JP2884935B2 - Nickel or nickel alloy etching solution, method using this etching solution, and method for manufacturing wiring board using this etching solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solution for etching away nickel or a nickel alloy and a method for using the same.

[0002]

2. Description of the Related Art With the development of electronic equipment, printed wiring boards are required to have a high wiring density, and miniaturization of wiring is one of the major technical problems. As a method of manufacturing such a printed wiring board, a copper-clad laminate in which copper foil is bonded to an insulating base material is used as a starting material, and a portion of the copper foil that is not a circuit conductor is removed by etching to form a circuit board. The active method, the additive method of forming a circuit by performing electroless plating on the surface of an insulating base material in the required circuit shape, and the partial additive method of forming a part of the circuit conductor such as the inner wall of a through hole by electroless plating are common. Is known.

[0003] Above all, the subtractive method has been used for a long time. In order to improve the wiring density, the thickness of the copper foil of the copper-clad laminate is usually reduced. The reason for this is that a so-called side etch occurs in which an etching resist is formed in the required circuit shape on the surface of the copper foil, and copper is corroded from the side surfaces of unnecessary circuit portions exposed from the etching resist with an etching solution, This is because the thicker the copper foil is, the more copper on the side surface is removed by the side etching, so that it becomes more difficult to form a fine circuit.

There is a solder peeling method using a solder as the etching resist of the subtract method. The solder is removed after the wiring is formed.
No. 8280 discloses a mixture of nitric acid and hydrogen peroxide containing iron ions and hydroxycarboxylic acid as main components. Further, as a copper foil for a circuit board with a resistor, a copper foil plated with nickel or a nickel-phosphorus alloy is disclosed in US Pat. No. 3,808,576.

Further, a first copper layer 1, an intermediate layer 2 made of a metal having high corrosion resistance to a solution corroding copper, and a second
A copper foil for a printed wiring board having a three-layer structure in which the intermediate layer 2 is sandwiched between the first copper layer 1 and the second copper layer 3 is also disclosed in JP-A-58-108785. It is known from U.S. Pat. Nickel and nickel-iron and nickel-tin alloys are used for the intermediate layer 2, and a method of stripping the same is a method of immersing in an acidic aqueous solution containing sulfuric acid and m-nitrobenzenesulfonic acid to perform electrolytic stripping. It is known from the gazette. Further, commercially available etching solutions for nickel or nickel alloy include alkaline Enstrip NP (trade name, manufactured by Meltex Corporation) and Metec SCB.
(McDermid, product name), Top Lip AZ
(Okuno Pharmaceutical Co., Ltd., trade name) and the like, and peeling method, acidic Melstrip N-950 (Meltex Co., trade name), Melstrip HN-841 (Meltex Co., trade name) A method of immersing in a solution such as) and stripping is known.

[0006]

By the way, the conventional rolled copper foil is difficult to handle when it is thin, has a low yield, and is too expensive to use for a printed wiring board. . In addition, a single electrodeposited copper foil having a thickness of less than 10 μm is not used for the same reason as a rolled foil.

[0007] Although a thin copper foil formed on a surface using an aluminum foil as a carrier is excellent in handleability, there is a problem that adhesion to an insulating substrate is low due to difficulty in roughening treatment. .

[0008] When using a composite metal foil having a three-layer structure on a printed wiring board, the first copper layer bonded to the insulating substrate, a second copper layer is selectively removed, to further remove the intermediate layer 2 Is used as a copper-clad laminate.
In order to remove nickel, nickel-iron and nickel-tin used in the above, it is necessary to immerse in an acidic aqueous solution containing sulfuric acid and m-nitrobenzenesulfonic acid disclosed in the gazette and perform electrolytic stripping, which is troublesome. .

Further, when a liquid Enstrip NP (trade name, manufactured by Meltex Co., Ltd.) which is chemically removed is used, an altered layer called smut, which is an undissolved residue of the intermediate layer, is formed. Is difficult to remove.
When Metec SCB (trade name, manufactured by McDermid) is used, the copper layer of the substrate may be dissolved, and if the copper layer is to be completely left, a part of the nickel alloy remains.
In the former case, the copper layer becomes discontinuous, and in the latter case, the adhesiveness decreases. Furthermore, when Top Lip AZ (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.) was used, the dissolution rate was extremely slow and not practical. Melstrip N-950
(Mertex Co., Ltd., trade name) and Melstrip HN-
When 841 (trade name, manufactured by Meltex Co., Ltd.) was used, there was a disadvantage that a black film was formed when the nickel-phosphorus alloy was peeled off, and copper was excessively etched.

It is an object of the present invention to provide an etching solution for easily and selectively removing nickel or a nickel alloy without excessively dissolving a copper substrate, and a method for using the same.

[0011]

The etching solution of the present invention comprises an acid solution containing nitric acid and hydrogen peroxide as main components, an organic acid containing a carboxyl group as an additive, and -NH- or = as a ring member. And a heterocyclic compound containing a nitrogen atom in the form of N-.

The main components of the etching solution used in the present invention are:
It is nitric acid and hydrogen peroxide, and the dissolution of nickel is considered to proceed by the following reaction. 3Ni + 2HNO ₃ → 3NiO + H ₂ O + 2NO ↑ Ni + H ₂ O ₂ → NiO + H ₂ O NiO + 2HNO ₃ → Ni (NO ₃ ) ₂ + H ₂ O Copper is also considered to react and dissolve in the same manner. 3Cu + 2HNO ₃ → 3CuO + H ₂ O + 2NO ↑ Cu + H ₂ O ₂ → CuO + H ₂ O CuO + 2HNO ₃ → Cu (NO ₃ ) ₂ + H ₂ O

Here, nitric acid is used to maintain the acidity required for stripping nickel, and the amount of nitric acid is 100 to 100%.
300 g / l. The concentration of nitric acid is 100-300 g /
The reason for setting l is that if the amount is less than 100 g / l, the peeling action is weak, and if it is more than 300 g / l, the acidity is too strong and the copper layer may be excessively etched when the substrate is used.

In addition, hydrogen peroxide acts as an oxidizing agent,
Nickel is oxidized to promote the peeling of nickel, and its use amount is preferably 5 to 20 ml / l. The reason is that if it is less than 5 ml / l, the effect as an oxidizing agent is not sufficient, and if it exceeds 20 ml / l, the oxidizing action is too strong and the copper layer of the substrate may be excessively etched.

The organic acid having a carboxyl group as the first additive component in the present invention has an acid strength Ka of 10%.
Those having ^-3 to 10 ^-5 are preferable, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, succinic acid, glutaric acid, lactic acid, malic acid, citric acid, tartaric acid and derivatives thereof. Such an organic acid is preferably used in an amount effective to sufficiently suppress the dissolution of the copper substrate when the nickel alloy layer is peeled off. The amount of the organic acid is preferably 10 to 200 g / l in the stripping solution. The concentration of organic acid is 10
The reason for setting it to 200 g / l is that if it is less than 10 g / l, the effect of inhibiting corrosion of the copper layer of the substrate is small, and if it exceeds 200 g / l, no further effect can be expected and it is practically uneconomical. . Therefore, the concentration of the organic acid is 10-20.
0 g / l is preferred.

As the second additive component of the present invention, a heterocyclic compound containing a nitrogen atom in the form of -NH- or = N- as a ring member, which is soluble in an acidic solution And triazole and derivatives thereof. Addition amount of triazole or its derivative is 1 to 10 g
/ L is preferred. The reason why the addition amount of triazole or a derivative thereof is set to 1 to 10 g / l is that if it is less than 1 g / l, the effect of inhibiting corrosion of the copper layer of the substrate is small, and if it exceeds 10 g / l, a further effect is expected. This is because it is practically uneconomical. Therefore, the addition amount of triazole or a derivative thereof is preferably 1 to 10 g / l.

The peeling method in the present invention may be any method as long as the nickel alloy layer can be peeled off. For example, a spraying method or the like may be used in addition to a generally used immersion method. Can be.

The method of using an etching solution according to the second invention of the present invention is characterized in that the above-mentioned etching solution is brought into contact with nickel or a nickel alloy formed on the surface of a copper substrate to form a nickel or nickel alloy. This is a method of etching and removing only. Instead of the copper substrate, a copper-clad laminate in which a copper foil is bonded to the surface of an insulating base material and the copper foil surface of which is formed with nickel or a nickel alloy can also be used.

As a third invention of the present invention, a wiring board can be manufactured by using such an etching solution and including the following steps. A. Step of forming a plating resist on the copper foil surface of a copper-clad laminate in which a copper foil is bonded to an insulating base material surface B. B. A step of plating nickel or a nickel alloy on the exposed portions, removing the plating resist, and etching and removing only the exposed copper foil. The acid solution containing nitric acid and hydrogen peroxide as main components described above, an organic acid containing a carboxyl group as an additive, and a nitrogen atom in the form of -NH- or = N- as a ring member. Of removing only nickel or a nickel alloy by contact with a solution containing a heterocyclic compound (hereinafter referred to as an etching solution of the present invention).

Further, the method may include the following steps. A. B. Steps of making a hole in a copper-clad laminate obtained by laminating a copper foil on an insulating substrate surface, performing electroless copper plating on the inner wall of the hole and the copper foil surface, and forming a plating resist on the copper surface. B. A step of plating nickel or a nickel alloy on the exposed portions, removing the plating resist, and etching and removing only the exposed copper foil. Step of etching and removing only nickel or a nickel alloy by contacting with the etching solution of the present invention

Further, a multilayer wiring board can be manufactured by performing the following steps. A. B. Steps of making a hole in a laminate obtained by laminating a prepreg and a copper foil on the surface of the inner circuit board, performing electroless copper plating on the inner wall of the hole and the surface of the copper foil, and forming a plating resist on the copper surface. B. A step of plating nickel or a nickel alloy on the exposed portions, removing the plating resist, and etching and removing only the exposed copper foil. Step of etching and removing only nickel or a nickel alloy by contacting with the etching solution of the present invention

When three composite metal layers are used, a wiring board can be manufactured by including the following steps. A. A copper layer of 1 to 15 μm and 0.04 to
B. Step of stacking a metal foil having a 1.5 μm nickel or nickel alloy layer so that the copper layer is in contact with the insulating base material, and applying heat and pressure to laminate and integrate. B. Step of contacting the laminate with the etching solution of the present invention to remove only nickel or nickel alloy by etching. Forming a hole in the laminate, performing electroless plating on the inner wall of the hole and the entire surface of the exposed copper surface, and further performing electrolytic plating, if necessary, to secure a required thickness as a circuit conductor D. Form the etching resist into the required circuit shape,
Step of etching away exposed copper

The following can also be performed. A. A copper layer of 1 to 15 μm and 0.04 to
B. Step of stacking a metal foil having a 1.5 μm nickel or nickel alloy layer so that the copper layer is in contact with the insulating base material, and applying heat and pressure to laminate and integrate. B. making a hole in the laminate and contacting it with the etching solution of the present invention to remove only nickel or nickel alloy by etching; A step of performing electroless plating on the inner wall of the hole of the laminate and the entire surface of the exposed copper surface and, if necessary, further performing electrolytic plating to secure a required thickness as a circuit conductor. Form the etching resist into the required circuit shape,
Step of etching away exposed copper

Further, it can be manufactured as follows. A. The insulating substrate surface, 15 a first copper layer and 0 [mu] m.
A layer of nickel or a nickel alloy of from 0.4 to 1.5 μm ;
B. Step of stacking a metal foil having a second copper layer so that the first copper layer is in contact with the insulating base material, and applying heat and pressure to laminate and integrate. B. Step of etching and removing only the second copper layer of the laminate. D. Step of contacting the laminate with the etching solution of the present invention to remove only nickel or nickel alloy by etching. D. Making a hole in the laminate, performing electroless plating on the inner wall of the hole and the entire surface of the exposed copper surface, and if necessary, further performing electrolytic plating to secure a necessary thickness as a circuit conductor. Form the etching resist into the required circuit shape,
Step of etching away exposed copper

Further, it can be manufactured as follows. A. The insulating substrate surface, 15 a first copper layer and 0 [mu] m.
A layer of nickel or a nickel alloy of from 0.4 to 1.5 μm ;
B. Step of stacking a metal foil having a second copper layer so that the first copper layer is in contact with the insulating base material, and applying heat and pressure to laminate and integrate. B. Step of etching and removing only the second copper layer of the laminate. D. Step of making a hole in the laminate and contacting it with the etching solution of the present invention to remove only nickel or nickel alloy by etching. E. a step of performing electroless plating on the inner wall of the hole of the laminate and the entire surface of the exposed copper surface and, if necessary, further performing electrolytic plating to secure a required thickness as a circuit conductor; Form the etching resist into the required circuit shape,
Step of etching away exposed copper

Further, in order to obtain a multilayer wiring board, it can be manufactured as follows. A. A metal foil having a prepreg, a first copper layer of 1 to 15 μm, a layer of nickel or a nickel alloy of 0.04 to 1.5 μm, and a second copper layer on the surface of the inner layer circuit board,
B. A process in which the copper layers are stacked so that they come into contact with the prepreg, and are heated and pressurized to integrate and laminate. B. Step of etching and removing only the second copper layer of the laminate. D. Step of making a hole in the laminate and contacting it with the etching solution of the present invention to remove only nickel or nickel alloy by etching. E. a step of performing electroless plating on the inner wall of the hole of the laminate and the entire surface of the exposed copper surface and, if necessary, further performing electrolytic plating to secure a required thickness as a circuit conductor; Form the etching resist into the required circuit shape,
Step of Etching and Removing Exposed Copper At this time, the step of making a hole in the laminate may be before etching in step B.

[0027]

The stripping solution used in the present invention contains a specific amount of nitric acid and hydrogen peroxide as main components, and as a copper corrosion inhibitor, an organic acid containing a carboxyl group, in particular, the strength of the acid is Ka: 10 ^-3 to ^10-3 .
Excessive dissolution of the copper substrate by adding an organic acid containing a carboxyl group of 10 ^-5 and a heterocyclic compound containing a nitrogen atom in the form of -NH- or = N- as a ring member. Can be prevented, and the nickel alloy can be peeled off.

[0028]

EXAMPLES The present invention will be described below in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 Nitric acid 200 g / l hydrogen peroxide 10 ml / l acetic acid ... 100 g / l Benzotriazole ... 5 g / l

Example 2 Nitric acid 300 g / l Hydrogen peroxide 10 ml / l propionic acid・ ・ ・ ・ ・ ・ ・ ・ ・ 100g / l Benzotriazole ・ ・ ・ 5g / l

Example 3 Nitric acid 200 g / l hydrogen peroxide 20 ml / l glutaric acid ·········· 100 g / l 5-methylbenzoisotriazole ······ 5 g / l

Example 4 Nitric acid 200 g / l hydrogen peroxide 10 ml / l propionic acid ... 100 g / l 1-hydroxybenzotriazole ... 10 g / l

Using the aqueous solution having the composition described in each of the above examples, a peeling test of the nickel and nickel-phosphorus layers was performed. In this test, nickel, nickel - as a sample having a phosphorus alloy layer, on a copper of 20 × 60 mm epoxy copper-clad laminate, Tsu nickel Rume below approximately 0.2μm in nickel Rume Kki solution and conditions (Test results
Are shown in Table 1. A), two on a resin substrate nickel - shows that the phosphorus plating was performed about 0.2μm (test results in Table 2
You. ) , Each having a copper wiring formed thereon. In addition, the film thickness of nickel and the nickel-phosphorus alloy was measured using Seiko Denshi Co., Ltd. fluorescent X-ray film thickness meter SFT-8000.

(Composition of nickel plating solution) Nickel sulfate: 240 g / l Nickel chloride: 45 g / l Boric acid: ······· 30 g / l (plating conditions) Temperature ········ 35 ° C Current density ···· ······· 1.5 A / dm ² hours · · · · · 4 minutes

(Composition of nickel-phosphorus plating solution) Nickel sulfate: 240 g / l Nickel chloride: 45 g / l Boric acid 30 g / l phosphorous acid 5 g / l (plating conditions) Temperature 35 ° C Current density 1.5A / dm ² hours ... 4 minutes

This sample was immersed in 100 ml of the aqueous solution of each example at 50 ° C., and the peelability of the nickel-phosphorus alloy and the decrease in the thickness of the base copper foil of each sample were measured. The film thickness was measured using the fluorescent X-ray film thickness meter. For comparison, an aqueous solution having the following composition was prepared and tested in the same manner as described above.

Comparative Example 1 Nitric acid 200 g / l Hydrogen peroxide 10 ml / l

Comparative Example 2 Nitric acid 200 g / l Hydrogen peroxide 10 ml / l Trichloroacetic acid 100 g / l Benzotriazole 5 g / l

Comparative Example 3 Merstrip N-950A 500 ml / l Merstrip N-950B 100 ml / l hydrogen peroxide water 100 ml / l

The obtained results are shown in Tables 1 and 2 below. In Table 1, 〇 indicates that there is no remaining Ni, x indicates that there is remaining Ni, and in Table 2, 〇 indicates that there is no Ni-P remaining, × _* ¹ indicates that Ni remaining
-P remaining, × _* ² indicates that a black film was formed.

[0041]

[Table 1]

[0042]

[Table 2]

Example 5 A plating resist was applied to the surface of a copper foil of MCL-E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.) which is a copper-clad laminate in which a copper foil was bonded to the surface of an epoxy resin insulating base material. Forming
The exposed portions were subjected to nickel plating shown in Examples 1 to 4, and after removing the plating resist, only the exposed copper foil was removed by etching with an alkali etchant.
By contacting with the etching solution used for (1), only nickel was removed by etching to obtain a single-sided circuit board.

Example 6 A hole was made by drilling MCL-E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.) which is a copper-clad laminate in which copper foil was bonded to the surface of an epoxy resin insulating base material, and the inner wall of the hole was formed. And electroless copper plating on the copper foil surface, forming a plating resist on the copper surface, and performing nickel plating shown in Examples 1 to 4,
After removing the plating resist, only the exposed copper foil was removed by etching with an alkali etchant, and the exposed copper foil was brought into contact with the etching solution of Example 2 to remove only nickel by etching to obtain a double-sided circuit board.

Example 7 A prepreg was prepared by processing an inner layer circuit of MCL-E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.) which is a copper-clad laminate in which a copper foil was bonded to the surface of an epoxy resin insulating base material. E
-67 (manufactured by Hitachi Chemical Co., Ltd., trade name) and 35μ
A hole is made in a laminated plate on which a copper foil having a thickness of m is bonded, electroless copper plating is performed on the inner wall of the hole and the surface of the copper foil, a plating resist is formed on the copper surface, and the exposed portions are exposed to Examples 1-4. After the nickel-phosphorus alloy plating shown in FIG. 1 was performed and the plating resist was removed, only the exposed copper foil was removed by etching and brought into contact with the etching solution of Example 2,
Only the nickel-phosphorus alloy was removed by etching to obtain a multilayer wiring board.

Example 8 A copper layer having a thickness of 1 to 15 μm and 0.04 μm was formed on the surface of an insulating substrate prepreg E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.).
A metal foil having a nickel layer of about 1.5 μm is laminated so that the copper layer is in contact with the insulating base material, and is laminated by heating and pressing, and the laminated plate is brought into contact with the etching solution of Example 3 Then, only nickel is removed by etching, a hole is made in the laminate, electroless plating is performed on the inner wall of the hole and the entire surface of the exposed copper surface, and electrolytic plating is performed to secure a required thickness of 35 μm as a circuit conductor, and etching is performed. A resist was formed in a required circuit shape, and the exposed copper was removed by etching to obtain a double-sided circuit board.

Example 9 A copper layer of 1 to 15 μm and 0.04 μm on the surface of an insulating substrate prepreg E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.)
A metal foil having a nickel-phosphorus alloy layer of about 1.5 μm is overlaid so that the copper layer is in contact with the insulating base material, and is laminated under heat and pressure to form a laminate. By contacting the solution, only the nickel-phosphorus alloy was removed by etching, and electroless plating was performed to a thickness of 20 μm on the entire inner wall of the hole of the laminate and the exposed copper surface,
An etching resist was formed in a required circuit shape, and the exposed copper was removed by etching to obtain a double-sided circuit board.

Example 10 A first copper layer of 1 to 15 μm was formed on the surface of an insulating base material prepreg E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.).
A nickel-phosphorus alloy layer of 0.04 to 1.5 μm and a metal foil having a second copper layer are stacked so that the first copper layer is in contact with the insulating base material, and heated and pressurized to be integrally laminated; Only the second copper layer was removed by etching with an alkali etchant, and only the nickel-phosphorus alloy was removed by contact with the etching solution of Example 1, a hole was formed in the laminate, and the inner wall of the hole and the exposed copper were removed. Electroless plating is performed on the entire surface, and then electrolytic plating is performed to secure a required thickness of 35 μm as a circuit conductor, an etching resist is formed in a required circuit shape, exposed copper is removed by etching, and wiring is performed. Board.

Example 11 A first copper layer of 1 to 15 μm was coated on the surface of an insulating base material prepreg E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.).
A nickel-phosphorus alloy layer of 0.04 to 1.5 μm and a metal foil having a second copper layer are stacked so that the first copper layer is in contact with the insulating base material, and heated and pressurized to be integrally laminated; Only the second copper layer is removed by etching with an alkali etchant, a hole is formed in the laminate, and the laminate is brought into contact with the etching solution of the present invention, whereby only the nickel-phosphorus alloy is removed by etching. Electroless plating is performed on the entire surface of the exposed copper, and further electrolytic plating is performed to secure a required thickness of 35 μm as a circuit conductor, an etching resist is formed in a required circuit shape, and the exposed copper is removed by etching. To make a wiring board.

An MCL-E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a copper-clad laminate obtained by laminating a copper foil on the surface of an epoxy resin insulating substrate, was processed into an inner layer circuit.
Prepreg E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.), a first copper layer of 1 to 15 μm, and 0.04 to 1.5
μm nickel-phosphorus alloy layer and a metal foil having a second copper layer are stacked so that the first copper layer is in contact with the prepreg, laminated under heat and pressure, and only the second copper layer is treated with alkali. The laminate was etched away with an etchant, holes were made in the laminate, and the laminate was brought into contact with the etching solution of Example 2 to remove only the nickel-phosphorus alloy by etching. Electroplating was performed, and further electrolytic plating was performed to secure a required thickness of 35 μm as a circuit conductor, an etching resist was formed in a required circuit shape, and exposed copper was removed by etching to obtain a multilayer wiring board. .

An MCL-E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a copper-clad laminate obtained by laminating a copper foil on the surface of an epoxy resin insulating base material, is processed into an inner layer circuit.
Prepreg E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.), a first copper layer of 1 to 15 μm, and 0.04 to 1.5
μm nickel-phosphorus alloy layer and a metal foil having a second copper layer are stacked so that the first copper layer is in contact with the prepreg, laminated under heat and pressure, and a hole is formed in the laminate. Only the second copper layer was removed by etching with an alkali etchant, and the nickel-phosphorus alloy alone was removed by contact with the etching solution of Example 2, leaving no residue on the inner wall of the hole of the laminate and the entire exposed copper surface. Electroplating was performed, and further electrolytic plating was performed to secure a required thickness of 35 μm as a circuit conductor, an etching resist was formed in a required circuit shape, and exposed copper was removed by etching to obtain a multilayer wiring board. .

[0052]

According to the present invention, the nickel or nickel alloy layer can be easily peeled off without excessively dissolving the copper substrate by wet treatment excellent in mass productivity.

────────────────────────────────────────────────── (5) References JP-A-57-134563 (JP, A) JP-A-58-58280 (JP, A) JP-A-58-108785 (JP, A) US Patent 3,808,576 (US , A) (58) Field surveyed (Int.Cl. ⁶ , DB name) C23F 1/16-1/30 H05K 3/06

Claims (14)

(57) [Claims] An acidic solution containing nitric acid and hydrogen peroxide as main components, an organic acid containing a carboxyl group as an additive, and a nitrogen atom in the form of -NH- or = N- as a ring member. An etching solution for nickel and / or a nickel alloy, comprising: a heterocyclic compound. 2. The nickel according to claim 1, wherein the heterocyclic compound containing a nitrogen atom in the form of —NH— or ＮN— as a ring member is triazole or a derivative thereof. Or a nickel alloy etchant. 3. The content of nitric acid is 10 to 30% by weight, 30% by weight.
It is characterized in that the content of aqueous hydrogen peroxide is 5 to 20 ml / l, the content of organic acid containing a carboxyl group is 1 to 20% by weight, and the content of triazole or its derivative is 0.1 to 1% by weight. The etching solution for nickel or nickel alloy according to claim 1. 4. An acid solution containing nitric acid and hydrogen peroxide as main components, an organic acid containing a carboxyl group as an additive, and a nitrogen atom in the form of -NH- or = N- as a ring member. A solution containing a heterocyclic compound and nickel or a nickel alloy formed on the surface of a copper substrate by contact with the solution to remove only the nickel or nickel alloy by etching. 5. An acidic solution containing nitric acid and hydrogen peroxide as main components, an organic acid containing a carboxyl group as an additive and a nitrogen atom in the form of -NH- or = N- as a ring member. By contacting a liquid containing a heterocyclic compound and a solution containing nickel or a nickel alloy on the copper foil surface of a copper-clad laminate obtained by laminating a copper foil on an insulating base material, by contacting the nickel or nickel alloy A method to remove only by etching. 6. The heterocyclic compound containing a nitrogen atom in the form of —NH— or ＮN— as a ring member is triazole or a derivative thereof. Of removing only nickel or nickel alloy by etching. 7. Nitric acid content of 10 to 30% by weight, 30%
It is characterized in that the content of aqueous hydrogen peroxide is 5 to 20 ml / l, the content of organic acid containing a carboxyl group is 1 to 20% by weight, and the content of triazole or its derivative is 0.1 to 1% by weight. The method for etching and removing only nickel or a nickel alloy according to claim 6. 8. A method for manufacturing a wiring board, comprising the following steps. A. Step of forming a plating resist on the copper foil surface of a copper-clad laminate in which a copper foil is bonded to an insulating base material surface B. B. A step of plating nickel or a nickel alloy on the exposed portions, removing the plating resist, and etching and removing only the exposed copper foil. A heterocyclic compound containing an organic acid containing a carboxyl group as an additive and a nitrogen atom as a ring member in the form of -NH- or = N- in an acidic solution containing nitric acid and hydrogen peroxide as main components. A step of etching and removing only nickel or a nickel alloy by contact with a solution containing 9. A method for manufacturing a wiring board, comprising the following steps. A. B. Steps of making a hole in a copper-clad laminate obtained by laminating a copper foil on an insulating substrate surface, performing electroless copper plating on the inner wall of the hole and the copper foil surface, and forming a plating resist on the copper surface. B. A step of plating nickel or a nickel alloy on the exposed portions, removing the plating resist, and etching and removing only the exposed copper foil. A heterocyclic compound containing an organic acid containing a carboxyl group as an additive and a nitrogen atom as a ring member in the form of -NH- or = N- in an acidic solution containing nitric acid and hydrogen peroxide as main components. A step of etching and removing only nickel or a nickel alloy by contact with a solution containing 10. A method for manufacturing a wiring board, comprising the following steps. A. B. Steps of making a hole in a laminate obtained by laminating a prepreg and a copper foil on the surface of the inner circuit board, performing electroless copper plating on the inner wall of the hole and the surface of the copper foil, and forming a plating resist on the copper surface. B. A step of plating nickel or a nickel alloy on the exposed portions, removing the plating resist, and etching and removing only the exposed copper foil. A heterocyclic compound containing an organic acid containing a carboxyl group as an additive and a nitrogen atom as a ring member in the form of -NH- or = N- in an acidic solution containing nitric acid and hydrogen peroxide as main components. A step of etching and removing only nickel or a nickel alloy by contact with a solution containing 11. A method for manufacturing a wiring board, comprising the following steps. A. A copper layer of 1 to 15 μm and 0.04 to
B. Step of stacking a metal foil having a 1.5 μm nickel or nickel alloy layer so that the copper layer is in contact with the insulating base material, and applying heat and pressure to laminate and integrate. The laminated plate is prepared by adding an organic acid containing a carboxyl group as an additive and a nitrogen atom in the form of -NH- or = N- as a ring member to an acidic solution containing nitric acid and hydrogen peroxide as main components. B. a step of etching and removing only nickel or a nickel alloy by contact with a liquid containing a heterocyclic compound. Forming a hole in the laminate, performing electroless plating on the inner wall of the hole and the entire surface of the exposed copper surface, and further performing electrolytic plating, if necessary, to secure a required thickness as a circuit conductor D. Form the etching resist into the required circuit shape,
Step of etching away exposed copper 12. A method for manufacturing a wiring board, comprising the following steps. A. A copper layer of 1 to 15 μm and 0.04 to
B. Step of stacking a metal foil having a 1.5 μm nickel or nickel alloy layer so that the copper layer is in contact with the insulating base material, and applying heat and pressure to laminate and integrate. A hole is formed in the laminate, and an organic solution containing a carboxyl group as an additive and a nitrogen atom in the form of -NH- or = N- as a ring member are added to an acidic solution containing nitric acid and hydrogen peroxide as main components. B. Step of etching and removing only nickel or a nickel alloy by contact with a liquid containing a heterocyclic compound contained therein. A step of performing electroless plating on the inner wall of the hole of the laminate and the entire surface of the exposed copper surface and, if necessary, further performing electrolytic plating to secure a required thickness as a circuit conductor. Form the etching resist into the required circuit shape,
Step of etching away exposed copper 13. A method for manufacturing a wiring board, comprising the following steps. A. The insulating substrate surface, 15 a first copper layer and 0 [mu] m.
A layer of nickel or a nickel alloy of from 0.4 to 1.5 μm ;
B. Step of stacking a metal foil having a second copper layer so that the first copper layer is in contact with the insulating base material, and applying heat and pressure to laminate and integrate. B. Step of etching and removing only the second copper layer of the laminate. The laminated plate is prepared by adding an organic acid containing a carboxyl group as an additive and a nitrogen atom in the form of -NH- or = N- as a ring member to an acidic solution containing nitric acid and hydrogen peroxide as main components. D. a step of etching and removing only nickel or a nickel alloy by contact with a liquid containing a heterocyclic compound. D. Making a hole in the laminate, performing electroless plating on the inner wall of the hole and the entire surface of the exposed copper surface, and if necessary, further performing electrolytic plating to secure a necessary thickness as a circuit conductor. Form the etching resist into the required circuit shape,
Step of etching away exposed copper 14. A method for manufacturing a wiring board, comprising the following steps. A. The insulating substrate surface, 15 a first copper layer and 0 [mu] m.
A layer of nickel or a nickel alloy of from 0.4 to 1.5 μm ;
B. Step of stacking a metal foil having a second copper layer so that the first copper layer is in contact with the insulating base material, and applying heat and pressure to laminate and integrate. B. Step of etching and removing only the second copper layer of the laminate. A hole is formed in the laminate, and an organic solution containing a carboxyl group as an additive and a nitrogen atom in the form of -NH- or = N- as a ring member are added to an acidic solution containing nitric acid and hydrogen peroxide as main components. A step of etching and removing only nickel or a nickel alloy by contact with a liquid containing a heterocyclic compound contained therein. E. a step of performing electroless plating on the inner wall of the hole of the laminate and the entire surface of the exposed copper surface and, if necessary, further performing electrolytic plating to secure a required thickness as a circuit conductor; Form the etching resist into the required circuit shape,
Step of etching away exposed copper