TW200934892A - Electrolytic copper foil and circuit board - Google Patents

Abstract

The present invention provides an electrolytic copper foil having the same or better softness and flexibility compared with a rolling copper foil, and also provides a printed circuit board having softness and flexibility that uses the above-mentioned electrolytic copper foil. Particularly with regard to the electrolytic copper foil, the mechanical properties and softness is improved during the thermal history while laminating the above-mentioned electrolytic copper foil to a polyimide film, so as to provide the electrolytic copper foil for using in the printed circuit board that may meet the requirement of the miniature of electrical appliances. The above-mentioned electrolytic copper foil is produced by a process of electrodeposing on a cathode. In the crystal distribution obtained after applying a thermal treatment of 900 or more of LMP value shown in formula 1 to the above-mentioned electrolytic copper foil, 80% or more of grains are with the maximum grain length of 4 μ m or more; formula 1: LMP=(T+273)×(20+Log(t)); wherein T represents temperature (oC) and t represents hours (Hr).

Description

200934892 IX. Description of the invention: [Technical field to which the invention pertains] Foil The present invention relates to electrolytic copper having excellent flexibility and flexibility

Further, the present invention relates to a printed circuit board using the above-described electrolytic copper flute, a multilayer printed circuit board, and a circuit substrate for a film flip chip package (the above-mentioned components are generally referred to as "circuit boards"), in particular It is a circuit board suitable for high-density, high-performance applications. [Prior Art] With regard to the miniaturization of current electrical products, the bending angle (R) of a chain part of a mobile phone tends to become smaller and smaller. The flexibility of the board is becoming more stringent. The characteristics of copper pigs that are important for improving flexibility are thickness, surface smoothness, grain size, mechanical properties, etc. In order to achieve high density of electrical products, an important issue is to use the p-bow as efficiently as possible. It is indispensable to use a polyimide film that can easily deform the circuit board. The adhesion strength of copper berth adhered to the polyimide film gradually becomes a necessary and indispensable property. The copper drop that satisfies the above characteristics is currently The Zhayan copper enamel is manufactured by a special process. However, the rolling of the copper slab is expensive due to its long process, and it is not possible to manufacture a wide (four) and difficult to manufacture thin (four). The industry needs electrolytic copper falling to meet the above characteristics. However, using the current manufacturing technology of electrolytic steel box, no dimension has been proposed.

2197-10191-PF 200934892 Electrolytic copper which satisfies all of the above requirements with smoothness. It has the same requirements as softness/releasability: electric = with the deferred copper box. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The problem to be solved by the invention is to provide an electrolytic copper foil having the same flexibility or flexibility as the rolled copper foil, and providing the use of the above-mentioned electrolytic copper Φ Flexible and flexible circuit board. In particular, in the electrolytic copper foil, it improves the mechanical properties and flexibility in the heat history when the electrolytic copper foil and the polyimide film are bonded, and provides a miniaturization of the electrical appliance. Electrolytic copper foil for circuit boards. [Means for Solving the Problem] The electrolytic copper foil of the present invention is produced by electrodeposition on the cathode. The LMp value shown in Formula 1 above the above-mentioned electrolytic copper foil is 9 〇〇〇 or more. In the crystal distribution after heat treatment, crystal grains having a maximum length of 4 vm or more are present in an amount of 80% or more; Formula 1 is: LMP = (T + 273) x (20 + Log (1)); and T is temperature (°C ), t is the number of hours (Hr) p The above-mentioned electrolytic copper foil is preferably a heat-treated electrolytic copper flute having a LMP value of 9000 or more, which has a tensile strength of 22 KN/cm 2 or less and a 2% lodging strength of 15 KN/cm 2 . the following. The above electrolysis/copper foil is preferably an electrolytic copper foil which has been subjected to heat treatment with an LMP value of 9000 Y, and has an elongation of 1% or less.

2197-10191-PF 6 200934892 The above-mentioned electrolytic copper foil is preferably one of the impurities contained in the cross section of the above-mentioned electrolytic copper foil 'at least in the secondary ion mass spectrometry (SIMS) of each part of the cross section of the above-mentioned electrolytic copper foil (at least gas ( The intensity (counts) of C1), nitrogen (N), sulfur (S), and oxygen (0) is: nitrogen of 20 or less, sulfur of 50 or less, chlorine of 500 or less, and oxygen of 1 or less. The above-mentioned electrolytic copper foil is preferably an electrolytic copper foil having a surface roughness of at least one side of Rz = 1.5 m or less.

Preferably, the electrolytic copper crucible is provided with a roughened particle layer on at least one of the coated surfaces of the electrodeposited copper foil, and a metal for heat resistance, chemical resistance, and corrosion resistance is provided on the roughened particle layer as needed. Surface treatment layer. Preferably, the electrodeposited copper foil has a surface treatment of nickel (Ni), zinc (Zn), chromium (Cr), bismuth (Si), cobalt (c), molybdenum (M〇), and the above alloy. One type is provided on the surface of the above-mentioned electrolytic copper foil or on the roughened particle layer. The present invention is a printed circuit board using the above electrolytic copper foil, a multilayer printed circuit board, or a circuit substrate for a film flip chip package (chip (10) fUm). [Effect of the Invention] The present invention can provide an electrolytic copper case having the same flexibility or flexibility as the rolled copper foil, and can provide a circuit board having flexibility and interchangeability using the above-mentioned electrolytic copper. In particular, in the electrolytic copper foil, the improvement in the thermal history of the yttrium imide film provides an electrolytic copper foil which is less expensive than that of the F. In the above-mentioned electrolytic copper foil and a combination thereof, the mechanical properties and flexibility thereof are used, and the electric device can be miniaturized for use in a circuit board. [Embodiment] 2197-10191-pp 200934892 [Best form for carrying out the invention] Usually electrolysis The copper foil is produced, for example, by an electrolytic foil-forming apparatus shown in Fig. 1. The electrolytic foil-forming apparatus is composed of a rotating drum cathode 2 (surface made of SUS series steel or titanium), and the cathode 2 is concentrically arranged with an anode 1 (a titanium electrode coated with a noble metal oxide). In the foil-forming apparatus, the electrolyte solution 3 is supplied while flowing an electric current between the two electrodes, and copper having a predetermined thickness is electrically analyzed on the surface of the cathode 2, and then peeled off from the surface of the cathode 2, A foil-like copper is obtained. This stage of copper foil is referred to as "untreated copper 4" in this specification. Further, the surface of the untreated copper splatter 4 which is in contact with the electrolytic solution is called a matte side, and the surface which is in contact with the rotating drum-shaped cathode 2 is called a shinny side. While the above description is directed to the foil forming apparatus using the rotating cathode 2, it is also possible to manufacture the copper foil using the foil forming apparatus of the plate cathode. In the present invention, copper is electrically analyzed on the drum-shaped cathode or the plate-shaped cathode to produce a copper foil. The cathode for the electrolysis of copper is a surface roughness of ® Rz: 0.1 to 2. Oym, whereby the roughness of the bright surface of the electrolytic copper foil of the present invention may be Rz : 0.1 to 1.5 # m. In consideration of factors such as the grinding technique of the cathode, the surface roughness Rz of the electrolytic copper foil is 0.1 or less, which is difficult to manufacture, and it is recognized that mass production is impossible. Further, when the surface roughness Rz of the cathode is 2.0 or more, the flexibility of the copper foil is extremely poor, and the characteristics required by the present invention cannot be achieved, and at the same time, it is difficult to make the copper foil bright. The roughness is up to Rz: 1.5 // m or less. • The roughness of the dark side of the electrolytic copper crucible is RZ: . About 2197-10I91-PF 8 200934892 0. The roughness below l/zm' is difficult to achieve even with gloss plating, and it is impossible to manufacture it in reality. Further, as described above, since the surface of the electrolytic copper crucible is rough, the flexibility is deteriorated, so the upper limit of the roughness of the dark surface of the electrolytic copper foil is 1.5 / zm. The roughness of the bright surface and/or the dark surface is preferably Rz: iwm or less. Further, the thick chain of the 7C surface and the dark surface is preferably Rz: 〇.3/Zffl or less, particularly preferably Rz: 0. 2 /z m or less. Further, the thickness of the above-mentioned electrolytic copper foil is preferably 2 to 21 〇 vm. A copper foil having a thickness of 2 "m or less cannot be manufactured smoothly due to the transfer (handHng) technique, and in reality, there is no copper pig having a thickness of 2//m or less. The upper limit of the thickness is 21 〇" according to the current state of use of the circuit board. It is difficult to consider an electrolytic copper foil having a thickness of 210 〆m or more as a copper ruthenium for a circuit substrate because the cost advantage of using electrolytic copper falling is lost.电解 In addition, as the electroplating solution for depositing the above-mentioned electrolytic copper foil, there are copper sulfate sulphuric acid copper sulphate ore, eGpper suif_te, etc., but the copper sulfate plating solution is considered in consideration of the cost surface. More suitable. In the present invention, the sulfuric acid concentration is preferably 3 〇 1 〇〇 g / 1, the copper concentration is preferably 15 to 7 Gg / q, the current density is preferably 1 () - 2, liquid ^ 20 ~ order, chlorine concentration Preferably 0 01~3() Qing. In order to produce an additive in a copper sulfate plating bath of an electrolytic copper foil, a necessary condition is, for example, a compound having a thiophene group and at least an organic compound other than the above. The amount of each additive is a change in the addition amount and addition ratio of the M ^ County in the range of 〇. In addition, adding additives

In the case of 2197-l〇19]-PF 9 200934892, the total organic carbon (TOC; the amount of carbon in the organic matter contained in the liquid) is preferably 4 〇〇 ppm or less. In the copper foil produced by the above conditions, at least chlorine (C1), nitrogen (N), sulfur (S), and oxygen (〇) are in the copper box of the elements entering the copper foil from the plating solution and the additive component. The intensity (counts) in the secondary ion mass spectrometry (SIMS) of each part of the cross section is preferably: nitrogen below 20, sulfur below 50, helium below 500, and oxygen below 1000, while nitrogen has an intensity (counts). More preferably 10 or less. (In the present specification, the measured value of nitrogen is a measured value for measuring the strength of 63Cu + 14N.) The electrolytic copper foil of the present invention is a whole and has a low content of paleo-pure impurities, and has no high content of local impurities (average distribution of impurities). . The electrolytic copper foil produced under the above conditions is subjected to heat treatment of 9000 or more by the application of the formula L1, and the electrolytic copper having a maximum length of 4 μm or more of each crystal grain is present in an electrolytic copper of 80% or more. Box 1; ❹ LMP = (T + 273) x (20 + Log (t)); where T is temperature (°c) and t is the number of hours (Hr). Further, the copper foil of the present invention is an electrolytic copper foil in which 80% or more of crystal grains having a maximum length of 4 #m or more of a crystal having a heat history of 125 〇〇 to 135 Å are present. . Fig. 2 is an electron micrograph of a cross section of a copper foil, wherein (a) is a photograph of a section 5 of the copper foil of the present invention, and (匕) is a photograph of a section 5 of a conventional copper crucible. The maximum length of the crystal is measured by taking a micrograph of the cross section of the copper foil and measuring the range of 50 #mx5〇m or the same area as above.

2197-10191-PF 10 200934892 The maximum length of the crystal grains is measured, and the area occupied by the crystal grains having a maximum length of 4" or more is determined as a percentage of the total area of the cross section of the measured area. The tensile strength of the box is preferably 20 KN/M or less, and the 0.2% lodging strength is preferably ΐ5κ_2 or less, and the 0.2% lodging strength is preferably 1 〇KN/cm2 or less. At this time, the elongation of the copper foil is better. It is 10% or less.

❹ At least one of the above-mentioned untreated electrolytic copper tanks or at least one of the metal surface treatment layers 4 is provided as a metal for forming a metal surface treatment layer on the surface which has been subjected to the roughening treatment as needed. Examples are recorded, zinc, complex, Shi Xi, recorded, Gu monomer, or its alloy, or its hydrate. An example of a treatment in which an alloy layer is used as a metal surface treatment layer to adhere thereto is to adhere a metal such as at least one of nickel, lanthanum, cobalt, and molybdenum or an alloy containing one of the above metals, and then attach the zinc to the rain. Chromium attached. In the case where the metal surface treatment layer is not formed of an alloy, it is preferred to use a metal such as nickel or molybdenum having a thickness of 0.8 mg/dni2 or less to lower the etching property. In the case where nickel or molybdenum is precipitated as an alloy, the thickness thereof is preferably 1.5 mg/dm2 or less. In addition, when the amount of zinc adhered is large, it dissolves during etching and causes deterioration in peel strength. Therefore, the amount of adhesion is preferably 2 mg/dm 2 or less. Examples of the plating solution and plating conditions for providing (attaching) the above metal layer are as follows. [铁录]

NiS〇4· 6H2O 10~500g/l * · H3BO3 1 ~5 0 g/1 2197-10191-PF 11 200934892 Current Density Bath Bath Temperature Treatment Time pH [Ni-Mo - Molybdenum]

NiS〇4-6H2〇 Na2Mo〇4*2H2〇 Trisodium citrate dihydrate Current density Bath temperature Temperature Treatment time pH value [Plating-gu] Ν&2Μ〇〇4· 2Η2〇

CoS〇4*7H2〇 Trisodium citrate dihydrate Current density Plating bath temperature Treatment time pH [galvanized] Zinc oxide Nano-hydride temperature 2197-10191-PF. 12

1~50A/dm2 10~70°C 1 second~2 minutes 2. 0-4. 0 10~500g/l 1~50g/1 30~200g/l 1~50A/dm2 10~70°C 1 second~ 2 minutes 1. 0-4. 0 l'30g/l 1~50g/l 30~200g/l 1~50A/dm2 10~70°C 1 second~2 minutes 1. 0-4. 0 2~40g/ Dm3 1 0~300g/dm 5~6 (TC 200934892 current density treatment time pH value [chromium plating] Cr〇3 pH plating bath temperature treatment time current density pH value 0. 1~1OA/dm2 1 second ~ 2 minutes 1. 0-4. 0

〇.5~40g/l 3. 0 or less 20~70〇C 1 second~2 minutes 〇.1~1 OA/dm2 1. 0*~4. 0 Applying the dreamy class on the above metal surface treatment layer substance. The decane-based substance to be coated' is an amine-based or cyano-based one in which an amine-based, hexene-based, cyano-based, or oxime-based special ruthenium film is generally used. The stone-like substance shows an effect of improving the peel strength. The electrolytic copper box which has been subjected to the above treatment becomes a circuit board attached to the film. The present invention is described with reference to the embodiments of the present invention, but the present invention is not limited to the following embodiments. (1) Foil Formation Examples 1 to 5, Comparative Example 3 Electrolyte Group] The main components are shown in Table 1. The copper sulfate plating solution having the composition shown in Table 1 (hereinafter referred to as "Thunder Electrolyte") was cleaned by an activated carbon filter. The electrolytic copper foil was produced by using a rotary mooring device to produce a thickness of 18 #m的去* * Untreated electrolytic copper foil.

Table 1 * 2197-10191-PF 13 200934892 Foil conditions ------1 --- Manufacturing conditions Copper (g/1) Sulfuric acid (g/1) Gas (ppm) Temperature (°C) Current density (A /dl!2 - Example 1 70 50 25 45 V ------- 35__ Example 2 Example 3 Example 4 80 40 30 ” 40 40__ 80 65 10 35 4〇______ 60 30 15 50 3L Implementation Example 5 Comparative Example 1 Comparative Example 2 60 45 25 38 45 — _70 60 50 55 55__ 80 90 45 60 55 Comparative Example 3 90 100 20 50 55____ The prepared untreated copper foil 'measured in the copper foil carrier The amount of the impurities and the surface roughness. Next, the heat treatment is performed at a temperature setting suitable for the thermal compression bonding with the polyimide film, and the crystal grains after the heat treatment (the maximum length of the particle diameter is 4/ζιη or more) are measured. Distribution (proportion) c> The measurement (calculation) method is as follows. [Impurity of copper foil cross section] In secondary ion mass spectrometry (SIMS), the impurity element of each part of the copper cross section cut in the depth direction is measured. The measurement elements were nitrogen (n), sulfur (S), chlorine (C1), and oxygen (0). The results of secondary ion mass spectrometry (31)^ were recorded in Table 2. In the present specification, the amount of the intensity of the secondary ion mass spectrometry (SIMS) is used instead of the amount of the impurity. [The heating condition of the copper foil for cross-section observation] 40 (TC, 1 hour heat treatment) was performed in a nitrogen atmosphere. *

2197-10191-PF 14 200934892 The cross section of the heat-treated copper foil was taken with an electron microscope, and the ratio of crystals having a maximum crystal grain length of 4 # m or more was measured and calculated. [Evaluation of Surface Roughness] The surface roughness rz and Ra of the untreated electrolytic copper foil of each of the examples and the comparative examples were measured using a contact surface roughness meter. The surface roughness Rz and Ra are defined in JIS B 0601-1 194 "Definition and Expression of Surface Roughness", in which Rz is "ten point flat. coarse sugar content" and Ra is "arithmetic average rough degree". The measurement was carried out with a reference length of 0.8 mm. 〇 [Evaluation of tensile strength and elongation characteristics] The untreated copper foil of each of the examples and the comparative examples was subjected to heat treatment under the above-described heating conditions, and then the tensile tester was used to measure the pulling of the copper foil after the heat treatment. Tensile strength, 0.2% drop strength, elongation characteristics. The 0.2% drop strength is defined as the relationship between the strain and the stress curve. The curve is extended from the point where the strain is 0% to the curve, and the point where the strain is 0.2% is pulled out parallel to the above wiring. The straight line, the stress value of the intersection of this line and the above curve is 0.2% of the drop strength. [Flexibility Test] After the untreated copper foil of each of the examples and the comparative examples was cut to a length of 250 mm and a width of 250 mm, the surface of the copper foil was contacted with a polyimide film of a thickness of 50 μm (UPILEX_VT manufactured by Ube Industries). The whole was placed between two smooth stainless steel plates, and subjected to vacuum pressing at 20 torr for 1 minute heat pressing at a temperature of 330 ° C and a pressure of 2 kg/cm 2 , followed by a temperature of 33 Torr. (:, pressurization at 5 〇 kg/cm2 for 5 minutes, and make a copper foil (circuit board) to which the film is attached, and then perform a folding strength test (Μίτ).

2197-10191-PF 15 200934892 The measurement was performed by applying a curvature (R) of 0.8 (mm) and a load of 50,000 g. In the evaluation of the flexibility, the flexibility was evaluated by a multiple of the number of times the bending of the copper foil of Comparative Example 1 having the lowest number of bending times was one. The results of the respective measurements are shown in Table 2 and Table 3. Table 2 Impurity content of untreated copper foil cross section • Surface roughness • Crystallization observations Impurity (Counts) Surface roughness: Degree (#m) Area ratio of crystal grains having a length of 4 or more (%) Dark surface bright NS Cl 0 Ra Rz Ra Rz Example 1 4 8 150 200 0.12 0. 55 0.1 0.65 85 Example 2 5 3 170 50 0.1 0.65 0.11 0. 75 93 Example 3 3.0 5 80 40 0.1 0.85 0.15 1.0 91 Example 4 1.0 20 120 400 0.15 0.6 0.12 0. 85 95 Example 5 7.0 25 150 50 0.09 0.5 0.13 0.75 82 Comparative Example 1 35 105 1000 1500 0.21 1.2 0.24 1.6 10 Comparative Example 2 35 130 900 1200 0.14 0.8 0.21 1.0 10 Comparative Example 3 7.0 150 150 450 0.3 1.6 0.35 2.1 35 Note 1) The amount of impurity element is the maximum value of the measurement results in each part in the depth direction. Note 2) The ratio of the presence of crystal grains is the ratio of the presence of crystals above the length of the cross-section observed after heat treatment. ❹ ❹ Table mechanical properties and flexibility evaluation results for the area ratio of crystal grains with a length of 4 or more (%) Comparison of mechanical properties bending times Tensile strength (KN/cm2) 0.2% Degradation strength (KN/cm2) Elongation (%) Example 1 85 18 12 16 2.5 Example 2 93 15 8.6 8 3. 2 Example 3 91 17 9.8 10 2. 9 Example 4 95 13 7.0 5 3.5 2197-10191-PF 16 200934892 Example 5 82 20 - 丨 - 15 _ 21 2.3 Comparative Example 1 10 23 20 ' 12 1 Comparative Example 2 10 22 _ 19 11 11 Comparative Example 3 35 20 —16 ϊ Η Α Α UL —14 1.4 Note 1) The number of mechanical properties is increased The results of the comparison of the number of times of bending of the copper foil in the first comparative example are the values of the case where the number of times of folding of the comparative example 1 is 丨. It is clear from Tables 2 and 3 that the copper foil which can achieve the following conditions: the copper cross section in the embodiment The amount of impurity elements is as low as nitrogen-i 〇 below, sulfur - 30 or less, chlorine - 200 or less, and oxygen - 40 〇 or less; and the surface roughness Rz on the dark surface and bright surface is below 111 at h5; heat treatment The ratio of crystal grains having a post length of 4 // m or more (crystal distribution) is 8% or more; and the Both the tensile strength and the 0.2% drop strength gave satisfactory results; compared with the comparative example, the number of times of bending of any of the examples was more than 2 times, and satisfactory results were obtained. Here, the less the amount of impurities, the better. Regarding the elongation, although the examples i and 5 both exceed 〇%, the number of bending times is worse than that of the other embodiments 2, 3, and 4, but the copper drop ratio φ of the prior art is improved. Its performance, without problems, can be applied to copper foil for flexible and flexible circuit boards. On the other hand, in the comparative examples, the crystal grain ratio (crystal distribution) of the length of 4/ζι or more after heating was 35% or less, and it was unsatisfiable, and the tensile strength was 20 KN/cm 2 or less and the 〇·2% fall strength. Any characteristic value of 15 KN/cm2 or less and elongation of 10% or less did not give satisfactory results even with the bending strength. As described above, the present invention has an excellent effect that it is possible to provide an electrolytic steel having the same or more 'flexibility and flexibility as the rolled copper foil.

2197-10191-PF 17 200934892 and a flexible and flexible circuit board using the above-mentioned electrolytic copper plating; in particular, it has another excellent effect, that is, an electrolytic copper crucible for a circuit board can be provided, which is in electrolysis In the copper flute, in the thermal history of the electrodeposited copper crucible and the polyimide film, the mechanical properties and flexibility can be improved, and the electrical device can be miniaturized. [Simplified Schematic Description] Fig. 1 is an explanatory view showing a foil-forming foil forming apparatus.

Fig. 2 is an electron micrograph of a cross section of a copper box. (a) is a cross section showing the first embodiment, and (b) is a cross section showing the comparative example 1. [Description of main components] 1 - anode 2 to cathode 3 to electrolyte 4 to untreated copper foil 5 to copper foil section

2197-10191-PF 18

Claims (1)

200934892 X. Application for Patent Park: 1. A type of electrolytic copper berthium electroplating (el ectrodeposi t) was fabricated on the cathode, and the LMp value indicated by the formula ^ was applied to the electrolytic copper foil at 9 〇〇〇 or more. In the crystal distribution after heat treatment, the maximum length of the crystal grains is 80% or more of the above crystal grains; Formula 2 is: LMP = (T + 273) x (20 + L 〇 g (t)); The electrolytic copper foil according to the first aspect of the invention is characterized in that the temperature is (. 〇), and t is the number of hours (jjr), and the electrolytic copper foil according to claim 1 is characterized in that the electrolytic copper foil having a LMP value of 9000 or more is resistant to heat treatment. The tensile strength is 22 KN/cm 2 or less, and the 〇·2% lodging strength is 15 KN/cm 2 or less. 3. The electrolytic copper foil according to the above aspect of the invention, characterized in that the electrolytic copper foil having a heat treatment value of 9000 or more has an elongation of 10% or less. 4. The electrolytic copper foil according to claim 1, wherein the secondary ion mass spectrometry (SIMS) of each part of the Φ section of the electrolytic copper box is among the impurities contained in the cross section of the electrolytic copper. Among them, at least the chlorine (C1), nitrogen (N), sulfur (S), and oxygen (counts) are: nitrogen __ 2 〇 or less, sulfur -50 or less, chlorine - 5 〇〇 or less, oxygen - 1 〇 〇〇The following. The electrolytic copper foil according to the first aspect of the invention is characterized in that the surface roughness of at least one side of the electrolytic copper foil is Rz = i.5 vm or less. 6. The electrolytic copper foil according to claim 1, wherein a roughened particle layer is disposed on at least one film surface of the electrolytic steel foil, and heat resistance is set on the roughened particle layer as required. · Resistance and corrosion resistance for the purpose of 2197-10191-PF. A metal finish on 200934892. 7. The electrolytic copper box according to claim 1, wherein the metal surface treatment layer is nickel (Ni), zinc (Zn), (Si), indium (Co), indium (M〇) and the above At least the surface of the electrolytic copper crucible or the layer of the roughened particles is formed in the alloy. 8. A circuit board which uses an electrolytic copper foil as claimed in the patent application. 'characterized in chromium (Cr), broken one is set in the seventh 2197-10191-PF 20