TW200927993A - Copper foil including resistive film layer - Google Patents

Abstract

Copper foil including an electric resistive film layer characterized in that a copper-zinc alloy layer containing 1000 [mu]g/dm2 to 9000 [mu]g/dm2 of zinc per unit area is provided on a roughened surface or a glossy surface of the copper foil, a stabilized layer with a thickness between 5 AA and 100 AA made of at least one component selected from among zinc oxide, chromium oxide, and nickel oxide is formed on the copper-zinc alloy layer, and a film layer made of an electric resistive material is provided on the stabilized layer. The additional formation of the electric resistive film layer in the copper foil enables a resistor to be embedded in a substrate, and the copper foil includes the resistive film layer with improved adhesiveness.

Description

[Technical Field] The present invention relates to a steel pig having a resistive film layer which is excellent in adhesion of a film and has high peeling strength. [Prior Art] As a wiring material of a printed circuit board, a copper foil is generally used. This copper 4 is classified into an electrolytic steel foil and a rolled copper foil according to the manufacturing method. The thickness of the copper foil © can be adjusted from a very thin copper foil of 5 μm to a thick copper foil of about 14 μm. These copper foils are bonded to a substrate made of a resin such as an epoxy resin or a polyimide resin to be used as a substrate for a printed circuit. In the copper foil, it is required to ensure the adhesion strength with the resin as the substrate, so that the 'electrolytic copper foil is used for the rough surface of the so-called matte surface formed at the time of manufacture' and further roughening the surface thereon. And use. Further, the rolled copper foil is similarly applied to the surface thereof by a roughening treatment. © Recently, a thin film layer composed of a resistive material has been further formed on a copper foil as a wiring material (see Patent Documents 1 and 2). Although the resistive element is indispensable in the electronic circuit board, if a copper drop having a resistive layer is used, the resistive element such as vaporized copper (Π) is used on the resistive film layer formed on the copper foil. Exposed. Therefore, compared with the prior art method of surface-mounting the chip resistor element on the substrate by soldering, the surface area of the substrate can be effectively utilized by the built-in substrate of the resistor. 200927993 In addition, the formation of a resistor element inside the multilayer substrate reduces the design restrictions, thereby shortening the circuit length, thereby improving the electrical characteristics. Therefore, when a copper foil having a resistance layer is used, soldering can be prevented or largely omitted, and the weight and reliability can be improved. As described above, a substrate having a resistive film built therein has many advantages. The copper foil used as the base material in these resistive materials is subjected to surface treatment before the resistive layer is further formed thereon. Therefore, although it is generally different from the copper pig used for general printed circuit board wiring, it is roughened by It is the same as that of the resin. In the case of evaluating the adhesion strength of the resistive material, it is necessary to study the strength between the copper foil and the resistive film and the strength between the resistive film and the resin, and the interface between the two of them is weak in the tensile test or the like. Peeling will occur. * In either case, the greater the surface roughness, the higher the subsequent strength. Then, the strength is generally considered to be affected by the surface roughness and other factors such as the surface type (element type). On the other hand, it is required to suppress the surface roughness of the resistive material because of the formation of a smaller resistance circuit or the improvement of high-frequency characteristics required for a continuously high-performance printed circuit board. In order to achieve this, a method of increasing the strength of the joint which does not depend on the surface roughness becomes indispensable. Patent Document 1: Japanese Patent No. 331 1338 Patent Document 2: Japanese Patent No. 3452557 SUMMARY OF INVENTION Technical Problem 发明 _gs 6 ❹ ❹ 200927993 The present invention provides a resistive film further formed on a resistive film layer The layer, and ', is due to the fact that the copper foil only wishes to have a resistance> to improve its adhesion. In order to solve the above problems, the inventors of the present invention have obtained the following findings: efforts have been made to study copper foil and electric resistance, and the force layer is effective. According to the above findings, the present invention provides a copper foil having a resistive film layer, 誃^7L·, and a resistive film layer in the copper foil. The zinc content per unit area is just 〇~ It is selected from the oxygen 1 copper-zinc alloy layer, and is formed on the steel/zinc alloy layer by =2? a layer of at least one of chromium and oxidized bromine and having a thickness of between 5 Å and 100 Å, and a layer composed of a resistive material on the stabilizing layer . When a copper pig having a resistive film layer is used as a film for a circuit board, it is considered that a stabilizing layer composed of at least one selected from the group consisting of oxidized and oxidized nickel oxide is formed on the copper case. Further, a resistive layer is formed thereon to obtain a sufficient bonding strength with the copper foil. However, in the case where a copper foil having a reduced roughness is used in the copper flute which is the base, there is a problem that the adhesion is insufficient. The present inventors have found that in order to improve this, it is effective to form a copper alloy layer having a zinc content per unit area of from 1 9000 to 9000 pg/dm 2 before the formation of the above-mentioned stabilizing layer. The improvement of the adhesion between the copper foil and the copper alloy layer and the stable layer and then the resistive layer can be evaluated by the peel strength. If necessary, on the surface of the copper foil subjected to the following surface treatment, a copper-alloy layer having a zinc content of 1 〇〇〇 to 9000 pg/dm 2 per unit area is formed, which is an important step for improving the adhesion strength. . The zinc content per unit area is less than 丨〇〇〇 μβ/(1ιη2 of copper_zinc alloy layer does not increase in strength. Moreover, the content per unit area exceeds 9〇〇〇 ^/dm2

In the copper-zinc alloy layer of G, the chemical resistance (corrosion of the etching solution) is poor, which is not preferable. The reason for this is that the presence of a large amount of zinc causes a problem of a decrease in corrosion resistance. The copper-zinc alloy layer can be formed by electroplating. The zinc content of the copper-zinc alloy in the plating is arbitrary.艮p, the copper-alloy layer includes a layer that is electrically forged and then diffused into the copper foil. The content of each unit area in the copper-internal alloy layer is ι〇〇〇~9_. As a result, the thickness of the copper alloy layer is approximately equivalent to the range of 100 to 1200 Å. On the copper-alloy layer thus formed, a stabilizing layer having a thickness of 5 a to i 〇〇 A, which is composed of at least one selected from the group consisting of oxidized, chromium oxide, and nickel oxide, is formed. As described above, although the stabilizing layer has a limit in effect, it also has an effect of improving the adhesion to the copper foil. Zinc oxide, chromium oxide, and nickel oxide are effective as a stabilizing layer, and the like can also be used in combination. The deuterated layer has a function of preventing (four) oxidative rot and preventing decomposition of the dielectric substrate caused by copper and maintaining stable separation strength. Then, usually, the stabilizing layer is between 5 A and _ υ A, and 300 A can be set to a thickness of 1 〇〇A or more as needed, that is, 200 to 8 200927993. Its force V: less than 5 A , it is impossible to play the role of the stabilizing layer, and the ugly power is also reduced. W 1 ,, according to electricity ===:::,: into::=, the layered system...: and =: ^ 70 pieces of material examples, such as hunger, tungsten, record, group, nickel , chrome and other materials. The above-mentioned needle has a relatively high resistance as described above, and can be used as a separate film or alloy film of other materials, even for Ming, Shi Xi, Tong, Tong, Zhan, Zhan, War # > _ ^ Materials with low resistance, such as 蛘, tin, etc., can be used as long as they are alloyed with other elements to become a material with high electrical resistance. For example, a resistive element such as a NiCr alloy or a NiCrA1Si alloy is a material which is attracting attention. X may also be a material oxide, a nitride or a telluride selected from the group consisting of oxides, nitrides, and tellurides of the above elements. As noted above, the choice of such materials is arbitrarily chosen in accordance with the circuit design and is therefore understood to be not limited to such materials. When the resistive film layer is formed, a physical surface treatment method such as a sputtering method, a vacuum vapor deposition method, or an ion beam plating method, or a chemical surface treatment method or an electroplating method such as a pyrolysis method or a gas phase reaction method may be used. It is formed by a wet surface treatment method such as electroless mining. In general, the electroplating method has the advantage of being able to be manufactured at low cost. Further, the sputtering method has the advantage that a high-quality resistive element can be obtained because the thickness of the film is uniform and isotropic. 9 200927993 The resistive film layer is formed according to the use of the film. Therefore, the adhesion method or the plating method at this time is preferably selected in accordance with the properties of the above-mentioned resistive film layer. The copper foil having the resistive film layer of the present invention 2) may be a copper foil having a foil thickness of 5 to 70 μm, particularly preferably a copper foil of 5 to 35 μm. The thickness of the copper foil can be arbitrarily selected depending on the use, but it is also limited by the production conditions, so that it is effective to manufacture in the above range. Further, the present invention provides a copper foil in which a resistive layer is formed on a matte side (rough side) of an electrolytic copper foil or a roughened surface of a rolled copper foil. Further, the roughening treatment of the attached agglomerated particles can be further performed on the matte surface of the electrolytic copper. Further, the rolled copper can be roughened as needed. By the above roughening treatment, a roughened surface of a low-distribution copper box or a standard distribution copper foil having an Rz of 〇·3 to 10.0 μϊη can be obtained. The effect of the invention is achieved by using the steel foil with the resistive film layer of the present invention, and it is not necessary to separately form the resistive element when the circuit is squirmed, as long as the vaporized copper is used on the resistive film layer formed on the copper drop. The (d) solution of (n) or the like allows the resistive element to be exposed, so that the soldering can be made unnecessary or largely omitted, thereby significantly simplifying the packaging step. In addition, the number of package parts or solder is reduced, and as a result, there is an advantage that the space can be expanded to a light weight. Thereby, the degree of freedom in circuit design can be improved. Further, by incorporating a resistor body into the copper foil as described above, it is effective to improve the signal characteristics in the high frequency region of 200927993. Further, the present invention has an excellent effect of improving the adhesion resistance, which is a disadvantage associated with the copper foil having the resistive film layer built therein, and thus has excellent heat resistance and acid resistance. [Embodiment] FIG. 1 shows an outline of an apparatus for manufacturing an electrolytic copper foil. The apparatus is provided with a cathode barrel in an electrolytic cell that receives the electrolyte. The cathode can 1 is rotated in a state where a part (substantially lower half) is immersed in the electrolytic solution. An insoluble anode (anode) 2 is provided so as to surround the lower half of the outer circumference of the cathode can 1 . There is a fixed gap 3 between the cathode barrel and the anode 2, and the electrolyte can flow therebetween. Two anode plates are arranged in the device. In this apparatus, it is configured as follows: an electrolyte is supplied from below, and the electrolyte passes through the cathode barrel! The gap 3 with the anode 2 overflows from the upper edge of the anode 2, and the electrolyte is circulated. A specific voltage can be maintained between the cathode barrel and the anode 2 via a rectifier. 13b, the rotation of the cathode can 1 is increased, and the thickness of the copper from the electrolyte is increased. After reaching a certain thickness or more, the green crucible 4 is peeled off and continuously wound. The green box thus manufactured can be adjusted in thickness by the distance between the cathode can 1 and the anode 2, the flow rate of the supplied electrolyte, or the amount of electricity supplied. In the copper swash produced by such a copper-making apparatus, the surface in contact with the cathode can is a mirror surface (glossy surface), and the surface on the opposite side is a rough surface (matte surface) in which convexities and concaves are present. The thickness of the electrolytic copper can be arbitrarily selected. Usually 200927993

It is possible to use a copper case thus manufactured having a thickness of 9 Km to 35 μm, followed by a purification step of removing the surface oxide film, and then a water washing step. In the purification step, an aqueous solution of sulfuric acid of 〇 80 g/L is usually used. In the above description, the production of the electrolytic copper foil has been described. However, for the pressure I copper 4, the dissolved and cast ingot can be annealed and hot rolled, and further cold rolled to produce copper of a desired thickness. silk. Calendered copper box = is a glossy surface so it can be roughened as needed. This roughening treatment can be carried out using a known roughening treatment.

One of the roughening processes is as follows. Further, the roughening treatment is also applicable to the shiny side and the matte side (rough side) of the electrolytic copper foil.

Cu ion concentration: 1〇~3〇g/L Sulfuric acid concentration: 20~1〇〇g/L Electrolyte temperature: 20~60°C Current density: 5~80 A/dm2 Processing time: 0.5~30 seconds The produced electrolytic copper foil or rolled copper foil is subjected to zinc-copper alloy plating treatment. The groove composition and plating conditions of the zinc-copper alloy plating treatment are as follows. (Zinc·copper alloy plating bath composition and processing conditions)

CuCN : 60~120 g/L Zn(CN) 2 : 1~10 g/L Na〇H : 40~1〇〇 g/L 12 200927993

Na(CN): 10~30 g/L pH: l〇~13 Slot temperature: 60~80°C Current density: 100~l〇〇〇〇A/dm2 Processing time: 21 ~ 1 60 seconds A copper-zinc alloy layer having a zinc content of 1 〇〇〇 to 9 〇〇〇 Pg/dm 2 per unit area can be formed. The above plating is a better term - copper alloy plating conditions. If a copper-zinc alloy layer having a content per unit area of 1 〇〇〇 to 9 〇〇〇 ^g/dm 2 © can be formed, it is not necessary to be limited to the above conditions. Therefore, galvanization can be performed on copper, followed by heating and diffusion to form a copper-zinc alloy layer. Further, since heat is generally generated in the pressurizing step, the copper-zinc alloy layer can be formed by heating and diffusion as long as galvanizing is formed, so that the above steps can be utilized. The following shows an example of a preferred galvanizing. (plating composition and plating conditions)

znS04.7H20 : 50~350 g/L ❹ pH value: 2.5 ～4.5 Slot temperature: 40~60°C Current density: 5~40 A/m2 Processing time: 1~3 0 sec Secondly on the copper alloy layer A stabilizing layer having a thickness of between 5 A and 1 〇〇 a, which is composed of at least one selected from the group consisting of zinc oxide, chromium oxide, and nickel oxide, is formed. As an embodiment, a coating layer may be formed using an electrolytic solution 13 200927993 containing zinc ions and chromium ions. As the source of the ion in the electrolytic solution, for example, ZnS〇4, ZnC〇3, ZnCr〇4 or the like can be used. As the complex ion source in the electrolytic solution, a hexavalent chromium salt or a compound such as ZnCr〇4 can be used. 〇 3 and so on. The concentration of zinc ions in the electrolytic solution may be in the range of 2 g/L, (iv) Μ 〇 〇. 6 g/L, more preferably 0.4 〇. 5 g/L. Further, the concentration of the chromium ion in the electrolytic solution may be 0.3 to 5 g/L, preferably 〇5 to about 3^, more preferably ❹ Ο ^~ to ^. Further, 'these conditions are only for the conditions for effective clocking' and may be set outside the range of the above conditions as needed. In another embodiment, in order to form the stabilizing layer, nickel oxide and nickel metal, or zinc oxide or chromium oxide, or - may be coated. The nickel ion source as the electrolytic solution may be either _〇4 or 〇3 temple, or a combination thereof. The concentration of the recorded ions in the electrolytic solution is preferably 〇2g/L~i 2g/L. = A scaly stabilizing layer as described in U.S. Patent No. 5,9,8,544 may be used. Furthermore, these conditions are only for stabilizing layers which are formed by at least one component selected from the group consisting of oxidized oxime and oxidized records and having a thickness between 5 a over-test. Conditions may also be set outside the range of the above conditions as needed. For the solution, the concentration of 5 〇 g / L, preferably i 〇 ~ 2 〇 W, and more preferably the concentration of 8 g / L of the additive may contain other conventional additions such as Na2S04. It is desirable that the positive value of the electrolytic solution is generally in the range of 3 to 6, preferably 4, more preferably 4.8 to 5.0. The temperature of the s electrolytic solution is $2 () ° C ~ 1 〇 i) <> C, preferably 25 ° C ~ 45 is preferably 26t ~ 44. (: is more suitable. 200927993 Figure [. 2 shows the outline of the surface treatment device. The symbol shown in Figure 2 is as described in 2 U. Raw material copper foil (raw foil), 12: copper foil, 14: glossy side, 2〇: 刖Processing step, 22: pre-treatment tank, 24: lower guide roller, 26: guide roller, 3〇 washing tank, 32: washing head, 34: washing tank, 40: stabilization step, 42: Electric trough, 44: lower guide roller, 46: guide roller (cathode roller), t anode 60. dryer 62: heater, 72: ore operation device, %: dry, 77: gas conduit, 100: copper-zinc step ❺

As shown in Fig. 2, in order to impart a current density to the copper pig 12, adjacent to each side of the copper slab 12, the anode 48 is disposed. The guide roller 46 is a cathode roller. If a voltage is applied to the anode 48 by a power source (not included), the gloss 14 and the extinction which are deposited on the copper foil 2, for example, by the oxidized and oxidized stabilization layer 49. On the face 16. Current density is! Up to 100 in/out (about 10.8 to about 1〇8〇A/m2), preferably 25~50 A/ft2 (about 27〇 to about 54〇A/m2), ^ preferably 30 A/ Ft2 (about 320 A/m2). When a plurality of anodes are provided, the current density can be varied between the anodes. The plating time for the mouth is seconds, preferably 5 to 2 seconds, more preferably about 15 seconds. In a particular embodiment, the cumulative processing time is about 3 to 1 second on the glossy side, i.e., on the smooth side, and about i to 5 seconds on the matte side. Further, as a preferred example, the molar ratio of chromium ions to zinc ions in the electrolytic solution may be 0.2 to 10, preferably 5, more preferably about i 4 . According to the present invention, the thickness of the stabilizing layer suitable for the copper foil may be 5 A to 1 Å. Preferably, in the embodiment described above, the stabilizing layer is composed of chromium oxide and zinc oxide 15 200927993, but the stabilizing layer may be formed only by chromium oxide. Preferred conditions for applying the grooves of the chromium oxide stabilizing layer are as follows. 1~1 0 g/L of Cr〇3 solution (preferably 5 g/L of Cr〇3) pH: 2

The temperature of the bath: 25 ° C 5 〜 10 seconds is ίο 〜30 A / ft2 (1 〇 8 〜 32 〇 A / m2) Immersion treatment: 10 seconds After the formation of the stabilization layer, the cleaning is carried out. In the cleaning step, for example, by spraying a copper tank (with a stabilizing layer) on the surface of the copper box, the surface is sprayed with water mist, and the surface is washed and cleaned, and removed from the surface. Residual electrolytic solution. The cleaned solution can be recovered by means of a container disposed below the spray nozzle. The copper foil having a stabilizing layer on the upper surface is further dried. As shown in the embodiment, the forced air dryer is disposed above and below the copper foil, and air is ejected from the forced air dryer to dry the surface of the copper foil. Further, a layer formed of a resistive material is further formed on the copper formed with the stabilizing layer. An example of the resistive layer is, for example, a resistive element such as a Nicr alloy or an alloy. It is composed of the resistor material: the layer is required from the design of the circuit board, and can be arbitrarily selected. Therefore, it needs to be limited to specific materials. Further, in order to improve the adhesion to the substrate (bottom material), it is possible to perform various calcination treatments on the resistive layer. However, the heat treatment of the stone is arbitrary. The present invention is not limited thereto. [Embodiment] 16 200927993 Next, an embodiment will be described. Further, the following embodiments are written to make the invention of the present invention easy to understand, but are not limited thereto. #, Variations, implementations, and other examples based on the technical idea of the present invention are included in the present invention. (Embodiment 1) In this embodiment, an electric mine copper pig having a thickness of i 8 is used. A copper-alloy layer is formed on the rough side (matte side) side of the electrolytic copper.

A steel-zinc alloy layer was applied under the following treatment conditions to form a copper-alloy layer having a zinc content per unit area of about 35 〇〇m2 (the last two digits were rounded off). The amount of coating is adjusted by the processing time. (Copper composition of zinc-zinc alloy plating and plating conditions)

CuCN : 90 g/L Zn(CN) 2 : 5 g/L NaOH : 7 〇 g/L Na(CN) : 20 g/L Slot temperature: 70.电流 Current density: 500 A/dm2 Treatment time: 5 to 20 seconds Formation of about 5 〇 Next, under the following treatment conditions, a stabilized layer composed of zinc oxide-chromium oxide on the copper alloy layer. (Stabilization treatment tank composition and processing conditions)

The composition of the groove is zinc as ZnS04: 〇53 g/L 17 200927993 Chromium as Cr〇3: 0.6 g/L Na2S04: 11 g/L pH of the tank: 5.0 Temperature of the tank: 42 °C Current density: 85~160 A/m2 plating time: 3 to 4 seconds, next 'under the following conditions', a resistive material of an alloy composed of 80% nickel (Ni) and 2% chromium (Cr) is attached to the above stabilizing layer. on. © Ni/Cr alloy sputtering: 14-inch sputtering device Power: 5~8 kw Linear speed: 1.4~2.2 ft/min (0.43~〇·67 m/min)

The thickness of the Ni/Cl alloy is about 100 A. Further, the resistive material has a sheet resistivity of about 16 Ω Ω/square. For the coating of the above (4) coating, the analysis of the normal peeling value, the peeling value of the moxibustion at the solder (heat resistance), and the peeling value after the hydrochloric acid treatment (the hydrochloric acid-resistant, peeling value after the solder treatment, is based on 26 (rc) The molten solder bath is responsible for the peeling value measured after the private state (that is, the state after the heat treatment of the party), and the peeling value after the material treatment indicates the treatment (the peeling value is received. This value is used to evaluate the heat resistance. The peeling value after room, θ, and acid treatment means that 18 wt% hydrochloric acid is used, and the value of the peeling is 2, and the peeling of the hydrochloric acid after the treatment is 200927993. The normal peeling value is 0.81 kg/cm, and the solder is treated. The peeling value (coinage property) was 0.77 kg/cm, and the peeling value (hydrochloric acid resistance) after hydrochloric acid treatment was 0.70 kg/cm, and the deterioration after solder treatment and hydrochloric acid treatment was small, and both showed good properties. 1]

Zinc content of copper-internal alloy layer (pg/dm2) Normal peel strength (kg/cm) After solder bath impregnation (kg/cm) After hydrochloric acid leaching (kg/cm) Example 1 3500 0.81 0.77 0.70 Example 2 2000 0.71 0.60 0.63 Example 3 2500 0.76 0.73 0.67 Example 4 3000 0.81 0.75 0.70 Example 5 4000 0.84 0.80 0.70 Example 6 4500 0.86 0.82 0.73 Example 7 5000 0.88 0.86 0.71 Example 8 5500 0.92 0.90 0.69 Example 9 6000 0.91 0.87 0.63 Example 10 6500 0.90 0.87 0.56 Example 11 7000 0.95 0.90 0.55 Comparative Example 1 500 0.49 0.49 0.45 Comparative Example 2 10000 0.93 0.91 0.44 wherein the value of the last two digits of the zinc content has been rounded off. After the solder bath is immersed: the peel strength after the molten solder bath at 260 ° C is impregnated. After leaching with hydrochloric acid: indicates the peel strength after immersion of 18% by weight of hydrochloric acid. (Examples 2 to 11) [Range content] Next, the condition of Example 1 showing good characteristics is used as a basic, and copper having a change in the content per unit area (1 〇〇〇 to 9000 pg/dm 2 ) is formed. - a zinc alloy layer. Similarly, rounding down is performed under 2 digits. The treatment conditions other than the zinc content of the copper-zinc alloy layer were the same as in the first embodiment. The amount of coating is adjusted by the processing time. The results are shown in Table 1. 19 200927993 Further, as a comparison, a copper-zinc alloy layer having a zinc content outside the conditions of the present invention was shown as Comparative Example 1 and Comparative Example 2. It can be seen from Table 1 that when the zinc content in the copper-zinc alloy layer is about 3,500 (two or less digits are rounded off) (Example 丨), the peel strength, heat resistance, and hydrochloric acid resistance are good, and it is shown that The nature of balance.

相对 In contrast, as the zinc content per unit area increases, the normal peel strength and heat resistance increase, but the tendency to reduce hydrochloric acid resistance is reversed, conversely, with the zinc content per unit area It is reduced, and the hydrochloric acid-resistant sulphate will rise, but it does not show a tendency to decrease the normal peel strength and heat resistance. In Comparative Example 1, it can be seen that the content of the element is small, so that the normal peel strength, the heat resistance, and the hydrochloric acid resistance are both low, and in Comparative Example 2 +, it is known that the amount of the octane 3 is too large, so the normal peel strength and heat resistance are normal. Although the sex is high, the hydrochloric acid property is poor and exceeds the allowable limit, so it is not suitable for practical use. As described above, in order to improve the normal peel strength, the heat resistance, and the hydrochloric acid resistance, the presence of the copper-alloy layer is extremely effective. (Example 1 to Example 丨-4) [Thickness of Copper Foil] Next, the conditions of the examples showing good characteristics are taken as a basic condition, and the normal peel strength and _heat property in the case where the thickness of the copper is changed are Hydrochloric acid resistance was analyzed. In addition to (four) thickness changes, other with the embodiment! the same. The amount of coating is adjusted by the processing time. The results are shown in Table 2. > In the case of the embodiment i, the electrolytic copper having a thickness of 18 μm is carried out, but when the shape is changed within the range of 9 μΐη to 35 μηη, the normal peel strength varies greatly with respect to thickness. . That is, as the copper box thickness increases by 200927993, the peel strength will also increase. However, the deterioration rate of the separation value after the solder treatment and the peeling deterioration rate after the hydrochloric acid treatment did not correspondingly change greatly. Therefore, from the viewpoint of the deterioration rate after the treatment, it is understood that the peel strength after the solder treatment and the peel strength after the salt acid treatment are not greatly affected by the thickness of the copper foil. The results are shown in Table 2. It is generally believed that an increase in the thickness of the copper foil results in an increase in peel strength. [Table 2]

Peel strength after treatment) / peeling before treatment (Example 12) [Hane treatment] In this example, an electroplated copper pig having a thickness of 18 pm and 35 pm was used, and when the rough surface of the electrolytic copper was directly used, And on the roughened surface, in the examples! Under the same conditions, the conditions of the above-described roughening treatment were as follows, that is, the conditions of the above-mentioned roughening treatment were carried out under the conditions of (b) of the copper alloy metal ore and the fourth (4). 21 200927993

Cu ion concentration: 20 g/L Sulfuric acid concentration: 60 g/L Electrolyte temperature: 40 ° C Current density: 30 A/dm 2 Treatment time: 5 seconds By the above, the content of each unit area is about 3500 mg. /m2 (the last 2 digits are rounded off) of the copper-zinc alloy layer. Next, a stabilizing layer of Cr-Zn lanthanum oxide was formed on the copper-alloy layer in the same manner as in the first embodiment. Further, on the stabilized layer of the Cr-Zn oxide, a resistive material of an alloy composed of 80% of nickel (Ni) and 20% of chromium (Cr) was formed by laser plating. The conditions are also the same as in the first embodiment. Next, on the resistive layer, decane treatment (TEOS: Tetraethoxysilane, tetraethoxy cerium oxide) was carried out. The results are shown in Table 3. As shown in Table 3, it is understood that the normal peel strength is increased, so the decane treatment is effective. [Table 3] Thickness of copper foil (μηι) Whether or not roughening treatment with or without decane treatment Normal peel strength (kg/cm) Example 12 18 No 1.00 Example 12-2 35 No 1.50 Example 12-3 18 1.30 Example 12-4 35 There are 1.60 words with a content of 3500 pg/dm2 and a decane treatment (TEOS) on the resistance layer (Example 13) [Cr resistance film] 22 200927993 Under the conditions of the above Example 1, formation The zinc content per unit area is about 3500 pg/dm2 (the last 2 digits are rounded off) of the copper-zinc alloy layer and a stabilizing layer of Cr_Zn oxide is formed on the Cu_Zn alloy layer. Next, a chromium resistive film is formed by sputtering on the stabilized layer of the Cr-Ζη oxide. The conditions for chrome sputtering are as follows. Use a 14-inch sputtering device. Power: 5~8 kw 线性 Linear speed: L8 ~ 2.8ft/min (〇55 ~ 〇85m/min) Thickness of chrome: 100 A, 1000 A, 1200 A, 2000 A, 3 A, 4000 A In the sixteenth embodiment, the normal peel strength, the heat resistance, and the hydrochloric acid resistance were analyzed. Since they were the same as in Example 1, they were not shown in the table, but all showed good properties. From the above, it is understood that the formation of the copper-zinc alloy layer is effective irrespective of the type and thickness of the resistance layer. (Example 14 to Example 14·4) [Ni/Cr/A1/Si alloy resistive film] Under the conditions of the above Example 1, the zinc content per unit area was formed to be about 3500 pg/dm2 (last 2 positions) The copper-zinc alloy layer is rounded off and a stabilizing layer of chromium-zinc oxide is formed on the copper-alloy layer. Next, under the following conditions, the nickel (Ni) of 56〇/〇, the chromium (Cr) of 38%, and the 4% (A1) and 2% (Si) of the dopant are used. The constituent alloy is attached to the stabilized layer of the chromium-zinc oxide. Sputtering of Ni/Cr/Al/Si alloy: 14-inch sputtering device 23 200927993 Power: 0.85 to 2.3 kw Linear velocity: 0.49 ft/min (0.15 m/min) Sheet resistivity: about 90~300 Ω/square In the present Example 14 to Example 14-4, the film resistance of the sheet shown in Table 4 was formed. The normal peel strength, heat resistance, and hydrochloric acid resistance at this time were analyzed, and the same as in Example 1, and as shown in Table 4, all showed good properties. From the above, it is known that it is not related to the Ni/Cr/Al/Si alloy resistance layer, and the formation of the copper-alloy layer is effective. © [Table 4] Sheet resistance value (ohm/sq) Normal peel strength (kg/cm) Peel strength after solder bath dipping (kg/cm) Peel strength after hydrochloric acid impregnation (kg/cm) Example 14 94 0.81 0.75 0.72 Example 14-2 135 0.79 0.77 0.70 Example 14-3 233 0.82 0.78 0.71 Example 14-4 286 0.80 0.74 0.73 The zinc content is 3500 pg/dm2 The thickness of the copper foil is 1 8 μm (Example I5 to Example 15-4) [rolled copper foil] In the present example, rolled copper pigs of 9 μm, 12 μm, 18 μm, and 35 μm were used. The rolled copper box was subjected to roughening treatment under the following conditions.

Cu ion concentration: 20 g/L Sulfuric acid concentration: 60 g/L Electrolyte temperature: 40 ° C Current density: 30 A/dm 2 Treatment time: 5 seconds 24 200927993 Next, under the following conditions, the roughened treatment A layer of 3,500 pg/dm2 of ore is formed on the calendered copper crucible. The thickness of the galvanizing is adjusted by the processing time. 0 The galvanizing tank consists of:

ZnS04*7H20 : 50~350 g/L pH value: 3 bath temperature: 50 °C current density: 20 A/m2 Processing time: 2~3 seconds at 300. (The copper foil on which the treated layer is formed is heat-treated to form a copper-zinc alloy layer. The copper content per unit area of the thus formed copper-zinc alloy layer is about 3500 pg/dm2 (last 2 positions) The number is rounded off. Next, under the following processing conditions, a stabilizing layer composed of zinc oxide-chromium oxide is formed on the copper alloy layer by about 5 Å. Stabilization treatment: 〇

Zinc as ZnS04: 0.53 g/L Chromium as Cr03: 0.6 g/L Na2S04: 11 g/L pH of the tank: 5.0 Temperature of the tank: 42 °C Current density: 85~160 A/m2 Plating time: 3 to 4 seconds secondly, under the following conditions, the electric resistance of the alloy formed by the road (Cr) is 80°/. Nickel (officidal) and 20% of the resistive material are attached to the above stabilizing layer. 25 200927993

Ni/Cr alloy reduction: 14-inch sputtering device Power: 5~8 kw Linear speed: 14~. / Λ .2 ft/min (0.43~0.67 m/min)

Thickness of Ni/Cr alloy: about l〇〇 A, again. The sheet resistivity of the mysterious resistive material is about (10) 〇 / square. Analysis of the normal peel strength and heat resistance of the coating layer coated with the above copper crucible

Sex (peel strength after solder treatment), hydrochloric acid resistance (peel strength after hydrochloric acid treatment). The result + venge c, , μ; Table 5. As shown in Table 5, the normal peel strength was 0.64 to 1.22 kg/cm, and the peel strength after solder dipping was 〇6 〇 to 1.16 kg/cm, and the peel strength after immersion of 18 wt% hydrochloric acid was 〜1. · 09 kg / cm, both showed good properties. Further, in the same manner as in the above Examples 2 to n, the test of the thickness of the cu_Zn alloy layer was changed, and the results were the same. Therefore, it is known that the electrolytic copper mooring and the rolled copper foil form a copper-zinc alloy layer having a zinc content of 1000 to 9000 pg/dm 2 per unit area, which can improve the adhesion (increased peeling strength) and is resistant to heat. Sexual and acid resistant. [Table 5] Example 15 Example 15-2 Example 15-3 Example 15-4 Thickness of copper foil (μιη) 9 12 18 35 Normal peel strength (kg/cm) 0.64 0.72 0.89 1.22 Immersion of the trough After (kg/cm) 0.60 0.69 0.85 1.16 Zinc content is 3500 pg/dm' After hydrochloric acid impregnation

26 200927993 j [Industrial Applicability] The present invention uses a copper foil having a resistive film layer built therein, and it is not necessary to separately form a resistive element in circuit design as long as it is formed on a resistive film layer formed in a copper foil. The etching solution of vaporized copper (n) or the like is used to expose the resistive element, so that the soldering can be omitted or largely omitted, thereby significantly simplifying the packaging step, due to the significant reduction in circuit design and fabrication steps, and in copper. Since the resistor is built in the foil, it has the effect of improving the signal characteristics in the high frequency region. Further, the present invention has an advantage that the copper foil having the resistive film layer described above can be improved, that is, the adhesive strength is improved, and the excellent heat resistance and acid resistance are excellent, so that it can be used as a printed circuit board. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an outline of an electrolytic copper box manufacturing apparatus. Fig. 2 is a view showing the outline of the surface treatment I. [Main component symbol description] 1 cathode roller

2 B Anode (insoluble anode) 3 Clearance 4 Raw foil 11 Raw material copper crucible (raw foil) 12 Steel foil 14 Gloss side 27 200927993

20 Pretreatment step 22 Pretreatment tank 24 Lower guide roller 26 Guide roller 30 Wash tank 32 Wash nozzle 34 Wash tank 40 Stabilization step 42 Tram 44 Lower guide roller 46 Guide roller (cathode roller) 48 Anode 60 Dryer 62 Heater 72 Sputtering Unit 76 77 Gas Pipeline 100 Copper-Zinc Step 28

Claims (1)

200927993 X. Application for patents: i-type copper box with resistive film layer has a micro-finished surface or a glossy surface with each enamel characteristic: the copper content of the copper box is "g/dm2 copper_zinc alloy area is Face ~ touched words, chrome oxide, oxidized bromine ... 2. The gold layer is formed with a thick choice of 5 Α 100 构成 composed of a component selected from the group consisting of oxygen A~1 ί) ΠΑ ' 乂The stable layer of Ray A is provided with a film layer composed of a resistive material on the stabilizing layer. 2. The thickness of the steel box having the resistive film layer in the i-th aspect of the patent application is 5~ 35 μιη。 一中冲3·, as in the scope of claim 1 or 2, the steel/white with a resistive layer, which is formed on the matte side of the electrolytic copper foil or the roughened side of the rolled copper foil There is a resistance layer. Eleven, circle: as the next page 29