JP2008101267A - Electrolytic copper foil, surface treated copper foil using the electrolytic copper foil, copper-clad laminated plate using the surface treated copper foil, and method for manufacturing the electrolytic copper foil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolytic copper foil, which has a low profile surface equivalent to conventional low-profile electrolytic copper foil and has very large mechanical strength, and to provide a method for manufacturing the same. <P>SOLUTION: In order to solve the problem, the electrolytic copper foil comprises fine precipitated crystal particles of copper, of which the particle diameters have a small variation unattainable by a prior art technique. The electrolytic copper foil has a lustrous surface with a low profile, has a very large mechanical strength of 70 to 100 kgf/mm<SP>2</SP>in terms of a normal-state tensile strength value, and even after heating (180°C×60 minutes), has a tensile strength value of not less than 85% of the normal-state tensile strength value. The electrolytic copper foil is manufactured by an electrolytic method using a sulfuric acid-type copper electrolysis solution containing a compound having a structure comprising a sulfone group attached to the benzene ring, a sulfonic acid salt of an active sulfur compound, and a quaternary ammonium salt polymer having a cyclic structure. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrolytic copper foil, a surface-treated copper foil using the electrolytic copper foil, a copper-clad laminate using the surface-treated copper foil, and a method for producing the electrolytic copper foil. In particular, the present invention relates to an electrolytic copper foil having a low precipitation profile and high mechanical strength, and a method for manufacturing the same.

  Along with the demands for so-called miniaturization and miniaturization such as miniaturization and weight reduction of electronic and electrical equipment, similar demands are made for recent printed wiring boards. Since this printed wiring board is required to form a circuit corresponding to miniaturization and high functionality within a limited mounting space, it is necessary to make the circuit finer by increasing the circuit pitch. . In order to obtain such a fine pitch circuit, a thinner copper foil has been adopted, and the roughness of the substrate contact surface of the copper foil has been reduced to shorten the overetching time.

  For this purpose, low profile electrolytic copper foil is generally used. Moreover, even if the foil is thinned, efforts have been made to increase the mechanical strength in order to improve the handling properties of the copper foil and the copper-clad laminate. Such an electrolytic copper foil having a low profile and excellent mechanical strength is disclosed in Patent Document 1 and Patent Document 2. These will be briefly described below.

  Patent Document 1 discloses a low rough surface electrolytic copper foil that has a low rough surface that is practical for use in printed wiring boards and negative electrode current collector applications for lithium secondary batteries and that is excellent in fatigue flexibility. A low roughness surface having a surface roughness Rz of 2.0 μm or less and having a rough surface with no unevenness and a uniform low roughness, and an elongation at 180 ° C. of 10.0% or more. For the purpose of providing an electrolytic copper foil, an aqueous solution of sulfuric acid-copper sulfate is used as an electrolytic solution, and an insoluble anode made of a titanium plate coated with a white metal element or its oxide element and a titanium drum on the cathode facing the anode. A method for producing an electrolytic copper foil that uses a direct current between both electrodes is disclosed. In this production method, the presence of an oxyethylene surfactant, polyethyleneimine or a derivative thereof, a sulfonic acid salt of an active organic sulfur compound, and a chloride ion in the electrolytic solution causes a roughness Rz of 2.0 μm or less. The rough surface has a rough surface with no unevenness and has a uniformly low roughness, and a low rough surface electrolytic copper foil having an elongation at 180 ° C. of 10.0% or more can be obtained. In the Example of this patent document 1, the surface roughness (Rz) of the deposition surface of the obtained electrolytic copper foil is 0.9 μm to 2.0 μm, the value of the normal elongation is 10% to 18%, at 180 ° C. It is disclosed that the elongation value was 10% to 20%, the normal tensile strength value was 340 MPa to 500 MPa, and the tensile strength value at 180 ° C. was 180 MPa to 280 MPa. Furthermore, it is disclosed that the glossiness [Gs (85 °)] in the width direction of the deposited surface of the electrolytic copper foil was 120 to 132.

  Patent Document 2 discloses a low-roughened electrolytic copper foil having a roughened surface that has a low roughness, a low rate of decrease in tensile strength with time or heat treatment, and an excellent elongation at high temperatures, and a method for producing the same. For the purpose of providing, an electrolytic solution comprising a sulfuric acid-copper sulfate aqueous solution contains five additives of hydroxyethyl cellulose, polyethyleneimine, acetylene glycol, sulfonate of an active organic sulfur compound, and chloride ion. The rough surface roughness Rz of the foil is 2.5 μm or less, the tensile strength at 25 ° C. measured within 20 minutes from the completion of electrodeposition is 500 MPa or more, and 25 ° C. measured after 300 minutes from the completion of electrodeposition. The rate of decrease in tensile strength at 10% or less, or 25 ° C. measured after heat treatment at 100 ° C. for 10 minutes from the completion of electrodeposition A technique for obtaining a low-roughened surface electrolytic copper foil having a tensile strength decrease rate of 10% or less and an elongation rate at 180 ° C. of 6% or more is disclosed.

In an example of this Patent Document 2, an electrolytic solution comprising a sulfuric acid-copper sulfate aqueous solution of sulfuric acid (H ₂ SO ₄ ): 100 g / L, copper sulfate pentahydrate (CuSO ₄ .5H ₂ O): 280 g / L. Insoluble anode made of titanium, in which hydroxyethyl cellulose, polyethyleneimine, sodium 3-mercapto-1-propanesulfonate, acetylene glycol and hydrochloric acid are added as additives and the electrolyte is coated with a white metal oxide And an electrolytic copper foil having a thickness of 18 μm obtained by electrodeposition at an electrolytic current density of 40 A / dm ² and an electrolyte temperature of 40 ° C. The surface roughness (Rz) of the surface is 1.5 μm to 2.3 μm, the normal tensile strength is 650 MPa to 900 MPa, and the rate of decrease in tensile strength after heating at 100 ° C. for 10 minutes is 0% to 7. % It had been at is disclosed.

  As mentioned above, according to each Example, the precipitation surface of the electrolytic copper foil manufactured using these manufacturing methods is a low profile. The level is excellent as a conventional low profile electrolytic copper foil, and can be effective in forming a fine pitch circuit. It is also disclosed that mechanical strength superior to that of conventional electrolytic copper foil can be obtained. In addition, although it describes for convenience, the low profile in the copper foil for printed wiring boards is used in the meaning that the unevenness | corrugation in the joining interface with the insulating layer constituent material of copper foil is low.

JP 2004-263289 A JP 2004-339558 A

  As described above, many products and varieties having various qualities exist in the electrolytic copper foil for printed wiring boards. In particular, tape automated bonding (TAB) substrates that directly mount devices such as IC chips are formed with fine pitch circuits that far exceed rigid printed wiring boards, and the demand for low profile electrolytic copper foil is remarkable. Met. However, the TAB substrate has a flying lead 1 as schematically shown in FIG. 1, and a device is directly mounted on this portion. Therefore, if the mechanical strength of the electrolytic copper foil used is small, there is a disadvantage that the flying lead 1 is extended by the pressure during bonding. In addition to the flying lead 1, FIG. 1 shows a circuit 2 made of copper foil, an adhesive 3, a base film (polyimide film) 4, a solder resist 5, a back side solder resist 6, and a device (IC chip) 7. , IC connection part (device hole) 8, gang bonding support base 9, first terminal part 10 as a connection part with a liquid crystal display panel, etc., second terminal part 11 as a connection part with a printed wiring board, bent part A cross section including a device hole portion of a TAB composed of 12 is schematically shown.

On the other hand, it is judged that there is a limit to the increase in the mechanical strength of the electrolytic copper foil, and the product manufactured from the TAB substrate to the COF substrate (chip-on-film substrate) without flying leads schematically shown in FIG. There is a movement to shift. When device mounting on a COF substrate becomes mainstream, the TAB substrate bonding machine possessed by those skilled in the art is not effectively used, and it can be said that it is a loss of social capital. In order to solve this problem, it is considered that a fine wire circuit can be formed on a TAB substrate, and the mechanical strength equivalent to that of a phosphor bronze hard material having a tensile strength exceeding 70 kgf / mm ² is an electrolytic copper foil. Has been desired. In addition to the bonding lead 1, FIG. 2 shows a circuit 2 ′ formed of copper foil, a base film (polyimide film) 4 ′, a solder resist 5 ′, a device (IC chip) 7 ′, an IC connection portion 8. A cross section of a COF having a configuration including a first terminal portion 10 'serving as a connection portion with a liquid crystal display panel, a second terminal portion 11' serving as a connection portion with a printed wiring board, and a bent portion 12 'is schematically illustrated. Indicated.

An electrolytic copper foil showing a tensile strength value exceeding 70 kgf / mm ² is disclosed in Patent Document 2. However, even if a trace experiment shown later as a comparative example is performed, high strength at the level described in Patent Document 2 cannot be obtained, and the value of tensile strength is only about 58 kgf / mm ² . Therefore, with electrolytic copper foil, it can be said that it is difficult to stably produce a product having a mechanical strength equivalent to that of phosphor bronze having a tensile strength value exceeding 70 kgf / mm ² .

  From the above, in the printed wiring board industry, there has been a demand for an electrolytic copper foil having a low profile surface and having a mechanical strength that is extremely large as compared with the conventional one and a stable manufacturing method thereof.

  Therefore, as a result of diligent research, the inventors of the present invention have provided a precipitation surface having a gloss with a low profile by reducing the variation in the particle diameter to a level unprecedented as a result of fine copper crystal grains. The inventors have come up with an electrolytic copper foil having a very high mechanical strength and a small change in mechanical properties with time, and a method for producing the same.

Electrolytic copper foil according to the present invention: electrolytic copper foil according to the present invention, the electrodeposited copper foil obtained by electrolyzing a copper electrolyte, the value of the normal tensile strength is 70kgf ^/ mm ² ~100kgf ^/ mm 2 It is characterized by that.

  And as for the electrolytic copper foil which concerns on this invention, it is preferable that the value of the tensile strength after a heating for 180 degreeC x 60 minutes is 85% or more of the value of a normal state tensile strength.

In addition, the electrolytic copper foil according to the present invention preferably has a normal tensile strength value of 65 kgf / mm ² or more after 30 days from the production.

  Furthermore, the electrolytic copper foil according to the present invention preferably has a normal elongation value of 3% to 15%.

  And the electrolytic copper foil which concerns on this invention is also characterized by the value of 180 degreeC x 60 minute post-heating elongation being lower than the value of normal state elongation.

  The electrolytic copper foil according to the present invention preferably has a glossiness [Gs (60 °)] value of 80 or more measured at an incident / reflection angle of 60 ° with respect to the width direction of the deposition surface.

Surface-treated electrolytic copper foil according to the present invention: The surface-treated electrolytic copper foil according to the present invention comprises one or more of roughening treatment, rust prevention treatment, and silane coupling agent treatment on the surface of the electrolytic copper foil. It is characterized by what has been done.

Manufacturing method of electrolytic copper foil according to the present invention: The manufacturing method of the electrolytic copper foil according to the present invention is a method of manufacturing an electrolytic copper foil by an electrolytic method using a sulfuric acid-based copper electrolytic solution. What contains the following additive A-additive C is used, It is characterized by the above-mentioned.

Additive A: a compound having a structure having a benzene ring and a heterocyclic ring containing a nitrogen atom (N), and a mercapto group bonded to the heterocyclic ring, or a thiourea compound.
Additive B: sulfonate salt of active sulfur compound.
Additive C: A quaternary ammonium salt polymer having a cyclic structure.

  In the method for producing an electrolytic copper foil according to the present invention, the additive A is any one of an imidazole compound, a thiazole compound, a tetrazole compound, or a thiourea compound having two or more alkane groups at both ends. It is preferable to use 1 type or 2 types or more.

  As for the said additive A used with the manufacturing method of the electrolytic copper foil which concerns on this invention, it is more preferable that the sulfone group has couple | bonded with the benzene ring.

  The additive A is any one of 2-mercapto-5-benzimidazolesulfonic acid, 3 (5-mercapto-1H-tetrazolyl) benzenesulfonate, 2-mercaptobenzothiazole, or NN diethylthiourea. Or it is preferable that they are 2 or more types.

  The total concentration of the additive A in the sulfuric acid-based copper electrolyte is preferably 1 ppm to 50 ppm.

  The additive B in the method for producing an electrolytic copper foil according to the present invention is preferably any one or a mixture of 3-mercapto-1-propanesulfonic acid and bis (3-sulfopropyl) disulfide.

  And it is preferable that the density | concentration in the said sulfuric acid type copper electrolyte solution of the said additive B is 1 ppm-80 ppm.

  The additive C in the method for producing an electrolytic copper foil according to the present invention is preferably a diallyldimethylammonium chloride polymer.

  And it is preferable that the density | concentration in the said sulfuric acid type copper electrolyte solution of the said additive C is 0.5 ppm-100 ppm.

  Furthermore, the ratio [(B concentration) / (C concentration)] of the concentration of the additive B and the concentration of the additive C in the sulfuric acid-based copper electrolyte is 0.07 to 1.4. It is preferable.

  In the method for producing an electrolytic copper foil according to the present invention, the chlorine concentration in the sulfuric acid copper electrolyte is preferably 5 ppm to 100 ppm.

Copper-clad laminate according to the present invention: The copper-clad laminate according to the present invention is obtained by bonding the surface-treated electrolytic copper foil and the insulating layer constituting material. And when the said insulating-layer constituent material which comprises the copper clad laminated board which concerns on this invention contains frame | skeleton material, it becomes a rigid copper clad laminated board. On the other hand, when the insulating layer constituting material constituting the copper clad laminate according to the present invention is a flexible material having flexibility, it becomes a flexible copper clad laminate.

Printed wiring board according to the present invention: A printed wiring board according to the present invention is obtained by performing an etching process for forming wiring on a copper-clad laminate obtained using the surface-treated electrolytic copper foil according to the present invention. It is done. That is, a rigid printed wiring board can be obtained by using the above-mentioned rigid copper clad laminate. And a flexible printed wiring board is obtained by using the above-mentioned flexible copper clad laminated board.

  The electrolytic copper foil according to the present invention is characterized in that the precipitated crystal particles of copper are fine and the variation in the particle diameter is so small as never before. As a result, it has a precipitation surface having gloss with a low profile equivalent to that of a conventional low profile electrolytic copper foil, and has extremely high mechanical strength. Further, the mechanical strength does not decrease greatly even when heated, and the change with time after production is small. Therefore, the surface-treated electrolytic copper foil obtained using the electrolytic copper foil also has the same large mechanical strength and low profile surface. If this surface-treated electrolytic copper foil is used, priority is given to ensuring the strength of the board. As a result, even for printed wiring boards where the copper foil layer could not be thinned, the copper foil layer is secured while ensuring the board strength in accordance with the required level. Can be thin. Therefore, the weight of the substrate can be reduced simultaneously with the formation of the fine pitch circuit.

  And the manufacturing method of this electrolytic copper foil and surface treatment copper foil is equipped with the characteristic in the composition of the copper electrolyte solution to be used. Therefore, no new equipment is required, the conventional equipment can be used, and productivity is not reduced. In addition, the copper electrolyte is excellent in solution stability and is economically superior because it withstands long-term continuous use.

  Furthermore, the copper clad laminate obtained using the surface-treated electrolytic copper foil is easy to handle even when the plate thickness is thin, due to the extremely large mechanical strength of the electrolytic copper foil, which reduces deflection and deformation during handling. . In particular, if the electrolytic copper foil is laminated with a film which is an insulating layer forming material to form a flexible copper clad laminate, and this is used for a TAB substrate where remarkably fine pitch is required, the mechanical strength of the electrolytic copper foil is extremely high. Therefore, it is possible to manufacture a TAB substrate having a thin wire flying lead that has been impossible to put into practical use.

Form of electrolytic copper foil according to the present invention: Before describing the electrolytic copper foil according to the present invention, a general method for producing an electrolytic copper foil will be described so that the explanation can be easily understood. The “electrolytic copper foil” according to the present invention is a state in which no surface treatment is performed, and is sometimes referred to as “untreated copper foil”, “deposited foil” or the like. In the present specification, this is simply referred to as “electrolytic copper foil”. In the production of this electrolytic copper foil, a continuous production method is generally adopted, and a drum-shaped rotating cathode and a lead-based anode or a dimensionally stable anode (faced with the rotating cathode) are arranged along the shape of the rotating cathode. A sulfuric acid-based copper electrolyte is allowed to flow between the surface and the surface of the rotating cathode (Dimention Stable Anode: DSA), and copper is deposited on the surface of the rotating cathode using an electrolytic reaction. Removed and wound up.

  The surface shape of the electrolytic copper foil that has been peeled off from the state in contact with the rotating cathode is a transfer of the shape of the surface of the rotating cathode that has been subjected to polishing treatment. ". On the other hand, the surface shape on the side of the precipitation side is often referred to as a “rough surface” because the crystal growth rate of the deposited copper differs depending on the crystal surface, and usually indicates a mountain-shaped uneven shape. However, since the present invention has a smooth shape, this side is referred to as a “deposition surface”.

  The electrolytic copper foil thus obtained is subjected to a surface treatment such as a roughening treatment for reinforcing the adhesive strength with the insulating layer constituent material by a mechanical anchor effect and a rust prevention treatment for preventing oxidation. As a result, a surface-treated electrolytic copper foil distributed in the market is obtained. On the other hand, it may be used without being roughened depending on the application.

Electrolytic copper foil according to the present invention, the value of the normal tensile strength provided that ^{70kgf / mm 2 ~100kgf / mm 2} , a very large mechanical strength unprecedented. This normal tensile strength is a mechanical characteristic obtained by conducting a tensile test at a constant speed at room temperature, measuring the transition of load until breakage, and calculating from the maximum load. The value of the tensile strength is a value obtained by measuring the electrolytic copper foil peeled off from the rotating cathode without any treatment. By this measurement, the measurement result of the normal elongation is obtained at the same time. For conventional electrolytic copper foil, the value of the normal tensile strength 60 kgf / mm ² or less ^(generally, in the range of ^{30kgf / mm 2 ~45kgf / mm 2} .) And is usually to say, 70 kgf There was no product showing a value of normal tensile strength exceeding / mm ² . That is, the electrolytic copper foil according to the present invention, the value of the normal tensile strength is ^{70kgf / mm 2 ~100kgf / mm 2} , a hard material of phosphor bronze (temper: EH) and high tensile strength of equal to or greater than the level Is equipped. Moreover, as will be described later, even when the copper foil is heated, there is a feature that the decrease in the value of the tensile strength is small.

  And the electrolytic copper foil which concerns on this invention is equipped with a very fine and uniform crystal grain. Therefore, since the crystal grains are fine, the precipitation surface is flattened and becomes a highly glossy surface. In addition, since the crystal grain boundary is preferentially dissolved in the etching, the finer the crystal grain, the better the side etching property of the wiring, and the linearity of the formed wiring.

Furthermore, consider the fracture mechanism when the metal foil is subjected to the measurement of folding resistance and the tensile test. It is considered that fracture occurs when microcracks occur at the edge of the specimen or circuit during the test, and bending stress or tensile stress concentrates on the microcracks, and crack propagation occurs. The crack propagation at this time is mainly propagation along the crystal grain boundary. Therefore, if fine crystal grains are provided, the grain boundary distance that becomes the propagation path of cracks is long, and the propagation of cracks, that is, the resistance to breakage, is increased. As a result, a high tensile strength value exceeding 70 kgf / mm ² is exhibited. And according to a more preferred embodiment, a tensile strength value exceeding 80 kgf / mm ² can be obtained.

  As a copper foil exhibiting such a large value of normal tensile strength, there is a rolled copper foil having a high workability. However, the rolled copper foil tends to exhibit an annealing effect by heating, and the mechanical strength is easily lowered. On the other hand, in the case of the electrolytic copper foil according to the present invention, there is little decrease in the value of tensile strength even when heated. That is, the electrolytic copper foil according to the present invention can maintain a tensile strength value after heating at 180 ° C. for 60 minutes of 85% or more, more preferably 90% or more of the normal tensile strength value. Here, the tensile strength after heating is the tensile strength measured by heating the electrolytic copper foil according to the present invention in an air atmosphere at 180 ° C. for 60 minutes and then allowing it to cool to room temperature. In the case of a conventional electrolytic copper foil, the value of the tensile strength after heating after heating at 180 ° C. for 60 minutes was usually 60% or less of the value of the normal tensile strength. The decrease in the value of the tensile strength after heating of the electrolytic copper foil according to the present invention is small because the crystal grains of the electrolytic copper foil according to the present invention are fine and the variation in the crystal grain size is small. This is thought to be because the distribution of the additive component contained during the electrolysis to the grain boundaries is uniform. This additive component functions as a diffusion barrier for metallic copper during heating and suppresses the enlargement of crystal grains, so that the effect of crystal grain refinement can be maintained even after heating. The reason why the heating condition of 180 ° C. × 60 minutes is selected here is that it is close to the temperature condition of the hot press employed in the most general copper clad laminate production.

In addition, the electrolytic copper foil according to the present invention preferably has a normal tensile strength value of 65 kgf / mm ² or more after 30 days from the production. Generally, the quality assurance period of the electrolytic copper foil is required to be at least 3 months. Therefore, it is preferable to perform quality assurance with the normal tensile strength after 3 months have passed since the production. However, the mechanical properties of electrolytic copper foil change over time even after storage at room temperature, stabilize after 30 days from manufacture, and stabilize as long as stored at room temperature. There tends to be no change. Then, if the normal state tensile strength 30 days after manufacture is measured, the quality assurance of the electrolytic copper foil according to the present invention becomes practically possible. Here, the upper limit of the value of the normal tensile strength after the lapse of 30 days after the production is not shown, but the change over time becomes smaller as the crystal grains are finer, so the same as the value of the normal tensile strength, 100 kgf / mm ² is considered.

  Furthermore, the electrolytic copper foil which concerns on this invention shows the value of the range whose values of a normal state elongation rate are 3%-15%. If the value of the normal elongation is 3% or more, foil cracks do not occur even when a hole is formed in a copper-clad laminate with a mechanical drill when forming a through-hole substrate. The upper limit of the normal elongation of the electrolytic copper foil according to the present invention is about 15% empirically because the crystal grains are fine. However, considering workability with the mechanical drill, it is more preferably 10% or less.

  Furthermore, the electrolytic copper foil according to the present invention is also characterized in that the value of elongation after heating at 180 ° C. for 60 minutes is lower than the value of normal elongation. The elongation after heating referred to here is the elongation measured after heating the electrolytic copper foil according to the present invention in an air atmosphere at 180 ° C. for 60 minutes and then allowing it to cool to room temperature. . Many conventional electrolytic copper foils exhibit an annealing effect when heated. Among them, in the electrolytic copper foil having good low-temperature annealing property, a decrease in the elongation rate is observed by heating at 180 ° C. for 5 minutes to 15 minutes, but the decrease rate is a level of less than 5%, and 180 ° C. × 60 When heating for a minute, the value of the elongation after heating becomes larger than the value of the normal elongation. On the other hand, the electrolytic copper foil according to the present invention has a low elongation value after heating at 180 ° C. for 60 minutes when compared with the normal elongation value, so that the behavior of the elongation due to heating is Different from conventional electrolytic copper foil.

  More specifically, the elongation percentage after heating of the electrolytic copper foil according to the present invention decreases in the range of 5% to 50% when the normal elongation percentage is 100%. Such a phenomenon in which the value of tensile strength and the value of elongation decrease when heated can be regarded as a phenomenon similar to the annealing and hardening in the field of copper products. Therefore, it is considered that when heating is further continued, the value of tensile strength after heating continues to decrease, and the elongation after heating starts to increase from a certain point.

Furthermore, considering the above-described method for producing an electrolytic copper foil, the fact that the obtained crystal grains are fine and uniform exhibits the effect of smoothing the uneven shape of the precipitation surface. When the glossiness is employed as an index indicating the smoothness of the deposition surface of the electrolytic copper foil according to the present invention, the glossiness [Gs (60 °)] of the deposition surface is 80 or more. Assuming that the manufacturing method described later is adopted, when the glossiness [Gs (60 °)] is 80 or more, the value of the normal tensile strength is 70 kgf / mm ^{2 to} 100 kgf / mm ² , 180 ° C. × 60. It exhibits mechanical properties such that the value of tensile strength after heating for 85 minutes is 85% or more, more preferably 90% or more of the value of normal tensile strength.

Surface-treated electrolytic copper foil according to the present invention: The surface-treated electrolytic copper foil according to the present invention is one or more of roughening treatment, rust prevention treatment, and silane coupling agent treatment on the surface of the electrolytic copper foil. Is given. Various surface treatments applied to the surface-treated electrolytic copper foil according to the present invention include roughening treatments on the surface for the purpose of imparting adhesive strength, chemical resistance, heat resistance, etc. in consideration of required properties according to applications. Rust prevention treatment, silane coupling agent treatment, etc. are performed.

  The roughening treatment referred to here is a treatment for physically improving the adhesion with the insulating layer constituting material, and is generally performed on the deposition surface. Specifically, either a method of depositing fine metal particles on the surface of the electrolytic copper foil or a roughened surface by an etching method is employed. In general, the former roughening treatment step in which fine metal particles are formed by adhesion is employed. And this roughening treatment process is composed of a burn plating process for depositing and adhering fine copper grains on the deposition surface of the electrolytic copper foil, and a covering plating process for preventing the fine copper grains from falling off. Is normal.

  Next, the rust prevention treatment will be described. In this rust prevention treatment, a coating layer is provided for preventing the surface of the surface-treated electrolytic copper foil from being oxidatively corroded in the course of manufacturing a copper-clad laminate and a printed wiring board. There are no problems with the rust-proofing method, either organic rust-proofing using benzotriazole, imidazole, etc., or inorganic rust-proofing using zinc, chromate, zinc alloy, etc. What is necessary is just to select the rust method. In the case of organic rust prevention, it is possible to adopt a technique such as a dip coating method, a shower ring coating method, or an electrodeposition method of an organic rust preventive agent. In the case of inorganic rust prevention, it is possible to deposit an antirust element on the surface of the electrolytic copper foil layer using an electrolysis method, an electroless plating method, a sputtering method, a displacement precipitation method, or the like.

  And a silane coupling agent process is a process for improving the adhesiveness with an insulating layer constituent material chemically after a roughening process, a rust prevention process, etc. are complete | finished. As used herein, the silane coupling agent used for the silane coupling agent treatment is not particularly limited, considering the properties of the insulating layer constituent material used, the plating solution used in the printed wiring board manufacturing process, and the like. , An epoxy silane coupling agent, an amino silane coupling agent, a mercapto silane coupling agent, and the like. And in order to form a silane coupling agent layer, methods, such as immersion application | coating using the silane coupling agent solution, showering application | coating, electrodeposition, are employable.

Manufacturing method of electrolytic copper foil according to the present invention: The manufacturing method of the electrolytic copper foil according to the present invention is a method of manufacturing an electrolytic copper foil by an electrolytic method using a sulfuric acid copper electrolytic solution, and the sulfuric acid copper electrolytic solution. Are characterized in that the following additives A to C are used. The copper concentration in the sulfuric acid-based copper electrolyte referred to here is 50 g / L to 120 g / L, and a more preferable range is 50 g / L to 80 g / L. The free sulfuric acid concentration is assumed to be 60 g / L to 250 g / L, and a more preferable range is assumed to be 80 g / L to 150 g / L. Hereinafter, the additives will be described in order.

  The highest concept of the additive A is a compound containing N and S, preferably a compound having a structure in which a benzene ring and a heterocyclic ring containing N are provided, and a mercapto group is bonded to the heterocyclic ring. . This additive A acts so as to impart a high tensile strength value to the obtained electrolytic copper foil. Additive A is easily distributed uniformly at the grain boundaries during electrodeposition of the electrolytic copper foil, is excellent in the effect of promoting the refinement of the crystal grains of the deposited copper, and contributes to the stabilization of the production of the electrolytic copper foil. On the other hand, in the case of thiourea, which is known to show the same effect as an additive, the decomposition product of thiourea has a low molecular weight, and its removal is difficult, and it is difficult to remove it into the electrodeposited electrolytic copper foil. There is a drawback that it is difficult to stabilize the inclusion state and the copper precipitation state. Therefore, it is preferable to use an additive having a stable structure called a benzene ring and having a heterocyclic structure containing N because it is difficult to decompose in a copper sulfate solution and has a stable structure. And if the structure which the mercapto group couple | bonded with the heterocyclic ring and the sulfone group couple | bonded with the benzene ring is taken, the polarity will become large, and it will become easy to melt | dissolve in aqueous solution system, Its stability can be maintained.

  The same applies to thiourea compounds that do not have a structure common to the additive A (a structure having a benzene ring and a heterocyclic ring containing N, and a structure in which a mercapto group is bonded to the heterocyclic ring). There are things that can be seen. For example, in a thiourea compound having an alkane group having 2 or more carbon atoms at both ends, the polarity of thiourea is weakened by the alkane group. Therefore, it is considered that the reactivity with copper ions does not exhibit the decomposition behavior like thiourea during the electrolytic reaction while maintaining the effect of having the structure of [= S]. Therefore, if these thiourea compounds are used, problems such as those when using thiourea itself are less likely to occur.

  More specifically, the additive A having the benzene ring and a heterocyclic ring containing N, and having a structure in which a mercapto group is bonded to the heterocyclic ring, imidazole compounds, thiazole compounds and tetrazole Are triazole compounds, and triazole compounds and oxazole compounds belong to the same category. The thiourea additive A is a thiourea compound having a functional group having 2 or more carbon atoms. In actual use, it is preferable to use one or more of the above.

  It is also preferable to use a material having a structure in which a sulfone group is bonded to the benzene ring of the additive A. A compound having a structure in which a sulfone group is bonded to a benzene ring exhibits extremely good stability in a sulfuric acid-based copper electrolyte, stabilizes the electrolytic state, and increases the solution life.

  Hereinafter, among the imidazoles, thiazoles, tetrazoles and the like as the additive A having the above-described structure, the benzene ring and a heterocyclic ring containing N are provided, and a mercapto group is bonded to the heterocyclic ring. 2-mercapto-5-benzimidazolesulfonic acid (hereinafter referred to as “2M-5S”), 3 (5-mercapto-1H-tetrazolyl) benzenesulfonate (hereinafter referred to as “MSPMT-C”) Or 2-mercaptobenzothiazole (hereinafter referred to as “WM”) is preferably used. Hereinafter, the structural formula of 2M-5S is shown in Chemical Formula 1, the structural formula of MSPMT-C is shown in Chemical Formula 2, and the structural formula of WM is shown in Chemical Formula 3. In actual use, it is practical to use readily water-soluble salts that are easily available, for example, Na salts similar to those in the examples described later.

  For the thiourea compound having an alkane group having 2 or more carbon atoms at both ends, it is preferable to use N, N-diethylthiourea (hereinafter referred to as “EUR”), which is structurally stable. The structural formula of EUR is shown in the following chemical formula 4. The EUR clearly has an effect as an additive because N and S contain the same structure as thiourea. In addition, it is considered that having an ethyl group at both ends results in weak end group activity and good stability in the electrolytic solution. It should be noted that the above additives are merely examples of which the effect has been confirmed, and any compound having the same structure and having confirmed the effect can be used. .

  And the combined density | concentration in the sulfuric acid type copper electrolyte solution of the said additive A is preferably 1-50 ppm, More preferably, it is 3-40 ppm. When the total concentration of the additive A in the sulfuric acid-based copper electrolyte is less than 1 ppm, the amount of the additive A taken into the electrolytic copper foil deposited by electrolysis is insufficient, and the obtained electrolytic copper foil is long. It becomes difficult to maintain a large mechanical strength over a period of time. On the other hand, when the total concentration of the additive A exceeds 50 ppm, the smoothness of the deposited surface of the electrolytic copper foil is impaired, the glossiness is lowered, and it is difficult to obtain a large mechanical strength. The content of the additive A in the copper electrolyte can be confirmed using HPLC (High Performance Liquid Chromatography).

  Additive B is a sulfonate salt of an active sulfur compound. This additive B acts to promote glossing of the surface of the obtained electrolytic copper foil. More specifically, additive B is 3-mercapto-1-propanesulfonic acid (hereinafter referred to as “MPS”) or bis (3-sulfopropyl) disulfide (hereinafter referred to as “SPS”). .)) Or a mixture thereof is preferably used. It is considered that SPS exhibits the effect as a brightener in the electrolytic solution. However, this SPS is also formed by dimerization in the solution when MPS is added to the sulfuric acid copper electrolyte. Therefore, MPS may be added without directly adding SPS. Here, the structural formula of MPS is shown below as chemical formula 5 and the structural formula of SPS as chemical formula 6. From the comparison of these structural formulas, it can be understood that SPS is a dimer of MPS.

  The concentration of the MPS or / and SPS in the sulfuric acid copper electrolyte is preferably 1 ppm to 80 ppm, more preferably 10 ppm to 70 ppm, and still more preferably 10 ppm to 60 ppm. When the concentration is less than 1 ppm, it is difficult to obtain gloss on the deposition surface of the electrolytic copper foil, and it is difficult to stably obtain an electrolytic copper foil having a large mechanical strength. On the other hand, if the concentration exceeds 80 ppm, the copper deposition state tends to be unstable, and it becomes difficult to stably obtain an electrolytic copper foil having a large mechanical strength. The concentration of SPS used was a value converted to the sodium salt of MPS (hereinafter referred to as “MPS-Na”), which is most readily available at the present time, in order to facilitate concentration calculation.

  Additive C is a quaternary ammonium salt polymer having a cyclic structure. And this additive C acts so that the smoothness of the surface of the obtained electrolytic copper foil may be accelerated | stimulated. Specifically, it is preferable to use a diallyldimethylammonium chloride (hereinafter referred to as “DDAC”) polymer as the additive C. DDAC forms a cyclic structure when taking a polymer structure, and a part of the cyclic structure is composed of a quaternary ammonium nitrogen atom. In addition, the DDAC polymer has a plurality of forms such as those in which the cyclic structure is a 5-membered ring or a 6-membered ring, and the actual polymer is considered to be any one or a mixture thereof depending on the synthesis conditions. . Therefore, here, a compound having a five-membered ring structure as a representative of these polymers and a chloride ion as a counter ion is shown as chemical formula 7 below. This DDAC polymer has a polymer structure in which DDAC is a dimer or more as shown in Chemical Formula 7 below.

  The concentration of the DDAC polymer in the sulfuric acid copper electrolyte is preferably 0.5 ppm to 100 ppm, more preferably 10 ppm to 80 ppm, and still more preferably 20 ppm to 70 ppm. If the concentration of the DDAC polymer in the sulfuric acid-based copper electrolyte is less than 0.5 ppm, the smoothing effect will be insufficient, and the deposition surface of electrodeposited copper will become rough no matter how high the SPS concentration is. It becomes difficult to obtain a low profile surface necessary for obtaining a large mechanical strength. On the other hand, even if the concentration of the DDAC polymer exceeds 100 ppm, the effect of smoothing the copper precipitation surface is not improved, but rather the precipitation state becomes unstable, and a large mechanical strength can be stably obtained. It becomes difficult.

  Furthermore, the ratio [(B concentration) / (C concentration)] of the concentration of the additive B and the concentration of the additive C in the sulfuric acid-based copper electrolyte is 0.07 to 1.4. It is preferable. As described above, both additive B and additive C become unstable when the concentration is high, but this tendency to become unstable is when only one component becomes high concentration. Seen in. Therefore, when the value of the ratio [(B concentration) / (C concentration)] between the concentration of the additive B and the concentration of the additive C is 0.07 to 1.4, both additives are stabilized. The effect can be demonstrated. And if the value of [(B density | concentration) / (C density | concentration)] is 0.07-1.4, since the effect of the chlorine addition mentioned later is easy to be exhibited, it is more preferable.

  The component balance of additive A to additive C in the sulfuric acid copper electrolyte is most important. When these quantitative balances deviate from the above range, the smooth and glossy precipitated surface becomes rough and the low profile cannot be maintained, and as a result, it becomes difficult to obtain a large mechanical strength. Therefore, by maintaining a good balance between these, it becomes possible to stably produce an electrolytic copper foil having an extremely large mechanical strength according to the present invention.

  The chlorine concentration in the sulfuric acid-based copper electrolyte is preferably 5 ppm to 100 ppm, more preferably 20 ppm to 60 ppm, with the additives A to C already added. When the chlorine concentration is less than 5 ppm, the mechanical strength of the electrolytic copper foil tends to decrease. On the other hand, when the chlorine concentration exceeds 100 ppm, it is difficult to stably obtain a large mechanical strength because the electrodeposition state of the electrolytic copper foil is not stable. For adjusting the chlorine concentration, hydrochloric acid or copper chloride is preferably used. This is because the properties of the sulfuric acid-based copper electrolyte are not changed.

Forms of copper clad laminate and printed wiring board according to the present invention: The present invention provides a copper clad laminate obtained by bonding the surface-treated electrolytic copper foil with an insulating layer constituting material. Regarding the manufacturing method of these copper clad laminated boards, if it is a rigid copper clad laminated board, it can be manufactured using a hot press system or a continuous laminating system. And if it is a flexible copper clad laminated board, it is possible to use the roll lamination system and the casting system which are the prior art.

  And in the case of the rigid copper clad laminated board using what contains the frame | skeleton material as the said insulating-layer constituent material, there is no restriction | limiting in particular in the thickness of the copper foil to be used, Usually, thickness of about 9 micrometers-about 300 micrometers. The copper foil is used. On the other hand, a flexible copper clad laminate composed of a flexible material having flexibility as the insulating layer constituent material is required to form a fine pitch circuit as a whole, so a copper foil having a thickness of 8 μm to 20 μm is used. It is preferable to do.

  In the rigid copper-clad laminate, efforts have been made to make the insulating layer thickness as thin as possible as a multilayer printed wiring board material, and the conductor layer is required to be thin and have a low profile. However, even when the insulating layer is sandwiched between copper foils, if the copper foil to be used is as thin as 12 μm or less, the mechanical strength of the laminated board is insufficient, and folding occurs during handling. There is a case. However, in the copper-clad laminate using the electrolytic copper foil according to the present invention, the mechanical strength of the copper foil is more than twice that of a normal electrolytic copper foil. Substrate strength close to that obtained by attaching a 35 μm copper foil is obtained, and handling is improved.

  The above-mentioned rigid printed wiring board obtained by using the above-mentioned rigid copper clad laminate according to the present invention has high mechanical strength of the electrolytic copper foil layer, so that it has high quality with little scratches due to physical external force, poor disconnection, etc. A fine pitch circuit. The processing from copper-clad laminates to printed wiring boards can be accomplished by using a subtractive method in which an etching resist is formed directly on the copper foil surface of the copper-clad laminate and etching away unnecessary copper, or a plating resist for pattern plating. After the formation, it is possible to use all known etching techniques such as a pattern plating method in which copper is plated on a necessary wiring portion including a through-hole portion and then unnecessary copper is removed by etching.

  The flexible copper-clad laminate is used for manufacturing a flexible printed wiring board that requires flexibility and lightness. In order to improve flexibility and lightness at the same time, the insulating layer constituent material is made thinner, the film strength of the flexible material is reduced, and the mechanical strength of the conductor made of electrolytic copper foil is flexible. And has become a factor in determining the tensile strength. Therefore, the flexible copper-clad laminate using the electrolytic copper foil according to the present invention exhibits high flexibility and high tensile strength because the mechanical strength of the formed conductor is extremely high. And since the electrolytic copper foil which concerns on this invention is a low profile, it becomes suitable also for formation of the fine pattern circuit of the level calculated | required by a flexible printed wiring board.

  Therefore, the flexible printed wiring board obtained by using the flexible copper-clad laminate according to the present invention has a fine pitch circuit as described above and is suitable as a wiring board when a relatively large load is applied. is there. More specifically, it is suitable for a fine pitch TAB or the like in which flying lead bending when bonding an IC chip or elongation due to bonding pressure during bonding of an IC or the like could not be produced due to problems.

  Although the embodiment has been described above, examples are shown below in order to facilitate understanding of the electrolytic copper foil and the like according to the present invention.

<Example 1 to Example 7>
As the sulfuric acid-based copper electrolyte, a basic solution which was a copper sulfate solution and was adjusted to have a copper concentration of 80 g / L and a free sulfuric acid concentration of 140 g / L was adjusted to the additive concentration shown in Table 1. For the concentration adjustment, MPS-Na, DDAC polymer (Unisense FPA100L manufactured by Senka Co., Ltd.), additive A, WM, MSPMT-C, 2M-5S, and one selected from EUR were used and hydrochloric acid. Specifically, as Examples 1 to 7, a plurality of electrolytic copper foils were produced using sulfuric acid-based copper electrolytes having different compositions of additives. The liquid compositions of the above examples are shown in Table 1 later together with the liquid compositions of the comparative examples.

The electrolytic copper foil was prepared by using a titanium plate electrode whose surface was polished with # 2000 polishing paper as the cathode, DSA as the anode, and a liquid temperature of 50 ° C. and a current density of 60 A / dm in Example 1. ² was used to prepare an electrolytic copper foil having a thickness of 15 μm. In Examples 2 to 7, electrolysis was performed at a liquid temperature of 50 ° C. and a current density of 51.5 A / dm ² to prepare an electrolytic copper foil having a thickness of 12 μm or 15 μm. For the evaluation of the characteristics, three electrolytic copper foils were prepared by continuous electrolysis, and the third obtained electrolytic copper foil was used. The surface roughness (Rzjis) of the glossy surface of this electrolytic copper foil is 0.84 μm, the surface roughness (Rzjis) of the deposited surface is 0.80 μm to 1.71 μm, and the glossiness [Gs (60 °)] is 121 to 530. Met. Then, the value of the normal tensile strength is ^{80.8kgf / mm 2 ~97.1kgf / mm 2} , the value of the normal growth rate was 4.0% to 6.0%. And the value of the tensile strength after heating of this electrolytic copper foil is 78.8 kgf / mm ^{2 to} 95.7 kgf / mm ² , which is reduced to 89.1% to 98.6% of the value of tensile strength before heating. It was. Moreover, the value of the elongation after heating was 3.2% to 4.5%, which was reduced to 58.9% to 85.0% of the value of the elongation before heating. Details of the results in the examples are shown in Table 2 later together with the results of Comparative Examples 1 to 3. In Table 2, the percentage of the value after heating with respect to the value before heating is expressed as “maintenance rate (%)”.

Comparative example

[Comparative Example 1]
In Comparative Example 1, the same basic solution as in the example was a copper sulfate solution, which was adjusted to have a copper concentration of 80 g / L and a free sulfuric acid concentration of 140 g / L. For the adjustment of the additive concentration, MPS-Na, DDAC polymer (Unicens FPA100L manufactured by Senka Co., Ltd.) and hydrochloric acid were used, and the same electrolyte solution composition as in the examples except that additive A was not included. did. The liquid composition is shown in Table 1 later together with the liquid composition of the examples.

The electrolytic copper foil was prepared by electrolyzing a titanium plate electrode whose surface was polished with # 2000 polishing paper as the cathode and DSA as the anode at a liquid temperature of 50 ° C. and a current density of 60 A / dm ^2. An electrolytic copper foil having a thickness of 15 μm was prepared. For the evaluation of the characteristics, three electrolytic copper foils were prepared by continuous electrolysis in the same manner as in the Examples, and the electrolytic copper foil obtained on the third sheet was used. The surface roughness (Rzjis) of the glossy surface of this electrolytic copper foil is 0.88 μm, the surface roughness (Rzjis) of the deposited surface is 0.44 μm, and the glossiness [Gs (60 °)] exceeds 600. It was. The normal tensile strength was 35.4 kgf / mm ² and the normal elongation was 14.3%. Furthermore, the value of the tensile strength after heating of this electrolytic copper foil was 30.7 kgf / mm ² , which was reduced to 86.7% of the value of tensile strength before heating. And the value of the elongation after heating was 14.8%, and increased to 103.5% of the value of the elongation before heating. The results are shown in Table 2 below together with the results of Examples and Comparative Examples 2 and 3.

[Comparative Example 2]
In Comparative Example 2, Example 2 disclosed in Patent Document 2 was traced. Specifically, a sulfuric acid-based copper sulfate aqueous solution having a sulfuric acid concentration of 100 g / L and a copper sulfate pentahydrate concentration of 280 g / L was prepared, and hydroxyethyl cellulose: 80 mg / L, polyethyleneimine: 30 mg / L, as additives. An electrolytic solution containing sodium 3-mercapto-1-propanesulfonate: 170 μmol / L, acetylene glycol: 0.7 mg / L and chloride ion: 80 mg / L was prepared.

The temperature of this electrolytic solution was set to 40 ° C., and electrolysis was performed at an electrolytic current density of 40 A / dm ² using the same apparatus as in the example, to prepare an electrolytic copper foil having a thickness of 18 μm. For the evaluation of the characteristics, three electrolytic copper foils were prepared by continuous electrolysis, and the third obtained electrolytic copper foil was used. The surface roughness (Rzjis) of the glossy surface of this electrolytic copper foil was 0.84 μm, as in the example. And the surface roughness (Rzjis) of the precipitation surface was 1.94 μm, the value of normal tensile strength was 57.7 kgf / mm ² , and the value of normal elongation was 6.8%. Moreover, the value of the tensile strength after heating of this electrolytic copper foil was 54.7 kgf / mm ² , which was reduced to 94.8% of the value of tensile strength before heating. Furthermore, the value of the elongation after heating was 7.3%, increasing to 107.4% of the value of the elongation before heating. Together with the results of Examples, Comparative Example 1 and Comparative Example 3, they are summarized in Table 2 below.

[Comparative Example 3]
In Comparative Example 3, Example 3 disclosed in Patent Document 2 was traced. Specifically, a sulfuric acid-based copper sulfate aqueous solution having a sulfuric acid concentration of 100 g / L and a copper sulfate pentahydrate concentration of 280 g / L was prepared. Hydroxyethyl cellulose: 6 mg / L, polyethyleneimine: 12 mg / L, An electrolyte containing sodium 3-mercapto-1-propanesulfonate: 60 μmol / L, acetylene glycol: 0.5 mg / L and chloride ion: 30 mg / L was prepared.

The temperature of this electrolytic solution was set to 40 ° C., and electrolysis was performed at an electrolytic current density of 40 A / dm ² using the same apparatus as in the example, to prepare an electrolytic copper foil having a thickness of 18 μm. For the evaluation of the characteristics, three electrolytic copper foils were prepared by continuous electrolysis, and the third obtained electrolytic copper foil was used. The surface roughness (Rzjis) of the glossy surface of this electrolytic copper foil was 0.84 μm, as in the example. And the surface roughness (Rzjis) of the precipitation surface was 1.42 μm, the value of normal tensile strength was 57.8 kgf / mm ² , and the value of normal elongation was 6.4%. Moreover, the value of the tensile strength after heating of this electrolytic copper foil was 55.0 kgf / mm ² , which was reduced to 95.2% of the value of tensile strength before heating. Furthermore, the value of the elongation after heating was 8.4%, which was increased to 131.3% of the value of the elongation before heating. The results are shown in Table 2 below together with the results of Examples and Comparative Examples 1 and 2.

<Contrast between Example and Comparative Example 1>
As shown in Table 1, the difference between the example and the comparative example 1 is the presence or absence of the additive A, and the electrolytic solution used in the example was added to the electrolytic solution used in the comparative example by adding the additive A (WM, MSPMT). -C, 2M-5S, and EUR). Therefore, by including the additive A, the value of the normal tensile strength of the obtained electrolytic copper foil is increased, and the decrease in the value due to heating is reduced. In addition, the normal elongation rate of the example shows a smaller value than the normal elongation rate of the comparative example, and at the same time, in the example, the value of the elongation rate tends to be further lowered by heating. This phenomenon can also be seen as an effect of annealing hardening. That is, the difference between the electrolytic copper foil obtained in the example and the electrolytic copper foil obtained in Comparative Example 1 is clear in terms of surface roughness, glossiness, and whether or not annealing hardening can be manifested.

<Contrast of Example with Comparative Example 2 and Comparative Example 3>
In Comparative Example 2 and Comparative Example 3, the production conditions described in Patent Document 2 were traced. However, as shown in Table 2, the normal tensile strength disclosed in the examples of Patent Document 2 was not obtained. In Example 2 of Patent Document 2, it is described as 890 MPa, but only 565 MPa (the result of Comparative Example 2 is converted in units) is obtained. Moreover, although it is described as 900 MPa in Example 3 of Patent Document 2, only 567 MPa (the result of Comparative Example 3 is converted into a unit) is obtained. And in the comparative example 2 and the comparative example 3, the raise of the elongation rate by heating is seen. In this respect, the value of the normal tensile strength greater than that of the electrolytic copper foil obtained in Comparative Example 1 is shown, but regarding the mechanical properties, the electrolytic property having the same characteristic tendency as that of the electrolytic copper foil obtained in Comparative Example 1 is shown. It can be said that it is copper foil. That is, when compared with the electrolytic copper foil according to the present invention, the surface roughness of the deposited surface is the same, but the difference is clear in the glossiness and the tendency of annealing hardening. In addition, the comparative example 2 and the comparative example 3 are the best data in which this inventor who is a party in the field of the electrolytic copper foil repeatedly performed the test while adjusting the conditions for several months.

  In the above-described embodiment, the thickness of the electrolytic copper foil to be prepared is two types, and the electrolysis is carried out at a high current density with a thick 15 μm copper foil. In order to manage the surface roughness, those skilled in the art recognize that it is more difficult to create a thick material with a high current density. However, in the above, data with a small surface roughness is obtained with a 15 μm copper foil. It has been. Therefore, it is considered that there is almost no influence of the electrolysis conditions on the characteristics of the 12 μm copper foil and the 15 μm copper foil, and the evaluation data can be directly compared. In addition, in the production of the electrolytic copper foil according to the present invention, good results are obtained with an electrolytic solution in which the copper concentration of the sulfuric acid-based copper electrolytic solution is 50 g / L to 120 g / L and the free sulfuric acid concentration is about 60 g / L to 250 g / L. However, in actual operation, it is possible to change the composition within the optimum range in consideration of equipment specifications. Then, regardless of the addition method or addition form of additive A and MPS, DDAC polymer, etc. described in the above examples, other alkali metals or alkaline earth metal salts may be used instead of MPS-Na. If possible, it is preferable to use an SPS salt.

  The sulfate-based copper electrolyte according to the present invention does not deny the presence of other additives, further enhances the effects of the additives, and contributes to quality stabilization during continuous production. If it is confirmed that it can be done, it may be added arbitrarily. In addition to filtration equipment for the purpose of removing foreign substances inside and outside the process, it is also useful to appropriately use means such as activated carbon adsorption if there is concern about the effects of decomposition products of additives. It is.

  The electrolytic copper foil according to the present invention is characterized in that the precipitated crystal particles of copper are fine and the variation in the particle diameter is so small as never before. As a result, it has a precipitation surface having gloss with a low profile equivalent to that of a low profile electrolytic copper foil that has been supplied to the market, and has a very large mechanical strength. Therefore, because of its extremely high mechanical strength, it is particularly suitable for the formation of fine pitch wiring on a tape automated bonding (TAB) substrate. Moreover, it can utilize also as a collector of the nonaqueous electrolyte secondary battery represented by the lithium ion battery as shown by patent document 1. FIG. In particular, it can be suitably used as a current collector for a negative electrode using an active material containing Si or Sn, which has a large volume change during charge and discharge.

It is a schematic diagram which shows the example of mounting of the device (IC) for LCD panel drive using TAB with a flying lead. It is a schematic diagram which shows the example of mounting of the device (IC) for LCD panel drive using COF with the backing by a film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Flying lead 2, 2 'Circuit formed with copper foil 3 Adhesive 4, 4' Base film (polyimide film)
5, 5 'Solder resist 6 Back side solder resist 7, 7' Device (IC chip)
8, 8 ′ IC connection (also called device hole in FIG. 1)
9 Support base for gang bonding 10, 10 '1st terminal part (connection part with a liquid crystal display panel)
11, 11 '2nd terminal part (connection part with a printed wiring board)
12, 12 'bent part

Claims (23)

In the electrolytic copper foil obtained by electrolyzing the copper electrolyte,
Tensile at normal strength (hereinafter, referred to as "normal tensile strength".) The value of ^the electrolytic copper foil is ^{70kgf / mm 2 ~100kgf / mm 2} . The electrolytic copper according to claim 1, wherein the value of tensile strength after heating at 180 ° C for 60 minutes (hereinafter referred to as "tensile strength after heating") is 85% or more of the value of normal tensile strength. Foil. The electrolytic copper foil according to claim 1 or ² , wherein the value of the normal tensile strength after 30 days from the production is 65 kgf / mm ² or more. The electrolytic copper foil according to any one of claims 1 to 3, wherein a value of elongation in a normal state (hereinafter referred to as "normal elongation") is 3% to 15%. 5. The electrolysis according to claim 1, wherein a value of elongation after heating at 180 ° C. for 60 minutes (hereinafter referred to as “elongation after heating”) is not more than a value of normal elongation. Copper foil. The value of glossiness (hereinafter referred to as “glossiness [Gs (60 °)]”) measured at a reflection angle of 60 ° with respect to the width direction of the deposition surface is 80 or more. The electrolytic copper foil in any one of 5. The surface treatment which performed any 1 type, or 2 or more types of the roughening process, the antirust process, and the silane coupling agent process on the surface of the electrolytic copper foil which concerns on any one of Claims 1-6 Electrolytic copper foil. In a method for producing an electrolytic copper foil by an electrolytic method using a sulfuric acid-based copper electrolyte,
The said sulfuric acid-type copper electrolyte solution contains the following additive A-additive C, The manufacturing method of the electrolytic copper foil in any one of Claims 1-6 characterized by the above-mentioned.
Additive A: a compound or thiourea compound comprising a benzene ring and a heterocyclic ring containing N, and having a structure in which a mercapto group is bonded to the heterocyclic ring.
Additive B: sulfonate salt of active sulfur compound.
Additive C: A quaternary ammonium salt polymer having a cyclic structure. 9. The additive A is any one or more of imidazole compounds, thiazole compounds, tetrazole compounds, or thiourea compounds having two or more alkane groups at both ends. The manufacturing method of the electrolytic copper foil of description. The said additive A is a manufacturing method of the electrolytic copper foil of Claim 8 or Claim 9 in which the sulfone group has couple | bonded with the benzene ring. The additive A is one or two selected from 2-mercapto-5-benzimidazolesulfonic acid, 3 (5-mercapto-1H-tetrazolyl) benzenesulfonate, 2-mercaptobenzothiazole, or NN diethylthiourea. It is a seed | species or more, The manufacturing method of the electrolytic copper foil in any one of Claims 8-10. The method for producing an electrolytic copper foil according to any one of claims 8 to 11, wherein a combined concentration of the additive A in the sulfuric acid-based copper electrolyte is 1 ppm to 50 ppm. The method for producing an electrolytic copper foil according to any one of claims 8 to 12, wherein the additive B is any one or a mixture of 3-mercapto-1-propanesulfonic acid and bis (3-sulfopropyl) disulfide. . The method for producing an electrolytic copper foil according to any one of claims 8 to 13, wherein the concentration of the additive B in the sulfuric acid-based copper electrolyte is 1 ppm to 80 ppm. The said additive C is a diallyldimethylammonium chloride polymer, The manufacturing method of the electrolytic copper foil in any one of Claims 8-14. The method for producing an electrolytic copper foil according to any one of claims 8 to 15, wherein a concentration of the additive C in the sulfuric acid-based copper electrolyte is 0.5 ppm to 100 ppm. The ratio [(B concentration) / (C concentration)] of the concentration of the additive B and the concentration of the additive C in the sulfuric acid-based copper electrolyte is 0.07 to 1.4. The manufacturing method of the electrolytic copper foil in any one of Claims 8-16. The method for producing an electrolytic copper foil according to any one of claims 8 to 17, wherein a chlorine concentration in the sulfuric acid-based copper electrolyte is 5 ppm to 100 ppm. A copper clad laminate obtained by bonding the surface-treated electrolytic copper foil according to claim 7 to an insulating layer constituting material. The rigid copper-clad laminate according to claim 19, wherein the insulating layer constituent material contains a skeleton material. A rigid printed wiring board obtained using the rigid copper clad laminate according to claim 20. 20. The flexible copper clad laminate according to claim 19, wherein the insulating layer constituting material is constituted by a flexible material having flexibility. A flexible printed wiring board obtained using the flexible copper-clad laminate according to claim 22.

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