JP2014029011A - Liquid composition for etching and method for producing multilayer printed board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid composition for etching, performing batch processing of densifying or roughening treatment of a wiring surface while efficiently eliminating a chemical copper plating which is a seed layer in a semiadditive process for producing a multilayer printed board, and to provide a method for producing the multilayer printed board by using the liquid composition for etching.SOLUTION: The liquid composition for etching used for producing a multilayer printed board contains 0.2 to 5 mass% of hydrogen peroxide, 0.5 to 8 mass% of sulfuric acid, 0.3 to 3 ppm of a halogen ion and 0.003 to 0.3 mass% of tetrazoles.

Description

  TECHNICAL FIELD The present invention relates to an etching liquid composition and a method for producing a multilayer printed wiring board using the same, and more specifically, an etching liquid composition used for producing a multilayer printed wiring board used in electrical and electronic equipment. The present invention relates to a method for manufacturing a multilayer printed wiring board, which includes etching a chemical copper plating and an electrolytic copper plating applied on a substrate and forming a copper wiring.

  With recent downsizing, weight reduction, and higher functionality of electronic devices, printed wiring boards are strongly required to have finer and multilayered copper wiring.

  One of the manufacturing methods for forming fine wiring is a semi-additive construction method. In this wiring formation method, a metal layer called a seed layer is formed on an insulating material (chemical copper plating is generally used as the metal layer), a plating resist layer is formed on the surface, and then exposed and developed to form a resist. Form a pattern. Thereafter, electrolytic copper plating is performed to remove the resist, and the seed layer is removed by etching to form a copper wiring.

  Further, an interlayer insulating material is laminated on the copper wiring formed as described above for multilayering, and wiring is formed in the same manner as described above. In the case of the outermost layer wiring, a resin called solder resist or coverlay is applied on the copper wiring in order to protect the copper wiring other than the external connection terminals.

  In order to improve the adhesion between the copper wiring and a resin such as an interlayer insulating material or a solder resist, the copper surface is roughened by a mechanical treatment such as buffing or scrubbing or a chemical polishing treatment such as a roughening agent.

  Conventionally, the chemical copper plating etching removal process (generally called flash etching process), which is the seed layer in the semi-additive method, and the copper wiring surface roughening process for multilayering are performed in separate steps (chemicals). Done.

  Etching liquid composition containing hydrogen peroxide, sulfuric acid, azoles, bromine ions (Patent Document 1), sulfuric acid, hydrogen peroxide, benzotriazole derivatives as a chemical copper plating etching liquid composition And an etching liquid composition (Patent Document 3) characterized by containing hydrogen peroxide and sulfuric acid as main components and an azole as an additive. In conventional chemical copper plating etching liquid compositions, the wiring surface cannot be roughened, so the adhesion to the resin such as the interlayer insulating material is not good, and therefore chemical copper plating removal and wiring roughening treatment cannot be performed at the same time. .

  Further, as a copper wiring roughening agent, an oxo acid, a peroxide, an azole, an etching liquid composition containing a halide of 50 mg / L or less (Patent Document 4), sulfuric acid, hydrogen peroxide, phenyltetrazole and nitro Liquid composition for etching containing benzotriazoles, chloride ions (Patent Document 5), sulfuric acid, hydrogen peroxide, phenyltetrazole, microetching agent containing chlorine ion source (Patent Document 6), sulfuric acid, hydrogen peroxide, 5-aminotetrazole, tetrazole compounds other than 5-aminotetrazole, surface roughening agent containing phosphonic acid chelating agent (Patent Document 7), sulfuric acid, peroxide, tetrazole compound, metal having a higher potential than copper Liquid composition for microetching containing ions (Patent Document 8), hydrogen peroxide, sulfuric acid, benzotriazol A surface-roughening solution containing chloride ions (Patent Document 9), a microetching agent comprising an aqueous solution containing a main agent composed of an inorganic acid and an oxidizing agent of copper and an auxiliary comprising an azole and an etching inhibitor ( Patent Document 10) and the like are disclosed. With conventional solutions, the dissolution rate of chemical copper plating is not greater than the dissolution rate of electrolytic copper plating, making it difficult to form fine wiring by the semi-additive method.

  In a conventional roughening agent (etching agent), the copper surface is roughened by etching several μm to ensure adhesion between copper and a resin such as an interlayer insulating material by a physical (anchor) effect. However, in recent years, the copper wiring width has been reduced to a minimum of several μm from the conventional 30-50 μm to 15 μm or less, and with the conventional roughening agent (etching agent), the copper wiring width becomes narrower and the wiring disappears. Moreover, since the roughness of the copper wiring surface is large (the unevenness in the depth direction is large), there are concerns about the occurrence of disconnection and the problem of transmission loss.

JP 2006-13340 A JP 2009-149971 A Japanese Patent Laid-Open No. 2006-9122 JP 2000-64067 A JP 2009-191357 A JP 2002-47583 A JP 2009-19270 A JP 2004-3020 A JP 2005-213526 A JP 2000-282265 A

  The present invention efficiently removes chemical copper plating, which is a seed layer in the semi-additive method in the production of multilayer printed wiring boards, and at the same time has excellent adhesion between wiring for multilayering and resin such as interlayer insulating material It aims at providing the manufacturing method of the liquid composition for etching which processes the dense roughening process of lump, and the printed wiring board using the same.

  The inventors of the present invention efficiently remove the chemical copper plating that is a seed layer in the semi-additive method for manufacturing a multilayer printed wiring board, and at the same time, have excellent adhesion between the wiring for multilayering and a resin such as an interlayer insulating material. The inventors have found a liquid composition for etching that collectively processes a dense roughening treatment on a wiring surface and a method for producing a printed wiring board using the same, and have completed the present invention.

That is, the present invention is as follows.
1. A liquid composition for etching used for manufacturing a multilayer printed wiring board,
0.2-5 mass% hydrogen peroxide,
0.5-8 mass% sulfuric acid,
0.3 to 3 ppm of halogen ions;
0.003 to 0.3% by mass of tetrazole,
An etching liquid composition comprising:
2. 2. The tetrazole is one or more selected from the group consisting of 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, 1,5-dimethyltetrazole, and 1,5-diethyltetrazole. Etching liquid composition.
3. 3. The etching liquid composition according to 1 or 2 above, wherein the halogen ions are one or more selected from the group consisting of fluorine ions, chloride ions, bromine ions, and iodine ions.
4). A method for producing a multilayer printed wiring board comprising etching chemical copper plating and electrolytic copper plating applied on a substrate to form a copper wiring,
0.2 to 5 mass% hydrogen peroxide, 0.5 to 8 mass% sulfuric acid, 0.3 to 3 ppm halogen ion, and 0.003 to 0.3 mass% tetrazole The manufacturing method of a multilayer printed wiring board which etches using the etching liquid composition which becomes.
5. 5. The method for producing a multilayer printed wiring board according to 4 above, wherein the chemical copper plating is removed and the electrolytic copper plating is roughened to form the copper wiring in a semi-additive construction method.
6). 6. The method for producing a multilayer printed wiring board according to 5 above, wherein etching is performed at a ratio of the dissolution rate of the chemical copper plating and the dissolution rate of the electrolytic copper plating of 3 or more.
7). The manufacturing method of the multilayer printed wiring board in any one of said 4-6 which etches and makes the specific surface area of the said copper wiring 1.2-2.
(However, the specific surface area of the copper wiring is the surface area per unit area of 1 μm long × 1 μm wide of the copper wiring, and the specific surface area of the copper wiring is obtained when the surface of the copper wiring is observed with a scanning tunneling microscope. Value)
8). 4-7 above, wherein the tetrazole is at least one 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.
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.

  With the printed wiring board manufacturing method of the present invention, in the printed wiring board manufacturing by the semi-additive method, which has been difficult in the past, the chemical copper plating as the seed layer is efficiently removed, and at the same time, the wiring and interlayer insulating material for multilayering, etc. Since the dense roughening treatment of the wiring surface, which has excellent adhesion to the resin, can be performed at once (processing in one step), the industrial utility value is extremely high. In this way, by selectively removing the chemical copper plating that is the seed layer, it is possible to suppress the amount of decrease in the wiring width and to prevent disconnection or omission.

The three-dimensional image (x30000) of the copper surface of Example 4. FIG. The three-dimensional image (x30000) of the copper surface of the comparative example 8. The wiring cross-sectional electron micrograph of Example 6 (x3000). The wiring cross-sectional electron micrograph of the comparative example 11 (x3000).

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

  The concentration of sulfuric acid is 0.5 to 8.0% by mass, preferably 0.6 to 7.0% by mass, more preferably 0.8 to 6.0% by mass, and particularly preferably 1 0.0 to 5.0% by mass. When the concentration of sulfuric acid is 0.5 to 8.0% by mass, a good copper dissolution rate is obtained, which is economically excellent.

  Halogen ions have the effect of roughening the copper or copper alloy surface, and the adhesion between the copper or copper alloy and the resin is good. Halogen ions include fluorine ions, chloride ions, bromine ions and iodine ions. Among these, preferred are chloride ions and bromine ions, and particularly preferred are chloride ions. The density | concentration of a halogen ion is 0.3-3 ppm, Preferably it is 0.5-3 ppm, Most preferably, it is 0.5-2 ppm.

  Tetrazoles, when used in combination with halogen ions, have the effect of minutely roughening the surface of copper or copper alloy, and improve the adhesion between copper or copper alloy and a resin such as an interlayer insulating material. 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-5-methyltetrazole, 1-cyclohexyl-5-methyltetrazole At least one 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 and 1,5-diethyltetrazole. The concentration of the tetrazole is 0.003 to 0.3% by mass, preferably 0.005 to 0.25% by mass, and particularly preferably 0.01 to 0.2% by 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 of problems in transmission loss.

  The dissolution rate of chemical copper plating varies under various conditions. For example, it is preferably 0.4 to 2 μm / min, more preferably 0.6 to 2 μm / min under the processing condition of 30 ° C. Particularly preferred is 0.8 to 1.5 μm / min.

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

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

  The peel strength (peel strength) of the copper foil is preferably 0.6 kgf / cm or more, more preferably 0.8 kgf / cm or more, although it depends on the target resin material such as an interlayer insulating material. More preferably, it is 0.9 kgf / cm or more, and particularly preferably 1.0 kgf / cm or more.

  Although there is no restriction | limiting in particular regarding the operating temperature of the liquid composition for an etching of this invention, Preferably it is 20-50 degreeC, More preferably, it is 25-40 degreeC, More preferably, it is 25-35 degreeC. 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, the decomposition of hydrogen peroxide can be suppressed.

  Although there is no restriction | limiting in particular regarding the processing time of the etching liquid composition of this invention, 1 to 600 second is preferable, 5 to 300 second is more preferable, 10 to 180 second is still more preferable, 15 to 120 second is especially preferable. It is appropriately selected depending on various conditions such as the state of the metal surface, the concentration of the etching liquid composition, the temperature, and the treatment method.

  Although there is no restriction | limiting in particular regarding the processing method by the etching liquid composition of this invention, By 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 [μm ² ] of copper can be calculated by observing the surface of copper with a scanning tunneling microscope. That is, the surface area [μm ² ] of copper can be calculated based on the three-dimensional shape data after obtaining the three-dimensional shape data by observing the copper surface with a scanning tunneling microscope.

  The observation magnification of the copper surface with a scanning tunneling microscope is, for example, 30000 times.

The specific surface area of copper is equal to a value obtained by dividing the surface area in consideration of the irregularities in a predetermined area of the copper surface by the surface area when the area is assumed to be flat. For example, the surface area when the unevenness in the region of 5 μm length × 5 μm width of the copper surface is taken into consideration is divided by the surface area when the region is assumed to be flat (that is, 5 μm × 5 μm = 25 μm ² ). equal.

  The specific surface area of copper is a value that takes into account the unevenness of the copper surface. Therefore, the specific surface area of copper tends to increase as the copper surface becomes denser. Here, “dense” means a state in which each of the convex portions on the copper surface is minute and the convex portions are densely packed.

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

EXAMPLES 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 tunneling microscope: L-trace II / manufactured by SII Nano Technology
Observation was performed at a magnification of 30,000 using a NanoNavi II station.
-Copper dissolution amount measuring method: It calculated by the mass method by the following formula | equation.
Dissolution amount = (mass before treatment−mass after treatment) / (treatment area × copper density)
(In the formula, the density of copper is 8.96 g / cm ^3. )
-Wiring width measurement Metal microscope Olympus MX61L was used.
-Measurement of peel strength (peel strength) of copper foil The peel strength was measured according to the method defined in JIS C 6481.

Example 1
Chemical copper plating substrate (dimensions 15 cm × 15 cm, plating thickness 1 μm), electrolytic copper plating substrate (dimensions 15 cm × 15 cm, plating thickness 10 μm), hydrogen peroxide 1 mass%, sulfuric acid 3 mass%, 5-methyltetrazole 0.1 Spray treatment was performed with a liquid composition for etching containing 1% by mass of chloride ions at a liquid temperature of 30 ° C. and a spray pressure of 0.1 MPa. The amount of copper dissolution was calculated from the difference in mass between the substrates before and after the treatment, and the copper dissolution rate per unit time was calculated. Furthermore, the ratio between the chemical copper plating dissolution rate and the electrolytic copper plating dissolution rate was calculated.

Example 2
An etching liquid composition comprising 0.5% by mass of hydrogen peroxide, 2.5% by mass of sulfuric acid, 0.01% by mass of 5-methyltetrazole, 0.01% by mass of 1,5-dimethyltetrazole, and 1 ppm of chloride ions. The same procedure as in Example 1 was performed except that it was used.

Example 3
An etching liquid composition containing 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 3 ppm of bromine ions is used. The procedure was the same as in Example 1 except that.

Comparative Example 1
Except for using an etching liquid composition containing 4% by mass of hydrogen peroxide, 9% by mass of sulfuric acid, 0.3% by mass of 5-aminotetrazole, and 10 ppm of chloride ions (the same composition as in Example 7 of Patent Document 4). Was carried out in the same manner as in Example 1.

Comparative Example 2
Etching liquid composition comprising hydrogen peroxide 2.5% by mass, sulfuric acid 13.7% by mass, 5-phenyltetrazole 0.03% by mass, 4-nitrobenzotriazole 0.07% by mass, chloride ion 8ppm (patent The same procedure as in Example 1 was performed except that the same composition as in Example 1 of Document 5 was used.

Comparative Example 3
Etching liquid composition containing 3% by mass of hydrogen peroxide, 10% by mass of sulfuric acid, 0.02% by mass of 5-phenyltetrazole, 0.2% by mass of toluenesulfonic acid, and 3 ppm of chloride ions (Example 1 of Patent Document 6) This was carried out in the same manner as in Example 1 except that the same composition was used.

Comparative Example 4
Hydrogen peroxide 5.25% by mass, sulfuric acid 12.5% by mass, 5-aminotetrazole 0.06% by mass, 5-methyltetrazole 0.02% by mass, 1-hydroxyethane-1,1-diphosphonic acid 0.4 This was performed in the same manner as in Example 1 except that an etching liquid composition containing mass% (the same composition as in Example 1 of Patent Document 7) was used.

Comparative Example 5
Etching liquid composition 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 (similar to Example 8 of Patent Document 8) This was carried out in the same manner as in Example 1 except that the above composition was used.

Comparative Example 6
Except for using an etching liquid composition containing 1.5% by mass of hydrogen peroxide, 5% by mass of sulfuric acid, 0.3% by mass of benzotriazole, and 5 ppm of chloride ions (the same composition as in Example 1 of Patent Document 9). Was carried out in the same manner as in Example 1.

Comparative Example 7
Except for using an etching liquid composition 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 (same composition as Example 1 of Patent Document 10). Was carried out in the same manner as in Example 1.

Example 4
A shiny liquid surface of 35 μm thick electric copper foil (size 150 mm × 150 mm) is an etching liquid composition containing 1% by mass of hydrogen peroxide, 3% by mass of sulfuric acid, 0.2% by mass of 5-methyltetrazole and 1 ppm of chloride ions. Spray treatment was performed at a liquid temperature of 30 ° C. and a spray pressure of 0.1 MPa for 1 minute. It was 0.3 micrometer as a result of computing copper dissolution amount from the mass difference of the copper foil before and behind a process. Next, the copper foil surface after the etching was observed with a scanning tunneling microscope at a magnification of 30000 times. FIG. 1 is a three-dimensional image of the copper foil surface observed at this time.

Using a scanning tunneling microscope, the surface area of the etched copper foil surface in a region of 5 μm length × 5 μm width 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 the etching was laminated on an interlayer insulating resin (trade name: HL832NS, manufactured by Mitsubishi Gas Chemical Co., Ltd.) by vacuum hot pressing to produce a copper clad laminate. In this copper clad laminate, the etched surface of the copper foil is in close contact with the interlayer insulating resin. Using the copper clad laminate thus obtained, the peel strength (peel strength) of the copper foil was measured. As a result, the peel strength of the copper foil was 1.00 kgf / cm.

Example 5
An etching liquid composition comprising 0.5% by mass of hydrogen peroxide, 2.5% by mass of sulfuric acid, 0.01% by mass of 5-methyltetrazole, 0.01% by mass of 1,5-dimethyltetrazole, and 1 ppm of chloride ions. The same procedure as in Example 4 was performed except that it was used.

Comparative Example 8
Etching liquid composition containing 2% by mass of hydrogen peroxide, 10% by mass of sulfuric acid, and 0.05% by mass of 1- (1,2-dicarboxyethyl) benzotriazole (composition similar to Example 4 of Patent Document 2) The same procedure as in Example 4 was performed except that was used.

Comparative Example 9
This was carried out in the same manner as in Example 4 except that an etching liquid composition containing 0.8% by mass of hydrogen peroxide, 4% by mass of sulfuric acid and 3 ppm of bromine ions (the same composition as Example 1 of Patent Document 1) was used. .

Comparative Example 10
For etching 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, 0.1% by mass of sodium phenolsulfonate monohydrate The same operation as in Example 4 was performed except that the liquid composition (the same composition as in Example 1 of Patent Document 3) was used.

Example 6
Electrode copper plating with a thickness of 18 μm was applied to the conductor using a dry film resist on a substrate (size 510 mm × 340 mm) on which a chemical copper plating 0.7 μm was formed on the resin. Next, the resist was stripped with an amine-based resist stripping solution (product name: R-100S manufactured by Mitsubishi Gas Chemical). As a result of measuring the wiring width of the conductor portion with a metal microscope (MX61L manufactured by Olympus Corporation), the wiring width was 10 μm. Next, a chemical copper plating (thickness 0.7 μm) of the seed layer is applied to an etching liquid composition containing 1% by mass of hydrogen peroxide, 3% by mass of sulfuric acid, 0.2% by mass of 5-methyltetrazole, and 1 ppm of chloride ions. (The same composition as in Example 4) was sprayed for 1 minute at a liquid temperature of 30 ° C. and a spray pressure of 0.1 MPa to completely remove the chemical copper plating. As a result of measuring the reduction amount of the wiring width after removing the seed layer (chemical copper plating) using a metal microscope (manufactured by Olympus Corporation, MX61L), as shown in FIG. It was good at 5 μm.

Comparative Example 11
Example 6 except that an etching liquid composition containing 4% by mass of hydrogen peroxide, 9% by mass of sulfuric acid, 0.3% by mass of 5-aminotetrazole, and 10 ppm of chloride ions (same composition as Comparative Example 1) was used. As well as. As a result of measuring the reduction amount of the wiring width after removing the seed layer (chemical copper plating) using a metal microscope (manufactured by Olympus Corporation, MX61L), the reduction in the line width is severe as seen in FIG. It was not usable.

  From the results of Tables 1 and 2, when treated with the etching liquid composition of the present invention, the ratio of the dissolution rate of chemical copper plating and the dissolution rate of electrolytic copper plating is 3 or more. It can be seen that at the same time that the electrolytic copper surface can be densely roughened, the peel strength from the interlayer insulating resin (peel strength) is strong.

Claims (9)

A liquid composition for etching used for manufacturing a multilayer printed wiring board,
0.2-5 mass% hydrogen peroxide,
0.5-8 mass% sulfuric acid,
0.3 to 3 ppm of halogen ions;
0.003 to 0.3% by mass of tetrazole,
An etching liquid composition comprising:   The tetrazole is at least one selected from the group consisting of 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, 1,5-dimethyltetrazole, and 1,5-diethyltetrazole. The liquid composition for etching as described.   The etching liquid composition according to claim 1 or 2, wherein the halogen ions are one or more selected from the group consisting of fluorine ions, chloride ions, bromine ions, and iodine ions. A method for producing a multilayer printed wiring board comprising etching chemical copper plating and electrolytic copper plating applied on a substrate to form a copper wiring,
0.2 to 5 mass% hydrogen peroxide, 0.5 to 8 mass% sulfuric acid, 0.3 to 3 ppm halogen ion, and 0.003 to 0.3 mass% tetrazole The manufacturing method of a multilayer printed wiring board which etches using the etching liquid composition which becomes.   The manufacturing method of the multilayer printed wiring board of Claim 4 which forms the said copper wiring by removing the said chemical copper plating and roughening the said electrolytic copper plating in a semi-additive construction method.   The manufacturing method of the multilayer printed wiring board of Claim 5 which etches by the ratio of the dissolution rate of the said chemical copper plating and the dissolution rate of the said electrolytic copper plating being 3 or more. The manufacturing method of the multilayer printed wiring board as described in any one of Claims 4-6 which carries out an etching process and sets the specific surface area of the said copper wiring to 1.2-2.
(However, the specific surface area of the copper wiring is the surface area per unit area of 1 μm long × 1 μm wide of the copper wiring, and the specific surface area of the copper wiring is obtained when the surface of the copper wiring is observed with a scanning tunneling microscope. Value)   The tetrazole is at least one selected from the group consisting of 1H-tetrazole, 1-methyltetrazole, 5-methyltetrazole, 1,5-dimethyltetrazole, and 1,5-diethyltetrazole. 8. The method for producing a multilayer printed wiring board according to any one of 7 above.   The production of a multilayer printed wiring board according to any one of claims 4 to 8, wherein the halogen ions are one or more selected from the group consisting of fluorine ions, chloride ions, bromine ions, and iodine ions. Method.