WO2014104233A1 - Low spring-back electrolytic copper foil, and circuit board and flexible circuit board using said electrolytic copper foil - Google Patents

Low spring-back electrolytic copper foil, and circuit board and flexible circuit board using said electrolytic copper foil Download PDF

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Publication number
WO2014104233A1
WO2014104233A1 PCT/JP2013/084970 JP2013084970W WO2014104233A1 WO 2014104233 A1 WO2014104233 A1 WO 2014104233A1 JP 2013084970 W JP2013084970 W JP 2013084970W WO 2014104233 A1 WO2014104233 A1 WO 2014104233A1
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Prior art keywords
copper foil
electrolytic copper
less
stress
numerical value
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PCT/JP2013/084970
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French (fr)
Japanese (ja)
Inventor
貴広 齋藤
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to KR20147034142A priority Critical patent/KR20150039711A/en
Priority to JP2014519329A priority patent/JP5607862B1/en
Priority to CN201380027695.6A priority patent/CN104321469A/en
Publication of WO2014104233A1 publication Critical patent/WO2014104233A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils

Definitions

  • the present invention relates to an electrolytic copper foil particularly excellent in low resilience and fine pattern properties. More specifically, the present invention is for a flexible wiring board excellent in low resilience and fine pattern property, in which excessive crystal coarsening is suppressed in the heat treatment applied in the film sticking step when manufacturing the flexible wiring board.
  • the present invention relates to a suitable electrolytic copper foil.
  • Electrolytic copper foil represents either one or both of electrolytic copper foil and electrolytic copper alloy foil.
  • the “untreated” state refers to a state in which the surface is subjected to rust prevention treatment after foil formation or after foil formation, or is subjected to adhesion improving treatment such as roughening treatment as necessary, and is not subjected to heat treatment.
  • Low resilience is a characteristic that can be bent with a small load and easily leads to plastic deformation.
  • wiring boards are used as substrates and connection materials for silicon chips and capacitors, and copper foil is generally used for the conductive layers of the wiring boards.
  • the copper foil of the wiring board is generally supplied in the form of a rolled copper foil or an electrolytic copper foil, and among them, an electrolytic copper foil that is highly productive and easily thinned is widely used.
  • a wiring board having low resilience (hereinafter referred to as a flexible wiring board) that can be mounted efficiently and without problems in a small space in such applications has low resilience also in the copper foil as the conductive layer. Desired.
  • a copper foil having such characteristics before the film sticking process generally tends to be wrinkled, making it difficult to handle in a production / processing line. On the other hand, even if the copper foil is excessively repulsive before the film sticking step, the foil breakage is likely to occur on the production / processing line, and handling becomes difficult.
  • the copper foil when copper foil is used for a flexible wiring board, it is necessary to be able to form a fine pattern circuit that can cope with higher wiring density.
  • the copper foil needs to have low roughness.
  • the crystal grain structure in the copper foil needs to be fine to some extent, and the copper foil in which the crystal grain structure becomes excessively coarse by the heat treatment adversely affects the fine pattern property.
  • the thickness of the copper foil conventionally used for flexible wiring boards has been 18 ⁇ m or 12 ⁇ m, but a copper foil of 12 ⁇ m or thinner has been demanded.
  • the manufacturing cost of the rolled copper foil whose thickness is 18 micrometers or less becomes about 2 times higher than an electrolytic copper foil.
  • Patent Document 1 Japanese Patent No. 43575478 discloses a rolled copper alloy foil excellent in bending workability by controlling crystal orientation and the like as an electrical / electronic component application such as a connector and a lead frame.
  • this rolled copper alloy foil is characterized in that it does not return after bending (does not spring back). At the bending stage, its repulsive force is strong because of its high strength, and it has characteristics different from the low repulsion required by the present invention. ing.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2009-242846 discloses a rolled copper alloy foil in which the repulsive force during bending is reduced by controlling the foil thickness, surface roughness, crystal orientation, and the like as a flexible wiring board application.
  • the rolled copper foil or the rolled copper alloy foil and the electrolytic copper foil of the present invention are completely different in the production method, and the required crystal structure control methods and components are also different.
  • Patent Document 3 Japanese Patent Laid-Open No. 2007-320083 discloses a copper clad laminate (CCL) in which spring back is suppressed by controlling the composition of polyimide and the thickness of the copper foil layer as a flexible wiring board.
  • the copper foil layer of this copper-clad laminate is only limited in thickness and does not improve the rebound itself as a crystal structure, but it is reduced by controlling the crystal structure of the copper foil layer itself. This is different from the present invention that realizes resilience.
  • Patent Document 4 (Patent No. 4712759) is excellent in fine pattern property by setting the surface roughness Rz of the mat surface (M surface) to 1.0 ⁇ m or less and Ra to 0.2 ⁇ m or less as a circuit board application.
  • An electrolytic copper foil is disclosed. However, this electrolytic copper foil is characterized by excellent surface smoothness, and the low resilience required by the present invention is not a target.
  • Patent Document 5 Patent No. 4,827,952 discloses an electrolytic copper foil having excellent flexibility by controlling the impurity concentration in the copper foil to be low for CCL (copper-clad laminate).
  • this electrolytic copper foil can be bent with a small load, but plastic deformation is unlikely to occur as can be easily imagined from the fact that it has high flexibility that requires a wide elastic deformation region, and bending Since the amount of return later increases, the low resilience required by the present invention is not provided.
  • the present invention is easy to handle in the production / processing line, exhibits low repulsion by the heat treatment applied in the film sticking process, or maintains low repulsion, and can cope with downsizing of electrical equipment, And it is providing the electrolytic copper foil which the excessive coarsening of a crystal grain structure is suppressed and is excellent also in fine pattern property.
  • the numerical value y1 indicating the rigidity represented by Equation 1 based on the stress X1 (MPa) of 0.2% strain measured at room temperature after heat treatment at 300 ° C. for 1 hour is less than 800
  • a numerical value y2 representing the degree of change in rigidity accompanying bending shown in Formula 2 based on the stress X1 (MPa) and the stress X2 (MPa) of 0.4% strain is 1.5 or more.
  • the electrolytic copper foil preferably has a numerical value y3 indicating a rigidity represented by Equation 3 based on a stress X3 (MPa) at 0.2% strain before heat treatment (untreated) of 600 or more and less than 1000.
  • y3 a rigidity represented by Equation 3 based on a stress X3 (MPa) at 0.2% strain before heat treatment (untreated) of 600 or more and less than 1000.
  • the electrolytic copper foil preferably has 5,000 or more crystal grains having a grain size of less than 2 ⁇ m in 300 ⁇ m square observed at room temperature after heat treatment at 300 ° C. for 1 hour.
  • the electrolytic copper foil preferably has a mat surface (M surface) having a surface roughness Rz of less than 3.0 ⁇ m and a shiny surface (S surface) having a surface roughness Rz of less than 3.0 ⁇ m.
  • the electrolytic copper foil of the present invention can be suitably used as a wiring board, and is particularly suitable for a flexible wiring board.
  • the electrolytic copper foil of the present invention is easy to handle in the production and processing line of the wiring board, is excellent in low resilience after the heat treatment applied in the film sticking process, and can cope with downsizing of electrical equipment, and Since both surfaces have low roughness and excessive coarsening of the crystal grain structure is suppressed, an electrolytic copper foil excellent in fine pattern property can be provided.
  • the numerical value y1 indicating the rigidity expressed by the mathematical formula 1 is less than 800 in the stress X1 (MPa) at 0.2% strain measured at room temperature after heat treatment at 300 ° C. for 1 hour, and A numerical value y2 representing the degree of change in rigidity accompanying bending shown in Formula 2 with a stress X1 (MPa) and a stress X2 (MPa) at 0.4% strain is 1.5 or more.
  • the numerical value y2 represents the degree of change in rigidity accompanying bending, and the larger the numerical value y2, the easier the plastic deformation occurs due to bending, and the smaller the return amount of the spring property after bending.
  • the numerical value of y2 is less than 1.5, plastic deformation due to bending hardly occurs, and the return amount of the spring property after bending increases. Even if the numerical value y2 is less than 1.5, if the stress X1 and the stress X2 are small, it seems that there is no problem in low resilience, but since the plastic deformation is difficult to occur, the return amount of the spring property after bending is small. Since it becomes large, the required low resilience cannot be obtained.
  • the numerical value y3 indicating the rigidity represented by the mathematical formula 3 at a stress X3 (MPa) at 0.2% strain is 600 or more and less than 1000.
  • the numerical value y3 indicating the rigidity is 600 or more and less than 1000, the rigidity is moderate and good handling properties are maintained.
  • the numerical value y3 is less than 600, the rigidity is too weak and wrinkles are likely to occur in the production / processing line, making handling difficult.
  • the numerical value y3 is 1000 or more, the rigidity is too strong, and the foil is easily cut off in the production / processing line, so that handling becomes difficult.
  • the electrolytic copper foil of the present invention is characterized in that the number of crystal grains having a particle size of less than 2 ⁇ m in 300 ⁇ m square observed at room temperature after heat treatment at 300 ° C. for 1 hour is 5,000 or more. If the number of crystal grains is 5,000 or more, the crystal structure is fine and good fine pattern properties are maintained. On the other hand, if the number of crystal grains having a grain size of less than 2 ⁇ m in a 300 ⁇ m square is less than 5,000, the crystal grain structure becomes coarse and adversely affects fine pattern properties.
  • the electrolytic copper foil of the present invention is characterized in that the surface roughness Rz of the M plane is less than 3.0 ⁇ m and the surface roughness Rz of the S plane is less than 3.0 ⁇ m. If Rz is less than 3.0 ⁇ m, the surface irregularities are small and good fine pattern properties are maintained. On the other hand, if Rz is 3.0 ⁇ m or more, the unevenness of the surface is large, and the fine pattern property is adversely affected.
  • the electrolytic copper foil is made by, for example, an electrolytic foil making apparatus shown in FIG.
  • the electrolytic foil making apparatus comprises a rotating drum-like cathode 2 (the surface is made of SUS or titanium), and an anode 1 (lead electrode or noble metal oxide-coated titanium electrode) arranged concentrically with respect to the cathode 2. While supplying the electrolytic solution 3 to the foil making apparatus, current is passed between both electrodes to deposit copper to a predetermined thickness on the surface of the cathode 2, and then the copper is peeled off from the surface of the cathode 2 in the form of foil.
  • the surface of the untreated (before electrolytic treatment) electrolytic copper foil 4 in contact with the electrolytic solution 3 is the mat surface (M surface), and the surface in contact with the drum-like cathode 2 is the shiny surface (S surface).
  • the foil manufacturing apparatus using the drum-like cathode 2 has been described.
  • the copper foil may be manufactured by a foil manufacturing apparatus having a plate-like cathode.
  • a copper sulfate plating solution is used as the electrolytic solution 3.
  • the sulfuric acid concentration of the copper sulfate plating solution is preferably 20 to 150 g / L, particularly 30 to 100 g / L.
  • the sulfuric acid concentration is less than 20 g / L, it becomes difficult to flow an electric current, so that practical operation becomes difficult, and the uniformity of plating and electrodeposition are also deteriorated.
  • the sulfuric acid concentration exceeds 150 g / L, the solubility of copper is lowered, so that a sufficient copper concentration cannot be obtained, and realistic operation becomes difficult. Also, corrosion of equipment is promoted.
  • the copper concentration is preferably 40 to 150 g / L, particularly 60 to 100 g / L.
  • the copper concentration is less than 40 g / L, it is difficult to secure a current density that allows practical operation in the production of electrolytic copper foil.
  • Increasing the copper concentration above 150 g / L is not practical because a considerably high temperature is required.
  • Organic additives to be added to the copper sulfate plating bath are two kinds of organic additives, a compound having a mercapto group and a polymer polysaccharide.
  • a compound having a mercapto group has an effect of promoting copper electrodeposition
  • a high molecular polysaccharide has an effect of suppressing copper electrodeposition.
  • the crystal structure control effect exerted by the optimum concentration of the two organic additives facilitates plastic deformation with a small bend, which is a feature of the present invention.
  • An excessively coarse grain structure is suppressed, and an electrolytic copper foil having low roughness is obtained.
  • the added chlorine acts as a catalyst that effectively exhibits the effects of the two organic additives.
  • MPS-Na sodium 3-mercapto-1-propanesulfonate
  • SPS-Na ⁇ bis (3-sulfopropyl) disulfide sodium ⁇ is selected.
  • SPS is a dimer of MPS, exhibits the same effect as an additive, and has the same required concentration.
  • the concentration is preferably from 0.25 ppm to 7.5 ppm, particularly preferably from 1.0 ppm to 5.0 ppm. If it is less than 0.25 ppm, it is difficult to exhibit the effect of promoting electrodeposition on the concave portions generated in the foil production, and the effect of controlling the crystal structure, which is a feature of the present invention, is also hardly exhibited.
  • the high molecular polysaccharide is HEC (hydroxyethyl cellulose), and the concentration is preferably 3.0 ppm or more and 30 ppm or less, and particularly preferably 10 ppm or more and 20 ppm or less. If it is less than 3.0 ppm, the electrodeposition suppressing effect on the convex portion is hardly exhibited, and the effect of controlling the crystal structure, which is a feature of the present invention, is hardly exhibited. On the other hand, if it exceeds 30 ppm, the generation of bubbles, which is an effect peculiar to polymer polysaccharides, becomes excessive, the supply of copper ions becomes insufficient, and it becomes difficult to produce a normal copper foil, and the organic matter in the electrolyte increases. By doing so, it causes “burn plating” to occur.
  • HEC hydroxyethyl cellulose
  • the chlorine concentration is preferably from 1 ppm to 20 ppm, particularly preferably from 5 ppm to 15 ppm.
  • Chlorine acts as a catalyst that effectively exhibits the effects of the two organic additives. If the chlorine concentration is less than 1 ppm, it is difficult to exert the catalytic action described above, and it is difficult to bring out the effect of the organic additive. is not. Further, if it exceeds 20 ppm, not only the catalytic action of chlorine on the organic additive but also the influence on the electrodeposition of chlorine itself becomes large, so the effect of controlling the crystal structure by the additive which is a feature of the present invention is also exhibited. It becomes difficult.
  • the current density for foil production is preferably 20 to 200 A / dm 2 , particularly preferably 30 to 120 A / dm 2 .
  • the current density is less than 20 A / dm 2 , production efficiency is very low in the production of electrolytic copper foil, which is not realistic. This is because, in order to increase the current density from 200 A / dm 2, a high copper concentration, a high temperature, and a high flow rate are required, which imposes a large burden on the electrolytic copper foil manufacturing facility and is not realistic.
  • the electrolytic bath temperature is preferably 25 to 80 ° C, particularly 30 to 70 ° C.
  • the bath temperature is less than 25 ° C., it is difficult to secure a sufficient copper concentration and current density in the production of the electrolytic copper foil, which is not realistic. Further, raising the temperature from 80 ° C. is very difficult in operation and facilities and is not realistic.
  • the above electrolysis conditions are appropriately adjusted from the respective ranges so as not to cause problems such as copper deposition and plating burns.
  • the surface roughness immediately after the production of the electrolytic copper foil transfers the roughness of the surface of the cathode 2
  • a cathode having a surface roughness Rz of 0.1 to 3.0 ⁇ m By using such a cathode, since the surface roughness of the S surface immediately after the production of the electrolytic copper foil is a transfer of the cathode surface, the surface roughness Rz of the S surface can be 0.1 to 3.0 ⁇ m. .
  • the reason why the surface roughness Rz of the S surface of the electrolytic copper foil is less than 0.1 ⁇ m is that the surface roughness Rz of the cathode is less than 0.1 ⁇ m. It is difficult to finish smoothly and is not suitable for mass production. On the other hand, when the roughness Rz of the S surface is 3.0 ⁇ m or more, the fine pattern property is lowered and the characteristics required by the present invention cannot be obtained.
  • the surface roughness Rz of the M surface of the electrolytic copper foil is preferably 0.05 to 3.0 ⁇ m. In order to finish the surface roughness Rz to a roughness of less than 0.05 ⁇ m, even if bright plating is performed, it is very difficult and practically impossible to manufacture. On the other hand, if the surface roughness Rz of the M-plane is 3.0 ⁇ m or more, the fine pattern property is lowered, and the characteristics required by the present invention cannot be obtained. It is more preferable that the roughness Rz of the S surface and the M surface is less than 1.5 ⁇ m.
  • the thickness of the electrolytic copper foil is preferably 3 ⁇ m to 210 ⁇ m.
  • a copper foil having a thickness of less than 3 ⁇ m is not practical because of severe manufacturing conditions due to handling techniques and the like.
  • the upper limit of the thickness is about 210 ⁇ m from the current usage state of the circuit board. This is because it is unlikely that an electrolytic copper foil having a thickness of 210 ⁇ m or more is used as a copper foil for a wiring board, and the cost merit of using the electrolytic copper foil is lost.
  • the thickness of the foil is preferably 18 ⁇ m or less, preferably 12 ⁇ m or less.
  • H 2 SO 4 copper sulfate
  • Examples 1-7 and Comparative Examples 1-5 were polished with # 1500 polishing cloth, and Examples 8 and 6 were polished with # 800 polishing cloth.
  • an electrolytic copper foil having a thickness of 12 ⁇ m was produced with reference to Example 4 (copper sulfate plating solution, copper 70 g / l, sulfuric acid 50 g / l) of Patent Document 5 (Japanese Patent No. 48279952). .
  • the resilience was measured using the apparatus shown in FIG.
  • the copper foil 5 to be a test piece was placed in a coiled shape, crushed until the crushing distance 7 became a specified distance, the load measured by the electronic balance 6 was measured as a repulsive load, and the resilience was evaluated.
  • Coil length 10mm Crushing distance: 1mm, 3mm Measurement time: 30 seconds after crushing Measuring method: Measured with electronic balance as repulsive load In repulsive measurement, repulsive load with crushing distance of 3 mm and 1 mm for “ease of bending with small load” A sample with a value of less than 25 gf was evaluated as ⁇ (passed), and a sample of 25 gf or higher was evaluated as x (failed).
  • the sample 5 was used to measure the surface roughness Rz using a contact-type surface roughness meter.
  • the surface roughness is indicated by Rz (10-point average roughness) defined in JIS-B-0601.
  • the reference length was 0.8 mm.
  • Rz 10-point average roughness
  • Table 3 shows the measurement results.
  • Fine Pattern Properties were evaluated using Sample 6.
  • the circuit pattern created in the above was used.
  • the circuit pattern was observed with a microscope from directly above, and the difference between the upper limit and the lower limit of the circuit width was measured at a circuit length of 100 ⁇ m.
  • the numerical value y1 indicating the rigidity expressed by Equation 1 is less than 800 and can be bent with a small load.
  • the numerical value y2 representing the degree of change in rigidity accompanying bending shown in Expression 2 is 1.5 or more, and plastic deformation due to bending is easily caused.
  • Examples 1 to 8 passed the evaluation of “ease of bending with a small load” and “ease of plastic deformation”.
  • the numerical value y3 indicating the rigidity represented by Expression 3 is 600 or more and less than 1000, and the rigidity is not too strong, so that handling in the production / processing line is easy.
  • the numerical value y1 is less than 1000, so that it can be used effectively. it can.
  • the heating condition may be less than 300 ° C.
  • the numerical value y1 after heat treatment at 300 ° C. ⁇ 1 hour is less than 600, and even a copper foil that is likely to have too low rigidity becomes 600 or more depending on the heating conditions. Can be used for
  • the number of crystal grains having a particle size of less than 2 ⁇ m measured at room temperature after heat treatment at 300 ° C. for 1 hour is 5,000 or more in 300 ⁇ m square, so that Since excessive coarsening of the crystal grain structure is suppressed and the surface roughness is less than 3.0 ⁇ m, the fine pattern property is excellent.
  • the surface roughness is less than 3.0 ⁇ m, but the number of crystal grains having a grain size of less than 2 ⁇ m measured at room temperature after 300 ° C. ⁇ 1 hour heat treatment is less than 5,000.
  • the heat treatment applied in the film sticking step or the like cannot be preferably used at about 300 ° C.
  • Example 8 since it is excellent in low resilience, it can be suitably used for products whose heat treatment is greatly below 300 ° C.
  • the number of crystal grains having a grain size of less than 2 ⁇ m measured at room temperature after heat treatment at 300 ° C. for 1 hour is equal to that in Example 2, but the surface roughness is 3.0 ⁇ m or more on both sides, and there are irregularities. Since it is large, the fine pattern property is inferior. However, since it has excellent low resilience, it can be effectively employed for a wiring board that does not require a fine circuit.
  • Comparative Example 6 has a surface roughness of 3.0 ⁇ m or more, large irregularities, and the number of crystal grains having a grain size of less than 2 ⁇ m measured at room temperature after heat treatment at 300 ° C. for 1 hour is less than 5,000. In addition, since the crystal grain structure is excessively coarse, the fine pattern property is very poor.
  • the electrolytic copper foil of the present invention is easy to handle in the production / processing line and exhibits low resilience in the heat treatment applied in the film sticking process (stacking process with the substrate).
  • the electrolytic copper foil of this invention is excellent in fine pattern property, of course, it can apply also to the wiring board which does not require flexibility.
  • the electrolytic copper foil of the present invention MPS-Na or SPS-Na is added as a compound having a mercapto group in a concentration range of 0.25 ppm to 7.5 ppm, and HEC is 3.0 ppm to 30 ppm as a polymer polysaccharide. It is possible to make a foil with an acidic copper electrolytic solution to which chlorine ions are added in the range of 1 ppm to 20 ppm.
  • the electrolytic copper foil of the present invention is subjected to surface treatment such as rust prevention treatment and then laminated with a film substrate as it is, it is excellent in surface smoothness, so it can be suitably used as a high-frequency flexible wiring board. Can do.
  • a roughening treatment layer for the purpose of improving the adhesion by the anchor effect can be provided on one surface. The roughening process is not an essential process as long as the target performance can be achieved.
  • the electrolytic copper foil of the present invention is also effective as a high-frequency wiring board by utilizing the smoothness of the surface. Since it has low resilience, it is effective as a high-frequency wiring board that requires such characteristics. In addition, the unique characteristics of both surface smoothness, “ease of bending under small load” and “ease of plastic deformation” make it possible to provide copper foil for various materials as well as wiring boards. is there.
  • Anode 2 Cathode 3: Electrolytic solution 4: Untreated electrolytic copper foil 5: Copper foil 6: Electronic balance 7: Crushing distance

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Abstract

Provided is an electrolytic copper foil for flexible circuit boards, the foil being easy to handle in production/processing lines, having excellent low spring-back after the heat treatment applied in the film application process, being able to cope with reductions in the size of electrical machinery, and for which excessive coarsening of crystal grain structure is limited and fine patterning properties are excellent. An electrolytic copper foil with excellent low spring-back for which a numerical value y1, which represents rigidity and is based on a stress X1 (MPa) of a 0.2% distortion measured at normal temperature after a 300°C × 1 hour heat treatment, is less than 800 and a numerical value y2, which represents the extent of change in rigidity associated with bending and is based on the stress X1 (MPa) and a stress X2 (MPa) of a 0.4% distortion, is 1.5 or more. For the electrolytic copper foil with excellent low spring-back, it is preferable that a numerical value y3, which represents rigidity and is based on a pre-heat treatment stress X3 (MPa) of a 0.2% distortion, is 600 or more and less than 1000. y1 = (X1/0.2) y2 = (X1/0.2)/(X2/0.4) y3 = (X3/0.2)

Description

低反発性電解銅箔、該電解銅箔を使用した配線板及びフレキシブル配線板Low resilience electrolytic copper foil, wiring board and flexible wiring board using the electrolytic copper foil
　本発明は、特に低反発性及びファインパターン性に優れた電解銅箔に関するものである。より詳しく述べるならば、本発明は、フレキシブル配線板を製造する際にフィルム貼付工程で掛かる熱処理における過度な結晶の粗大化を抑制させた、低反発性及びファインパターン性に優れたフレキシブル配線板用に好適な電解銅箔に関するものである。 The present invention relates to an electrolytic copper foil particularly excellent in low resilience and fine pattern properties. More specifically, the present invention is for a flexible wiring board excellent in low resilience and fine pattern property, in which excessive crystal coarsening is suppressed in the heat treatment applied in the film sticking step when manufacturing the flexible wiring board. The present invention relates to a suitable electrolytic copper foil.
　なお本明細書において、下記の如く定義する。
「電解銅箔」とは、電解銅箔或いは電解銅合金箔のいずれか一方、または、両方を表現する。
「未処理」状態とは、製箔後、或いは製箔後に表面を防錆処理し、或いは必要により粗化処理等の密着性改善処理を施した状態を云い、加熱処理を施していない状態を表現する。
「低反発性」とは、小さな荷重で曲げることが可能で且つ容易に塑性変形に至るという特性である。 In this specification, the definition is as follows.
“Electrolytic copper foil” represents either one or both of electrolytic copper foil and electrolytic copper alloy foil.
The “untreated” state refers to a state in which the surface is subjected to rust prevention treatment after foil formation or after foil formation, or is subjected to adhesion improving treatment such as roughening treatment as necessary, and is not subjected to heat treatment. Express.
“Low resilience” is a characteristic that can be bent with a small load and easily leads to plastic deformation.
　各種電子機器類においてシリコンチップやコンデンサ類の基板や接続材料として配線板が用いられており、配線板の導電層には銅箔が一般的に使用されている。 In various electronic devices, wiring boards are used as substrates and connection materials for silicon chips and capacitors, and copper foil is generally used for the conductive layers of the wiring boards.
　上記配線板の銅箔は一般的に圧延銅箔や電解銅箔の形態で供給されているが、その中でも生産性が高く薄層化が容易な電解銅箔が広く用いられている。 The copper foil of the wiring board is generally supplied in the form of a rolled copper foil or an electrolytic copper foil, and among them, an electrolytic copper foil that is highly productive and easily thinned is widely used.
　現在、情報機器端末を始めとする高機能電子機器の小型化が進んでおり機器内部体積の縮小が課題となっている。そのため、そのような用途において小スペースに効率良く且つ問題なく実装可能な低反発性を持つ配線板（以降、フレキシブル配線板と呼称する）には、導電層である銅箔にも低反発性が求められる。 At present, miniaturization of high-performance electronic devices such as information device terminals is progressing, and reduction of the internal volume of the device is an issue. Therefore, a wiring board having low resilience (hereinafter referred to as a flexible wiring board) that can be mounted efficiently and without problems in a small space in such applications has low resilience also in the copper foil as the conductive layer. Desired.
　銅箔は一般的に上記フレキシブル配線板に加工される際に、フィルム貼付工程等において３００℃前後の熱履歴がかかる。そのため、熱履歴がかかった後の銅箔において上記の低反発性が必要とされており、その特性の制御が重要である。 When copper foil is generally processed into the above-mentioned flexible wiring board, a heat history of around 300 ° C. is applied in a film sticking process or the like. Therefore, the low resilience described above is required in the copper foil after the thermal history is applied, and control of the characteristics is important.
　小さな荷重で曲げることが可能で且つ容易に塑性変形に至る、即ち、「低反発性」はフィルム貼付工程を通過した後に必要とされる特性である。フィルム貼付工程前からそのような特性を持っている銅箔は一般にシワが発生し易く、製造・加工ラインでのハンドリングが難しくなる。また、反対にフィルム貼付工程前に過度に反発性が強い銅箔であっても製造・加工ライン上で箔切れが発生し易く、ハンドリングが難しくなる。 It can be bent with a small load and easily leads to plastic deformation, that is, “low resilience” is a characteristic required after passing the film sticking process. A copper foil having such characteristics before the film sticking process generally tends to be wrinkled, making it difficult to handle in a production / processing line. On the other hand, even if the copper foil is excessively repulsive before the film sticking step, the foil breakage is likely to occur on the production / processing line, and handling becomes difficult.
　加えて、銅箔がフレキシブル配線板に使用される場合には配線の高密度化に対応できるファインパターンの回路が形成できることも必要であり、そのためには銅箔が低粗度である必要がある。また、銅箔中の結晶粒組織がある程度微細である必要もあり、上記加熱処理によって過度に結晶粒組織が粗大となる銅箔はファインパターン性に悪影響を及ぼす。 In addition, when copper foil is used for a flexible wiring board, it is necessary to be able to form a fine pattern circuit that can cope with higher wiring density. For this purpose, the copper foil needs to have low roughness. . Further, the crystal grain structure in the copper foil needs to be fine to some extent, and the copper foil in which the crystal grain structure becomes excessively coarse by the heat treatment adversely affects the fine pattern property.
　さらに、ファインパターン性を高めるためには，銅箔を薄くすることも不可欠である。すなわち，従来フレキシブル配線板に用いられていた銅箔の厚みは１８μｍまたは１２μｍが主流であったが，１２μｍあるいはこれより薄い銅箔が要求されるようになってきている。なお、厚さが１８μｍ以下の圧延銅箔の製造コストは電解銅箔より約２倍高くなる。 Furthermore, in order to improve fine pattern properties, it is indispensable to make the copper foil thinner. That is, the thickness of the copper foil conventionally used for flexible wiring boards has been 18 μm or 12 μm, but a copper foil of 12 μm or thinner has been demanded. In addition, the manufacturing cost of the rolled copper foil whose thickness is 18 micrometers or less becomes about 2 times higher than an electrolytic copper foil.
　特許文献１（特許第４３５７５４８号公報）は、コネクター、リードフレーム等の電気・電子部品用途として、結晶方位等の制御により曲げ加工性に優れた圧延銅合金箔を開示している。しかし、この圧延銅合金箔は曲げ加工後に戻らない（スプリングバックしない）ことが特徴であり、曲げ加工段階ではその高強度ゆえに反発力は強く、本発明の求める低反発性とは異なる特性となっている。 Patent Document 1 (Japanese Patent No. 4357548) discloses a rolled copper alloy foil excellent in bending workability by controlling crystal orientation and the like as an electrical / electronic component application such as a connector and a lead frame. However, this rolled copper alloy foil is characterized in that it does not return after bending (does not spring back). At the bending stage, its repulsive force is strong because of its high strength, and it has characteristics different from the low repulsion required by the present invention. ing.
　特許文献２（特開２００９－２４２８４６号公報）は、フレキシブル配線板用途として、箔厚、表面粗さ、結晶方位等の制御により曲げ時の反発力を低減した圧延銅合金箔を開示している。しかし、圧延銅箔又は圧延銅合金箔と本発明の電解銅箔とでは製造方法が全く異なっており、必要とされる結晶組織制御の方法・構成要素も異なる。 Patent Document 2 (Japanese Patent Application Laid-Open No. 2009-242846) discloses a rolled copper alloy foil in which the repulsive force during bending is reduced by controlling the foil thickness, surface roughness, crystal orientation, and the like as a flexible wiring board application. . However, the rolled copper foil or the rolled copper alloy foil and the electrolytic copper foil of the present invention are completely different in the production method, and the required crystal structure control methods and components are also different.
　特許文献３（特開２００７－３２００８３号公報）では、フレキシブル配線板用途として、ポリイミドの組成制御、銅箔層の厚み制御によりスプリングバックを抑えた銅張積層板（ＣＣＬ）を開示している。しかし、この銅張積層板の銅箔層は厚みを薄く制限しているだけであり、その結晶組織としての反発性自体を改善しているわけではなく、銅箔層自体の結晶組織制御により低反発性を実現している本発明とは異なっている。 Patent Document 3 (Japanese Patent Laid-Open No. 2007-320083) discloses a copper clad laminate (CCL) in which spring back is suppressed by controlling the composition of polyimide and the thickness of the copper foil layer as a flexible wiring board. However, the copper foil layer of this copper-clad laminate is only limited in thickness and does not improve the rebound itself as a crystal structure, but it is reduced by controlling the crystal structure of the copper foil layer itself. This is different from the present invention that realizes resilience.
　特許文献４（特許第４７１２７５９号公報）は、回路基板用途として、マット面（Ｍ面）の表面粗さＲｚを１．０μｍ以下、Ｒａを０．２μｍ以下とすることにより、ファインパターン性に優れた電解銅箔を開示している。しかし、この電解銅箔は優れた表面平滑性を特徴としており、本発明の求める低反発性は目標ではない。 Patent Document 4 (Patent No. 4712759) is excellent in fine pattern property by setting the surface roughness Rz of the mat surface (M surface) to 1.0 μm or less and Ra to 0.2 μm or less as a circuit board application. An electrolytic copper foil is disclosed. However, this electrolytic copper foil is characterized by excellent surface smoothness, and the low resilience required by the present invention is not a target.
　特許文献５（特許第４８２７９５２号公報）は、ＣＣＬ用（銅張積層板）として、銅箔中の不純物濃度を低く制御することにより、屈曲性に優れた電解銅箔を開示している。しかし、この電解銅箔は小さな荷重で曲げることは可能であるが、広い弾性変形領域が求められる高屈曲性を有していることからも容易に想像できるように塑性変形は起こりにくく、曲げ加工後の戻り量が大きくなってしまうので本発明の求める低反発性は有していない。 Patent Document 5 (Patent No. 4,827,952) discloses an electrolytic copper foil having excellent flexibility by controlling the impurity concentration in the copper foil to be low for CCL (copper-clad laminate). However, this electrolytic copper foil can be bent with a small load, but plastic deformation is unlikely to occur as can be easily imagined from the fact that it has high flexibility that requires a wide elastic deformation region, and bending Since the amount of return later increases, the low resilience required by the present invention is not provided.
特許第４３５７５４８号公報Japanese Patent No. 4357548 特開２００９－２４２８４６号公報JP 2009-2442846 A 特開２００７－３２００８３号公報JP 2007-320083 A 特許第４７１２７５９号公報Japanese Patent No. 4712759 特許第４８２７９５２号公報Japanese Patent No. 4827952
　本発明は、製造・加工ラインでのハンドリングが容易であり、フィルム貼付工程で掛かる熱処理で低反発性が発揮され、或いは低反発性が維持され、電気機器の小型化に対し対応可能であり、且つ結晶粒組織の過度な粗大化が抑制され、ファインパターン性にも優れる電解銅箔を提供することにある。 The present invention is easy to handle in the production / processing line, exhibits low repulsion by the heat treatment applied in the film sticking process, or maintains low repulsion, and can cope with downsizing of electrical equipment, And it is providing the electrolytic copper foil which the excessive coarsening of a crystal grain structure is suppressed and is excellent also in fine pattern property.
　本発明の電解銅箔は、３００℃×１時間熱処理後に常温で測定した０．２％歪の応力Ｘ１（ＭＰａ）に基づく数式１で示される剛性を示す数値ｙ１が８００未満であり、且つ前記応力Ｘ１（ＭＰａ）と０．４％歪の応力Ｘ２（ＭＰａ）に基づく数式２で示される曲げに伴う剛性の変化の程度を表わす数値y２が１．５以上となることを特徴とする。
〔数式１〕
　　　　　　ｙ１＝（Ｘ１／０．２）＜８００
〔数式２〕
　　　　　　ｙ２＝（Ｘ１／０．２）／（Ｘ２／０．４）≧１．５
In the electrolytic copper foil of the present invention, the numerical value y1 indicating the rigidity represented by Equation 1 based on the stress X1 (MPa) of 0.2% strain measured at room temperature after heat treatment at 300 ° C. for 1 hour is less than 800, and A numerical value y2 representing the degree of change in rigidity accompanying bending shown in Formula 2 based on the stress X1 (MPa) and the stress X2 (MPa) of 0.4% strain is 1.5 or more.
[Formula 1]
y1 = (X1 / 0.2) <800
[Formula 2]
y2 = (X1 / 0.2) / (X2 / 0.4) ≧ 1.5
　前記電解銅箔は、熱処理前（未処理）の０．２％歪時の応力Ｘ3（ＭＰａ）に基づく数式３で示される剛性を示す数値ｙ３が６００以上、且つ１０００未満であることが好ましい。
〔数式３〕
　　　　　　６００≦ｙ３＝（Ｘ３／０．２）＜１０００ The electrolytic copper foil preferably has a numerical value y3 indicating a rigidity represented by Equation 3 based on a stress X3 (MPa) at 0.2% strain before heat treatment (untreated) of 600 or more and less than 1000.
[Formula 3]
600 ≦ y3 = (X3 / 0.2) <1000
　前記電解銅箔は、３００℃×１時間熱処理後に、常温で観察した３００μｍ四方における粒径２μｍ未満の結晶粒個数が５，０００個以上であることが好ましい。 The electrolytic copper foil preferably has 5,000 or more crystal grains having a grain size of less than 2 μm in 300 μm square observed at room temperature after heat treatment at 300 ° C. for 1 hour.
　前記電解銅箔は、マット面（Ｍ面）の表面粗さＲｚが３．０μｍ未満、且つシャイニー面（Ｓ面）の表面粗さＲｚが３．０μｍ未満であることが好ましい。 The electrolytic copper foil preferably has a mat surface (M surface) having a surface roughness Rz of less than 3.0 μm and a shiny surface (S surface) having a surface roughness Rz of less than 3.0 μm.
　本発明の前記電解銅箔は配線板として好適に使用でき、特にフレキシブル配線板に適している。 The electrolytic copper foil of the present invention can be suitably used as a wiring board, and is particularly suitable for a flexible wiring board.
　本発明の電解銅箔は、配線板の製造・加工ラインでのハンドリングが容易であり、フィルム貼付工程で掛かる熱処理後の低反発性に優れ、電気機器の小型化に対し対応可能であり、且つ両面共に低粗度であり結晶粒組織の過度な粗大化が抑制されるのでファインパターン性にも優れる電解銅箔を提供することができる。 The electrolytic copper foil of the present invention is easy to handle in the production and processing line of the wiring board, is excellent in low resilience after the heat treatment applied in the film sticking process, and can cope with downsizing of electrical equipment, and Since both surfaces have low roughness and excessive coarsening of the crystal grain structure is suppressed, an electrolytic copper foil excellent in fine pattern property can be provided.
ドラム式製箔装置を示す説明図である。It is explanatory drawing which shows a drum type foil making apparatus. 反発性測定の測定器具を示す説明図である。It is explanatory drawing which shows the measuring instrument of a resilience measurement.
　本発明の電解銅箔は、３００℃×１時間熱処理後に常温で測定した０．２％歪時の応力Ｘ１（ＭＰａ）にて数式１で示される剛性を示す数値ｙ１が８００未満であり、且つ応力Ｘ１（ＭＰａ）と０．４％歪時の応力Ｘ２（ＭＰａ）にて数式２で示される曲げに伴う剛性の変化の程度を表わす数値ｙ２が１．５以上であることを特徴とする。
〔数式１〕　ｙ１＝（Ｘ１／０．２）＜８００
〔数式２〕　ｙ２＝（Ｘ１／０．２）／（Ｘ２／０．４）≧１．５
　数値ｙ１が８００未満であると剛性が小さいので小さな荷重で曲げることが可能である。一方、８００以上であると剛性が大きくなるので小さな荷重では曲げることが難しくなる。 In the electrolytic copper foil of the present invention, the numerical value y1 indicating the rigidity expressed by the mathematical formula 1 is less than 800 in the stress X1 (MPa) at 0.2% strain measured at room temperature after heat treatment at 300 ° C. for 1 hour, and A numerical value y2 representing the degree of change in rigidity accompanying bending shown in Formula 2 with a stress X1 (MPa) and a stress X2 (MPa) at 0.4% strain is 1.5 or more.
[Formula 1] y1 = (X1 / 0.2) <800
[Formula 2] y2 = (X1 / 0.2) / (X2 / 0.4) ≧ 1.5
If the numerical value y1 is less than 800, the rigidity is small, so that bending with a small load is possible. On the other hand, if it is 800 or more, the rigidity becomes large, so it is difficult to bend with a small load.
　数値ｙ２は曲げに伴う剛性の変化の程度を表しており、数値ｙ２が大きいほど曲げによる塑性変形が起こり易く、曲げ加工後のばね性の戻り量が小さくなることを示している。ｙ２の数値が１．５未満であると、曲げによる塑性変形は起こり難く、曲げ加工後のばね性の戻り量が大きくなる。
　なお、上記数値ｙ２が１．５未満であっても応力Ｘ１、応力Ｘ２が小さければ低反発に問題がないように見えるが、塑性変形が起こり難い以上、曲げ加工後のばね性の戻り量が大きくなってしまうので必要とされる低反発性は得られない。 The numerical value y2 represents the degree of change in rigidity accompanying bending, and the larger the numerical value y2, the easier the plastic deformation occurs due to bending, and the smaller the return amount of the spring property after bending. When the numerical value of y2 is less than 1.5, plastic deformation due to bending hardly occurs, and the return amount of the spring property after bending increases.
Even if the numerical value y2 is less than 1.5, if the stress X1 and the stress X2 are small, it seems that there is no problem in low resilience, but since the plastic deformation is difficult to occur, the return amount of the spring property after bending is small. Since it becomes large, the required low resilience cannot be obtained.
　本発明の電解銅箔は、熱処理前（未処理）で０．２％歪時の応力Ｘ3（ＭＰａ）にて数式３で示される剛性を示す数値ｙ３が６００以上、且つ１０００未満であることを特徴とする。
〔数式３〕６００≦　ｙ３＝（Ｘ３／０．２）＜１０００
　剛性を示す数値y３は６００以上、且つ１０００未満であれば剛性が適度であり良好なハンドリング性が保たれる。一方、数値ｙ３が６００未満であると剛性が弱過ぎて、製造・加工ラインでシワが発生し易いため、ハンドリングが難しくなる。また、数値ｙ３が１０００以上であっても剛性が強過ぎて、製造・加工ラインで箔切れが発生し易いためハンドリングが難しくなる。 In the electrolytic copper foil of the present invention, before the heat treatment (untreated), the numerical value y3 indicating the rigidity represented by the mathematical formula 3 at a stress X3 (MPa) at 0.2% strain is 600 or more and less than 1000. Features.
[Formula 3] 600 ≦ y3 = (X3 / 0.2) <1000
If the numerical value y3 indicating the rigidity is 600 or more and less than 1000, the rigidity is moderate and good handling properties are maintained. On the other hand, if the numerical value y3 is less than 600, the rigidity is too weak and wrinkles are likely to occur in the production / processing line, making handling difficult. Further, even if the numerical value y3 is 1000 or more, the rigidity is too strong, and the foil is easily cut off in the production / processing line, so that handling becomes difficult.
　本発明の電解銅箔は、３００℃×１時間熱処理後に、常温で観察した３００μｍ四方における粒径２μｍ未満の結晶粒個数が５，０００個以上であることを特徴とする。
　結晶粒個数が５，０００個以上ならば結晶組織が微細であり、良好なファインパターン性が保たれる。
　一方、３００μｍ四方における粒径２μｍ未満の結晶粒個数が５，０００個未満であると結晶粒組織が粗大となり、ファインパターン性に悪影響を与える。 The electrolytic copper foil of the present invention is characterized in that the number of crystal grains having a particle size of less than 2 μm in 300 μm square observed at room temperature after heat treatment at 300 ° C. for 1 hour is 5,000 or more.
If the number of crystal grains is 5,000 or more, the crystal structure is fine and good fine pattern properties are maintained.
On the other hand, if the number of crystal grains having a grain size of less than 2 μm in a 300 μm square is less than 5,000, the crystal grain structure becomes coarse and adversely affects fine pattern properties.
　本発明の電解銅箔は、Ｍ面の表面粗さＲｚが３．０μｍ未満、且つＳ面の表面粗さＲｚが３．０μｍ未満であることを特徴とする。
　Ｒｚが３．０μｍ未満ならば表面の凹凸が小さく、良好なファインパターン性が保たれる。
　一方、Ｒｚが３．０μｍ以上ならば表面の凹凸が大きく、ファインパターン性に悪影響を与える。 The electrolytic copper foil of the present invention is characterized in that the surface roughness Rz of the M plane is less than 3.0 μm and the surface roughness Rz of the S plane is less than 3.0 μm.
If Rz is less than 3.0 μm, the surface irregularities are small and good fine pattern properties are maintained.
On the other hand, if Rz is 3.0 μm or more, the unevenness of the surface is large, and the fine pattern property is adversely affected.
　以下本発明の一実施形態につき詳細に説明する。
　通常、電解銅箔は、例えば図１に示す電解製箔装置により製箔される。電解製箔装置は、回転するドラム状のカソード２（表面はＳＵＳ又はチタン製）、該カソード２に対して同心円状に配置されたアノード１（鉛電極又は貴金属酸化物被覆チタン電極）からなり、該製箔装置に電解液３を供給しつつ両極間に電流を流してカソード２表面に所定の厚さに銅を電析させ、その後カソード２表面から銅を箔状に剥ぎ取る。また、未処理（電解処理前）電解銅箔４の電解液３と接していた面がマット面（Ｍ面）、ドラム状のカソード２と接していた面がシャイニー面（Ｓ面）である。
　なお、上記はドラム状のカソード２を採用した製箔装置につき説明したがカソードを板状とする製箔装置で銅箔を製造することもある。 Hereinafter, one embodiment of the present invention will be described in detail.
Usually, the electrolytic copper foil is made by, for example, an electrolytic foil making apparatus shown in FIG. The electrolytic foil making apparatus comprises a rotating drum-like cathode 2 (the surface is made of SUS or titanium), and an anode 1 (lead electrode or noble metal oxide-coated titanium electrode) arranged concentrically with respect to the cathode 2. While supplying the electrolytic solution 3 to the foil making apparatus, current is passed between both electrodes to deposit copper to a predetermined thickness on the surface of the cathode 2, and then the copper is peeled off from the surface of the cathode 2 in the form of foil. In addition, the surface of the untreated (before electrolytic treatment) electrolytic copper foil 4 in contact with the electrolytic solution 3 is the mat surface (M surface), and the surface in contact with the drum-like cathode 2 is the shiny surface (S surface).
In the above description, the foil manufacturing apparatus using the drum-like cathode 2 has been described. However, the copper foil may be manufactured by a foil manufacturing apparatus having a plate-like cathode.
　図１に示す装置で電解銅箔を製箔するには、電解液３として硫酸銅めっき液を使用する。硫酸銅めっき液の硫酸濃度は２０～１５０ｇ／Ｌ、特に３０～１００ｇ／Ｌが好ましい。硫酸濃度が２０ｇ／Ｌ未満となると電流が流れにくくなるので現実的な操業が困難となり、さらにめっきの均一性、電着性も悪くなる。硫酸濃度が１５０ｇ／Ｌを超えると銅の溶解度が下がるので十分な銅濃度が得られなくなり現実的な操業が困難となる。また、設備の腐食も促進される。 In order to form an electrolytic copper foil with the apparatus shown in FIG. 1, a copper sulfate plating solution is used as the electrolytic solution 3. The sulfuric acid concentration of the copper sulfate plating solution is preferably 20 to 150 g / L, particularly 30 to 100 g / L. When the sulfuric acid concentration is less than 20 g / L, it becomes difficult to flow an electric current, so that practical operation becomes difficult, and the uniformity of plating and electrodeposition are also deteriorated. When the sulfuric acid concentration exceeds 150 g / L, the solubility of copper is lowered, so that a sufficient copper concentration cannot be obtained, and realistic operation becomes difficult. Also, corrosion of equipment is promoted.
　銅濃度は４０～１５０ｇ／Ｌ、特に６０～１００ｇ／Ｌが好ましい。銅濃度が４０ｇ／Ｌ未満となると電解銅箔の製造において現実的な操業が可能な電流密度を確保することが難しくなる。銅濃度を１５０ｇ／Ｌより上げるのは相当な高温が必要となり現実的ではない。 The copper concentration is preferably 40 to 150 g / L, particularly 60 to 100 g / L. When the copper concentration is less than 40 g / L, it is difficult to secure a current density that allows practical operation in the production of electrolytic copper foil. Increasing the copper concentration above 150 g / L is not practical because a considerably high temperature is required.
　硫酸銅めっき液には有機添加物と塩素を添加する。硫酸銅めっき浴に添加する有機添加物は、メルカプト基を持つ化合物と高分子多糖類の２種の有機添加剤である。メルカプト基を持つ化合物には銅の電析を促進する効果が有り、高分子多糖類には銅の電析を抑制する効果が有る。両者の促進・抑制効果が適度に発揮されることにより、製箔中に発生する凹部に対して銅の電析が促進され、且つ凸部に対して銅の電析が抑制されて、結果として析出表面の平滑効果が得られる。
　また、２種の有機添加剤が最適な濃度となることによって発揮される結晶組織制御効果により、本発明の特徴となっている小さな曲げで塑性変形が容易に進み、ハンドリング性に優れ、熱処理後の結晶粒組織の過度な粗大化が抑制され、低粗度となる電解銅箔が得られる。
　添加する塩素は上記２種の有機添加剤の効果を有効に発揮させる触媒のような作用をする。 An organic additive and chlorine are added to the copper sulfate plating solution. Organic additives to be added to the copper sulfate plating bath are two kinds of organic additives, a compound having a mercapto group and a polymer polysaccharide. A compound having a mercapto group has an effect of promoting copper electrodeposition, and a high molecular polysaccharide has an effect of suppressing copper electrodeposition. By appropriately exerting both of the promotion and suppression effects, copper electrodeposition is promoted with respect to the concave portions generated in the foil making, and copper electrodeposition is suppressed with respect to the convex portions. A smoothing effect on the precipitation surface is obtained.
In addition, the crystal structure control effect exerted by the optimum concentration of the two organic additives facilitates plastic deformation with a small bend, which is a feature of the present invention. An excessively coarse grain structure is suppressed, and an electrolytic copper foil having low roughness is obtained.
The added chlorine acts as a catalyst that effectively exhibits the effects of the two organic additives.
　メルカプト基を持つ化合物はＭＰＳ－Ｎａ（３－メルカプト－１－プロパンスルホン酸ナトリウム）またはＳＰＳ－Ｎａ｛ビス（３－スルホプロピル）ジスルフィドナトリウム｝いずれかを選択する。有機構造的にはＳＰＳはＭＰＳの２量体となっており、添加剤として同等の効果を発揮し、必要な濃度は同等である。
　濃度としては０．２５ｐｐｍ以上７．５ｐｐｍ以下、特に１．０ｐｐｍ以上５．０ｐｐｍ以下が好ましい。０．２５ｐｐｍ未満では製箔中に発生する凹部に対する電析促進効果が発揮され難くなり、本発明の特徴である結晶組織制御の効果も発揮され難くなる。また、７．５ｐｐｍを超えると、凸部に対する電析促進効果が過剰となり、部分的な異常析出が起こりやすく、正常な外観の銅箔の製造が困難となり、単に添加剤のコストが嵩むだけで、物性の改善は期待できない。 For the compound having a mercapto group, either MPS-Na (sodium 3-mercapto-1-propanesulfonate) or SPS-Na {bis (3-sulfopropyl) disulfide sodium} is selected. In terms of organic structure, SPS is a dimer of MPS, exhibits the same effect as an additive, and has the same required concentration.
The concentration is preferably from 0.25 ppm to 7.5 ppm, particularly preferably from 1.0 ppm to 5.0 ppm. If it is less than 0.25 ppm, it is difficult to exhibit the effect of promoting electrodeposition on the concave portions generated in the foil production, and the effect of controlling the crystal structure, which is a feature of the present invention, is also hardly exhibited. On the other hand, if it exceeds 7.5 ppm, the electrodeposition promoting effect on the convex portion becomes excessive, partial abnormal precipitation is likely to occur, it becomes difficult to produce a copper foil with a normal appearance, and the cost of the additive only increases. The improvement of physical properties cannot be expected.
　高分子多糖類はＨＥＣ（ヒドロキシエチルセルロース）であり、その濃度は３．０ｐｐｍ以上３０ｐｐｍ以下、特に１０ｐｐｍ以上２０ｐｐｍ以下が好ましい。３．０ｐｐｍ未満となると凸部に対する電析抑制効果が発揮され難くなり、本発明の特徴である結晶組織制御の効果も発揮され難くなる。また、３０ｐｐｍを超えると高分子多糖類特有の効果である泡の発生が過剰となり、銅イオンの供給が不足し、正常な銅箔の製造が困難となるばかりか、電解液中の有機物が増加することにより「ヤケめっき」が発生する原因となる。 The high molecular polysaccharide is HEC (hydroxyethyl cellulose), and the concentration is preferably 3.0 ppm or more and 30 ppm or less, and particularly preferably 10 ppm or more and 20 ppm or less. If it is less than 3.0 ppm, the electrodeposition suppressing effect on the convex portion is hardly exhibited, and the effect of controlling the crystal structure, which is a feature of the present invention, is hardly exhibited. On the other hand, if it exceeds 30 ppm, the generation of bubbles, which is an effect peculiar to polymer polysaccharides, becomes excessive, the supply of copper ions becomes insufficient, and it becomes difficult to produce a normal copper foil, and the organic matter in the electrolyte increases. By doing so, it causes “burn plating” to occur.
　電解液に塩素を添加する。塩素濃度は１ｐｐｍ以上２０ｐｐｍ以下、特に５ｐｐｍ以上１５ｐｐｍ以下が好ましい。塩素は上記２種の有機添加剤の効果を有効に発揮させる触媒のような作用をする。塩素濃度が１ｐｐｍ未満では、上記の触媒的作用を発揮させることが困難であり、有機添加剤の効果を引き出すことが困難となるばかりか、非常に低濃度となるため管理制御が困難となり現実的ではない。また、２０ｐｐｍを超えると塩素の有機添加剤への触媒的作用だけでなく、塩素自体の電析への影響が大きくなるため、本発明の特徴である添加剤による結晶組織制御の効果も発揮され難くなる。 Add chlorine to the electrolyte. The chlorine concentration is preferably from 1 ppm to 20 ppm, particularly preferably from 5 ppm to 15 ppm. Chlorine acts as a catalyst that effectively exhibits the effects of the two organic additives. If the chlorine concentration is less than 1 ppm, it is difficult to exert the catalytic action described above, and it is difficult to bring out the effect of the organic additive. is not. Further, if it exceeds 20 ppm, not only the catalytic action of chlorine on the organic additive but also the influence on the electrodeposition of chlorine itself becomes large, so the effect of controlling the crystal structure by the additive which is a feature of the present invention is also exhibited. It becomes difficult.
　製箔する電流密度は２０～２００Ａ／ｄｍ２、特に３０～１２０Ａ／ｄｍ２が好ましい。電流密度が２０Ａ／ｄｍ２未満となると電解銅箔の製造において生産効率が非常に低く現実的ではない。電流密度を２００Ａ／ｄｍ２より上げるには相当な高銅濃度、高温、高流速が必要であり、電解銅箔製造設備に大きな負担がかかり現実的ではないためである。 The current density for foil production is preferably 20 to 200 A / dm 2 , particularly preferably 30 to 120 A / dm 2 . When the current density is less than 20 A / dm 2 , production efficiency is very low in the production of electrolytic copper foil, which is not realistic. This is because, in order to increase the current density from 200 A / dm 2, a high copper concentration, a high temperature, and a high flow rate are required, which imposes a large burden on the electrolytic copper foil manufacturing facility and is not realistic.
　電解浴温度は２５～８０℃、特に３０～７０℃が好ましい。浴温が２５℃未満となると電解銅箔の製造において十分な銅濃度、電流密度を確保することが困難となり現実的ではない。また、８０℃より上げるのは操業上および設備上非常に困難で現実的ではない。
　上記の電解条件は、それぞれの範囲から、銅の析出、めっきのヤケ等の不具合が起きないような条件に適宜調整して行う。 The electrolytic bath temperature is preferably 25 to 80 ° C, particularly 30 to 70 ° C. When the bath temperature is less than 25 ° C., it is difficult to secure a sufficient copper concentration and current density in the production of the electrolytic copper foil, which is not realistic. Further, raising the temperature from 80 ° C. is very difficult in operation and facilities and is not realistic.
The above electrolysis conditions are appropriately adjusted from the respective ranges so as not to cause problems such as copper deposition and plating burns.
　電解銅箔の製造直後の表面粗さはカソード２表面の粗さを転写するため、その表面粗さＲｚを０．１～３．０μｍであるカソードを使用するのが好ましい。このようなカソードを用いることで電解銅箔の製造直後のＳ面の表面粗さはカソード表面の転写であるので、Ｓ面の表面粗さＲｚを０．１～３．０μｍとすることができる。電解銅箔のＳ面の表面粗さＲｚを０．１μｍ未満とするのは、カソードの表面粗さＲｚを０．１μｍ未満とすることであり、現在の研磨技術などを考えると０．１μｍより平滑に仕上げることは難しく、また量産製造するには不向きであると考えられる。また、Ｓ面の粗さＲｚを３．０μｍ以上とすると、ファインパターン性が落ちることとなり、本発明が求める特性が得られなくなる。 Since the surface roughness immediately after the production of the electrolytic copper foil transfers the roughness of the surface of the cathode 2, it is preferable to use a cathode having a surface roughness Rz of 0.1 to 3.0 μm. By using such a cathode, since the surface roughness of the S surface immediately after the production of the electrolytic copper foil is a transfer of the cathode surface, the surface roughness Rz of the S surface can be 0.1 to 3.0 μm. . The reason why the surface roughness Rz of the S surface of the electrolytic copper foil is less than 0.1 μm is that the surface roughness Rz of the cathode is less than 0.1 μm. It is difficult to finish smoothly and is not suitable for mass production. On the other hand, when the roughness Rz of the S surface is 3.0 μm or more, the fine pattern property is lowered and the characteristics required by the present invention cannot be obtained.
　電解銅箔のＭ面の表面粗さＲｚは０．０５～３．０μｍであることが望ましい。表面粗さＲｚを０．０５μｍ未満の粗さに仕上げるには、光沢めっきを行ったとしても非常に難しく現実的に製造は不可能に近い。また、Ｍ面の表面粗さＲｚを３．０μｍ以上とすると、ファインパターン性が落ちることとなり、本発明が求める特性が得られなくなる。Ｓ面及びＭ面の粗さＲｚを１．５μｍ未満とするとより好適である。 The surface roughness Rz of the M surface of the electrolytic copper foil is preferably 0.05 to 3.0 μm. In order to finish the surface roughness Rz to a roughness of less than 0.05 μm, even if bright plating is performed, it is very difficult and practically impossible to manufacture. On the other hand, if the surface roughness Rz of the M-plane is 3.0 μm or more, the fine pattern property is lowered, and the characteristics required by the present invention cannot be obtained. It is more preferable that the roughness Rz of the S surface and the M surface is less than 1.5 μm.
　また、上記電解銅箔の厚みは３μｍ～２１０μｍであることが望ましい。厚さが３μｍ未満の銅箔はハンドリング技術などの関係上製造条件が厳しく、現実的ではない。厚さの上限は現在の回路基板の使用状況から２１０μｍ程度である。厚さが２１０μｍ以上の電解銅箔が配線板用銅箔として使用されることは考え難く、また電解銅箔を使用するコストメリットもなくなるからである。
　本発明においてファインパターン性を高めるには箔の厚さを１８μｍ以下、好ましくは１２μｍ以下と薄くすることが好ましい。 The thickness of the electrolytic copper foil is preferably 3 μm to 210 μm. A copper foil having a thickness of less than 3 μm is not practical because of severe manufacturing conditions due to handling techniques and the like. The upper limit of the thickness is about 210 μm from the current usage state of the circuit board. This is because it is unlikely that an electrolytic copper foil having a thickness of 210 μm or more is used as a copper foil for a wiring board, and the cost merit of using the electrolytic copper foil is lost.
In the present invention, in order to improve the fine pattern property, the thickness of the foil is preferably 18 μm or less, preferably 12 μm or less.
　以下に本発明を実施例に基づいて説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.
（１）製箔
　実施例１～８、比較例１～６
　実施例１～８、比較例１～６については、（ａ）表１に示す組成の硫酸銅（Ｈ２ＳＯ４）めっき液を活性炭フィルターに通して清浄処理し、同じく表１に示す添加剤を添加し所定の濃度とした後、（ｂ）表１に示す電流密度で図１に示す回転ドラム式製箔装置により電解製箔し、厚さ１２μｍの電解銅箔を製造した。なお、製箔前に研磨布でドラム表面の研磨処理を行った。その際、実施例１～７、比較例１～５は＃１５００の研磨布で、実施例８、比較例６は＃８００の研磨布で研磨を行なった。
　比較例７については特許文献４（特許第４７１２７５９号公報）の実施例６（ＭＰＳ比率＝３、ＰＢＦ比率１５、ＨＥＣ比率４）を参考にして、厚さ１２μｍの電解銅箔を製造した。
　比較例８については特許文献５（特許第４８２７９５２号公報）の実施例４（硫酸銅めっき液、銅７０ｇ／ｌ、硫酸５０ｇ／ｌ）を参考にして、厚さ１２μｍの電解銅箔を製造した。 (1) Foil making Examples 1-8, Comparative Examples 1-6
For Examples 1 to 8 and Comparative Examples 1 to 6, (a) a copper sulfate (H 2 SO 4 ) plating solution having the composition shown in Table 1 was passed through an activated carbon filter for cleaning treatment, and the additives shown in Table 1 were also used. Was added to obtain a predetermined concentration, and (b) electrolytic foil formation was performed at a current density shown in Table 1 using the rotary drum type foil making apparatus shown in FIG. 1 to produce an electrolytic copper foil having a thickness of 12 μm. Note that the surface of the drum was polished with a polishing cloth before the foil formation. At that time, Examples 1-7 and Comparative Examples 1-5 were polished with # 1500 polishing cloth, and Examples 8 and 6 were polished with # 800 polishing cloth.
For Comparative Example 7, an electrolytic copper foil having a thickness of 12 μm was produced with reference to Example 6 (MPS ratio = 3, PBF ratio 15, HEC ratio 4) of Patent Document 4 (Japanese Patent No. 4712759).
For Comparative Example 8, an electrolytic copper foil having a thickness of 12 μm was produced with reference to Example 4 (copper sulfate plating solution, copper 70 g / l, sulfuric acid 50 g / l) of Patent Document 5 (Japanese Patent No. 48279952). .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（１）測定・試験用サンプルの作製
　作成した各実施例、各比較例の未処理電解銅箔を６サンプル（サンプル１～６）に分割し下記測定・試験に使用した。
サンプル１
　始めに、サンプル１を使用して未処理のまま（＝熱処理前）引張試験を行い、０．２％歪時の応力を測定した。
サンプル２、３
　２つのサンプルを使用して窒素雰囲気中にて３００℃×１時間熱処理した後に、一方のサンプル２を使用して引張試験を行い、常温で０．２％歪時の応力と０．４％歪時の応力を測定した。残ったもう一方のサンプル３を使用して反発性測定を行った。
サンプル４
　サンプル４を使用して３００℃×１時間熱処理した後に常温で、ＥＢＳＤ測定により結晶粒径の分布の算出を行った。
サンプル５
　サンプル５を使用して表面粗さの測定を行った。
サンプル６
　サンプル６を使用してファインパターン性の評価を行った。 (1) Preparation of measurement / test samples Untreated electrolytic copper foils of each of the Examples and Comparative Examples prepared were divided into 6 samples (Samples 1 to 6) and used for the following measurement / test.
Sample 1
First, the sample 1 was used untreated (= before heat treatment) and a tensile test was performed to measure the stress at 0.2% strain.
Samples 2 and 3
After two samples were heat-treated in a nitrogen atmosphere at 300 ° C. for 1 hour, one sample 2 was subjected to a tensile test, and stress at 0.2% strain and 0.4% strain at room temperature. The stress at the time was measured. The remaining sample 3 was used for rebound measurement.
Sample 4
The sample 4 was heat-treated at 300 ° C. for 1 hour, and then the distribution of crystal grain size was calculated by EBSD measurement at room temperature.
Sample 5
Sample 5 was used to measure surface roughness.
Sample 6
Sample 6 was used to evaluate fine pattern properties.
　各測定・試験の詳細を以下に記す。
（２）引張試験 
　サンプル１を６インチ×幅０．５インチの試験片に裁断し引張試験機を用いて０．２％歪時の応力を測定した。なお、引張速度は５０ｍｍ／ｍｉｎとした。
　サンプル２を長さ６インチ×幅０．５インチの試験片に裁断し引張試験機を用いて０．２％歪時の応力と０．４％歪時の応力を測定した。なお、引張速度は５０ｍｍ／ｍｉｎとした。
　なお、常温で０．２％歪時の応力とはその名の通り、常温で０．２％歪時に示す応力値のことであり、０．４％歪時の応力も同様である。測定結果を表２に示す。 Details of each measurement and test are described below.
(2) Tensile test
Sample 1 was cut into a 6 inch × 0.5 inch wide test piece, and a stress at 0.2% strain was measured using a tensile tester. The tensile speed was 50 mm / min.
Sample 2 was cut into a test piece having a length of 6 inches and a width of 0.5 inches, and a stress at 0.2% strain and a stress at 0.4% strain were measured using a tensile tester. The tensile speed was 50 mm / min.
The stress at 0.2% strain at room temperature is, as the name suggests, the stress value shown at 0.2% strain at room temperature, and the stress at 0.4% strain is the same. The measurement results are shown in Table 2.
（３）反発性測定
　図２に示す装置を用いて反発性を測定した。試験片となる銅箔５をコイル状に丸めて設置し、押し潰し距離７が指定の距離となるまで押し潰し、電子天秤６で測定される荷重を反発荷重として測定し、反発性を評価した。
　具体的には、サンプル３を長さ４０ｍｍ×幅１５ｍｍの試験片に裁断し、コイル長さ１０ｍｍ（＝コイルの円周１０ｍｍ）で丸めて、下記の条件にて反発性の測定を行った。
　　　コイル長さ：１０ｍｍ
　　　押し潰し距離：１ｍｍ、３ｍｍ
　　　測定時間：押し潰し後３０秒後
　　　測定方法：電子天秤にて測定される荷重を反発荷重として測定
　反発性測定において、「小さな荷重での曲げ易さ」について、押し潰し距離３ｍｍ及び１ｍｍの反発荷重が２５ｇｆ未満のサンプルは○（合格）、２５ｇｆ以上のサンプルは×（不合格）と評価した。
　さらに、「塑性変形のし易さ」については、
（押し潰し距離１ｍｍの反発荷重）÷（押し潰し距離３ｍｍの反発荷重）
の数値が１．０５未満のサンプルは○（合格）、１．０５以上のサンプルは×（不合格）と評価した。この数値が小さいことは、押し潰し距離３ｍｍとさらに押し潰した距離１ｍｍの反発荷重の差異が少ないことを表している。即ち、数値が小さい程、変形量と反発荷重が比例する弾性領域での変形よりも、塑性領域での変形が主になっており、曲げ加工後の戻り量が少ないことを表している。
　測定結果を表２に示す。 (3) Measurement of resilience The resilience was measured using the apparatus shown in FIG. The copper foil 5 to be a test piece was placed in a coiled shape, crushed until the crushing distance 7 became a specified distance, the load measured by the electronic balance 6 was measured as a repulsive load, and the resilience was evaluated. .
Specifically, the sample 3 was cut into a test piece having a length of 40 mm and a width of 15 mm, rounded with a coil length of 10 mm (= coil circumference of 10 mm), and rebound characteristics were measured under the following conditions.
Coil length: 10mm
Crushing distance: 1mm, 3mm
Measurement time: 30 seconds after crushing Measuring method: Measured with electronic balance as repulsive load In repulsive measurement, repulsive load with crushing distance of 3 mm and 1 mm for “ease of bending with small load” A sample with a value of less than 25 gf was evaluated as ◯ (passed), and a sample of 25 gf or higher was evaluated as x (failed).
Furthermore, regarding "ease of plastic deformation"
(Repulsive load with a crushing distance of 1 mm) / (Repulsive load with a crushing distance of 3 mm)
A sample having a numerical value of less than 1.05 was evaluated as ◯ (pass), and a sample of 1.05 or more was evaluated as × (fail). A small numerical value indicates that there is little difference in the repulsive load between the crushing distance of 3 mm and the crushing distance of 1 mm. That is, as the numerical value is smaller, the deformation is mainly in the plastic region than the deformation in the elastic region where the deformation amount and the repulsive load are proportional, and the return amount after bending is smaller.
The measurement results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（４）ＥＢＳＤ測定による粒径２μｍ未満の結晶粒の個数の算出
　サンプル４のＭ面の表面を薬品にてエッチング処理して測定面とし、視野３００μｍ四方、ステップサイズ０．５μｍの測定条件にて粒径２μｍ未満の結晶粒の個数の算出を行った。なお、解析・算出にあたってはＴＳＬ社製の解析ソフト「ＯＩＭ」を使用した。
　結晶粒の個数については５°以上のずれを粒界と定義し、各結晶粒の面積と同じ面積の円の直径を結晶粒径として算出した。測定結果を表３に示す。 (4) Calculation of the number of crystal grains having a particle size of less than 2 μm by EBSD measurement The surface of the M surface of sample 4 is etched with a chemical to form a measurement surface, with measurement conditions of a field of view of 300 μm square and a step size of 0.5 μm. The number of crystal grains having a particle size of less than 2 μm was calculated. For analysis and calculation, analysis software “OIM” manufactured by TSL was used.
Regarding the number of crystal grains, a deviation of 5 ° or more was defined as a grain boundary, and the diameter of a circle having the same area as each crystal grain area was calculated as the crystal grain diameter. Table 3 shows the measurement results.
（５）表面粗さ測定
　サンプル５を用いて表面粗さＲｚを接触式表面粗さ計を用いて測定した。
　表面粗さはＪＩＳ－Ｂ－０６０１に規定されるＲｚ（１０点平均粗さ）で示している。基準長さは０．８ｍｍで行った。本計測機を用いると一回の測定で、Ｒａ、Ｒｙ、Ｒｚの三つの測定値を得ることができる。本発明においては、Ｒｚを表面粗さとして採用した。測定結果を表３に示す。 (5) Surface roughness measurement The sample 5 was used to measure the surface roughness Rz using a contact-type surface roughness meter.
The surface roughness is indicated by Rz (10-point average roughness) defined in JIS-B-0601. The reference length was 0.8 mm. When this measuring instrument is used, three measurement values of Ra, Ry, and Rz can be obtained by one measurement. In the present invention, Rz is adopted as the surface roughness. Table 3 shows the measurement results.
（６）ファインパターン性の評価
　サンプル６を用いてファインパターン性の評価を行った。評価はＭ面側をポリイミドフィルムに３００℃×１時間で熱プレス圧着した後、Ｓ面側をＬ／Ｓ（Ｌｉｎｅ　ａｎｄ　Ｓｐａｃｅ）＝２５μｍ／２５μｍにてマスキングし、塩化銅溶液にてエッチングを行って作成した回路パターンにて行った。
　評価方法は、回路パターンを真上から顕微鏡で観察し、１００μｍの回路長さで、回路幅の上限と下限の差を測定した。回路幅の上限と下限の差が１μｍ未満を◎（特に良）、３μm未満を○（合格）、それ以外を×（不合格）と判断した。
　結果を表３に示す。 (6) Evaluation of Fine Pattern Properties Fine pattern properties were evaluated using Sample 6. For evaluation, after heat-pressing the M surface to a polyimide film at 300 ° C. for 1 hour, the S surface is masked with L / S (Line and Space) = 25 μm / 25 μm and etched with a copper chloride solution. The circuit pattern created in the above was used.
In the evaluation method, the circuit pattern was observed with a microscope from directly above, and the difference between the upper limit and the lower limit of the circuit width was measured at a circuit length of 100 μm. When the difference between the upper limit and the lower limit of the circuit width was less than 1 μm, ◎ (particularly good), and less than 3 μm were judged as ◯ (pass), and the others were judged as x (fail).
The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２から明らかなように、実施例１～８は数式１で示される剛性を示す数値ｙ１が８００未満であり、小さな荷重で曲げることが可能となっている。
　さらに、実施例１～８は数式２で示される曲げに伴う剛性の変化の程度を表わす数値ｙ２が１．５以上であり、曲げによる塑性変形が容易に起こり易くなっている。
　実際に、反発性測定において実施例１～８は「小さな荷重での曲げ易さ」と「塑性変形のし易さ」の評価において合格となっている。
　また、実施例１～６及び８は数式３で示される剛性を示す数値ｙ３が６００以上、１０００未満であり、剛性が強すぎず、製造・加工ラインでのハンドリングが容易である。 As is apparent from Table 2, in Examples 1 to 8, the numerical value y1 indicating the rigidity expressed by Equation 1 is less than 800 and can be bent with a small load.
Further, in Examples 1 to 8, the numerical value y2 representing the degree of change in rigidity accompanying bending shown in Expression 2 is 1.5 or more, and plastic deformation due to bending is easily caused.
Actually, in the resilience measurement, Examples 1 to 8 passed the evaluation of “ease of bending with a small load” and “ease of plastic deformation”.
Further, in Examples 1 to 6 and 8, the numerical value y3 indicating the rigidity represented by Expression 3 is 600 or more and less than 1000, and the rigidity is not too strong, so that handling in the production / processing line is easy.
　ＣＣＬ製造・加工ラインにおいては、未処理銅箔と基板とを積層後加熱処理する製造方法だけでなく、先ず銅箔を加熱処理しその後に製造・加工ラインを通す製造方法も想定される。
　後者の場合には、未処理銅箔段階での剛性を示す数値ｙ３が１０００以上であっても、３００℃×１時間熱処理後の剛性を示す数値ｙ１が１０００未満であればハンドリングが容易となる。例えば、実施例７は剛性を示す数値ｙ３が１０００以上であるが、製造・加工ラインを通す前に３００℃×１時間熱処理を施せば数値ｙ１は１０００未満であるので効果的に使用することができる。
　また、配線板によっては加熱条件が３００℃未満の場合もある。このような場合には、実施例６のように３００℃×１時間熱処理後の数値ｙ１が６００未満となって剛性が小さくなり過ぎる懸念のある銅箔でも加熱条件によっては６００以上となるので有効に使用することができる。 In the CCL manufacturing / processing line, not only a manufacturing method in which an unprocessed copper foil and a substrate are laminated and heat-treated, but also a manufacturing method in which the copper foil is first heat-treated and then passed through the manufacturing / processing line is assumed.
In the latter case, even if the numerical value y3 indicating the rigidity at the untreated copper foil stage is 1000 or more, if the numerical value y1 indicating the rigidity after the heat treatment at 300 ° C. × 1 hour is less than 1000, handling becomes easy. . For example, in Example 7, the numerical value y3 indicating rigidity is 1000 or more. However, if heat treatment is performed at 300 ° C. for 1 hour before passing through the manufacturing / processing line, the numerical value y1 is less than 1000, so that it can be used effectively. it can.
Depending on the wiring board, the heating condition may be less than 300 ° C. In such a case, as shown in Example 6, the numerical value y1 after heat treatment at 300 ° C. × 1 hour is less than 600, and even a copper foil that is likely to have too low rigidity becomes 600 or more depending on the heating conditions. Can be used for
　表２から明らかなように、比較例３，４、７は数式１で示される剛性を示す数値ｙ１が８００以上となっているので、小さな荷重で曲げることが難しくなっている。さらに、比較例１～７は数式２で示される曲げに伴う剛性の変化の程度を表わす数値ｙ２が１．５未満となっているので、曲げによる塑性変形が容易に起こり難くなっている。
　実際に、反発性測定において比較例３，４，７は「小さな荷重での曲げ易さ」で不合格となっており、比較例１～８は「塑性変形のし易さ」の評価において不合格となっている。
　また、比較例１，２及び５，６は剛性を示す数値ｙ３が１０００以上となっているので、剛性が強過ぎて、製造・加工ラインで箔切れが発生し易いためハンドリングが難しくなる。 As is clear from Table 2, in Comparative Examples 3, 4, and 7, the numerical value y1 indicating the rigidity expressed by Equation 1 is 800 or more, so it is difficult to bend with a small load. Further, in Comparative Examples 1 to 7, since the numerical value y2 representing the degree of change in rigidity accompanying bending shown in Equation 2 is less than 1.5, plastic deformation due to bending is difficult to occur.
Actually, Comparative Examples 3, 4, and 7 were rejected because of “easiness of bending with a small load” in the resilience measurement, and Comparative Examples 1 to 8 were not acceptable in the evaluation of “ease of plastic deformation”. It has passed.
Moreover, since the numerical value y3 which shows rigidity is 1000 or more in Comparative Examples 1, 2 and 5, 6, the rigidity is too strong, and the foil breakage easily occurs in the manufacturing / processing line, so that handling becomes difficult.
　表３から明らかなように、実施例１～５及び７は３００℃×１時間熱処理後の常温で測定した粒径２μｍ未満の結晶粒個数が３００μｍ四方で５，０００個以上であるので熱処理による結晶粒組織の過度な粗大化が抑制されており、表面粗さも３．０μm未満であるので、ファインパターン性に優れている。
　また、実施例６は表面粗さは３．０μm未満であるが、３００℃×１時間熱処理後の常温で測定した粒径２μｍ未満の結晶粒個数は５，０００個未満となっているので、フィルム貼付工程等において掛かる加熱処理が３００℃程度では好ましく使用できない。しかしながら、低反発性としては優れていることから、加熱処理が３００℃を大きく下回る製品に対しては好適に使用することができる。
　また、実施例８は３００℃×１時間熱処理後の常温で測定した粒径２μｍ未満の結晶粒個数は実施例２と同等であるが、表面粗さが両面共に３．０μｍ以上であり凹凸が大きいので、ファインパターン性が劣っている。しかしながら、低反発性としては優れていることから、ファインな回路を必要としない配線板には有効に採用することができる。 As is apparent from Table 3, in Examples 1 to 5 and 7, the number of crystal grains having a particle size of less than 2 μm measured at room temperature after heat treatment at 300 ° C. for 1 hour is 5,000 or more in 300 μm square, so that Since excessive coarsening of the crystal grain structure is suppressed and the surface roughness is less than 3.0 μm, the fine pattern property is excellent.
In Example 6, the surface roughness is less than 3.0 μm, but the number of crystal grains having a grain size of less than 2 μm measured at room temperature after 300 ° C. × 1 hour heat treatment is less than 5,000. The heat treatment applied in the film sticking step or the like cannot be preferably used at about 300 ° C. However, since it is excellent in low resilience, it can be suitably used for products whose heat treatment is greatly below 300 ° C.
In Example 8, the number of crystal grains having a grain size of less than 2 μm measured at room temperature after heat treatment at 300 ° C. for 1 hour is equal to that in Example 2, but the surface roughness is 3.0 μm or more on both sides, and there are irregularities. Since it is large, the fine pattern property is inferior. However, since it has excellent low resilience, it can be effectively employed for a wiring board that does not require a fine circuit.
　表３から明らかなように、比較例１、２は３００℃×１時間熱処理後の常温で測定した粒径２μｍ未満の結晶粒個数は５，０００個以上であるが、Ｍ面の表面粗さが３．０μｍ以上であり凹凸が大きいので、ファインパターン性が劣っている。
　また、比較例５は表面粗さは３．０μm未満であるが、３００℃×１時間熱処理後の常温で測定した粒径２μｍ未満の結晶粒個数は５，０００個未満となっており、結晶粒組織が過度に粗大であるので、ファインパターン性に悪影響が出ている。
　さらに、比較例６は表面粗さが３．０μm以上であり凹凸が大きく、且つ３００℃×１時間熱処理後の常温で測定した粒径２μｍ未満の結晶粒個数も５，０００個未満となっており、結晶粒組織が過度に粗大にもなっているので、ファインパターン性が非常に悪くなっている。 As is apparent from Table 3, in Comparative Examples 1 and 2, the number of crystal grains having a grain size of less than 2 μm measured at room temperature after heat treatment at 300 ° C. for 1 hour is 5,000 or more, but the surface roughness of the M-plane Is 3.0 μm or more and the unevenness is large, so that the fine pattern property is inferior.
In Comparative Example 5, the surface roughness is less than 3.0 μm, but the number of crystal grains having a grain size of less than 2 μm measured at room temperature after heat treatment at 300 ° C. for 1 hour is less than 5,000, Since the grain structure is excessively coarse, the fine pattern property is adversely affected.
Further, Comparative Example 6 has a surface roughness of 3.0 μm or more, large irregularities, and the number of crystal grains having a grain size of less than 2 μm measured at room temperature after heat treatment at 300 ° C. for 1 hour is less than 5,000. In addition, since the crystal grain structure is excessively coarse, the fine pattern property is very poor.
　本実施例の結果より明らかなように、本発明の電解銅箔は、製造・加工ラインでのハンドリングが容易であり、フィルム貼付工程（基板との積層工程）で掛かる熱処理で低反発性が発揮され、電気機器の小型化に対し対応可能であり、且つ結晶粒組織の過度な粗大化が抑制され、ファインパターン性にも優れるフレキシブル配線板用の電解銅箔が提供可能となる。
　また、本発明の電解銅箔はファインパターン性に優れるため、フレキシブル性を要求しない配線板にも適用できることは勿論である。 As is clear from the results of this example, the electrolytic copper foil of the present invention is easy to handle in the production / processing line and exhibits low resilience in the heat treatment applied in the film sticking process (stacking process with the substrate). Thus, it is possible to provide an electrolytic copper foil for a flexible wiring board that can cope with downsizing of electrical equipment, suppresses excessive coarsening of the crystal grain structure, and is excellent in fine pattern properties.
Moreover, since the electrolytic copper foil of this invention is excellent in fine pattern property, of course, it can apply also to the wiring board which does not require flexibility.
　本発明の電解銅箔は、メルカプト基を持つ化合物としてＭＰＳ－Ｎａ又はＳＰＳ－Ｎａを０．２５ｐｐｍ以上７．５ｐｐｍ以下の濃度範囲で添加し、高分子多糖類としてＨＥＣを３．０ｐｐｍ以上３０ｐｐｍ以下の範囲で添加し、塩素イオンを１ｐｐｍ以上２０ｐｐｍ以下の範囲で添加した硫酸酸性銅電解液で製箔することができる。
　また、本発明の電解銅箔を防錆処理等の表面処理を施した後、そのままフィルム基材と積層すれば表面平滑性に優れているので、高周波用フレキシブル配線板としても好適に使用することができる。また、片方の面にアンカー効果による密着性の改善を目的とした粗化処理層を設けることもできる。なお、粗化処理は目的の性能を達成できるなら必須の処理ではない。 In the electrolytic copper foil of the present invention, MPS-Na or SPS-Na is added as a compound having a mercapto group in a concentration range of 0.25 ppm to 7.5 ppm, and HEC is 3.0 ppm to 30 ppm as a polymer polysaccharide. It is possible to make a foil with an acidic copper electrolytic solution to which chlorine ions are added in the range of 1 ppm to 20 ppm.
In addition, since the electrolytic copper foil of the present invention is subjected to surface treatment such as rust prevention treatment and then laminated with a film substrate as it is, it is excellent in surface smoothness, so it can be suitably used as a high-frequency flexible wiring board. Can do. Further, a roughening treatment layer for the purpose of improving the adhesion by the anchor effect can be provided on one surface. The roughening process is not an essential process as long as the target performance can be achieved.
本発明の電解銅箔は、表面の平滑性を利用して高周波用配線板としても有効である。低反発性を有するため、そのような特性を要求される高周波配線板として効力を発揮するものである。
　また、表面平滑性と「小さな荷重での曲げ易さ」と「塑性変形のし易さ」を両立しているという特異な特性により、配線板のみならず各種材料用銅箔としても提供可能である。 The electrolytic copper foil of the present invention is also effective as a high-frequency wiring board by utilizing the smoothness of the surface. Since it has low resilience, it is effective as a high-frequency wiring board that requires such characteristics.
In addition, the unique characteristics of both surface smoothness, “ease of bending under small load” and “ease of plastic deformation” make it possible to provide copper foil for various materials as well as wiring boards. is there.
１：アノード
２：カソード
３：電解液
４：未処理電解銅箔
５：銅箔
６：電子天秤
７：押し潰し距離 1: Anode 2: Cathode 3: Electrolytic solution 4: Untreated electrolytic copper foil 5: Copper foil 6: Electronic balance 7: Crushing distance

Claims (6)

  1. 　電解銅箔であって、３００℃×１時間熱処理後に常温で測定した０．２％歪の応力Ｘ１（ＭＰａ）に基づく数式１で示される剛性を示す数値ｙ１が８００未満であり、且つ前記応力Ｘ１（ＭＰａ）と０．４％歪の応力Ｘ２（ＭＰａ）に基づく数式２で示される曲げに伴う剛性の変化の程度を表わす数値ｙ２が１．５以上となる電解銅箔。
    〔数式１〕
    　　　　　　ｙ１＝（Ｘ１／０．２）
    〔数式２〕
    　　　　　　ｙ２＝（Ｘ１／０．２）／（Ｘ２／０．４）     An electrolytic copper foil, the numerical value y1 indicating the stiffness represented by Formula 1 based on 0.2% strain stress X1 (MPa) measured at room temperature after heat treatment at 300 ° C. for 1 hour is less than 800, and the stress An electrolytic copper foil in which a numerical value y2 representing a degree of change in rigidity accompanying bending shown by Formula 2 based on X1 (MPa) and a stress X2 (MPa) of 0.4% strain is 1.5 or more.
    [Formula 1]
    y1 = (X1 / 0.2)
    [Formula 2]
    y2 = (X1 / 0.2) / (X2 / 0.4)
  2. 　熱処理前の０．２％歪の応力Ｘ3（ＭＰａ）に基づく数式３で示される剛性を示す数値ｙ３が６００以上、且つ１０００未満である請求項１に記載の電解銅箔。
    〔数式３〕
    　　　　　　６００≦ｙ３＝（Ｘ３／０．２）＜１０００     2. The electrolytic copper foil according to claim 1, wherein a numerical value y <b> 3 indicating rigidity represented by Formula 3 based on a stress X3 (MPa) of 0.2% strain before heat treatment is 600 or more and less than 1000. 3.
    [Formula 3]
    600 ≦ y3 = (X3 / 0.2) <1000
  3. 　３００℃×１時間熱処理後、常温で観察した３００μｍ四方における粒径２μｍ未満の結晶粒個数が５，０００個以上である請求項１または２に記載の電解銅箔。 3. The electrolytic copper foil according to claim 1, wherein the number of crystal grains having a grain size of less than 2 μm in a 300 μm square observed at room temperature after heat treatment at 300 ° C. for 1 hour is 5,000 or more.
  4. 　Ｍ面の表面粗さＲｚが３．０μｍ未満、且つＳ面の表面粗さＲｚが３．０μｍ未満である請求項１～３のいずれかに記載の電解銅箔。 4. The electrolytic copper foil according to claim 1, wherein the surface roughness Rz of the M surface is less than 3.0 μm and the surface roughness Rz of the S surface is less than 3.0 μm.
  5. 　請求項１～４のいずれかに記載の電解銅箔を用いて製造される配線板。 A wiring board manufactured using the electrolytic copper foil according to any one of claims 1 to 4.
  6. 　請求項１～４のいずれかに記載の電解銅箔を用いて製造されるフレキシブル配線板。 A flexible wiring board manufactured using the electrolytic copper foil according to any one of claims 1 to 4.
PCT/JP2013/084970 2012-12-27 2013-12-26 Low spring-back electrolytic copper foil, and circuit board and flexible circuit board using said electrolytic copper foil WO2014104233A1 (en)

Priority Applications (3)

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KR20147034142A KR20150039711A (en) 2012-12-27 2013-12-26 Low spring-back electrolytic copper foil, and circuit board and flexible circuit board using said electrolytic copper foil
JP2014519329A JP5607862B1 (en) 2012-12-27 2013-12-26 Low resilience electrolytic copper foil, wiring board and flexible wiring board using the electrolytic copper foil
CN201380027695.6A CN104321469A (en) 2012-12-27 2013-12-26 Low spring-back electrolytic copper foil, and circuit board and flexible circuit board using said electrolytic copper foil

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JP2020109213A (en) * 2020-03-30 2020-07-16 福田金属箔粉工業株式会社 Electrolytic copper foil for printed wiring board, and copper-clad laminate using the electrolytic copper foil
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KR102037846B1 (en) * 2015-09-05 2019-10-29 가부시키가이샤 유에이씨제이 Manufacturing method of electrolytic aluminum foil
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JP2020109213A (en) * 2020-03-30 2020-07-16 福田金属箔粉工業株式会社 Electrolytic copper foil for printed wiring board, and copper-clad laminate using the electrolytic copper foil

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JP5607862B1 (en) 2014-10-15
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JPWO2014104233A1 (en) 2017-01-19
TWI498457B (en) 2015-09-01
KR20150039711A (en) 2015-04-13

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