KR20200046001A - Liquid composition for etching and preparing method of multilayer printed wiring board by using the same - Google Patents

Abstract

Provided are a liquid composition for etching that efficiently removes chemical copper plating, which is a seed layer in a semi-additive construction method in manufacturing a multilayer printed wiring board, and simultaneously performs a dense roughening treatment on a wiring surface, and a method of manufacturing a multilayer printed wiring board using the same. According to the present invention, the liquid composition for etching used in the manufacture of the multilayer printed wiring board comprises 0.2 to 5 wt% hydrogen peroxide, 0.5 to 8 wt% sulfuric acid, 0.3 to 3 ppm halogen ion, and 0.003 to 0.3 wt% tetrazole compound.

Description

Liquid composition for etching and manufacturing method of multilayer printed wiring board using the same {LIQUID COMPOSITION FOR ETCHING AND PREPARING METHOD OF MULTILAYER PRINTED WIRING BOARD BY USING THE SAME}

[Related applications]

This application is an application involving claims of priority to the Paris Convention based on Japanese Patent Application No. 2012-147081. Therefore, this application includes all matters disclosed in this Japanese patent application.

Field of invention

The present invention relates to a liquid composition for etching and a method for manufacturing a multilayer printed wiring board using the same, and more particularly, a liquid composition for etching and a substrate for processing used in the production of a multilayer printed wiring board used in electric, electronic devices, etc. It relates to a method of manufacturing a multilayer printed wiring board comprising etching copper chemical plating and electrical copper plating to form copper wiring.

In recent years, miniaturization and multilayering of copper wiring has been strongly required in printed wiring boards in accordance with miniaturization, weight reduction, and high functionality of electronic devices.

One of the manufacturing methods for forming fine wiring is a semi-additive construction method. In this wiring forming method, a metal layer called a seed layer is formed on an insulating material (generally using chemical copper plating as a metal layer), a plating resist layer is formed on the surface, and then exposed and developed to develop a resist pattern. To form. Thereafter, the electrolytic copper plating treatment is performed, the resist is peeled off, and the seed layer is etched away to form copper wiring.

Then, in order to multi-layer, an interlayer insulating material is laminated on the copper wiring formed on the substrate to form wiring in the same manner as the substrate. In the case of the wiring of the outermost layer, a resin called solder resist or coverlay is coated on the copper wiring to protect the copper wiring other than the external connection terminal.

In order to improve the adhesion between the copper wiring and the resin such as interlayer insulating material or solder resist, the copper surface is harmonized through mechanical treatment such as buff polishing and scrub polishing, or chemical polishing treatment such as a roughening agent. .

Conventionally, the etching removal treatment (generally referred to as a flash etching treatment) of the chemical copper plating which is a seed layer in the semi-additive construction method and the surface treatment of copper wiring for multilayering are performed in each process (pharmaceutical).

As a liquid composition for etching chemical copper plating, a liquid composition for etching containing hydrogen peroxide, sulfuric acid, azoles, and bromine ions (Japanese Patent Publication No. 2006-13340: Patent Document 1), sulfuric acid, hydrogen peroxide, benzotriazole derivatives Etching agent characterized in that it contains (Japanese Patent Publication No. 2009-149971 Publication: Patent Document 2), hydrogen peroxide, sulfuric acid as the main component, etchant liquid composition characterized in that it comprises an azole as an additive (Japanese Patent Publication 2006 -9122 publication: Patent document 3) and the like are disclosed. In the case of a conventional liquid composition for chemical copper plating etching, since the wiring surface cannot be matched, adhesion to a resin such as an interlayer insulating material is not good, and chemical copper plating removal and wiring conditioning cannot be performed simultaneously. .

Further, as a copper wiring conditioner, an oxo acid, peroxide, azoles, and a liquid composition for etching containing 50 mg / L or less of a halide (Japanese Patent Publication No. 2000-64067: Patent Document 4), sulfuric acid, hydrogen peroxide, and phenyl Liquid composition for etching containing tetrazoles, nitrobenzotriazoles, chloride ions (Japanese Patent Laid-Open No. 2009-191357: Patent Document 5), microetching agent containing sulfuric acid, hydrogen peroxide, phenyltetrazole, and chlorine ion source ( Japanese Patent Laid-Open No. 2002-47583: Patent Literature 6), sulfuric acid, hydrogen peroxide, 5-aminotetrazole, tetrazole compounds other than 5-aminotetrazole, surface conditioning agent containing phosphonic acid-based chelating agent (Japanese Patent Laid-Open) 2009-19270 Publication: Patent Document 7), sulfuric acid, peroxide, tetrazole compound, liquid composition for microetching containing a metal ion having a potential noble than copper (Japanese Patent Publication No. 2004-3020: Patent 8), a surface-conditioning treatment liquid containing hydrogen peroxide, sulfuric acid, benzotriazoles, and chloride ions (Japanese Patent Laid-Open No. 2005-213526: Patent Literature 9), a main azole and an oxidizing agent of inorganic acid and copper Micro etching agents (Japanese Patent Laid-Open No. 2000-282265 Publication: Patent Literature 10) made of an aqueous solution containing a crude agent composed of a flow agent and an etching inhibitor are disclosed. In the conventional solution, since the dissolution rate of chemical copper plating is not greater than that of electric copper plating, it is difficult to form microwiring by the semi-additive method.

In a conventional roughening agent (etching agent), the copper surface is etched several µm to roughen the copper surface to secure adhesion between copper and a resin such as an interlayer insulating material with a physical (anchor) effect. However, in recent years, the copper wiring width has been refined to a minimum of 30 to 50 µm to 15 µm or less to the minimum (smallest), and the reduction of the copper wiring width is increased in the conventional roughening agent (etching agent). Because of the loss of wiring and the roughness of the surface of the copper wiring is large (the unevenness in the depth direction is large), the problem of disconnection and transmission loss is concerned.

DETAILED DESCRIPTION OF THE INVENTION The present invention efficiently removes chemical copper plating, which is a seed layer in a semi-additive construction method in the manufacture of a multilayer printed wiring board, and at the same time, densely coordinates a wiring surface excellent in adhesion between the wiring for multilayering and a resin such as an interlayer insulating material. It is an object of the present invention to provide a liquid composition for etching for batch processing and a method of manufacturing a printed wiring board using the same.

The present inventors efficiently remove chemical copper plating, which is a seed layer in a semi-additive construction method in the manufacture of a multilayer printed wiring board, and at the same time, densely coordinate the wiring surface with excellent adhesion between the wiring for multilayering and a resin such as an interlayer insulating material. A liquid composition for etching to batch-process a process and a method of manufacturing a printed wiring board using the same were found, thereby completing the present invention.

That is, the present invention is as follows.

1. In the liquid composition for etching used for manufacturing a multilayer printed wiring board,

0.2 to 5% by mass of hydrogen peroxide,

0.5 to 8% by mass of sulfuric acid,

0.3-3 ppm of halogen ions,

0.003 to 0.3% by mass of tetrazoles,

It comprises, a liquid composition for etching.

2. The tetrazoles are at least one member selected from the group consisting of 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, 1,5-dimethyltetrazole and 1,5-diethyltetrazole. The liquid composition for etching according to 1.

3. The liquid composition for etching according to 1 or 2, wherein the halogen ion is at least one selected from the group consisting of fluorine ion, chloride ion, bromine ion and iodine ion.

4. A method of manufacturing a multilayer printed wiring board comprising etching copper chemically and electrolytic copper plating processed on a substrate to form copper wiring,

Multi-layered print etched using a liquid composition for etching containing 0.2 to 5% by mass hydrogen peroxide, 0.5 to 8% by mass sulfuric acid, 0.3 to 3 ppm halogen ion, and 0.003 to 0.3% by mass tetrazole Method of manufacturing a wiring board.

5. The method for manufacturing the multilayer printed wiring board according to the above 4, wherein the copper wiring is formed by removing the chemical copper plating in a semi-additive construction method and simultaneously harmonizing the electrical copper plating.

6. The manufacturing method of the multilayer printed wiring board according to 5, wherein the ratio of the dissolution rate of the chemical copper plating and the dissolution rate of the electrical copper plating is etched to 3 or more.

7. A method of manufacturing the multilayer printed wiring board according to any one of 4 to 6, wherein the specific surface area of the copper wiring is 1.2 to 2 by etching.

(However, the specific surface area of the copper wiring is a surface area per unit area of 1 µm x 1 µm of the copper wiring, and the specific surface area of the copper wiring is a value obtained when the surface of the copper wiring is observed with a scanning tunnel microscope. to be)

8. The tetrazoles are at least one member selected from the group consisting of 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, 1,5-dimethyltetrazole and 1,5-diethyltetrazole. The manufacturing method of the multilayer printed wiring board in any one of 4-7.

9. The method for producing a multilayer printed wiring board according to any one of 4 to 8, wherein the halogen ion is at least one selected from the group consisting of fluorine ion, chloride ion, bromine ion and iodine ion.

Through the method for manufacturing a printed wiring board of the present invention, in the production of a printed wiring board by a semi-additive construction method that has been difficult in the past, chemical copper plating as a seed layer is efficiently removed, and resins such as wiring and interlayer insulating materials for multilayering Since it is possible to batch-process (process in one process) the dense roughening of the wiring surface with excellent adhesion, the value of industrial use is very high. As described above, by selectively removing the chemical copper plating as the seed layer, the amount of wiring width reduction can be suppressed, and disconnection or short circuit can be prevented.

1 is a three-dimensional image (× 30000) of the copper surface of Example 4.
2 is a three-dimensional image (× 30000) of the copper surface of Comparative Example 8.
3 is a cross-sectional electron micrograph (× 3000) of Example 6;
4 is a cross-sectional electron micrograph (× 3000) of Comparative Example 11.

The liquid composition for etching of the present invention comprises hydrogen peroxide, sulfuric acid, halogen ions, and tetrazoles, and preferably contains water. The concentration of hydrogen peroxide is 0.2 to 5.0 mass%, preferably 0.3 to 3.0 mass%, more preferably 0.4 to 2.5 mass%, and particularly preferably 0.5 to 2.0 mass%. When the concentration of hydrogen peroxide is 0.2 to 5.0% by mass, good copper dissolution rate is obtained, and thus it is economically excellent.

The concentration of sulfuric acid is 0.5 to 8.0 mass%, preferably 0.6 to 7.0 mass%, more preferably 0.8 to 6.0 mass%, and particularly preferably 1.0 to 5.0 mass%. When the concentration of sulfuric acid is 0.5 to 8.0% by mass, good copper dissolution rate is obtained, and thus it is economically excellent.

Since the halogen ion has the effect of harmonizing the surface of the copper or copper alloy, the adhesion between the copper or copper alloy and the resin becomes good. Halogen ions include fluorine ions, chloride ions, bromine ions, and iodine ions. Preferred of these are chloride ions and bromine ions, and particularly preferably chloride ions. The concentration of the halogen ion is 0.3 to 3 ppm, preferably 0.5 to 3 ppm, and particularly preferably 0.5 to 2 ppm.

Tetrazoles, when used in combination with halogen ions, have an effect of finely coordinating the surface of copper or copper alloy, thereby improving adhesion between copper or copper alloy and resins such as interlayer insulating materials. Among tetrazoles, 1H-tetrazole, 1-methyltetrazole, 1-ethyltetrazole, 5-methyltetrazole, 5-ethyltetrazole, 5-n-propyltetrazole, 5-mercaptotetrazole, 5- Mercapto-1-methyltetrazole, 1,5-dimethyltetrazole, 1,5-diethyltetrazole, 1-methyl-5-ethyltetrazole, 1-ethyl-5-methyltetrazole, 1-isopropyl At least one of -5-methyltetrazole and 1-cyclohexyl-5-methyltetrazole is preferred. More preferably, 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, 5-ethyltetrazole, 5-mercapto-1-methyltetrazole, 1,5-dimethyltetrazole, 1,5 -Diethyltetrazole, 1-ethyl-5-methyltetrazole, particularly preferably 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, 1,5-dimethyltetrazole, 1,5- Diethyltetrazole. The concentration of tetrazoles is 0.003 to 0.3 mass%, preferably 0.005 to 0.25 mass%, and particularly preferably 0.01 to 0.2 mass%.

The surface roughness (Ra value) of the copper wiring is preferably 0.5 µm or less, more preferably 0.4 µm or less, and particularly preferably 0.3 µm or less from the viewpoint of transmission loss. If it exceeds 0.5 µm, there is a high possibility that a problem occurs in transmission loss.

The dissolution rate of the chemical copper plating varies under various conditions, for example, under treatment conditions of 30 ° C., preferably 0.4 to 2 μm / min, more preferably 0.6 to 2 μm / min, particularly preferably 0.8 ~ 1.5㎛ / min.

The dissolution rate of the electrolytic copper plating varies under various conditions, for example, under a treatment condition of 30 ° C., preferably 0.1 to 0.5 μm / min, more preferably 0.15 to 0.4 μm / min, particularly preferably 0.2 ~ 0.35 µm / min.

The ratio of the dissolution rate of the chemical copper plating and the dissolution rate of the electrical copper plating (dissolution rate of the chemical copper plating / dissolution rate of the electrical copper plating) is preferably 3 or more, more preferably 3.5 or more and 8 or less, and particularly preferably It is 4 or more and 7.5 or less. If the ratio of the dissolution rate of the chemical copper plating and the dissolution rate of the electrical copper plating is within the above range, the surface of the electrical copper plating can be harmonized while efficiently removing the chemical copper plating.

Peel strength of the copper foil varies depending on the resin material such as the interlayer insulating material to be targeted, but is preferably 0.6 kgf / cm or more, more preferably 0.8 kgf / cm or more, and more preferably Is 0.9 kgf / cm or more, particularly preferably 1.0 kgf / cm or more.

The use temperature of the liquid composition for etching of the present invention is not particularly limited, but is preferably 20 to 50 ° C, more preferably 25 to 40 ° C, and still more preferably 25 to 35 ° C. If the operating temperature is 20 ° C or higher, the dissolution rate of copper can be increased, and if it is 50 ° C or lower, decomposition of hydrogen peroxide can be suppressed.

The treatment time of the liquid composition for etching of the present invention is not particularly limited, but 1 to 600 seconds are preferable, 5 to 300 seconds are more preferable, 10 to 180 seconds are more preferable, and 15 to 120 seconds are particularly preferable, but metal It is appropriately selected according to various conditions such as the condition of the surface, the concentration of the liquid composition for etching, temperature, and treatment method.

Regarding the treatment method with the liquid composition for etching of the present invention, there is no particular limitation, but it depends on means such as immersion and spraying. Further, the processing time is appropriately selected depending on the thickness of the copper or copper alloy to be dissolved.

The surface area of copper [µm ² ] can be calculated by observing the surface of copper with a scanning tunnel microscope. That is, the surface area of copper [µm ² ] can be calculated based on the three-dimensional shape data after obtaining the three-dimensional shape data by observing the surface of the copper with a scanning tunnel microscope.

The observation magnification in a scanning tunnel microscope on the surface of copper is, for example, 30000 times.

The specific surface area of copper is equal to the value obtained by dividing the surface area in the case where irregularities in a predetermined area of the copper surface are considered, and the surface area when the area is assumed to be flat. For example, dividing the surface area in the case of irregularities in an area of 5 µm × 5 µm in width on the copper surface by dividing it by the surface area when the region is assumed to be flat (ie, 5 µm × 5 µm = 25 µm ² ) Same as value.

The specific surface area of copper is a value considering the unevenness of the surface of copper. Therefore, the denser the surface of copper, the larger the specific surface area of copper tends to be. Here, the term "density" refers to a state in which the convex portions are dense while each of the convex portions on the copper surface is smiling.

A scanning tunnel microscope is a microscope that detects tunnel current flowing between a metal probe and a sample. When a metal probe such as platinum or tungsten with a sharp tip is brought close to the sample and a small bias voltage is applied therebetween, the tunnel current flows due to the tunnel effect. By scanning the probe to keep this tunnel current constant, the surface shape of the sample can be observed at the atomic level.

Example

The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

· Surface area measurement

Scanning tunnel microscope: Observed 30,000 times using L-trace II / NanoNavi II Station manufactured by SII NanoTechnology Inc.

Copper dissolution measurement method; It was calculated by the mass method through the following equation.

Dissolution amount = (mass before treatment-mass after treatment) / (treatment area × density of copper)

(In the formula, the density of copper is 8.96 g / cm ^3. )

· Wiring width measurement

A metal microscope MX61L manufactured by Olympus Corporation was used.

· Peel strength measurement of copper foil

Peel strength was measured according to the method specified in JIS C 6481.

Example 1

Chemical copper-plated substrate (dimension 15 cm × 15 cm, plating thickness 1 µm), electric copper-plated substrate (dimension 15 cm × 15 cm, plating thickness 10 µm), hydrogen peroxide 1 mass%, sulfuric acid 3 mass%, 5-methyl A liquid composition for etching containing 0.1% by mass of tetrazole and 1 ppm of chloride ions was sprayed at a liquid temperature of 30 ° C and a spray pressure of 0.1 MPa. The copper dissolution amount was calculated from the mass difference between the substrates before and after the treatment, and the copper dissolution rate per unit time was calculated. Then, the ratio of the chemical copper plating dissolution rate and the electrical copper plating dissolution rate was calculated.

Example 2

Example 1 except that a liquid composition for etching containing 0.5% by mass of hydrogen peroxide, 2.5% by mass of sulfuric acid, 0.01% by mass of 5-methyltetrazol, 0.01% by mass of 1,5-dimethyltetrazol, and 1ppm of chloride ion was used. The same was done.

Example 3

Example 1, except that 1.5% by mass of hydrogen peroxide, 4.5% by mass of sulfuric acid, 0.02% by mass of 1-methyltetrazole, 0.02% by mass of 1,5-dimethyltetrazole, and an etching liquid composition containing 3 ppm of bromine ion The same was done.

Comparative Example 1

Example 1, except that a liquid composition for etching (same composition as Example 7 in Patent Document 4) containing 4% by mass of hydrogen peroxide, 9% by mass of sulfuric acid, 0.3% by mass of 5-aminotetrazole, and chloride ion was used. It was performed in the same manner as.

Comparative Example 2

2.5% by mass of hydrogen peroxide, 13.7% by mass of sulfuric acid, 0.03% by mass of 5-phenyltetrazole, 0.07% by mass of 4-nitrobenzotriazole, and a liquid composition for etching containing 8 ppm of chloride ion (same composition as in Example 1 of Patent Document 5) ) Was carried out in the same manner as in Example 1 except for using.

Comparative Example 3

What used the etching liquid composition (same composition as Example 1 of patent document 6) containing 3 mass% of hydrogen peroxide, 10 mass% of sulfuric acid, 0.02 mass% of 5-phenyltetrazol, 0.2 mass% of toluene sulfonic acid, and 3 ppm of chloride ion Except that it was carried out in the same manner as in Example 1.

Comparative Example 4

Etching liquid containing 5.25% by mass of hydrogen peroxide, 12.5% by mass of sulfuric acid, 0.06% by mass of 5-aminotetrazole, 0.02% by mass of 5-methyltetrazole, and 0.4% by mass of 1-hydroxyethane-1,1-diphosphonic acid It carried out similarly to Example 1 except having used the composition (the same composition as Example 1 of patent document 7).

Comparative Example 5

Except for using a liquid composition for etching (same composition as Example 8 in Patent Document 8) containing 1.5% by mass of hydrogen peroxide, 9% by mass of sulfuric acid, 0.1% by mass of 5-methyltetrazole, 0.05% by mass of tetrazole, and 1 ppm of palladium Then, it was carried out in the same manner as in Example 1.

Comparative Example 6

Same as Example 1, except that 1.5% by mass of hydrogen peroxide, 5% by mass of sulfuric acid, 0.3% by mass of benzotriazole, and a liquid composition for etching containing 5 ppm of chloride ions (same composition as in Example 1 of Patent Document 9) were used. Was done.

Comparative Example 7

Example 1 except that a liquid composition for etching (same composition as Example 1 in Patent Document 10) containing 10% by mass of hydrogen peroxide, 16% by mass of sulfuric acid, 0.2% by mass of tolyltriazole, and 1% by mass of phosphorous acid was used. The same was done.

Example 4

For etching 35 g thick electric copper foil (dimension 150 mm x 150 mm) containing a shiny side, 1 mass% hydrogen peroxide, 3 mass% sulfuric acid, 0.2 mass% 5-methyltetrazol, 1 ppm chloride ion The liquid composition was sprayed at a liquid temperature of 30 ° C and a spray pressure of 0.1 MPa for 1 minute. It was 0.3 micrometers when the copper dissolution amount was computed from the mass difference of the copper foil before and after a process. Next, the surface of the copper foil after etching was observed at a magnification of 30000 times using a scanning tunnel microscope. 1 is a three-dimensional image of the copper foil surface observed at this time.

Using a scanning tunnel microscope, the surface area in the region of 5 µm × 5 µm in length on the surface of the copper foil after etching was measured. As a result, the surface area of the copper foil was 42.5 [µm ² ]. The specific surface area was 42.5 [µm ² ] / 25 [µm ² ] = 1.7.

The copper foil after etching was laminated to an interlayer insulating resin (trade name: HL832NS manufactured by Mitsubishi Gas Chemical Company, Inc.) by vacuum heat pressing to prepare a copper-clad laminate. In this copper-clad laminate, the surface on the etched side of the copper foil is in close contact with the interlayer insulating resin. Using the copper-clad laminate thus obtained, the peel strength of the copper foil was measured. As a result, the peeling strength of the copper foil was 1.00 kgf / cm.

Example 5

Example 4, except that 0.5% by mass of hydrogen peroxide, 2.5% by mass of sulfuric acid, 0.01% by mass of 5-methyltetrazol, 0.01% by mass of 1,5-dimethyltetrazol, and a liquid composition for etching containing 1 ppm of chloride ion The same was done.

Comparative Example 8

Except for using a liquid composition for etching (same composition as Example 4 in Patent Document 2) containing 2% by mass of hydrogen peroxide, 10% by mass of sulfuric acid, and 0.05% by mass of 1- (1,2-dicarboxyethyl) benzotriazole Then, it was carried out in the same manner as in Example 4.

Comparative Example 9

It was carried out in the same manner as in Example 4, except that a liquid composition for etching (same composition as in Example 1 of Patent Document 1) containing 0.8% by mass of hydrogen peroxide, 4% by mass of sulfuric acid, and 3 ppm of bromine ions was used.

Comparative Example 10

Etching liquid composition containing 2% by mass of hydrogen peroxide, 9% by mass of sulfuric acid, 0.025% by mass of benzotriazole, 0.1% by mass of 1,2,3-triazole, and 0.1% by mass of sodium phenolsulfonate monohydrate (Patent Document 3 It carried out similarly to Example 4 except having used the same composition as Example 1).

Example 6

An electric copper plating with a thickness of 18 µm was applied to the conductor portion using a dry film resist on a substrate (dimension 510 mm × 340 mm) on which a chemical copper plating of 0.7 µm was formed on the resin. Next, the resist was stripped with an amine-based resist stripping solution (Mitsubishi Gas Chemical Company, Inc. product name: R-100S). When the wiring width of the conductor portion was measured with a metal microscope (Olympus Corporation, MX61L), the wiring width was 10 µm. Subsequently, a chemical copper plating (thickness of 0.7 µm) of the seed layer was etched into a liquid composition for etching containing 1% by mass of hydrogen peroxide, 3% by mass of sulfuric acid, 0.2% by mass of 5-methyltetrazol, and 1 ppm of chloride ion. Chemical copper plating was completely removed by spraying at a liquid temperature of 30 ° C and a spray pressure of 0.1 MPa for 1 minute. As a result of measuring the reduction in the wiring width after removing the seed layer (chemical copper plating) using a metal microscope (manufactured by Olympus Corporation, MX61L), as shown in Fig. 3, the reduction in line width was as good as 0.5 µm.

Comparative Example 11

Performed in the same manner as in Example 6, except that a liquid composition for etching (same composition as Comparative Example 1) containing 4% by mass of hydrogen peroxide, 9% by mass of sulfuric acid, 0.3% by mass of 5-aminotetrazol, and 10 ppm of chloride ion was used. Did. As a result of measuring the reduction in the wiring width after removing the seed layer (chemical copper plating) using a metal microscope (Olympus Corporation, MX61L), as shown in Fig. 4, the reduction in line width was severe and could not be used.

From the results of Table 1 and Table 2, when the treatment with the liquid composition for etching of the present invention, the ratio of the dissolution rate of the chemical copper plating and the dissolution rate of the electrical copper plating is 3 or more, so that the chemical copper plating can be selectively dissolved. At the same time, it can be seen that the electric copper surface can be closely matched, so that the peel strength with the interlayer insulating resin is strong.

Claims (5)

In the liquid composition for etching used for manufacturing a multilayer printed wiring board,
0.2 to 5% by mass of hydrogen peroxide,
0.5 to 8% by mass of sulfuric acid,
0.3-3 ppm of chloride ions,
0.01 to 0.3% by mass of at least one tetrazole selected from the group consisting of 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, 1,5-dimethyltetrazole and 1,5-diethyltetrazole ,
It comprises, a liquid composition for etching.
In the method of manufacturing a multilayer printed wiring board comprising etching the chemical copper plating and electrical copper plating processed on the substrate to form copper wiring,
0.2 to 5% by mass of hydrogen peroxide, 0.5 to 8% by mass of sulfuric acid, 0.3 to 3 ppm of chloride ions, 0.01 to 0.3% by mass of 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, A method for producing a multilayer printed wiring board, which is subjected to etching treatment using a liquid composition for etching comprising at least one tetrazole selected from the group consisting of 1,5-dimethyltetrazole and 1,5-diethyltetrazole.
According to claim 2,
A method of manufacturing a multilayer printed wiring board, wherein the copper wiring is formed by removing the chemical copper plating in a semi-additive method and roughening the electrical copper plating.
According to claim 3,
A method of manufacturing a multilayer printed wiring board, wherein the ratio of the dissolution rate of the chemical copper plating and the dissolution rate of the electrical copper plating is etched to 3 or more.
The method according to any one of claims 2 to 4,
A method of manufacturing a multilayer printed wiring board, wherein the specific surface area of the copper wiring is 1.2 to 2 by etching.
(However, the specific surface area of the copper wiring is a surface area per unit area of 1 µm x 1 µm of the copper wiring, and the specific surface area of the copper wiring is a value obtained when the surface of the copper wiring is observed with a scanning tunnel microscope. to be)

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