TW201137183A - Copper foil for printed circuit board and copper-clad laminate for printed circuit board - Google Patents

Abstract

Disclosed is a copper foil for printed circuit boards which comprises a copper foil and, deposited on a surface thereof, a layer comprising nickel, zinc, and copper (hereinafter, referred to as "copper-nickel-zinc layer"), characterized in that the amount of deposited zinc in the copper-nickel-zinc layer is 200-2,000 [μ]g/dm2 and that in the copper-nickel-zinc layer, the amount of Ni is 1-50 wt.%, (amount of deposited zinc (mass%))/{100-(amount of deposited copper (mass%))} is 0.3 or more, and (amount of deposited copper (mass%))/{100-(amount of deposited zinc (mass%))} is 0.3 or more. A method for treating a surface of a copper foil has been established with which it is possible to effectively prevent a circuit erosion phenomenon that occurs when a copper foil laminated to a resin base is subjected to soft etching of a circuit with a sulfuric acid/hydrogen peroxide etchant.

Description

[Technical Field] The present invention relates to a copper-clad laminate for a printed circuit board and a copper-clad laminate for a printed circuit board, which are excellent in heat resistance and chemical resistance, and more particularly to a copper foil. At least a layer containing nickel, zinc, and copper (hereinafter referred to as a "copper-nickel-zinc layer"), and a chromate coating layer on the layer, and further optionally A copper foil for a printed circuit board of a decane coupling layer, and a copper-clad laminate for a printed circuit board produced using the copper foil. [Prior Art] A semiconductor package substrate is a type of printed circuit board used for a printed circuit board in which a semiconductor ic chip and other semiconductor elements are mounted. Since the circuit formed on the semiconductor package substrate is finer than the usual printed circuit board, the substrate material is a resin-based semiconductor package substrate different from the general printed circuit board, and is usually produced by the following steps. First, the copper is deposited on a substrate such as a synthetic resin at a high temperature. This is called a copper clad laminate or simply a laminate. Then, as a target, a conductive circuit is formed on the laminate, and the same pattern as the circuit is printed on the copper box by the rice-resistant tree. Then, the unnecessary part of the exposed (four) is removed by the characterization process. (4) After that, the printed portion is removed to form a conductive circuit on the substrate. Finally, the specified components are connected to &&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&& ) Resin substrate bonding β Generally, the quality requirements for the copper foil for printed circuit boards are not the same as the substrate (the so-called roughened surface) and the non-adhesive surface (the so-called shiny surface) of the substrate. Satisfy both. Requirements for glossy surface are required (1) good appearance and no oxidative discoloration during storage, (2) good solder wettability, (3) no oxidative discoloration when heated at high temperature, (4) dense with resist Good compatibility, etc. On the other hand, for the roughened surface, (1) there is no oxidative discoloration during storage, and (7) the peel strength with the substrate even after high-temperature heating, wet processing, welding, drug treatment, etc.; (3) After the layer and the substrate are laminated, (4), no so-called build-up stains or the like are generated. Further, in recent years, as the circuit printing pattern is miniaturized, the surface of the copper foil is required to have a low thickness. In the electronic devices such as personal computers and mobile communications, as the speed of A is faster and the capacity is increased, the electrical signals are moving toward higher frequencies. Therefore, it is required to provide printed circuit boards and copper boxes in response to the above requirements. If the frequency of the electrical signal is on the frequency, the effect of the skin effect of the current flowing through the surface of the conductor becomes mixed. _ % can't ignore the unevenness of the surface and cause a change in the current transmission path. The effect of babbling and hpedance is greater. Considering this point, it is also hoped that the surface roughness of the copper box is small. In order to respond to this It, a number of surface treatment methods for the copper phase of the printed circuit board have been made.

The surface treatment method of the copper ferrule and the electrolysis 隹 Mi y A is the same as the surface treatment method of the electrolytic copper treatment, for example, the following method. 201137183, that is, 'first' in order to improve the adhesion (peeling strength) between copper and resin substrate, generally, particles composed of copper and copper oxide are attached to the surface of the copper foil (roughening treatment), and then in order to have heat resistance characteristics. And a heat-resistant layer (barrier layer) such as brass or rhodium is formed. Further, in order to prevent the occurrence of surface oxidation or the like during transportation or storage, rust-preventing treatment such as chromic acid treatment or electrolytic zinc chromic acid treatment by dipping or electrolysis is applied. Made into products. Among them, the surface treatment method for forming the heat-resistant layer is an important factor for determining the surface I of the copper foil. Therefore, the metal or alloy forming the heat-resistant layer may be Zn, Cu-Ni alloy, Cu-c bismuth alloy, and Cu_z^ gold formed by, for example, Zn, Cu-Ni alloy, Cu-c 〇 alloy, and Cu-zn alloy. (4) The majority of the layers (4) have been put into practical use (for example, 'refer to the patent document n. Among them, a copper layer formed of a Cu-Zn alloy (brass) formed of a ruthenium resistant layer is used in the epoxy resin. When the printed circuit board is formed, the resin layer has no stains, and the peeling strength deterioration of the copper drop after holding the printed circuit board at a high temperature is excellent, and it is widely used in the industry. The method of forming a heat-resistant layer made of brass is described in detail in Patent Document 2. However, in recent years, in the manufacturing steps of a printed circuit board, particularly a package substrate, in order to improve the anti-contact agent or the build-up resin substrate, The adhesion of the shiny side of the copper surface of the circuit surface is treated by soft etching using a mixture of sulfuric acid and hydrogen peroxide to roughen the shiny side of the copper foil, except that the above sulfuric acid is used. Hydrogen peroxide mixture The soft surface of the copper foil circuit of the printed circuit board (using the 201137183 copper foil with the known heat-resistant layer described in the patent reading, etc.) is soft-etched, and both ends of the previously formed circuit pattern are formed (edge P) invaded rice (circuit erosion), and peeling from the resin substrate 3..., etched) is still a problem of deterioration of residual strength. The circuit intrusion phenomenon, the damage buckle μ „, the ss smelting circuit and the resin substrate substrate boundary layer is etched by the above mixed sulphuric acid and hydrogen peroxide σ liquid, thus causing the peeling strength of the π / knife copper slab is significantly inferior The phenomenon of Gehua. In addition, if this phenomenon occurs in the entire circuit pattern, the electric 踗 "¥路 pattern will be peeled off from the substrate, and become a problem of prestige. It is generally known that nickel is added to brass and the bismuth-zinc-copper layer is effective as a surface treatment layer which can prevent circuit erosion. However, although the addition of nickel can prevent the circuit from invading the rice, and the phenomenon of eclipse, the inventors found that depending on the amount of brocade added, sometimes _舍古' weizi has heat resistance (heat-resistant peeling) When the strength is lowered or the circuit is formed, the copper layer qqj, the white residual 荨 is worse than the surface layer formed by the Cu-Zn alloy (brass). [Patent Document 1] Japanese Patent Publication No. Sho 511-5571 1 Patent Document 2: 曰本特公昭54_67〇1 SUMMARY OF THE INVENTION The object of the present invention is to develop a Cu-Zn alloy (brass) The characteristics of the surface layer to be formed are deteriorated (the normal peel strength of the copper foil of the printed circuit board formed by laminating the copper pig and the resin substrate, and the peel strength after holding the printed circuit board for a predetermined time at both temperatures (below) In the case of the heat-resistant peeling strength and the chemical resistance (hydrochloric acid), the circuit erosion phenomenon described above is reduced as a copper foil for a semiconductor package substrate. In particular, when the copper foil is laminated on the resin substrate, the heat resistance 201137183 peel strength is greatly improved, and when the circuit is etched using sulfuric acid or hydrogen peroxide-based etching solution, the circuit can be effectively prevented from being invaded by the contact liquid. The phenomenon of the remaining phenomenon (hereinafter referred to as "chemical resistance") is the surface of the copper enamel. In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive studies on the conditions of surface treatment on a copper foil, and found that the following "peeling resistance to peeling 2 and chemical resistance", that is, sulfuric acid, peroxidizing gas It is effective to resist the repellency (road penetration resistance) of the roughened surface when the liquid J is exposed to the soft surface of the copper foil. The above invention provides: 1) A copper foil for a printed circuit board, which is copper The surface of the foil is provided with a layer containing nickel, copper and copper (hereinafter referred to as "copper nickel zinc layer"), and the zinc-zinc layer has a zinc adhesion weight per unit area of 200 //g/dm2 or more and 2〇〇. 〇wg/dm2 or less, in the copper-nickel-zinc layer, i~5〇% by mass, (zinc adhesion amount (% by mass))/{1〇〇(copper adhesion amount (% by mass))} is 0.3 or more (copper adhesion (% by mass)) / {1〇〇 (zinc adhesion (% by mass))} is 0.3 or more. The copper foil for a printed circuit board according to the first aspect of the invention, wherein the steel nickel-zinc layer is provided with a chromate film layer. (3) The copper foil for a printed circuit board according to the second aspect, wherein the chromium coating layer has a chromium adhesion weight per unit area of 3 g or more and 1 barium g/dm2 or less. . (4) The copper foil for a printed circuit board according to the second or third aspect, wherein, in the case of the chromate coating layer, the layer of the coupling agent is further provided on the chromate coating layer. In the fifth aspect of the invention, the copper of the printed circuit board as described in any one of the items 2 to 4, the steel boll is an electrolytic copper foil, and the copper-nickel-zinc layer is formed on the rough surface or the electrolysis of the electric M-day # The shiny surface of the steel. In the case of the electric ore, the copper foil of the printed circuit board as described in any one of the items J & 5, wherein the steel foil is a rolled copper foil. 7) A copper-clad laminate for printed circuit boards, which is made up of (4) i to 6 items. The printed circuit board is bonded to the printed circuit board by a copper slab. As described above, the copper substrate of the printed circuit board of the present invention is used to reduce the peel strength of the copper foil after the printed circuit board is maintained at a high temperature, thereby using a steel nickel-zinc layer. Heat resistant peel strength. In addition, it is possible to obtain a characteristic that can effectively prevent the circuit from being invaded by the drug, and in particular, to improve the resistance of sulfuric acid and ammonia peroxide, as a copper case for a printed circuit board (especially for a semiconductor package substrate) It is effective to form a copper-clad laminate (particularly a copper-clad laminate for a semiconductor package substrate) 35 which is formed by laminating a copper crucible and a resin substrate. Of course, a copper foil for a general printed circuit board can also be used. [Embodiment] The present invention will be specifically and specifically described, and the present invention will be understood. In the mi of the present invention, although both the electrolysis (4) and the prolonged copper junction can be used, in the case of electrolytic copper falling, it can be applied to the rough surface of the electric chain or the shiny surface of the electrolytic copper junction. Moreover, it is also possible to apply a rough 201137183 treatment to the surface of the surface. For example, in order to increase the peel strength of the resin substrate and the copper foil after lamination, an electrolytic copper foil which is subjected to roughening treatment (for example, "tumor" electrodeposition of copper) on the surface of the copper foil after degreasing is used. It can be used directly. Generally, in the drum type electrolytic copper foil manufacturing apparatus, the one side (the drum side) is the glossy side, and the opposite side is the rough side. In the case of a rolled copper foil, it is a calendered surface which is glossy. In the present invention, although the electrolytic copper foil has a rough surface and a glossy surface, it can be used as it is when it is a rough surface. On the other hand, in order to further improve the peeling strength, the shiny surface of the electrolytic copper foil may be subjected to a roughening treatment to form a roughened surface. The rolled copper foil was similarly subjected to a roughening treatment. The roughening process is used in any case where it is known to be roughened and limited; The roughened surface of the present invention refers to an electrolytic copper crucible or a copper foil which is subjected to roughening treatment. The rough surface of the copper foil and the roughened surface of the copper foil can be applied to the copper fg for the semiconductor package substrate of the invention, which is formed by the formation of the film layer and \^ (for the purpose of the tree The copper-zinc layer and the osmium acid salt of the surface are described as being formed by calendering. For copper matte, the upper copper or copper foil can be used. Two: layer of acid 9 film layer ' can use the electrolytic film salt layer or impregnation and copper Γ: two on the second? If it is formed on the surface of copper*, it contains the "copper nickel zinc layer". ). In order not to make the copper foil high, π the above copper recording layer of copper:: force: peeling strength deterioration after heat 'must make the mother early area of the zinc adhesion amount of 2〇0#g / 201137183 dm or more. The reason is that, regardless of the composition of the copper-nickel-zinc layer, if the weight of the zinc attached is less than 200"g/dm2, there is no effect of layer formation, and the deterioration of the peel strength after high-temperature heating is intensified. On the other hand, when the zinc adhesion weight exceeds 2000 Wdm2, the corrosion of the end portion of the circuit due to the sulfuric acid or the peroxidation gas system (four) liquid becomes remarkable. Therefore, the amount of zinc adhered per unit area of the copper foil of the copper-nickel-zinc layer is preferably 2 〇〇Vg/dm 2 or more and 2000 β g/dm 2 or less. And the inventors have found that the balance of the metal composition in the copper-recorded zinc layer is important, and the zinc-bearing zinc layer in the region X shown in the composition region of the kCu_Ni_Zl^ alloy is formed to enable the intensity of the high-temperature heating product. Excellent (hydrochloric acid resistance, sulfuric acid resistance, hydrogen peroxide resistance). The following J3* secret DCJ _ 1 Dan in order to reduce the copper level as described in the road intrusion, the zinc-plated layer and the corrosion resistance of the copper-nickel-zinc layer (% by mass)) It must be added, and the nickel in the copper-nickel-zinc layer can be more than the above. If it is less than 1%, it cannot effectively prevent the electric motor. However, if the recording ratio in the zinc-coated zinc layer exceeds, then ==: The balance of copper will collapse, and the copper peel will often occur when the peeling is strong, so it is not good. Therefore, the copper recording ratio is preferably 1% or more and 5% or less. The ratio of the words in the copper and copper-bearing zinc layers to the ratio of copper (up to 5%) to the heat-resistant peel strength or (or sour acid). Specifically, the following formula must be satisfied. ;) (}Zinc;; two (% by mass)) / _1 copper adhesion / Sichuan. ~ (Zinc: 'In 〇.3 or more, (copper adhesion amount (mass zinc adhesion amount (% by mass) Μ (Formula 2) must be 201137183 at 0.3 or more (in the area of Figure kx). Another for Rongwei # 2). Note: For example, if the amount of zinc adhered is too large, /{1001 (steel adhesion amount (mass h (% by mass)) or more, but the amount of steel adhesion will decrease, although it will be 0.3 / (10)-(Sentence amount (quality 2 = quantity (quality... (area in Fig. 1). In this case, due to phase ^), it may be lower than 〇.3, the amount is less, so 荜^± f @ + When the amount of adhesion is changed, the copper is attached to the strip. The hydrochloric acid is reduced. On the other hand, if the copper adhesion amount is over / {_- (the amount of adhesion (% by mass))} (:: amount (% by mass)) or more , but (the amount of resignation (% by mass)); {10 although f will be at 0·3 (interesting)"... will be lower than .3 (in the case of this clearing, due to the amount of copper attached, zinc ... Therefore, the heat-resistant peel strength is lowered. Therefore, the copper-nickel layer is lessened: the ratio of the amount is preferably satisfied (the attached copper-attachment)

(Steel adhesion amount (mass (4))} (Formula W amount (% by mass or more) (copper adhesion (quality (...) (2) , usually formed under the following conditions. However, as long as the copper adhesion layer per unit area of the zinc adhesion weight is, for example, 2 〇 /, 2 〇〇〇 / ^ plus 2 or less 'the copper zinc layer Nl4l ~ 5 〇weight '(zinc adhesion amount (% by mass)) /{1〇〇_ (steel adhesion amount (mass 0 (formula 1) above 0·3' (copper adhesion amount (mass%/ 201137183 ((10)-(zinc adhesion) The amount (mass %))} (Formula 2) is not particularly limited as long as it is 电3 or more. It is also possible to use other ore conditions. (Mineral composition) Nl. 〇lg/L~ 3〇g/L, Zn: 〇.lg/L~12g/L, Cu: 〇.lg (L~2g 八's sulphuric acid (Η 。..: 〇々8~i〇g8 is basic mine cold.χ 'Other inorganic acids or organic citric acid (worry acid 'malic acid, etc.) can also be used instead of sulfuric acid. (Current density) 3~25 A/dm2 Next, the chromate coating is made, and chromic acid treatment can be applied to electrolytic chromium. Acid treatment, impregnation chromic acid treatment, and chromate plating The bath contains zinc zinc chromic acid. In either case, if the chromium adhesion weight is less than 30〆g/dm2', the effect of increasing (4) acidity and heat resistance is small, so the adhesion weight is 3"g. //dm2 or more. Also, if the attached weight exceeds i〇〇m / dm, the effect of chromic acid treatment will be saturated, and the chrome adhesion weight can no longer be increased. If this is summarized, then the unit area per unit of chromic acid treatment layer The adhesion weight of the network is preferably 30 to 1 〇〇ag/dm 2 . Examples of the conditions for forming the above-mentioned chromate layer are as follows. However, as described above, it is not necessary to be limited by this condition, and chromium is known. Acid treatment can be used. Generally, in the case of chromic acid treatment, the chromium adhesion weight per unit area can be 30~, g/dm2. In addition, in the case of electrolytic acid treatment, chromium adhesion per unit area can be achieved. Weight 3〇~1〇〇" g//dm2. This anti-recording treatment is one of the factors affecting the acidity and heat resistance of the copper box 12 201137183, which can be further enhanced by chromic acid treatment. Foil is economical and heat resistant, so it is effective (a) An example of impregnation of chromic acid

Cr03 or K2Cr2〇7 : 1~12g/L ' Zn ( OH) 2 or ZnS04 · 7H20: 〇~i〇g/L, Na2S〇4: 〇~20g/L, pH 2.5~12.5, Temperature: 20~ 60 ° C, time: 0.5 to 20 seconds (b) an example of electrolytic chromic acid treatment

Cr03 or K2Cr207: 1 to 12g/L, Zn(OH) 2 or ZnS〇4 · 7H2〇: 〇~10g/L, Na2S04: 0~20g/L, ρΗ2·5~12·5, temperature: 20~60 °C 'current density: 0.5 to 5 A/dm2, time: 0 5 to 2 sec. The decane coupling agent used in the copper box for a printed circuit board of the present invention preferably has at least a tetraalkane, and has One or more kinds of oxyalkylene oxides having a functional group reactive with a resin. The choice of the zebra coupling agent is also arbitrary, but it is preferably selected in consideration of the adhesion to the resin. The present invention provides a copper clad laminate obtained by laminating a copper foil for a printed circuit board according to any one of the above items 1 to 6 and a resin substrate. Next, this rustproof layer was treated with a decane coupling agent (after coating, dried). The conditions under which the decane coupling agent is treated are as follows. The water-soluble night of 0.5% by volume of epoxy broth (ep〇xysiiane) was adjusted to pH 7, coated, and then dried. [Test method] 13 201137183 The following two types of resin substrates are used for the resin substrate. FR-4 resin (glass cloth substrate epoxy resin) BT resin (three lectures - double malayanamide resin, trade name: Mitsubishi Gas Chemical Co., Ltd. GHPL-830) In addition, BT resin, high heat resistance It is a material used for a printed circuit board for semiconductor packaging. (1) Measurement of normal peel strength and heat-resistant peel strength of the FR-4 substrate The copper foil on the laminate plate formed by laminating the surface of the copper foil with the copper-nickel-zinc layer and the FR_4 resin substrate was etched. A 1 mm wide copper foil circuit is formed on the board. This circuit was peeled off and the normal peel strength was measured. Next, the laminate in which the above-described copper junction circuit having a width of 10 mm was formed was measured at 18 Torr in the atmosphere.剥离 The peel strength after heating for 2 days (hereinafter referred to as heat-resistant peel strength) and the relative deterioration rate (loss %) compared with the normal peel strength, the heat resistance is inferior if the substrate is compared with the BT substrate. Therefore, when the FR-4 substrate is used, if the BT substrate is used with good heat-resistant peel strength and low deterioration rate, sufficient heat-resistant peel strength and deterioration rate are obtained. (2) Measurement of the normal peel strength and the sulfuric acid-resistant nitrogen peroxide property of the BT substrate, and the contact of the layer of the copper-plated zinc layer on the laminated plate made of the steel substrate and the resin substrate is carried out. Formed on the laminate. 4 Yan Kuan's copper smelting circuit μ This circuit is peeled off and the normal peel strength is measured. Next, 201137183, using the above-mentioned acid and hydrogen peroxide forming a 0.4 mm wide copper-plated circuit, and (4) acid test, the sulfur-tolerant test was carried out, and the n 1 i was impregnated with sulfur. ....% by volume and peroxygen path =: (4) Thickness of the circuit (4) After the 2 hearts are dropped, the relative deterioration rate (loss %) of the measured intensity is pure. The peel strength measurement in this case, when using the FR-4 plate _ /疋In a harsh environment, when you pull it, it is more harsh than the normal one. The evaluation of the endurance of the order is even more so when using the BT substrate, if it is a & t hydrogen-hydrogen m4 Also combined with disulfuric acid, peroxysulfuric acid, and bismuth peroxide. (Specially resistant to hydrochloric acid test, the steel on the laminated board is 12% by weight of 6 (the liquid of rc is tributed to 3 with 1 acid Μ μ night body) After the boring tool 4, the peeling strength and the relative deterioration rate (loss %) compared with the bismuth normal peel strength were measured. (3) The nickel per unit area and the plating adhesion were made of copper and nickel in the copper box. The surface of the zinc layer "on the surface of the disk Fr__ 4 resin substrate layer, making a product. Yu Jing η product (four) receiver The chemical concentration of the copper-nickel layer on the surface of the laminate and the copper layer in the mother layer is measured by hydrochloric acid or nitric acid to measure the adhesion weight per unit surface = dry zinc (4) zinc Analysis of the existence ratio of nickel and copper = XPS (X-ray photoelectron spectroscopy) to measure the existence ratio of brocade, rhetoric and copper contained in copper. Measurement, system, and edge by chlorine 15 15 201137183 a The thickness of the berth is (4), which is intermittently carried out from the outermost surface to the copper layer (the base of the steel recording layer), and the depth from the outermost surface is used to compare the existence ratio of the brocade, zinc and copper obtained from each ice. Integral, thereby calculating the average existence ratio of zinc and copper in the copper-zinc layer. The machine used for the measurement is the output of AXIS~HS' argon ion splashing manufactured by KRATOS & 52 5w. Under these conditions, The thickness of the copper drop was etched away by about 20 in one minute. The sputtering time was α 15 : conditions were observed. Examples of the examples Next, the examples and comparative examples will be described. The results are shown in the following tables. In order to display one of the preferred {columns, the invention is not limited The present invention is also included in the present invention. The other embodiments or aspects included in the present invention are all included in the present invention. Eighth, in order to compare with the present invention, a comparative example is disclosed. Examples 1 to 9) Using a thickness of 12" electrolysis (4), a copper-nickel-zinc layer was formed on the copper by electroplating under the conditions shown below, and the roughened surface of g (surface average roughness: 3·8 μη〇). The ratio of the presence of nickel, zinc, and copper is shown in Table i. (Composition of plating solution of Example 1)

Ni: 3 g/L, Zn: 6 g/L, Cu: 〇 5 g/L, sulfuric acid (H 2 s 〇 4):

7-5 g/L (composition of the plating solution of Example 2) sulfuric acid (h2so4):

Ni: 20g/L, Zn: 3g/L, Cu: 〇.2g/L

8.5g/L 201137183 (the composition of the plating solution of Example 3)

Ni: 13 g/L, Zn: lg/L, Cu: 2 g/L, sulfuric acid (H2SO4): 8.5 g/L (composition of the plating solution of Example 4)

Ni: 10 g/L, Zn: 12 g/L, Cu: 0.2 g/L, sulfuric acid (H2S〇4): 8.5 g/L (composition of the plating solution of Example 5)

Ni : 28 g / L, Zn : 8 g / L ′ Cu : 0.5 g / L, sulfuric acid (H 2 S 〇 4 ): 8.5 g / L (composition of the plating solution of Example 6)

Ni : 10g / L, Zn : 5g / L, Cu : l.Og / L, sulfuric acid (H2S〇4):

8.5 g/L (composition of the liquid money solution of Example 7)

Ni: 0.3 g/L, Zn: 0.3 g/L, Cu: 2.0 g/L, sulfuric acid (H2S〇4): 8.5 g/L (composition of the plating solution of Example 8)

Ni: 28 g/L, Zn: lg/L, Cu: 0.8 g/L, sulfuric acid (H2S〇4): 8-5 g/L (composition of the plating solution of Example 9)

Ni: 7g/L, Zn: 10g / L, Cu: 0.5g / L, sulfuric acid (H2S〇4): 8.5g / L (current density) 5A / dm2 or 10A / dm2 and, on this copper zinc layer , chromic acid treatment to form an anti-money layer. The processing conditions are shown below. 17 201137183

Cr〇3 : 4.0g/L ' ZnS〇4 . 7H2〇: 2.0g/L, Na2S04 : I5g /L, pH : 4.2, temperature: 45〇c, current density 3.0A/dm2, time: 1.5 seconds (implementation Example 1) In Example 1, the adhesion amount of zinc (Zn) in the plating film was 924 #g / dm2, in the plating film, Ni: 9 mass%, Zn: 42 mass%, Cu: 49 mass% ' Formula ι (zinc adhesion (% by mass)) / {1〇〇—(copper adhesion (% by mass)) } is 0.83, formula 2 (copper adhesion (mass) / {100—(zinc adhesion (% by mass) ) ) } is 〇 _85, which is within the scope of the present invention. As a result, the normal peel strength of the FR substrate of this example 1 is 1.47 kN/m, and the peel strength after 2 days of aging is 12 〇. kN / m, the deterioration rate is 18%. Moreover, the normal peel strength of the BT substrate (under severe environment) is 丨〇5kN / m, the peel strength after hydrochloric acid treatment is 〇.85kN/m, and the degradation rate is 2〇%. And the peeling strength of sulfuric acid resistant 'hydrogen peroxide' was 〇98 kN/m, and the deterioration rate was 7%, which was a good result. The above results are shown in Table 1. 18 201137183 BT substrate sulfuric acid, hydrogen peroxide% loss 〇\ (Ν Ο kN/m 0.98 0.86 0.88 0.92 0.93 0.98 0.96 0.95 0.98 % hydrochloric acid loss ι—Η F—Η inch 00 m kN/m 0.85 0.89 0.93 0.86 0.91 0.87 0.98 0.95 0.92 φΕ- kN/mis 0.99 0.99 1.01 1.04 1.10 1.02 1.03 1.06 FR—4 Substrate 2 days aging % loss oo ΟΝ (Ν rs m (Ν in ι—Η CN kN/m 1.20 1.42 1.53 00 CN 1.43 1.42 1.40 1.46 1.42 woven <dE- kN/m 1.47 1.55 1.46 1.48 JO 1.48 1.47 1.45 (N 0.85 0.54 0.79 0.77 0.37 0.79 0.92 0.33 0.35 0.83 0.52 0.39 0.98 0.47 0.39 0.56 0.39 0.78 Cu% by mass Os ΓΛ Ο Ο m CN Zn % by mass <Ν m 〇\ m (Ν Η C\ Ο m ON Ni mass% 〇\ 00 00 1···^ (Ν ο οο Zn adhesion amount / zg / dm2 924 320 ιη 390 378 617 1860 746 220 Embodiment 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Implementation Example 8 Example 9 201137183 (Example 2) In Example 2, the amount of zinc (Zn) adhered in the plating film was 320 # g / dm 2 ' in the plating film, Ni : 3 i% by mass, zn : 34 Mass%, Cu: 36% of the mass 'Form 1 (zinc adhesion (% by mass)) / {100—(copper attached The amount (% by mass) is 〇·52, and the formula 2 (copper adhesion amount (% by mass)) / {100~ (zinc adhesion amount (% by mass))} is 0.54, which is within the scope of the present invention. As a result, in Example 2, the normal peel strength of the FR substrate was 1.5 6 kN/m, and the peel strength after 2 days of aging was i.42 kN/m, and the deterioration rate was 9%. In addition, the normal peel strength of the BT substrate (under harsh environment) is 〇99kN /m', the peel strength after hydrochloric acid treatment is 〇89kN/m, the deterioration rate is 10%' and the peeling strength of the sulfuric acid and hydrogen peroxide is O. MkN/m, the degradation rate of 14%' is a good result. The above results are also shown in Table 1. (Example 3) In Example 3, the amount of zinc (zn) adhered in the plating film was 465 μg /dm 2 'in the plating film, Ni: 18% by mass, Zn: 12% by mass, Cu: % by mass 'Formula 1 (zinc adhesion amount (mass / {1 〇〇 - (copper adhesion amount (% by mass))} is 0.39, formula 2 (copper adhesion amount (mass) / {100 - (zinc adhesion amount (% by mass)) The value of 0.79 is within the range of the conditions of the present invention. As a result, in the third embodiment, the normal peel strength of the FR substrate was UAN/m, and the peel strength after aging for 2 days was i_53 kN/m, and the deterioration rate was 2%.

In addition, the normal peel strength of the 'BT substrate (under harsh environment) is 〇.99kN 201137183 /m', the peel strength after hydrochloric acid treatment is 〇.93kN/m, the degradation rate is 6%, and it is resistant to sulfuric acid and hydrogen peroxide. The strength was 〇.88 kN/m, and the deterioration rate Π%' was a good result. The above results are also shown in Table 1. (Example 4). In Example 4, the amount of zinc (zn) adhered in the plating film was 390 #g / dm2, and in the money coating, 'm: 2% by mass, Zn: 93% by mass, Cu: 5 Mass %, Formula 1 (zinc adhesion amount (% by mass)) / {1〇〇_ (copper adhesion 3: (% by mass)) } is 0.98, Formula 2 (copper adhesion amount (mass / {100 - (exclusion amount) (% by mass)) } is 〇77, which is within the scope of the present invention. As a result, in this Example 4, the normal peel strength of the FR substrate was l_46 kN/m, and the peel strength after 2 days of aging was 1 28 kN/m. The deterioration rate is 12%. The normal peel strength of the BT substrate (under severe environment) is 丨〇1 / m, the peel strength after hydrochloric acid treatment is 86.86kN/m, the degradation rate is 15%, and it is resistant to sulfuric acid. The peeling strength of hydrogen peroxide was 0.92 kN/m, and the deterioration rate was 9%, which was a good result. The above results are also shown in Table 1. (Example 5) ^In Example 5, zinc in the plating film (Zn) adhesion amount is 378 " e , plating is in the pancreas, Ni: 4〇 mass%, Zn: 36 mass%, Cu: 24 mass% 'Formula 1 (zinc adhesion amount (% by mass)) / {1 〇〇 着 ( (quality) 0.47, Formula 2 (copper adhesion amount (% by mass)) / {100-(zinc adhesion amount (% by mass))} is 〇 37, both in the present invention

21 S 201137183 The scope of the article. As a result, in this Example 5, the normal peel strength of the FR substrate was 1.48 kN/m, and the peel strength after aging for 2 days was l_43 kN/m, and the deterioration rate was 3%. In addition, the normal peel strength of the BT substrate (under harsh environment) is 1 〇 4kN / m'. The peel strength after hydrochloric acid treatment is 〇.91kN/m, the degradation rate is 13%, and the peeling strength of sulfuric acid and hydrogen peroxide is resistant. For 〇93kN/m, the degradation rate is 11%, which is a good result. The above results are shown in Table 1. (Example 6) In Example 6, the amount of (Zn) adhesion in the plating film was 617 "g /dm2' in the plating film, (4): 18% by mass, Zn: 12% by mass, Cu: % by mass 'Formula 1 (zinc adhesion (% by mass)) / {1〇〇—(copper adhesion (% by mass)) } is 〇·39, formula 2 (copper adhesion (% by mass)) / {100—(zinc) The amount of adhesion (% by mass) } } is 〇79, which is within the scope of the conditions of the present invention. As a result, in the Example 6, the normal peel strength of the FR substrate was 1.45 kN/m, the peel strength after the 2-day aging was 1.42 kN/m, and the deterioration rate was 2%.

Moreover, the normal peel strength of the BT substrate (in a severe environment) is i. 1〇kN, the peel strength after hydrochloric acid treatment is 0.87 kN/m, the deterioration rate is 21%, and the peeling strength of sulfur-resistant and hydrogen peroxide is resistant. It was 0.98 kN/m and the deterioration rate was 11%, which was a good result. The above results are also shown in Table 1. (Example 7) In Example 7, the amount of zinc (Zn) adhered in the ore film was 1860 / zg 22 201137183 / dm 'plated in the crucible, Ni: 7 mass%, Zn: 9 mass%, Cu 84% by mass 'Form 1 (zinc adhesion (% by mass)) / {100-(steel adhesion (% by mass)) } is 〇56, formula 2 (copper adhesion (% by mass)) /{loo-( The amount of zinc adhesion (% by mass) } is 〇92, which is within the scope of the present invention. As a result, in this Example 7, the normal peel strength of the FR substrate was 1.48 kN/m, the peel strength after 2 days of aging was 1.40 kN/m, and the deterioration rate was 5%. In addition, the normal peel strength of the BT substrate (under harsh environment) is 1 〇 2kN / m, the peel strength after hydrochloric acid treatment is 〇.98kN / m, the degradation rate is 4%, and the peeling strength of sulfuric acid and hydrogen peroxide is resistant. A value of 0.96 kN/m and a degradation rate of 2%' are good results. The above results are also shown in Table 1. (Example 8) In Example 8, the amount of zinc (Zn) adhered in the plating film was 746 g/dm2, and in the plating film, 47% by mass, Zn: 30% by mass, and Cu: 23 mass. % 'Formula i (zinc adhesion amount (% by mass)) / {1〇〇—(copper adhesion amount (% by mass)) } is 0.39, formula 2 (copper adhesion amount (mass) / {100—(zinc adhesion amount ( The mass % } is 〇_33, which is within the range of the conditions of the present invention. Results 'The normal peel strength of the FR substrate of this Example 8' is 1-147 kN/m, and the peel strength after 2 days aging is 1.46 kN/m, and the deterioration rate is It is 1%. The normal peel strength of the 'BT substrate (under harsh environment) is 1.03kN /m'. The peel strength after hydrochloric acid treatment is 〇.95kN/m, the degradation rate is 8%, and it is resistant to sulfuric acid and hydrogen peroxide. The peeling strength was 〇95 kN/m, and the deterioration rate was 23 201137183 〇%, which was a good result. The results of β or more are shown in Table 1. (Example 9) In Example 9, 'zinc in the plating film ( Ζη) adhesion amount is 22 /dm2, plating is in the crucible, Ni: 2〇 mass%, Ζη: 69% by mass, Cu: :: mass%, formula 1 (zinc adhesion amount (% by mass)) / {1〇 〇~(copper attachment (mass/6)) } is 〇78' type 2 (copper adhesion amount (mass%)) zinc adhesion amount (mass%)) } is 〇35, both of which are within the scope of the present invention. 9. The normal separation strength of the FR substrate is 1.45 kN/m, and the peel strength after aging for 2 days is / claw, and the deterioration rate is 2%. Moreover, the normal peel strength of the BT substrate (under severe environment) is i. The peeling strength after the hydrochloric acid treatment was 〇.92 kN/m, the deterioration rate was 13%, and the peeling strength against sulfuric acid and hydrogen peroxide was 〇98 kN/m, and the deterioration rate was 11%, which was a good result. The results are similarly shown in Table 1. As described above, the adhesion weight of zinc per unit area of the plating layer of the examples was 220 yg/dm2 to 丨860 #g/dm2, and the normal peel strength of the FR-4 substrate was l_45 kN/m. ~l_56kN/m, the heat-resistant peel strength is 丨2〇kN/m~1.53kN/m, and the deterioration rate is 18% or less, which shows good normal peel strength and heat-resistant peel strength. Further, normal peeling of BT substrate The strength is in the range of 〇99kN/m~ll〇kN/m, and the peel strength after treatment with hydrochloric acid and sulfuric acid hydrogen peroxide solution is 0.8 respectively. 5kN/m~〇.93kN/m, 0.86kN/m~〇.98kN/m, inferior 24 201137183 The rate of A 4%~21%, 0%~14% respectively showed good properties. (Comparative Example 1 ~7) The composition of the plating bath was changed under the following conditions to form a steel nickel-zinc layer. The ratio of the amount of zinc adhered per unit area to the presence of nickel, zinc, and steel in the plating film is shown in Table 2. (Compound composition of Comparative Example 1)

Ni : 13 g / L, Zn : 5 g / L ' Cu : Og / L, sulfuric acid (H2S04):

8-5 g/L (composition of plating solution of Comparative Example 2)

Ni : 13 g / L ' Zn : Og / L, Cu : 6.5 g / L, sulfuric acid (H 2 SO 4 ): 8.5 g / L (composition liquid of Comparative Example 3)

Ni : Og / L ′ Zn : 5 g / L ′ Cu : 0.5 g / L, sulfuric acid (H 2 SO 4 ): 8.5 g / L (composition of the plating solution of Comparative Example 4)

Ni: 13 g/L, Zn: 15 g/L, Cu: 0.9 g/L, sulfuric acid (H2S04): 8-5 g/L (composition of plating solution of Comparative Example 5)

Ni: 15 g/L, Zn: 〇.lg/L, Cu: 3 g/L, sulfuric acid (H2S04): 8.5 g/L (composition of plating solution of Comparative Example 6)

Ni: 3 g/L, Zn: 16 g/L, Cu: O.lg/L, sulfuric acid (H2S04): lg/L (composition of plating solution of Comparative Example 7)

Ni : 13g / L, Zn : 3g / L, Cu : 0.5g / L, sulfuric acid (h2S04): 25 201137183

Lg/L (composition of plating solution of Comparative Example 8) Chuan: 4〇g/L, Zn: 3g/L, Cu: 〇 lg/L, sulfuric acid (H2S〇 lg/L ' (composition of plating solution of Comparative Example 9)

Ni: 32 g/L' Zn: 0.05 g/L, Cu: 3 4 g/L, sulfuric acid (H2s〇4): lg/L (composition liquid of Comparative Example 1)

Ni: 25 g / L, Zn: 16 g / L 'Cu: 〇〇 5 g / Lu ^ (H2S 〇 lg / L 4; ' (current density) 2.5 A / dm2 ~ 30A / dm2 (Comparative Example 1) in the comparative example There is no copper in the plating film, and the presence ratio in the plating film is more than 5 G mass%, which is inconsistent with the present invention. Further, although the formula (zinc adhesion amount (% by mass)) / {1001 (copper adhesion amount) (% by mass, two) is 0.49, but the formula 2 (copper adhesion amount (% by mass)) / {ι〇〇-(zinc adhesion amount (% by mass)) } is G.GG, which is not within the scope of the present invention. In this comparative example, the normal peel strength of the FR substrate is i 5 〇 kN/m, the peel strength after aging for 2 days is 1.47 kN/m, and the degradation rate is 2%. Further, the BT substrate (under severe environments) Although the normal peel strength is 〇98kN/paw, the peel strength after hydrochloric acid treatment is 〇15kN/m, the deterioration rate is remarkably reduced to 85%, and the peeling strength against sulfuric acid and hydrogen peroxide is 〇75kN/m, which is deteriorated. The rate is 24%, and the drug resistance is greatly reduced for any of them. 26 201137183 The above results are shown in Table 2 201137183 BT substrate sulfuric acid, hydrogen peroxide% loss oo (N ON inch ΙΤϊ CN inchtH kN/m 0.75 0.92 0.69 0.62 0.96 0.78 0.99 0.86 1.00 0.86 hydrochloric acid % loss yr\ 00 〇\ (N cn § 〇\ IT) 00 m in ro kN/m 0.15 0.90 0.65 0.20 0.91 0.16 1.00 0.92 1.02 0.71 {〇& kN/m 0.98 0.99 0.96 1.02 1.00 1.04 s 0.97 o FR-4 substrate 2 days aging % loss (N in (N omm < N (N iN ro kN/m 1.47 1.06 1.46 1.50 1.12 1.35 1.01 1.10 1.19 Weaving <00- kN/m 1.50 ...... in 1.48 (N in 1.50 1.35 1.46 1.42 fN F-H (N 0.00 0.45 1.00 0.49 0.83 0.20 0.49 0.31 0.54 0.28 f-H < 0.49 0.00 1.00 0.48 0.20 0.74 0.48 0.27 0.25 0.55 Cu mass % 〇mm § in CN iT) Zn mass % 〇VO yn CN m inch o (N 宕m Ni mass% in 〇v〇in mo 00 m Zn adhesion amount "g/dm2 452 O 620 2564 380 856 1649 1251 1089 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10

00 <N 201137183 (Comparative Example 2) Zinc was not present in the plating film of Comparative Example 2', and the existence ratio of the recorded film in the plating film was more than 50% by mass. Further, although the formula 2 (copper adhesion 1: (mass 罝%)) / {1001 (zinc adhesion amount (% by mass))) is 〇_45, but the formula i (the amount of adhesion (% by mass)) / {ι〇 〇—(copper adhesion (% by mass))} is (). 〇〇' is not within the scope of the present invention. In Comparative Example 2, the normal peel strength of the FR substrate was 151 kN/m, and the peel strength after aging for 2 days was 3% by mass, and the heat-resistant peel strength of the fr-4 substrate was largely lowered. The above results are also shown in Table 2. (Comparative Example 3) In Comparative Example 3, the zinc (Zn) adhesion amount in the plating film was 62 〇 "g /dm2', but nickel was not present in the plating film, which was inconsistent with the present invention.丨 (the amount of affixed (% by mass)) / {100—(copper adhesion (mass} is 1.00' type 2 (copper adhesion (% by mass)) / {1〇〇_ (word attachment amount (mass%) } is 1.00. In Comparative Example 3, the normal peel strength of the BT substrate (under severe environment) is 0.96 kN/m', but the peel strength after hydrochloric acid treatment is 〇65 kN/m, and the deterioration rate is remarkably reduced to 32%. Moreover, the peeling strength against sulfuric acid and peroxygen gas was 0.69 kN/m, and the deterioration rate was 28%, and the chemical resistance was greatly lowered for any of them. The above results are also shown in Table 2. (Comparative Example 4) In Comparative Example 4, the amount of zinc adhesion per unit area was 2564 g/dm 2 , which was inconsistent with the present invention. In Comparative Example 4, the BT substrate (in a severe environment) 29 201137183 hangs the i' peel strength although i 02kN / m, but the peel strength after hydrochloric acid treatment is 〇.20kN / m, the deterioration rate is significantly reduced to, and the peeling strength of sulphuric acid and cerium peroxide is G.62kN / m, the deterioration rate is 39%, no matter which The chemical resistance was greatly reduced. The above results are also shown in Table 2. (Comparative Example 5) In Comparative Example 5, it was present in plating. The amount of copper in the film is as high as 8% by mass, and zinc is 4% by mass. 'Nickel is 16% by mass, (zinc adhesion amount (% by mass)) / {1 〇〇 _ (copper adhesion amount (% by mass)) } is 02 It is beyond the scope of the present invention. In Comparative Example 5, the normal peel strength of the FR-4 substrate is 1.50 kN/m, but the peel strength after hydrochloric acid treatment is i 12 kN/m, and the deterioration rate is 25%, FR- 4. The heat-resistant peel strength of the substrate was greatly lowered. The above results are similarly shown in Table 2. (Comparative Example 6) In Comparative Example 6, zinc was present in the plating film as much as 7 〇 mass%, and copper was only 6 mass%. %, therefore (the amount of copper adhesion (mass / {1^ - (the amount of adhesion (% by mass))} is 0_20, which is beyond the scope of the present invention. In Comparative Example 6, the normal peel strength of the BT substrate is 1〇. 4kN/m, but the peel strength after hydrochloric acid treatment was 〇16kN/m, the deterioration rate was as high as 85%, and the chemical resistance (hydrochloric acid) was greatly reduced. The above results are also shown in Table 2. (Comparative Example 7) In Example 7, the adhesion amount of zinc per unit area was only i5 〇 yg / dm 2 ', which did not conform to the present invention. In Comparative Example 7, the peeling of the FR 〜 4 substrate after 2 days of aging was strong. The degree was l.〇lkN/m, the deterioration rate was as high as 31%, and the heat resistance 201137183 was drastically lowered. The above results are also shown in Table 2. (Comparative Example 8) The existence ratio of zinc in the bond film of Comparative Example 8 More than $ 〇 mass %, (zinc adhesion amount (% by mass)) / {1 〇〇 (copper adhesion amount (% by mass))) is 0.27, which is beyond the scope of the present invention. In this Comparative Example 8, the fr_4 substrate The peel strength after aging for 2 days was KiokN/m, the deterioration rate was as high as 23%, and the heat-resistant peel strength of the FR-4 substrate was greatly lowered. The above results are also shown in Table 2. (Comparative Example 9) In Comparative Example 9, (zinc adhesion amount (% by mass)) / {1〇〇_ (copper adhesion amount (Berry%))} was 0.25, which was outside the scope of the present invention. In Comparative Example 9, the peel strength after aging of the FR-4 substrate for 2 days was i·丨 m, the deterioration rate was as high as 22%, and the heat-resistant peel strength of the FR-4 substrate was drastically lowered. The above results are also shown in Table 2. Further, in Comparative Example 10, (copper adhesion amount (% by mass)) / {1 〇〇 - (zinc adhesion amount (% by mass))} was 0.28, which was outside the scope of the present invention. In Comparative Example 10, the normal peel strength of the BT substrate was 丨〇lkN/m, but the peel strength after the hydrochloric acid treatment was 7171 kN/m, the deterioration rate was as high as 3%, and the chemical resistance (hydrochloric acid) was drastically lowered. The above results are also shown in Table 2. From the above, the plating bath conditions for producing the copper-nickel-zinc layer of the present invention are preferably Ni: 〇.lg/L 〜30 g/L, Zn: 〇lg 八~% eight, cu: 〇_lg/L 〜 2g / L, sulfuric acid (H2S 〇 4): 〇 lg 八 ~ 1 〇 g eight base 31 201137183 this plating bath. If the right is not in the concentration range, the concentration of nickel, zinc or copper will become thicker, which will cause the situation of the wastewater treatment. Therefore, the conditions for the key bath are not good, and when the concentration of the right component is low, It is difficult to manage the main original plating bath due to changes in the concentration of plating, etc. The current efficiency is extremely lowered, so the conditions as a plating bath are not good. In the above, although the case of applying to the roughened surface of the electrolytic copper foil is described, it is of course also applicable to the electrolytic copper which has been subjected to the roughening treatment on the shiny side and is subjected to the roughening treatment (4) The same is true. If the roughened surface of electrolytic copper drop and calendering (4) is used, the absolute value of normal peel strength may be different depending on the shape and surface roughness of the roughening treatment, but the heat-resistant peel strength and sulfuric acid and peroxidation may be lowered. The relative deterioration rate of the peel strength after the gas water treatment compared with the normal peeling. The copper falling of the printed circuit board of the present invention, in particular, the optimum condition for selecting copper toward the zinc layer is a central issue of the invention. Thereby, the sulfuric acid and hydrogen peroxide properties are constantly and stably exerted with a large (four) heat-resistant peel strength of the copper bobbin and effectively preventing the circuit from being invaded. Therefore, the choice of the surface can be easily selected by arbitrarily selecting the choice of electrolytic copper drop and calendering or rough visual purpose. INDUSTRIAL APPLICABILITY As described above, in the copper case for a printed circuit board of the present invention, the copper recording layer is used in order to prevent deterioration of the peeling strength of the resin after heating at a high temperature, and the heat of the copper junction can be greatly improved. Peeling strength...this can provide effective protection against circuit erosion. 'The chemical resistance (sulfuric acid, peroxidation 32 201137183 hydrogen system) value can also be used to improve the effectiveness of the J-circuit circuit foil and the tree conductor seal. The characteristics of the road _ # &&>, steep, in recent years _ 茱 及 and the development of frequency, copper foil for the board (material B 乍 for printing ^ special 疋 + copper foil for conductor package substrate) and A copper-clad laminate for a printed circuit board (particularly: a substrate) produced by laminating a lunar base material. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a Cu-Ni-Ζπ ternary alloy suitable for the region of the present invention. [Main component symbol description] None 33

Claims (1)

201137183 VII. Patent scope of the application: 1) A copper foil for a printed circuit board, which is provided on the surface of a copper foil and has a layer containing nickel, zinc and copper (hereinafter referred to as "copper nickel zinc layer"), the copper nickel zinc The adhesion weight per unit area of the layer is 2 〇〇# g/dm2 or more and 2000 A g/dm or less. In the copper-nickel-zinc layer, Ni is i ～5 〇% by weight, (zinc-attached 篁 (quality (copper) Adhesion amount (% by mass))} 〇·3 or more, (copper adhesion amount (% by mass)) / {100_ (zinc adhesion amount (% by mass))} is above 0 3 2. If the scope of application for patents is 丨A copper foil for a printed circuit board, comprising a chromate coating layer on the copper-nickel-zinc layer. 3. A copper case for a printed circuit board according to the second aspect of the invention, wherein the chrome-tantalum film is used. In the layer, the adhesion weight per unit area is 3 〇 Wdm2 or more and 100 Å/g/dm2 or less. 4. A copper box for a printed circuit board according to item 2 or 3 of Uli La, where 'in the chromate On the coating layer, a layer of a decane coupling agent is further provided. 5. For a printed circuit board according to any one of claims 1-4 to 4 Copper foil, wherein the copper foil is Lei # horse electrolytic copper is difficult, the copper nickel zinc layer is formed on the rough surface of the electroplating or the shiny surface of the electrolytic steel foil. 6 · Printing as claimed in the first item of the patent scope Copper foil for a circuit board, wherein the copper foil is a rolled copper foil. 7. A copper-clad laminate for a circuit board is made of a copper foil for a printed circuit board and a resin for a printed circuit board. Made by fitting. 34