JPS6058698A - Copper foil for printed circuit and method of producing same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a copper foil for printed circuits and a method for manufacturing the same, and more specifically, the present invention relates to a copper foil for printed circuits and a method for manufacturing the same, and more particularly, it has a method that prevents bleeding between the copper foil and a resin substrate and maintains adhesive strength before and after heating. The present invention relates to a copper foil for printed circuits that maintains its strength and does not cause etching residue or undercuts during etching, and a method for manufacturing the same.

[Technical background of the invention and its problems]

Printed circuits are used in radios, televisions, and computers.

Printed circuit boards are widely used as circuits in various electrical equipment such as telephone exchanges, but recently, with significant technological progress in this field, the quality required of printed circuit boards has become increasingly sophisticated.

Currently, copper-clad laminates are widely used as printed circuits, but they have the following problems. That is, first of all, brown stains often occur on the bonding surface between the copper foil and the resin substrate, which not only impairs the appearance of the circuit board but also adversely affects the dielectric properties of the substrate resin. Even if the above stains are not observed when the copper foil is etched away, the above stains may appear when the circuit board is heated in the air during the processing process. Even brown stains are disliked.Moreover, during the heat treatment described above, a phenomenon in which the adhesive strength between the copper foil and the substrate resin decreases is observed, which is also a practical problem. There is.

Although the mechanism responsible for such brown stains or decreased adhesive strength has not been completely elucidated, it is believed to be primarily based on a chemical reaction between the copper foil and the substrate resin.

In order to solve these problems, the following methods have been proposed so far as countermeasures.

First, in British Patent No. 1,211,494 and the corresponding Japanese Patent Publication No. 53-43555, nickel is added to the surface of the copper foil that is to be bonded to the resin substrate (hereinafter referred to as the surface to be bonded of the copper foil). , cobalt, chromium, or stainless steel to form a thin layer of 0.2-1.09/m'' plating.

Further, in Japanese Patent Publication No. 51-35711, indium, zinc, tin, nickel, cobalt, copper-zinc alloy or copper-tin alloy is added to the surface of copper foil to be bonded in an amount of 10.16 x 1.
A method of electrodeposition to a thickness of 0-8 cm (4 microinches) or greater is disclosed.

In Japanese Patent Publication No. 53-39376, zinc, brass, nickel, and cobalt are used on the surface of the copper foil to be bonded.

A method of plating chromium, cadmium, tin or bronze is disclosed.

Furthermore, in Japanese Patent Publication No. 49-16863, metals baser than copper, such as aluminum, chromium,
Manganese, iron, cobalt, nickel, zinc, cadmium, tin, lead, indium or copper alloys or other alloys thereof, such as copper-zinc, copper-cadmium, copper-tin,
A method of forming a tin-zinc layer is disclosed.

In these prior art, the layer formed on the surface of the copper foil to be bonded is for suppressing the chemical reaction between the copper foil and the substrate resin.

However, these layers cannot be put to practical use if they merely have the above-mentioned functions. That is,
An etching removal process of the copper foil is essential for forming the desired circuit, and the layer must be removed together with the copper foil. In addition, it is undesirable that the layer etches as quickly as copper foil and causes so-called undercuts, and furthermore, it must not be so sensitive that it will peel off the printed circuit during various chemical treatments in the circuit board manufacturing process. be.

Considering this point, among the metals and alloys mentioned above, nickel, tin, cobalt, copper-tin alloys, etc.
Ammonium persulfate solution, which is one of the commonly used etching solutions, does not etch or etches with difficulty.

Recently, weaker alkaline etching solutions have begun to be frequently used, so the above method is not practical.

On the other hand, in the case of zinc layers, undercuts occur during etching using ammonium persulfate solutions or cupric chloride solutions, and undercuts also occur during treatment with hydrochloric acid-containing solutions during the circuit board manufacturing process. There is a problem that This is a fatal drawback in the current trend of increasingly narrow circuit widths.

Furthermore, in the case of brass layers, there is currently no practical method other than using a cyanide bath when forming the layer (plating), so there is a risk of deteriorating the working environment and causing pollution problems. Undesirable.

In the formation of the nickel layer described above, a method has been proposed in which the nickel layer can also be etched with an ammonium persulfate solution. For example, in British Patent Publication No. 201091OA, 0 sulfur is added to the nickel layer.
．． It is disclosed that the copper foil and the nickel layer can be etched with the same etching solution by containing 05 to 1O90 by weight. However, according to the inventor's additional tests, the etching properties of the nickel layer using the ammonium sulfate solution were not sufficiently improved, and the etching properties of the cupric chloride solution were actually impaired. It was something.

Further, JP-A-56-155592 proposes an electroplated nickel layer containing phosphorus, and JP-A-56-155593 proposes an electroplated nickel layer whose surface is cathodic electrolytically treated in a chromic acid-containing solution.

These layers suppress the occurrence of brown bleed and the decrease in adhesion between the copper foil and the resin, and are etched at approximately the same speed as the copper foil when etched with an ammonium persulfate solution. It has the following problems.

In other words, when the nickel layer is sufficiently thick to exhibit its effectiveness, the rate of etching removal is not fast enough when using the alkaline etching solution that is commonly used these days, and the resin after copper foil etching is The surface of the substrate is clean to a certain extent, but there is so much dirt left on the surface that it changes color when heated and held. Therefore, this improvement is strongly desired.

Now, there are roughly two types of copper foil for printed circuits based on the relationship with lamination on resin substrates. One is used for the outermost layer of a copper-clad laminate, and the other is used inside a multilayer board. In the former case, only one side of the copper foil is the surface to be bonded, and the other side is the surface exposed to the surface of the completed printed circuit board, on which etching resist and solder resist ink are printed in the subsequent process.

Soldering processing etc. are performed. In the latter case, both sides of the copper foil are the surfaces to be joined. Conventional copper foil for printed circuits is heat-treated when laminated onto a resin substrate, which causes the so-called non-treated side of the copper foil that forms the circuit pattern to oxidize and discolor. Otherwise, there were drawbacks such as poor adhesion of resist inks and poor solder wettability. Further, even when there is no oxidative discoloration, drawbacks such as insufficient solder wettability have been pointed out in recent high-speed soldering. Therefore, when processing to form another metal layer on the surface of copper foil, the resulting layer has the required characteristics such as the appearance of the untreated surface of the copper foil, adhesion of resist inks, and solder wettability. It was hoped that it would not be a detriment, but rather something that would improve it.

[Purpose of the invention]

The present invention solves the above-mentioned problems, leaves no etching residue on the surface to be bonded, does not bleed between the bonded surface and the substrate f14m, and does not cause a decrease in adhesive strength with the resin substrate before and after heat treatment. The purpose of the present invention is to provide a copper foil for printed circuits that does not cause undercuts, does not discolor due to oxidation during lamination on the untreated surface, has excellent solder wettability, and also has rust prevention properties, and a method for producing the same. do.

[Summary of the invention]

The copper foil for printed circuits of the present invention has a metallic thin layer formed on the surface of the copper foil to be bonded to at least a resin substrate, the thin layer having a phosphorus-containing nickel layer,
The surface of the thin layer is characterized by being subjected to chromate treatment, and the manufacturing method includes forming a thin metallic layer having at least a phosphorus-containing nickel layer on the surface of the copper foil to be bonded to the resin substrate. The method is characterized in that the surface of the thin layer is then subjected to chromate treatment.

The present invention will be explained in detail below.

First, the copper foil to be used may be of any type as long as it is normally used as copper foil for printed circuits.
Examples include electrolytic copper foil, rolled copper foil, etc., and ultrathin copper foil with a temporary base may also be used. In order to improve the adhesion of the copper foil surface, for example, surface roughening treatment such as pickling and etching, or U.S. Pat. No. 3,220°89
No. 7, the electrodeposition roughening treatment described in U.S. Pat. No. 3,
It may be subjected to electrodeposition roughening treatment as described in No. 293,109 Mei a@ (・.

A thin metallic layer having a phosphorus-containing nickel layer is formed on the surface of the copper foil to be joined, and the surface of this thin layer, that is,
The surface that is directly bonded to the resin substrate is subjected to the chromate treatment described below.As for the O thin layer, ■the phosphorus-containing nickel layer itself;■for example, an alloy of zinc and phosphorus-containing nickel that coexists with zinc. Either a phosphorus-containing nickel layer, or a composite layer consisting of a phosphorus-containing nickel layer and a zinc layer. In the embodiment (2), the order of the phosphorus-containing nickel layer and the zinc layer is not particularly limited. In particular, a composite layer in which a zinc layer is laminated on a phosphorous-containing nickel layer has a strong effect (・
Therefore, it is useful.

This thin layer, especially the phosphorus-containing nickel layer, is an effective layer for suppressing the occurrence of bleeding and deterioration of adhesive strength on the joint surface, and for preventing undercuts, but if the surface is subjected to the chromate treatment described below, The effect is even more pronounced, and even if the resin substrate after the copper foil etching is heated in air, the phenomenon of discoloration does not occur.

Furthermore, by forming a zinc layer on top of this phosphorus-containing nickel layer to form a composite layer, and applying chromate treatment to the surface of this zinc layer, the adhesive strength between the copper foil and the resin substrate is further reduced during heating. This is preferable because it is significantly suppressed.

A thin layer as described above may be formed on the other surface of the copper foil, that is, the surface that will not be bonded to the resin substrate and will be the exposed surface of the printed circuit board; Alternatively, a zinc layer may be simply formed and the surface of the zinc layer may be subjected to chromate treatment.

The thickness of the above-mentioned phosphorus-containing nickel layer is 000
It is preferably 1 to 003 μm, more preferably 0.0
It is preferable that it is 02-0.015 micrometer.

If the thickness is less than 0.001 μm, the above-mentioned effects will not be exhibited, and if the thickness exceeds 0.03 μm, it is not only an unnecessary thickness from the viewpoint of characteristics, but also a decrease in the pure copper content of the copper foil. This is undesirable because it lowers the electrical conductivity, becomes industrially uneconomical when forming the layer, and unnecessarily lengthens the processing time when etching with an alkaline etching solution having a weak etching power.

Further, in the phosphorus-containing nickel layer, the phosphorus contained is a component that is effective in easily etching and removing the layer even when using a weak etching solution such as an alkaline etching solution, and suppresses a decrease in adhesive strength. This phosphorus component must be contained in a uniformly dispersed manner within the layer, and its content is preferably 0.02 to 25% by weight, particularly 0.05% by weight, based on the nickel component. Preferably, it is 10% by weight. Phosphorus content is 0.02 weight -
If the amount is less than 25% by weight, the effect that this layer can be easily and completely etched away is reduced, and if it exceeds 25% by weight, it is not only unnecessary in terms of properties but also uneconomical; This results in a disadvantage that the current density applied when forming the stone by electroplating method is significantly reduced.

This phosphorus-containing nickel layer is preferably formed on the surface of the copper foil to be joined by electroplating. Although it can be formed by a so-called chemical plating method, some of the layers formed in that case are difficult to remove by etching using an etching solution with weak etching power, such as an alkaline etching solution.

In addition to the nickel plating bath used in the electroplating method, for example, in addition to the one containing nickel sulfate as the main component, which is currently used industrially, a normal nickel plating solution using a chloride bath, a sulfamic acid bath, etc. sodium phosphate,
Disodium sulfite, sodium phosphotungstate.

Sodium metaphosphate, sodium phosphate.

A bath prepared by dissolving a phosphorus compound such as nickel phosphate or nickel phosphite is used.

Furthermore, the conditions during plating, such as bath temperature and '#L flow density, are not particularly limited and may be those of the usual nickel electroplating method.

In the copper foil of the present invention, the above-mentioned phosphorus-containing nickel layer may be subjected to the chromate treatment described below, but before that, a zinc layer is formed on the phosphorus-containing nickel layer, and the surface of this zinc layer is further subjected to chromate treatment. It is preferable to apply it.

This zinc layer may be formed by immersion in a zinc-containing solution or by applying a zinc electroplating method. When applying the electroplating method, either an alkaline bath or an acidic bath may be used as the electroplating bath, but a good zinc layer can be formed from an inexpensive, low-toxicity bath with a simple composition without additives. Therefore, an alkaline bath is preferable. Additives such as glutinous agents and brighteners may also be added. The bath temperature may normally be room temperature, but the bath may be heated. During electroplating, the phosphorus-containing nickel layer that has already been formed is used as a cathode. The current density at this time may be approximately α1 to 10 A/dm2. During this electric storm,
Since the total amount of current Vi to be used is not large, it is preferable to conduct current for several seconds at a relatively small current rather than for a short time. In any case, the current density is preferably about 0.1 to IA/dm2. In the case of simple immersion treatment, the immersion time is several seconds ~
The time period may be approximately several tens of seconds, and it may be selected appropriately depending on the relationship with the processing equipment and other processes.

In the case of the zinc layer formed on the surface of the phosphorus-containing nickel layer, the thickness is preferably 0.0006 to 0.015 μm. If it is less than 0.0006 μm, the effect of zinc layer formation will not be exhibited, and if it exceeds 0.015 μm,
The adhesive strength between the copper foil and the resin substrate may decrease when immersed in hydrochloric acid, and the surface of the resin substrate after copper foil etching may change color when heated in the air. The thickness of the zinc layer formed on the bonding surface is approximately 0.0005 to 0.002 μm in the case of a zinc layer formed on the surface of the copper foil that is not the bonded surface, that is, the exposed surface of a single-circuit printed board. It is preferable that If the thickness is less than 0.0005 μm, oxidative discoloration is likely to occur during lamination with a resin substrate. Also, 0.
If the thickness exceeds 0.002 μm, coloring due to zinc plating will be observed with the naked eye, resulting in poor appearance, and furthermore, solder wettability in the latter half of lamination will deteriorate, which is undesirable.

In the present invention, chromate treatment is applied to the outermost surface of the thin layer formed on the copper foil, regardless of whether it is the bonded surface or the untreated surface (the surface that constitutes the exposed surface of the printed circuit board). .

The chromate treatment may be performed by immersing the copper foil on which the thin layer has been formed in a chromate treatment solution or by electrolyzing the copper foil using the copper foil as a cathode. The latter method is particularly preferred for surfaces to be joined.

This cathodic electrolytic chromate treatment is not a method of electroplating ordinary metal chromium, black metal chromium, etc., but is published in "Metal Surface Technology" Vol. 23, No. 9, 1972, p. 525, and Vol. 15, No. 8, 1964. , page 303, is a method in which cathodic electrolysis is performed in a dilute aqueous solution of chromic acid or dichromic acid, and chromium oxide or water-use oxide is deposited on the surface to be treated. be.

The chromic acid treatment liquid used in the present invention is not only an aqueous solution of chromic acid alone but also an aqueous solution of an alkali metal salt or ammonium salt of chromic acid. The concentration of the treatment liquid is chromic acid (Cr
ys) is preferably 0.3 to 209/Q, particularly preferably 0.8 to 129/Q. If the concentration is less than 0.3 gA, the effect of the chromate treatment may not be sufficiently achieved and bleeding may occur during heating in air after removing the copper foil etching. Also, 209/
Exceeding Q will cause inconveniences in terms of handling, wastewater treatment, etc.

The treatment liquid may be acidic or alkaline, but
In the case of acidity, compared to the case of alkaline treatment, the surface film (chromate film) after treatment has superior corrosion resistance, improves bonding with resin substrates, and prevents discoloration when heated in air after copper foil etching is removed. Although the effect of suppressing this phenomenon can be obtained, on the other hand, disadvantageous problems such as a decrease in solder wettability and a slow etching rate also occur.

The current density during cathodic electrolytic treatment is 0.2 to 20 A/dm2, preferably 1 to 10 A7'dm2, and the treatment time is 1
-60 seconds, preferably 1-20 seconds. Further, the bath temperature may be room temperature or about 60C. During electrolytic treatment, it is preferable that the current be small; increasing the current value will form a stronger romate film and improve the rust prevention effect; however, on the other hand,
The film is too strong and stiff, requiring a long time to remove by etching, and also causing problems such as insufficient soldering unless a highly active solder flux is used.

[Embodiments of the invention]

Example 1 Nickel sulfate macrohydrate 240g/Q, nickel chloride hexahydrate 459711. Boric acid 309/1. A nickel plating bath containing sodium hypophosphite 59/Q was prepared.

The bath temperature was maintained at 50C. Using this electrolytic bath, a thickness of 35
2 at a current density IA/dm2 on the surface to be joined of electrolytic copper foil of μm.
Electroplating was performed for seconds. Note that at this time, no current was applied to the other surface (untreated surface) of the copper foil, so that the condition was equivalent to a simple immersion treatment.

A nickel layer was formed containing approximately 6 weights of phosphorus.

The appearance of this layer is a matte, grayish salmon flesh color, and the apparent amount of nickel electrodeposited per area is 0.007 μm thick.
The amount was equivalent to .

Next, the silver foil is washed with water, and zinc sulfate superhydrate 249/Q (hydroxide) is applied on top of this phosphorus-containing nickel layer.
A current density of 0.4 at room temperature using an electrolyte of 859/Q
Electroplating was performed at A/dm2 for 2 seconds. At the same time, a current density of 0.4 A/dm2 is applied to the other surface, that is, the untreated surface of the copper foil.
Electroplating was performed for 3 seconds.

The apparent amount of zinc electrodeposited per area on the phosphorus-containing nickel layer is equivalent to a thickness of 0.002 μm, and the amount of zinc electrodeposited on the other side of the silver foil is an amount equivalent to a thickness of 0.003 μm. there were. In addition, the overall appearance was only slightly grayer, and there was almost no change in 1.

Then, the whole was washed with water, and the whole was immersed in a chromic acid aqueous solution having a bath temperature of 55C239/Q. The surface to be joined of the copper foil is used as the cathode and the current density is 3A/dm! Electrolytic treatment was performed for 5 seconds. Further, the other surface K of the copper foil (the surface on which only the zinc layer is formed) was subjected to a state equivalent to a simple immersion treatment for about 6 seconds without passing any current.

No change in appearance was observed on both sides, and almost no dissolution of zinc was observed.

Example 2 Nickel plating bath is nickel sulfate hexahydrate 2849/Q
, boric acid 30g/Q, sodium hypophosphite 1g/Q
The same treatment as in Example 1 was carried out, except that the bath temperature was room temperature, and no treatment was performed to form a zinc layer on the side of the copper foil to be bonded. did. The phosphorus content in the phosphorus-containing nickel layer was approximately 1% by weight.

Example 3 Example 1 except that the temperature of the chromic acid aqueous solution was room temperature and the immersion time during zinc layer formation was 10 seconds.
The same treatment was applied.

Example 4 Nickel plating liquid nickel sulfate hexahydrate 284μ.

Boric acid 30 f/It, hypophosphite sodium Vcum 15
fil, the bath was adjusted to pi (2,5) by adding sulfuric acid, the bath temperature was room temperature, and a chromic acid aqueous solution of 1 l/l was used. The same treatment as in Example 1 was performed.

The phosphorus content in the phosphorus-containing nickel layer is approximately 7% by weight.
Met.

Example 5 The chromic acid aqueous solution was an aqueous solution of chromic anhydride 3/l and adjusted to pH 13 by adding caustic soda.
The same treatment as in Example 1 was carried out, except that the solution temperature was room temperature and the immersion time during formation of the zinc layer was 0 seconds.

Comparative Example 1 The same treatment as in Example 1 was carried out, except that the nickel plating solution did not contain sodium hypophosphite.

Comparative Example 2 The same treatment as in Example 1 was performed except that the zinc layer formation treatment and chromate treatment were not performed.

Comparative Example 3 The same treatment as in Example 1 was performed except that the phosphorus-containing nickel layer and the zinc layer were not formed.

Comparative Example 4 The same treatment as in Example 1 was performed except that the phosphorus-containing nickel layer was not formed and the chromate treatment was not performed.

Comparative Example 5 The same treatment as in Example 1 was carried out, except that the chromate treatment was not performed.

Comparative Example 6 The same treatment as in Example 1 was performed except that the phosphorus-containing nickel layer was not formed.

Comparative Example 7 The same treatment as in Example 1 was performed except that no zinc layer was formed.

The 13 types of copper foils mentioned above were measured for their etchability with an alkaline etching solution and their properties when laminated and bonded to a glass-epoxy substrate. The results are summarized in the table.

In addition, to determine whether or not etching is possible, stir a stock solution of an alkaline etching solution manufactured by JMF at 500 °C, immerse each copper foil in the solution, and observe whether 35 μm of copper foil is etched away in 10 minutes. I judged it.

〔Effect of the invention〕

From the results in the table, it is clear that after lamination on the glass-epoxy resin substrate, no brown stains were observed on the bonding surface between the copper foil and the substrate resin, and the peel resistance showed a sufficient value after lamination. Moreover, it takes 3 minutes at 300C.

Even after heating at 180C for 5 hours, heating in air at 150t:' for 1 day, or immersing in boiling water for 2' hours, the adhesive strength hardly deteriorates.

Also, when etching, use a ferric chloride solution.

Whether using a cupric chloride solution, an ammonium persulfate solution, or an alkaline etching solution, the portion of the foil to be etched is easily and completely removed, leaving a clear substrate resin surface. Furthermore, no undercut (C) intrusion of the etching solution into the copper foil-substrate resin bonding surface was observed. Furthermore, even in a hydrochloric acid test assuming a treatment process using a hydrochloric acid-containing solution, no corrosion by hydrochloric acid was observed on the copper foil-to-substrate resin bonding surface.

Furthermore, if the copper foil is etched, the brown a+17
'11 λshi; wide cut? - Oroku Noi J visiting Kaguchi? Even when a glass-epoxy resin substrate, which tends to generate brown stains when heated during sale, was used, no brown stains were observed on the surface of the wood substrate after heating in air.

Furthermore, when copper foil was laminated on a polyimide substrate, greenish brown stains that were conventionally seen on the substrate surface after removing the etched steel foil were not observed at all when the copper foil treated according to the present invention was used.

Furthermore, when laminated on a substrate using a polyester resin, no bleeding occurred on the substrate surface, and almost no deterioration of adhesive strength due to heating was observed.

Furthermore, the peeling resistance was improved when copper foil was laminated to a phenolic resin-based substrate using an adhesive, and in particular, the peeling resistance was significantly improved when copper foil was laminated to a phenolic resin-based flame-retardant substrate. .

The thickness of each thin layer formed on the surface of the copper foil is much smaller than the thickness of the conventional contact prevention layer between the same type of copper foil and resin substrate, and it exhibits better characteristics. In this case, the copper purity of the copper foil should be decreased/J? This also has the advantage of reducing the aerobic conductivity, which is particularly useful in this field of technology where the trend is toward decreasing the thickness of copper foil.

As described above, the copper foil of the present invention eliminates the surface quality defects of conventional copper foils, and has significant quality and economic effects such as improved quality, reduced defective rate, and elimination of the polishing process. and,
In the manufacturing method of the present invention, each thin layer can be formed continuously by running the material copper foil through a series of processing steps, and is suitable for industrial mass production.

Namely, a) In the production of foil that is electroplated with a phosphorus-containing nickel layer on both sides, the material copper foil is first run through a tank of nickel electroplating solution, and both sides are continuously plated with nickel.
The surface is then washed with water in a water tank, and then run through a zinc immersion tank or zinc electroplating tank to form a zinc layer, washed with water, and then run through a chromic acid treatment tank to become a cathode. It can be subjected to electrolytic chromate treatment and washed with water and dried. b) In the case of only one side, the material copper foil is passed through a tank of nickel electroplating liquid, and nickel plating is continuously applied to only substantially one side, and then in the next zinc electroplating tank, nickel plating is applied substantially only to the other side. After electroplating, this side is treated in the next chromate bath so that it is simply immersed with no current applied, and then electrolytic chromate treatment is applied by applying current only to the other nickel-plated side. Can be washed with water and dried.

As described above, the present invention has extremely great industrial value.

Claims (1)

[Claims] 1. A copper foil for printed circuits in which a metallic thin layer is formed on at least the surface of the copper foil to be bonded to a resin substrate, the thin layer having a phosphorus-containing nickel layer, and A copper foil for printed circuits that is characterized by a chromate treatment applied to the surface of the layer. 2. The copper foil for printed circuits according to claim 1, wherein the thin layer is a phosphorus-containing nickel layer whose surface has been subjected to chromate treatment. 3. The copper foil for printed circuits according to claim 1 or 2, wherein zinc coexists in the phosphorus-containing nickel layer. 4. The copper foil for printed circuits according to claim 1, wherein the thin layer is a composite layer of a phosphorus-containing nickel layer and a zinc layer, and the surface thereof is subjected to chromate treatment. 5. A chromate-treated nickel layer containing phosphorus is formed on the surface of the copper foil that is to be bonded to the resin substrate, and a zinc layer that is chromate-treated is formed on the surface of the silver foil that is not to be bonded to the resin substrate. A copper foil for printed circuits according to claim 1. 6. A phosphorous-containing nickel layer and a zinc layer are formed in this order on the surface of the copper foil to be bonded to the resin substrate, a zinc layer is formed on the surface of the copper foil that is not to be bonded to the resin substrate, and the surface of the lead layer on both plates is formed. The copper foil for printed circuits according to claim 1 or 4, wherein the copper foil is subjected to chromate treatment. L A copper foil for printed circuits, characterized in that a metallic thin layer having at least a phosphorus-containing nickel layer is formed on the surface of the copper foil to be bonded to at least a resin substrate, and then a chromate treatment is applied to the surface of the thin layer. Production method. & A thin metallic layer with a phosphorous-containing nickel layer is formed on the surface of the copper foil to be bonded to the resin substrate, a zinc layer is formed on the surface of the copper foil that is not bonded to the resin substrate, and a thin metal layer is formed on the surface of both thin layers. A method for producing a copper foil for printed circuits according to claim 7, wherein the copper foil is subjected to chromate treatment. 9. The printing according to claim 7 or 8, wherein the thin layer is any one of a phosphorus-containing nickel layer, a phosphorus-containing nickel layer containing zinc, or a composite layer of a phosphorus-containing nickel layer and a zinc layer. A method for manufacturing copper foil for circuits. 10. The method for producing a copper foil for circuit printing according to any one of claims 7 to 9, wherein the phosphorus-containing nickel layer is formed by electroplating.