functional silane coupling agents or mercapto functional silane coupling agents. Can be used.

  These silane coupling agents are used at a room temperature level by dissolving 0.5 g / l to 10 g / l in water as a solvent. The silane coupling agent forms a film by condensation bonding with the OH group protruding from the surface of the circuit forming layer, and even if a solution with an excessively high concentration is used, the effect is remarkably increased. Absent. Therefore, it should be originally determined according to the processing speed of the process. However, if it is less than 0.5 g / l, the adsorption rate of the silane coupling agent is slow, which is not suitable for general commercial profit, and the adsorption is not uniform. Even if the concentration exceeds 10 g / l, the adsorption rate is not particularly increased, which is uneconomical. Through the above steps, finally, the first copper foil 1a with carrier foil is obtained by sufficiently washing with water and drying as necessary.

(Method for producing electrolytic copper foil with second carrier foil)
The method for producing the electrolytic copper foil with the second carrier foil uses a copper sulfate solution containing 300 ppm to 3000 ppm of one or more of glue, gelatin, and collagen peptide, and having a liquid temperature of 20 ° C. to 52 ° C. Forming a circuit which is a pure copper layer having a purity of 99.9 wt% or more by electrolysis at a density of 5 A / dm ^{2 to} 10 A / dm ² and using a high carbon-containing copper foil as a carrier foil and electrolyzing a copper electrolyte on the carrier foil The layer is formed by precipitation.

  In this manufacturing method, a high carbon content copper foil to be a carrier foil is first manufactured, and a circuit forming layer, which is a pure copper layer having a purity of 99.9 wt% or more, is deposited on the surface thereof. Since the manufacturing concept regarding the circuit forming layer which is a high carbon content copper foil as a carrier foil and a pure copper layer having a purity of 99.9 wt% or more is similar to the manufacturing method of the electrolytic copper foil with the first carrier foil, The description in is omitted.

(Method capable of producing both electrolytic copper foil with first carrier foil and electrolytic copper foil with second carrier foil)
In this manufacturing method, a pure copper layer having a purity of 99.9 wt% or more used as a circuit forming layer or a carrier foil is deposited on the surface of an electrode plate made of titanium or stainless steel by electrolysis with a copper electrolyte. Then, a copper sulfate solution containing 300 ppm to 3000 ppm of one or more of glue, gelatin and collagen peptide on the pure copper layer and having a liquid temperature of 20 ° C. to 52 ° C. is used, and a current density of 1 A / dm ² to The high carbon content copper layer which electrolyzes at 20 A / dm < ² > and becomes a carrier foil or a circuit formation layer is deposited, and it peels off from an electrode plate, It is characterized by the above-mentioned. Accordingly, when a copper layer having a purity of 99.9 wt% or more is used as the carrier foil layer, the high carbon-containing copper layer to be formed thereafter becomes a circuit forming layer and the electrolytic copper foil with the first carrier foil. And when using a copper layer of purity 99.9 wt% or more as a circuit formation layer, the high carbon content copper layer formed after that turns into a carrier foil layer, and becomes an electrolytic copper foil with the 2nd carrier foil.

  In this way, using an electrode plate made of titanium or stainless steel as a raw material, the layer structure of the electrolytic copper foil with carrier foil according to the present invention is planarly formed on the surface, and bent into a hard and brittle high carbon content copper layer. The addition of stress can be eliminated and the occurrence of microcracks can be prevented. 11 and 12 show the procedure of this manufacturing method. The reason why the electrode plate 4 made of titanium or stainless steel is used is that it is easy to peel off the copper foil layer from the surface and is excellent in durability. Since the manufacturing concept regarding the high carbon content copper foil and the circuit forming layer which is a pure copper layer having a purity of 99.9 wt% or more is the same as the manufacturing method of the electrolytic copper foil with the first carrier foil, the explanation here is Omitted.

<Copper-clad laminate obtained using the electrolytic copper foil with carrier foil according to the present invention>
In the electrolytic copper foil with carrier foil according to the present invention, the carrier foil does not peel off accidentally until the press molding is completed, so the copper-clad laminate obtained using this electrolytic copper foil with carrier foil is surely a circuit. The surface of the circuit formation layer used for formation can be protected from contamination. Then, the surface of the circuit forming layer after the carrier foil is peeled off has a minute uneven shape that does not exist on the surface of the normal electrolytic copper foil. The presence of this concavo-convex shape increases the contact interface area with the chemical polishing liquid when performing the leveling in the etching process, so that the chemical polishing rate is increased even if physical polishing such as buffing is omitted. . In addition, it improves resist adhesion when an etching resist layer such as a dry film is formed on the surface, eliminates exposure blur when exposing and developing the etching pattern, and improves the etching factor of the circuit. .

  The electrolytic copper foil with a carrier foil according to the present invention does not require an essential bonding interface layer for a normal peelable copper foil with a carrier foil. For this reason, there is no residue on the surface of the circuit formation layer of components constituting the bonding interface layer, and circuit etching is not hindered. In addition, since the step of forming the bonding interface layer can be omitted, the manufacturing cost can be suppressed, and the market supply as an inexpensive product can be achieved.

  Moreover, it becomes possible to produce the said electrolytic copper foil with a carrier foil efficiently by using the manufacturing method which concerns on this invention. In particular, when forming a high carbon content copper layer constituting a carrier foil or a circuit forming layer, the use of organic compounds such as glue, gelatin, and collagen peptide having a number average molecular weight of 3500 or more further improves the quality stability. Efficient production of electrolytic copper foil with carrier foil becomes possible.

  Hereinafter, the results of measuring the peeling strength of the carrier foil after press molding after producing the above-described electrolytic foil with carrier foil will be described through examples.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, an electrolytic copper foil 1a with a carrier foil in which the circuit forming layer 3 shown in FIG. That is, an electrolytic copper foil having a thickness of 35 μm is used as the carrier foil 2, and the surface of the carrier foil 2 is pickled to remove contaminants such as adhering oil and fat components and to remove excess surface oxide film. It was. This pickling treatment was performed using a dilute sulfuric acid solution having a concentration of 100 g / l and a liquid temperature of 30 ° C., and an immersion time of 30 seconds. The purity of the electrolytic copper foil used as the carrier foil 2 was 99.9 wt% or more.

The carrier foil 3 after the pickling treatment formed a high carbon-containing copper layer as a circuit forming layer on one side. The circuit forming layer uses a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (number average molecular weight 3500 glue) concentration of 1000 ppm, and a liquid temperature of 40 ° C., and a current density of 2.5 A / dm ^2. Is obtained by directly depositing high carbon-containing copper on the surface of the carrier foil. In addition, the carbon content of this high carbon content copper is 0.35 wt%, the high carbon content copper is present in a state where the organic agent is dispersed in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal. Thus, an electrolytic copper foil 1a with a carrier foil according to the present invention was obtained.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil was measured. The circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil is bonded to the FR-4 base material by hot pressing at 185 ° C. for 1 hour, and simultaneously etched while the carrier foil and the circuit forming layer are overlapped, 10 mm A linear circuit with a width was formed, and this was used as a sample for measuring the peel strength of the carrier foil. As a result, the peel strength of the carrier foil from the circuit forming layer was 83 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, an electrolytic copper foil 1a with a carrier foil in which the circuit forming layer 3 shown in FIG. That is, an electrolytic copper foil having a thickness of 35 μm was used as the carrier foil 2, and pickling treatment was performed in the same manner as in Example 1 to form a high carbon-containing copper layer as a circuit forming layer on one side. The circuit forming layer uses a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 4000) concentration of 900 ppm, and a liquid temperature of 40 ° C., and a current density of 2.5 A / dm ^2. Is obtained by directly depositing high carbon-containing copper on the surface of the carrier foil. In addition, the carbon content of this high carbon content copper is 0.33 wt%, the high carbon content copper has a dispersed organic agent in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal. Thus, an electrolytic copper foil 1a with a carrier foil according to the present invention was obtained.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 68 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, an electrolytic copper foil 1a with a carrier foil in which the circuit forming layer 3 shown in FIG. That is, an electrolytic copper foil having a thickness of 35 μm was used as the carrier foil 2, and pickling treatment was performed in the same manner as in Example 1 to form a high carbon-containing copper layer as a circuit forming layer on one side. The circuit forming layer uses a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (number average molecular weight 4500 glue) concentration of 800 ppm, and a liquid temperature of 40 ° C., and a current density of 5.0 A / dm ^2. Is obtained by directly depositing high carbon-containing copper on the surface of the carrier foil. In addition, the carbon content of this high carbon content copper is 0.32 wt%, the high carbon content copper has an organic agent dispersed in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal. Thus, an electrolytic copper foil 1a with a carrier foil according to the present invention was obtained.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 40 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, an electrolytic copper foil 1a with a carrier foil in which the circuit forming layer 3 shown in FIG. That is, an electrolytic copper foil having a thickness of 35 μm was used as the carrier foil 2, and pickling treatment was performed in the same manner as in Example 1 to form a high carbon-containing copper layer as a circuit forming layer on one side. The circuit forming layer uses a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (number average molecular weight 8800 glue) concentration of 700 ppm, and a liquid temperature of 40 ° C., and a current density of 5.0 A / dm ^2. Is obtained by directly depositing high carbon-containing copper on the surface of the carrier foil. In addition, the carbon content of this high carbon content copper is 0.28 wt%, the said high carbon content copper exists in which the organic agent is dispersed in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal. Thus, an electrolytic copper foil 1a with a carrier foil according to the present invention was obtained.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 37 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, an electrolytic copper foil 1b with a carrier foil in which the carrier foil layer 2 shown in FIG. That is, an electrolytic copper foil composed of high carbon content copper having a thickness of 35 μm was used as the carrier foil 2, and a circuit forming layer having a purity of 99.9 wt% or more was formed as a circuit forming layer on one surface thereof. The carrier foil uses a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 3500) concentration of 300 ppm, and a liquid temperature of 40 ° C., and a current density of 2.5 A / dm ² . It is a 30 cm square high carbon-containing copper sheet which peeled off what was electrolyzed and deposited on the titanium plate. In addition, the carbon content of this high carbon content copper is 0.17 wt%, the high carbon content copper has a dispersed organic agent in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal.

And this high carbon content copper sheet is put in a copper sulfate solution having a free sulfuric acid concentration of 150 g / l, a copper concentration of 65 g / l, and a liquid temperature of 45 ° C., and a flat anode electrode is arranged in parallel to the high carbon content copper sheet. Then, electrolysis was performed under smooth plating conditions with a current density of 15 A / dm ² , and a circuit forming layer having a purity of 99.9 wt% or more having a thickness of 5 μm was formed on one side of the high carbon-containing copper sheet. As described above, an electrolytic copper foil 1b with a carrier foil according to the present invention was obtained.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1b with carrier foil was measured. Here, since the carrier foil layer 2 is a high carbon-containing copper foil and lacks toughness, if the carrier foil layer 2 is peeled off from the electrolytic copper foil layer 3, there is a high possibility that the measurement error of the peeling strength will increase. Therefore, the carrier foil layer 2 of the electrolytic copper foil with carrier foil 1b is bonded to the FR-4 substrate by hot pressing at 185 ° C. for 1 hour, and the circuit forming layer is plated up to 12 μm to form the carrier foil and the circuit. Etching was performed simultaneously with the layers overlapping to form a 10 mm-wide linear circuit, and the circuit-forming layer plated up with the circuit was peeled off to measure the peel strength. As a result, the peel strength of the carrier foil from the circuit forming layer was 82 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, an electrolytic copper foil 1b with a carrier foil in which the carrier foil layer 2 shown in FIG. That is, an electrolytic copper foil composed of high carbon content copper having a thickness of 35 μm was used as the carrier foil 2, and a circuit forming layer having a purity of 99.9 wt% or more was formed as a circuit forming layer on one surface thereof. The carrier foil uses a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 4000) concentration of 400 ppm, a liquid temperature of 40 ° C., and a current density of 2.5 A / dm ² . It is a 30 cm square high carbon-containing copper sheet which peeled off what was electrolyzed and deposited on the titanium plate. In addition, the carbon content of this high carbon content copper is 0.17 wt%, the high carbon content copper has a dispersed organic agent in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal. Thereafter, in the same manner as in Example 5, a circuit forming layer having a purity of 99.9 wt% or more was formed on one side of the high carbon content copper sheet. As described above, an electrolytic copper foil 1b with a carrier foil according to the present invention was obtained.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1b with carrier foil was measured in the same manner as in Example 5. As a result, the peel strength of the carrier foil from the circuit forming layer was 67 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, an electrolytic copper foil 1b with a carrier foil in which the carrier foil layer 2 shown in FIG. That is, an electrolytic copper foil composed of high carbon content copper having a thickness of 35 μm was used as the carrier foil 2, and a circuit forming layer having a purity of 99.9 wt% or more was formed as a circuit forming layer on one surface thereof. The carrier foil uses a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 4500) concentration of 300 ppm, and a liquid temperature of 40 ° C., and a current density of 2.5 A / dm ² . It is a 30 cm square high carbon-containing copper sheet which peeled off what was electrolyzed and deposited on the titanium plate. In addition, the carbon content of this high carbon content copper is 0.18 wt%, the said high carbon content copper exists by disperse | distributing an organic agent in the particle | grains of a deposited crystal, and the crystal shape when cross-sectional observation is carried out is carried out. It was a fine and continuous columnar crystal. Thereafter, in the same manner as in Example 5, a circuit forming layer having a purity of 99.9 wt% or more was formed on one side of the high carbon content copper sheet. As described above, an electrolytic copper foil 1b with a carrier foil according to the present invention was obtained.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1b with carrier foil was measured in the same manner as in Example 5. As a result, the peel strength of the carrier foil from the circuit forming layer was 38 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, an electrolytic copper foil 1b with a carrier foil in which the carrier foil layer 2 shown in FIG. That is, an electrolytic copper foil composed of high carbon content copper having a thickness of 35 μm was used as the carrier foil 2, and a circuit forming layer having a purity of 99.9 wt% or more was formed as a circuit forming layer on one surface thereof. The carrier foil uses a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 8800) concentration of 400 ppm and a liquid temperature of 40 ° C., and a current density of 2.5 A / dm ² . It is a 30 cm square high carbon-containing copper sheet which peeled off what was electrolyzed and deposited on the titanium plate. In addition, the carbon content of this high carbon content copper is 0.21 wt%, the said high carbon content copper exists in the particle | grains of a precipitation crystal, the organic agent disperse | distributes, and the crystal shape when cross-sectional observation is carried out It was a fine and continuous columnar crystal. Thereafter, in the same manner as in Example 5, a circuit forming layer having a purity of 99.9 wt% or more was formed on one side of the high carbon content copper sheet. As described above, an electrolytic copper foil 1b with a carrier foil according to the present invention was obtained.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1b with carrier foil was measured in the same manner as in Example 5. As a result, the peel strength of the carrier foil from the circuit forming layer was 36 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this embodiment, a titanium plate is used as an electrode plate in the procedure shown in FIG. 12, a pure copper layer having a purity of 99.9 wt% or more is formed on one surface, and a high carbon content copper layer is formed on the surface of the pure copper layer. It formed and peeled from between an electrode plate and a pure copper layer, and manufactured electrolytic copper foil with carrier foil. That is, the surface of a titanium plate as an electrode plate is placed in a copper sulfate solution having a free sulfuric acid concentration of 150 g / l, a copper concentration of 65 g / l, and a liquid temperature of 45 ° C., and electrolyzed under smooth plating conditions with a current density of 15 A / dm ^2. Then, a pure copper layer having a purity of 99.9 wt% or more and having a thickness of 35 μm used as a carrier foil layer was formed.

On the pure copper layer, a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (a glue having a number average molecular weight of 3500) of 800 ppm and a liquid temperature of 40 ° C. is used. Electrolysis was performed at 5 A / dm ² to form a high carbon-containing copper layer having a thickness of 5 μm used as a circuit formation layer. In addition, the carbon content of this high carbon content copper is 0.33 wt%, the high carbon content copper has a dispersed organic agent in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal. And after fully washing and drying, it peeled off from the interface of an electrode plate and a high carbon content copper layer, and obtained electrolytic copper foil 1a with a carrier foil which concerns on this invention.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 86 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, a titanium plate was used as an electrode plate in the procedure shown in FIG. 12, and a pure copper layer having a purity of 99.9 wt% or more was formed as a 35 μm-thick carrier foil layer on one side in the same manner as in Example 9. Then, a high carbon-containing copper layer was formed on the surface of the pure copper layer, and peeled from between the electrode plate and the pure copper layer to produce an electrolytic copper foil with a carrier foil.

On the pure copper layer, a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 4000) concentration of 600 ppm and a liquid temperature of 40 ° C. is used. Electrolysis was performed at 5 A / dm ² to form a high carbon-containing copper layer having a thickness of 5 μm used as a circuit formation layer. In addition, the carbon content of this high carbon content copper is 0.28 wt%, the said high carbon content copper exists in which the organic agent is dispersed in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal.

  And after fully washing and drying, it peeled off from the interface of an electrode plate and a pure copper layer, and obtained electrolytic copper foil 1a with a carrier foil which concerns on this invention.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 74 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, a titanium plate was used as an electrode plate in the procedure shown in FIG. 12, and a pure copper layer having a purity of 99.9 wt% or more was formed as a 35 μm-thick carrier foil layer on one side in the same manner as in Example 9. Then, a high carbon-containing copper layer was formed on the surface of the pure copper layer, and peeled from between the electrode plate and the pure copper layer to produce an electrolytic copper foil with a carrier foil.

On this pure copper layer, a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 4500) concentration of 700 ppm and a liquid temperature of 40 ° C. is used. Electrolysis was performed at 5 A / dm ² to form a high carbon-containing copper layer having a thickness of 5 μm used as a circuit formation layer. In addition, the carbon content of this high carbon content copper is 0.29 wt%, the high carbon content copper has a dispersed organic agent in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal.

  And after fully washing and drying, it peeled off from the interface of an electrode plate and a pure copper layer, and obtained electrolytic copper foil 1a with a carrier foil which concerns on this invention.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 45 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this example, a titanium plate was used as an electrode plate in the procedure shown in FIG. 12, and a pure copper layer having a purity of 99.9 wt% or more was formed as a 35 μm-thick carrier foil layer on one side in the same manner as in Example 9. Then, a high carbon-containing copper layer was formed on the surface of the pure copper layer, and peeled from between the electrode plate and the pure copper layer to produce an electrolytic copper foil with a carrier foil.

On the pure copper layer, a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 8800) concentration of 750 ppm and a liquid temperature of 40 ° C. is used. Electrolysis was performed at 5 A / dm ² to form a high carbon-containing copper layer having a thickness of 5 μm used as a circuit formation layer. In addition, the carbon content of the high carbon content copper is 0.30 wt%, the high carbon content copper has a dispersed organic agent in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal.

  And after fully washing and drying, it peeled off from the interface of an electrode plate and a pure copper layer, and obtained electrolytic copper foil 1a with a carrier foil which concerns on this invention.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1a with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 31 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this embodiment, a titanium plate is used as an electrode plate in the procedure shown in FIG. 12, a pure copper layer having a purity of 99.9 wt% or more is formed on one surface, and a high carbon content copper layer is formed on the surface of the pure copper layer. It formed and peeled from between an electrode plate and a pure copper layer, and manufactured electrolytic copper foil with carrier foil. That is, the surface of a titanium plate as an electrode plate is placed in a copper sulfate solution having a free sulfuric acid concentration of 150 g / l, a copper concentration of 65 g / l, and a liquid temperature of 45 ° C., and electrolyzed under smooth plating conditions with a current density of 15 A / dm ^2. Then, a pure copper layer having a purity of 99.9 wt% or more and having a thickness of 5 μm used as a circuit forming layer was formed.

On the pure copper layer, a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (a glue having a number average molecular weight of 3500) of 300 ppm and a liquid temperature of 40 ° C. is used. Electrolysis was performed at 5 A / dm ² to form a 35 μm thick high carbon-containing copper layer used as a carrier foil layer. In addition, the carbon content of this high carbon content copper is 0.17 wt%, the high carbon content copper has a dispersed organic agent in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal. And after fully washing and drying, it peeled off from the interface of an electrode plate and a high carbon content copper layer, and obtained electrolytic copper foil 1b with carrier foil which concerns on this invention.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1b with carrier foil was measured in the same manner as in Example 5. As a result, the peel strength of the carrier foil from the circuit forming layer was 88 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this embodiment, a titanium plate is used as an electrode plate in the procedure shown in FIG. 12, a pure copper layer having a purity of 99.9 wt% or more is formed on one surface, and a high carbon content copper layer is formed on the surface of the pure copper layer. It formed and peeled from between an electrode plate and a pure copper layer, and manufactured electrolytic copper foil with carrier foil. That is, a pure copper layer having a purity of 99.9 wt% or more having a thickness of 5 μm and used as a circuit forming layer was formed on the surface of a titanium plate as an electrode plate in the same manner as in Example 13.

On the pure copper layer, a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 4000) concentration of 350 ppm and a liquid temperature of 40 ° C. is used. Electrolysis was performed at 5 A / dm ² to form a 35 μm thick high carbon-containing copper layer used as a carrier foil layer. In addition, the carbon content of this high carbon content copper is 0.19 wt%, the high carbon content copper has a dispersed organic agent in the grains of the precipitated crystal, and the crystal shape when the cross section is observed. It was a fine and continuous columnar crystal. And after fully washing and drying, it peeled off from the interface of an electrode plate and a high carbon content copper layer, and obtained electrolytic copper foil 1b with carrier foil which concerns on this invention.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1b with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 73 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this embodiment, a titanium plate is used as an electrode plate in the procedure shown in FIG. 12, a pure copper layer having a purity of 99.9 wt% or more is formed on one surface, and a high carbon content copper layer is formed on the surface of the pure copper layer. It formed and peeled from between an electrode plate and a pure copper layer, and manufactured electrolytic copper foil with carrier foil. That is, a pure copper layer having a purity of 99.9 wt% or more having a thickness of 5 μm and used as a circuit forming layer was formed on the surface of a titanium plate as an electrode plate in the same manner as in Example 13.

On the pure copper layer, a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 4500) concentration of 350 ppm and a liquid temperature of 40 ° C. is used. Electrolysis was performed at 5 A / dm ² to form a 35 μm thick high carbon-containing copper layer used as a carrier foil layer. In addition, the carbon content of this high carbon content copper is 0.21 wt%, the said high carbon content copper exists in the particle | grains of precipitation crystal | crystallization, disperse | distributes an organic agent, and the crystal shape when cross-sectional observation is carried out It was a fine and continuous columnar crystal. And after fully washing and drying, it peeled off from the interface of an electrode plate and a high carbon content copper layer, and obtained electrolytic copper foil 1b with carrier foil which concerns on this invention.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1b with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 46 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

<Manufacture of electrolytic copper foil with carrier foil>
In this embodiment, a titanium plate is used as an electrode plate in the procedure shown in FIG. 12, a pure copper layer having a purity of 99.9 wt% or more is formed on one surface, and a high carbon content copper layer is formed on the surface of the pure copper layer. It formed and peeled from between an electrode plate and a pure copper layer, and manufactured electrolytic copper foil with carrier foil. That is, a pure copper layer having a purity of 99.9 wt% or more having a thickness of 5 μm and used as a circuit forming layer was formed on the surface of a titanium plate as an electrode plate in the same manner as in Example 13.

On this pure copper layer, a solution having a free sulfuric acid concentration of 70 g / l, a copper sulfate concentration of 250 g / l, an organic agent (glue having a number average molecular weight of 8800) concentration of 350 ppm and a liquid temperature of 40 ° C. is used. Electrolysis was performed at 5 A / dm ² to form a 35 μm-thick high carbon-containing copper layer used as a circuit forming layer. In addition, the carbon content of this high carbon content copper is 0.22 wt%, the high carbon content copper is present in the form of a crystal when the organic agent is dispersed in the grains of the precipitated crystal and the cross section is observed. It was a fine and continuous columnar crystal. And after fully washing and drying, it peeled off from the interface of an electrode plate and a high carbon content copper layer, and obtained electrolytic copper foil 1b with carrier foil which concerns on this invention.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 of the electrolytic copper foil 1b with carrier foil was measured in the same manner as in Example 1. As a result, the peel strength of the carrier foil from the circuit forming layer was 31 gf / cm. It was difficult to peel off the carrier foil in a normal state before heating.

Comparative Example 1

<Manufacture of electrolytic copper foil with carrier foil>
In this comparative example, the organic agent (glue having a number average molecular weight of 8800) when forming the high carbon-containing copper layer of Example 1 was reduced to a concentration of 10 ppm and electrolysis was performed at a current density of 5 A / dm ^2. A product having the same layer structure as that of the electrolytic copper foil 1a with carrier foil according to the present invention, in which copper having a low carbon content (0.003 wt%) is directly deposited on the surface of the carrier foil composed of a pure copper layer. It was.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer 2 and the circuit forming layer 3 was measured. As a result, it was not possible to peel off the carrier foil in both the normal state before heating and after being bonded to the FR-4 substrate by hot pressing at 185 ° C. for 1 hour.

Comparative Example 2

<Manufacture of electrolytic copper foil with carrier foil>
In this comparative example, when the high carbon content copper layer of Example 1 is formed, the concentration of the organic agent (glue having a number average molecular weight of 8800) is 3000 ppm, and electrolysis is performed at a current density of 20 A / dm ² that is outside the appropriate range of the current density. As a matter of fact, high carbon-containing copper was directly deposited on the surface of the carrier foil composed of a pure copper layer, and a product having a layer structure similar to that of the electrolytic copper foil 1a with carrier foil according to the present invention was obtained. In addition, although the carbon content of this high carbon content copper was 0.27 wt%, the crystal shape when the cross section of the said high carbon content copper was observed was not a continuous and columnar crystal.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer and the circuit forming layer was measured. As a result, it was not possible to peel off the carrier foil in both the normal state before heating and after being bonded to the FR-4 substrate by hot pressing at 185 ° C. for 1 hour.

Comparative Example 3

<Manufacture of electrolytic copper foil with carrier foil>
In this comparative example, a glue having a low number average molecular weight (number average molecular weight 2200) is used as the organic agent when forming the high carbon-containing copper layer of Example 1 at a concentration of 1000 ppm, and the current density is 2.5 A / dm ^2. As a result of the electrolysis, the high carbon-containing copper was directly deposited on the surface of the carrier foil composed of a pure copper layer to obtain a product having the same layer structure as the electrolytic copper foil 1a with a carrier foil according to the present invention. The carbon content of the high carbon content copper at this time was 0.34 wt%, but the crystal shape when the cross section of the high carbon content copper was observed was not a complete columnar crystal.

<Peeling strength of carrier foil of electrolytic copper foil with carrier foil>
The peel strength between the carrier foil layer and the circuit forming layer was measured. As a result, it was not possible to peel off the carrier foil in both the normal state before heating and after being bonded to the FR-4 substrate by hot pressing at 185 ° C. for 1 hour.

  As described above, the peelable-type electrolytic copper foil with a carrier foil according to the present invention does not require a bonding interface layer that is essential for a normal peelable-type copper foil with a carrier foil. Therefore, the components constituting the bonding interface layer do not remain on the surface of the circuit formation layer, and circuit etching is not hindered, which is suitable for forming a fine pitch circuit. Moreover, the process management for forming the bonding interface layer is unnecessary, and the manufacturing process can be shortened, so that the manufacturing cost of the electrolytic copper foil with carrier foil can be suppressed. As a result, the copper-clad laminate using this The price of the board and the printed wiring board can be reduced.

The schematic cross section of the electrolytic copper foil with carrier foil which concerns on this invention. The schematic cross section of the electrolytic copper foil with carrier foil which concerns on this invention. Crystal structure seen from a cross section of a high carbon content copper layer. Crystal structure seen from a cross section of a high carbon content copper layer. The TEM image showing the dispersed state of the organic substance (glue) which disperse | distributes in the precipitation crystal | crystallization of the high carbon content copper layer sample-adjusted by focused ion beam processing. The TEM image showing the dispersed state of the organic substance (glue) which disperse | distributes in the precipitation crystal | crystallization of the high carbon content copper layer sample-adjusted by focused ion beam processing. The TEM image showing the dispersed state of the organic substance (glue) which disperse | distributes in the precipitation crystal | crystallization of the high carbon content copper layer sample-adjusted by focused ion beam processing. The TEM image showing the dispersed state of the organic substance (glue) which disperse | distributes in the precipitation crystal | crystallization of the high carbon content copper layer sample-adjusted by focused ion beam processing. The scanning ion microscope image of the peeling surface of a circuit formation layer. Scanning ion microscope image of the peeled surface of the carrier foil. The schematic diagram which shows the manufacture flow of the electrolytic copper foil with a carrier foil at the time of using an electrode plate. The schematic diagram which shows the manufacture flow of the electrolytic copper foil with a carrier foil at the time of using an electrode plate. The schematic cross section of the conventional electrolytic copper foil with carrier foil.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a Electrolytic copper foil with 1st carrier foil 1b Electrolytic copper foil with 2nd carrier foil 2 Carrier foil 3 Circuit formation layer 4 Electrode board 5 High carbon containing copper layer 6 Pure copper layer 7 Bonding interface layer 8 Electrolytic copper foil with carrier foil

Claims (11)

An electrolytic copper foil with a carrier foil provided with a circuit forming layer on the surface of the carrier foil,
The circuit forming layer is a deposited copper layer containing an organic agent formed by electrolysis, and the deposited crystal of the deposited copper layer is a continuous columnar crystal with a fine crystal shape,
An electrolytic copper foil with a carrier foil, wherein the carrier foil is a pure copper layer having a purity of 99.9 wt% or more. 2. The electrolytic copper foil with carrier foil according to claim 1, wherein the deposited copper layer constituting the circuit forming layer contains 0.1 wt% to 0.4 wt% as a carbon content. 3. The electrolytic copper foil with carrier foil according to claim 1, wherein the deposited copper layer constituting the circuit forming layer is an organic agent dispersed in the grains of the deposited crystal. . An electrolytic copper foil with a carrier foil provided with a circuit forming layer on the surface of the carrier foil,
The circuit forming layer is a pure copper layer having a purity of 99.9 wt% or more,
The carrier foil is a deposited copper layer containing an organic agent formed by electrolysis, and the deposited crystal of the deposited copper layer has a fine crystal shape and is a continuous columnar crystal. . The deposited copper layer constituting the carrier foil is an electrolytic copper foil with a carrier foil according to claim 4, containing 0.1 wt% to 0.4 wt% as a carbon content. 6. The electrolytic copper foil with carrier foil according to claim 4 or 5, wherein the deposited copper layer constituting the carrier foil is one in which an organic agent is dispersed in the grains of precipitated crystals. A method for producing an electrolytic copper foil with a carrier foil according to any one of claims 1 to 3,
Copper sulfate containing 300 ppm to 3000 ppm of one or more of glue, gelatin and collagen peptide on the surface of a pure copper layer having a purity of 99.9 wt% or more as a carrier foil and having a liquid temperature of 20 ° C. to 52 ° C. A method for producing an electrolytic copper foil with a carrier foil, comprising using a solution and electrolyzing at a current density of 1 A / dm ^{2 to} 10 A / dm ² to form a circuit forming layer. It is a manufacturing method of the electrolytic copper foil with a carrier foil in any one of Claims 4-6,
Electrolysis at a current density of 1 A / dm ^{2 to} 10 A / dm ² using a copper sulfate solution containing 300 ppm to 3000 ppm of any one or more of glue, gelatin and collagen peptides and having a liquid temperature of 20 ° C. to 52 ° C. With a carrier foil, a high-carbon copper foil is used as a carrier foil, and a copper electrolyte is electrolyzed on the carrier foil to form a circuit forming layer, which is a pure copper layer having a purity of 99.9 wt% or more. Manufacturing method of electrolytic copper foil. A method for producing an electrolytic copper foil with a carrier foil according to any one of claims 1 to 6,
On the surface of an electrode plate made of titanium or stainless steel, a pure copper layer having a purity of 99.9 wt% or more used as a circuit forming layer or a carrier foil by electrolyzing a copper electrolyte is deposited,
A copper sulfate solution containing 300 ppm to 3000 ppm of one or more of glue, gelatin and collagen peptide on the pure copper layer and having a liquid temperature of 20 ° C. to 52 ° C. is used, and a current density of 1 A / dm ^{2 to} 10 A / A method for producing an electrolytic copper foil with a carrier foil, characterized by depositing a high carbon-containing copper layer to be electrolyzed at dm ² to be a carrier foil or a circuit forming layer and peeling it off from an electrode plate. The method for producing an electrolytic copper foil with a carrier foil according to any one of claims 7 to 9, wherein glue, gelatin, and collagen peptide have a number average molecular weight of 3500 or more. The copper clad laminated board obtained using the electrolytic copper foil with a carrier foil in any one of Claims 1-6.