JPH04120290A - Copper electroplating solution - Google Patents

Abstract

PURPOSE:To obtain a plating soln. having excellence in uniform deposition and ensuring satisfactory physical properties of a deposited film by adding a small amt. of at least one among formaldehyde, a formaldehyde polymer, a hydrazine compd. and polyacrylamide to an aq. soln. contg. copper complex salts formed with specified org. chelating agents. CONSTITUTION:This copper electroplating soln. has 0.01-1mol/l concn. of a copper compd. such as copper sulfate or copper chloride, contains about 0.01-2mol/l EDTA and salts thereof represented by general formulae I, II as chelating agents used to form copper complexes and further contains at least one among formaldehyde, a formaldehyde polymer, a hydrazine compd. and polyacrylamide as additives, about 0.006-1mol/l additives represented by general formulae III, IV and at least one of halides and sulfates of alkali metals, alkaline earth metals and ammonium.

Description

[Detailed description of the invention] Industrial applications The present invention relates to an electrolytic copper plating solution.

Conventional technology and its challenges In copper plating on base metal materials such as iron and zinc,
If an acidic plating bath such as copper sulfate plating solution is used, it is not possible to directly form a plating film with good adhesion, so copper sulfate plating should be performed after base plating with copper cyanide plating solution. is common. however,
Copper cyanide plating solution is highly toxic and poses many problems in terms of working environment and wastewater treatment, and an alternative to it is desired.

In addition, if the object to be plated contains materials that are easily attacked by strong acids or strong bases, such as lead glass, zinc, sintered tungsten, and ceramics, such as chip capacitors, chip resistors, ceramic substrates, and ceramic substrates, etc. In some cases, there is a need for a copper plating solution that does not attack these materials.

On the other hand, in recent years, with the increasing density and multilayering of printed circuit boards, the number of printed circuit boards with thick boards and small through-hole diameters, that is, high aspect ratios (board thickness/hole diameter), is increasing. As an electrolytic copper plating solution for through-hole plating, there is a demand for a plating solution that has excellent uniform electrodeposition properties and has good physical properties of the deposited film.

Conventionally, as an electrolytic copper plating solution for through-hole plating, a copper birophosphate plating solution containing copper birophosphate and potassium pyrophosphate as main components has been mainly used. However, in the copper pyrophosphate plating solution, orthophosphoric acid is formed by hydrolysis of the large amount of pyrophosphoric acid contained in the solution, which has a negative effect on the current efficiency and physical properties of the plating film, so periodic disposal of the solution is unavoidable. However, in addition to high costs, wastewater treatment is complicated. Moreover, the deposited film has insufficient physical properties such as elongation, and there is also room for improvement in uniform electrodeposition.

In addition, acidic copper plating solutions containing copper sulfate, sulfuric acid, etc. as main components are also used for through-hole plating of printed circuit boards, but the tensile strength of the deposited film is low and there are also problems in controlling trace amounts of additives. be.

In addition, this type of plating solution uses a plating solution with a high sulfuric acid concentration (concentrated sulfuric acid 300 g/r) and a low copper sulfate concentration (10 g/7 or less as Cu) to improve uniform electrodeposition. However, it has poor workability and problems with acid resistance of substrates, resist films, etc., and its applications are limited.

Means for Solving the Problems The present inventor has conducted extensive research in order to obtain an electrolytic copper plating solution that can solve the problems of the prior art as described above. As a result, a plating solution prepared by adding a small amount of at least one of formaldehyde, formaldehyde polymer, hydrazine compound, and polyacrylamide to an aqueous copper complex salt solution using a specific organic chelating agent has been found to produce a good plating film over a wide pH range. It is possible to form a plating solution with very good uniform electrodeposition and physical properties of the deposited film.Furthermore, a plating solution in which a specific nitrogen-containing compound is added to this plating solution,
It has been found that the physical properties of the deposited film are further improved. These plating solutions are excellent as electroplating solutions for through-hole plating, and at the same time have a wide pH range.
By adjusting the pH appropriately, it is possible to form a plating film with good adhesion directly on various materials including base metal materials such as iron, and it can also be used on materials that are easily attacked by strong acids, strong bases, etc. It was also discovered that it is possible to attach the metal without damaging it. Furthermore, by further adding at least one compound of alkali metal halides and sulfates, alkaline earth metal halides and sulfates, and ammonium halides and sulfates to these plating solutions, It has been found that the uniform electrodeposition properties are further improved, making it an extremely excellent electrolytic copper plating solution for through-hole plating. The present invention was completed based on these findings.

That is, the present invention provides the electrolytic copper plating solution shown below.

(1) a) Copper compound 0.01 to 1 mol/lb) General formula (wherein xl is a hydrogen atom or a group -COOM4, and X2 is a group -COOM or a group -CH2CH2OH.

n represents an integer of 0 to 2, and Ml, M2, M, , M4 and M5 are the same or different and each is a hydrogen atom, KSNa or NH), and a compound represented by the general formula (wherein, , is a hydrogen atom, a group -CH2COOM6, a group -
CH2CH2COOMl or the group -CH2CH2OH,X, is the group -CH2C00MB
, the group -CH2CH2COOMg or the group -CH2CH20
H, x5 is a group -CH2COOM1°, a group -CH2CH2
COOMI 1 or represents the group -CH2CH2OH, M6
, M7, Ma, Mg, Ml. and Ml 1 are the same or different and each is a hydrogen atom, KSNa or NH4)
0.01-2 mol/l of a chelate on the north side consisting of at least one of the compounds represented by C) formaldehyde 0.01-1 mol/l, formaldehyde polymer 0.3-30 g/l, hydrazine compound 0.0005 Electrolytic copper plating solution consisting of an aqueous solution containing at least one of ~0.1 mol/I and polyacrylamide 0.005 to 10 g/7 (hereinafter referred to as "invention plating solution (I)"), ■a) Copper Compound CLOI ~ 1 mol/lb) General formula (wherein, Xl is a hydrogen atom or a group -COOM4, X2 is a group -COOM, or a group -CH2CH2OH1n represents an integer of 0 to 2, Ml, M2, M3, M4 and M5 are the same or different and each is a hydrogen atom, K, Na or NH), and a compound represented by the general formula /X3N-X.

\X5 (wherein, X is a hydrogen atom, a group -CH2000M s, a group -CH2CIll COOM? or a group -CH2CH2OH%
Group -CH2CH2COOMg or group -CH2CH20H
%X5 is the group -CH2COOM1°, the group -(H2CH2C
OOMI 1 or the group -CH2CH2OH, M6,
M7, Ma, M9, Mlo and Ml are the same or different and each is a hydrogen atom, K, Na or NH)
C) 0.01 to 2 mol/l of a chelate consisting of at least one compound represented by C) formaldehyde of 0.01 to 1 mol/l.

Formaldehyde polymer 0.3-30g/1. at least one of a hydrazine compound from 0.0005 to 0.1 mol/l and a polyacrylamide from 0.005 to Log/7, and d) a general formula (wherein zl, Z2, z3 and Z4 are the same or different and each Hydrogen atom or methyl group, QI is hydrogen atom, K, Na
or NH4, m represents an integer of 1 to 15. ), and the general formula (wherein A is a hydrogen atom, a hydroxyl group,
-8H.

group NH2CO-1 group -COOQ3, amino group, group NH2
-C-NH-1 group CH, cHi s- or group NH NH2CONH-1Z, , Z, and Z7 are the same or different and are each a hydrogen atom, a methyl group, or an ethyl group, ! is 0~
an integer of 4, k represents 0 or 1, Q2 and Q3 are the same or different and each is a hydrogen atom, K1Na or NH4)
an electrolytic copper plating solution consisting of an aqueous solution containing 0.006 to 1 mol/l of at least one of the compounds represented by (hereinafter referred to as "the plating solution of the present invention (■)"); (2) an alkali metal halide and a sulfate; At least one of alkaline earth metal halides and sulfates and ammonium halides and sulfates from 0.01 to
3 mol/l of the electrolytic copper plating solution according to claim 1 or 2 (hereinafter referred to as "the plating solution of the present invention (■
)”).

In the plating solution of the present invention, the copper compound is not particularly limited as long as it forms a copper complex with the chelating agent of component b) and exists stably in an aqueous solution, such as copper sulfate, copper chloride, copper oxide, etc. Copper, copper carbonate, copper acetate, copper birophosphate,
Copper oxalate or the like can be used. Of these,
Copper sulfate, copper chloride, copper oxide, etc. are preferably used. The concentration of the copper compound in the aqueous solution is about 0.01 to 1 mol/l, preferably about 0.05 to 0.5 mol/l.

If the concentration is less than 0.01 mol/l, the precipitation rate of the plating film will be slow, so it is not practical.
If the concentration exceeds the above, the precipitation rate will not be further improved, and the stability of the plating film may be impaired, which is not preferable.

Chelating agents used to form copper complexes include:
A compound represented by the general formula (wherein Xl, X2, Ml, M2, M8 and n are the same as above) and at least one compound represented by the general formula (wherein X3, X4 and X5 are the same as above) Use seed compounds. Preferred specific examples of these chelating agents include ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetraacetic acid disodium salt (EDTA・2Na), hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), and nitrilotriacetic acid (
NTA), triethylenetetraaminehexaacetic acid (TTHA)
), iminodiacetic acid (IDA), iminodipropionic acid (
IDP) etc. By adding such a chelating agent, the copper compound can stably exist in the plating solution as a copper complex, and a good plating film can be formed.

Particularly preferred chelating agents are ethylenediaminetetraacetic acid and its salts. Chelate, the amount added on the north side is 0.
About 0.01 to 2 mol/l, preferably 0.05 to 1 mol/l
It should be about l. If the concentration is less than 0.01 mol/l, the stability of the plating solution will be insufficient, while if the concentration exceeds 2 mol/l, the stability of the plating solution will not be further improved, which is uneconomical.

In the electrolytic copper plating solution of the present invention, at least one of formaldehyde, formaldehyde polymer, hydrazine compound, and polyacrylamide (hereinafter referred to as "additive component (A)") is used as an additive. Additive component (A)
By adding , the physical properties such as tensile strength and elongation of the deposited film are excellent, and the uniform electrodeposition property is also improved.

Among the additive components (A), formaldehyde polymers having a wide range of polymerization degrees can be used,
For example, those having a degree of polymerization of about 2 to 1000 can be used. As the hydrazine compound, for example, hydrazine, hydrazine hydrochloride, hydrazine acetate, hydrazine sulfate, etc. can be used. Polyacrylamide having a wide range of molecular weights can be used, for example, weight average molecular weight (Mw) = 100 to 100,000.
Good results can be obtained in all cases when using a compound of about 0.00.

Among these additive components (A), it is particularly preferable to use formaldehyde, paraformaldehyde, hydrazine, polyacrylamide, and the like.

The amount of additive component (A) added is formaldehyde 0.0
About 1 to 1 mol/l, preferably about 0.02 to 0.5 mol/l, formaldehyde polymer 0.3 to 30 g/I
degree, preferably 0.6 to 15 g/7, hydrazine compound about 0.0005 to 0.1 mol/l, preferably about 0.001 to 0.05 mol/l, polyacrylamide 0.005 to 10 g/l j approximately, preferably 0.02~
The amount should be about 5 g/l. If the amount of additive component (A) added is less than the above range, the effect of improving the physical properties will be insufficient, while even if the concentration exceeds the above range, the physical properties will not be further improved, which is uneconomical. In the present invention, the above-mentioned additive component (A) can be used alone or in combination of two or more.

The plating solution (I) of the present invention comprises the above-mentioned a) copper compound, b)
It is obtained by dissolving the chelating agent and C) additive component (A) in water. This plating solution has excellent uniform electrodeposition properties compared to conventional through-hole plating solutions such as copper pyrophosphate plating solution and copper sulfate plating solution. Furthermore, with the conventional plating solution for through-hole plating, it was not possible to obtain a plating film with good properties in both tensile strength and elongation, but with the plating solution of the present invention, a plating film with good properties in both properties can be obtained. can be formed. In addition, since the plating solution of the present invention can perform plating in a wide range of pH values, by adjusting the pH value to an appropriate value,
It is possible to form a plating film with good adhesion directly onto base metal materials such as iron materials, and it can also be used as an alternative to copper cyanide plating solution. Furthermore, it is possible to form a plating film on materials that are easily attacked by strong acids and strong bases without damaging them.

The plating solution (II) of the present invention is the plating solution (II) of the present invention described above (
I), and further the general formula: (wherein Z l , ZQ %z3s Z4 % Qt
% and m are the same as above), and a compound represented by the general formula: (wherein As Z5 , Z6 , z7 , Q2 ,
' and k are the same as above) (hereinafter referred to as "additive component (B)"), the physical properties such as tensile strength and elongation of the deposited film are further improved. This is an improvement. Preferred specific examples of the additive component (B) include glycine, alanine, N-methylglycine, valine, norvaline, leucine, norleucine, isoleucine, serine, cysteine, asparagine, aspartic acid, glutamic acid, ornithine, lysine, and arginine. Among them, glycine, alanine, N-methylglycine, lysine and the like are particularly preferred.

The amount of additive component (B) added is 0.006 to 1 mol/l
level, preferably about 0.01 to 0.5 mol/l. If the amount added is less than 0.006 mol/l, it will not contribute sufficiently to improving the physical properties, while if it is added in an amount exceeding 1 mol/l, the physical properties will not be further improved, which is uneconomical.

In the present invention, the above-mentioned present invention plating solution (I) or (II)
), further comprising alkali metal halides and sulfates,
By adding at least one of alkaline earth metal halides and sulfates and ammonium halides and sulfates, the uniform electrodeposition of the plating solution is further improved without substantially reducing the physical properties of the deposited film. be able to. The plating solution containing such a compound (the plating solution of the present invention (■)) has extremely excellent uniform electrodeposition properties and the physical properties of the deposited film, and can be used as an electrolytic copper plating solution for through-hole plating of printed circuit boards. Especially useful.

Examples of alkali metals include potassium and sodium, examples of alkaline earth metals include calcium and magnesium, and examples of halogens include chlorine, iodine, and oxaline.

Specific examples of preferred compounds include potassium chloride, magnesium chloride, calcium chloride, ammonium chloride, potassium iodide, potassium oxalide, potassium sulfate, sodium sulfate, ammonium sulfate, and the like. The amount of these compounds added is about 0.01 to 3 mol/l, preferably about 0.05 to 2 mol/l. If the amount added is less than 0.01 mol/l, the effect of improving uniform electrodeposition will not be sufficiently exhibited, while if the amount added is more than 3 mol/l, the uniform electrodeposition will not be further improved. Moreover, it is not preferable because it may not be completely dissolved in the plating solution.

The plating solutions (I) to (Illr) of the present invention are not particularly limited in pH value during plating, and can form a good plating film in any pH range, and can be used depending on the type of material used. The pH value may be appropriately set depending on the required physical properties of the deposited film. For example, by using it at a pH of about 8 or higher, a plating film can be directly formed on the iron material with good adhesion. Also, pH 6-8
By adjusting the amount to a certain degree, a plating film can be formed without attacking materials that are easily attacked by strong acids or strong bases.

Furthermore, when used for through-hole plating, the pH
By using within the range of about 6 to 8, a plated film excellent in all of uniform electrodeposition, tensile strength, elongation, etc. can be obtained. In particular, in order to improve uniform electrodeposition, it is preferable to use the solution at a pH of about 8 to 9. To adjust the pH of the plating solution, acids such as hydrochloric acid and sulfuric acid, and alkaline compounds such as sodium hydroxide and potassium hydroxide can be used as appropriate.

The plating solution of the present invention can be used at a bath temperature of about 10 to 90°C, but from the viewpoint of workability and physical properties of the deposited film,
It is preferable to use it at about 60°C.

The cathode current density can be selected within a wide range depending on the temperature and flow state of the plating solution. But usually 0, 1~10
It may be about A/dm2, preferably about 0.5 to 5 A/dm''.

Effects of the Invention The plating solution of the present invention has the following excellent characteristics.

(2) It has good uniform electrodeposition, tensile strength and elongation of the deposited film, and is suitable as a plating solution for through-hole plating of printed circuit boards. In particular, the plating solution (III) of the present invention
has extremely excellent uniform electrodeposition properties.

(2) Plating is possible in a wide pH range; for example, by using it at a pH of about 8 or higher, a copper plating film can be formed directly on the iron substrate with good adhesion. In addition, items to be plated include materials that are easily attacked by strong acids and bases, such as lead glass, zinc, sintered tungsten, and ceramics, such as chip capacitors, chip resistors,
Even in the case of ceramic substrates, deep dip ICs, etc.
By appropriately adjusting the pH of the plating solution, it becomes possible to perform copper plating without damaging these materials.

■ Bright plating can be formed without using sulfur-based brighteners that are added to ordinary copper sulfate plating solutions.

Therefore, even when thickening is performed, there is no adverse effect of sulfur eutectoid on the deposited film, and it is suitably used as a copper plating solution for electroforming.

■ The plating solution is easy to maintain and manage, and it can be used stably for a long period of time because it generates few impurities that can adversely affect the deposited film.

■ It is a plating solution with low toxicity.

Example Hereinafter, the present invention will be explained in more detail by showing examples.

Example 1 A plating solution having the following composition was prepared.

A bath B bath mol/l mol/I ocuc72 ・2H200,250,250 ethylenediaminetetraacetic acid 0.4 0.40 formaldehyde 0. 05 0.050 Glycine
0.03 Using the above A bath and B bath,
pH 6-10, bath temperature 50℃, cathode current density 3A/dm2
30μ on a 60mm x 100mm titanium plate under zero conditions.
Plating was applied to a thickness of m, and then the plating film was peeled off.

A dumbbell-shaped sample with a measuring part width of 4.2 mm was punched out from the obtained plating film, a tensile test was performed, and a stress-strain curve was determined to determine the tensile strength and elongation rate.

The results are shown in Figures 1 and 2.

From FIG. 1, it can be seen that the precipitated film exhibits high tensile strength in both baths A and B at pH 6 to 10. This tensile strength value is comparable to that of a plating film obtained from a copper pyrophosphate plating solution, and is much higher than that of a plating film obtained from a copper sulfate plating solution. Moreover, from FIG. 2, it can be seen that the deposited film exhibits a large elongation rate in both baths A and B at pH 6 to 10. This elongation rate is comparable to the elongation rate of a plating film obtained from a copper sulfate plating solution, and is much larger than the elongation percentage of a plating film obtained from a copper pyrophosphate plating solution.

From the above results, it can be seen that the plating solution of the present invention is excellent in both the tensile strength and elongation of the precipitated film.

In particular, when bath B is used, a plated film exhibiting high values of both tensile strength and elongation can be obtained.

Example 2 A plating solution having the following composition was prepared.

oCuC72”2H200, 25 mol/lO chelation north side 0.4 mol/l0 formaldehyde
0.05 mol/lQ glycine 0
．． 03 mol/l* Chelating agents include disodium ethylenediaminetetraacetate (EDTA-2Na), hydroxyethylethylenediaminetriacetic acid (HEDTA)
, diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), triethylenetetraminehexaacetic acid (
TTHA), iminodiacetic acid (IDA) and iminodipropionic acid (IDP) were each used alone.

A plating sample was prepared in the same manner as in Example 1, and its tensile strength and elongation were measured. As a result, no matter which chelating agent was used, the tensile strength was 50 to 80 kg/mm2 and the elongation rate was 2.5 to 4.0% in the pH range of 6 to 10.
A plating film was formed.

Example 3 A plating solution having the following composition was prepared.

oCuC72・2H200, 25 mol/l0 Ethylenediaminetetraacetic acid 0.4 mol/l0 Additive component (A) 7 0 Glycine 0.03 mol/l rice Additive component (A) is 1.5 g/l for paraformaldehyde. 7. 0.005 for hydrazine, hydrazine hydrochloride, hydrazine acetate and hydrazine sulfate
Mol/I! , polyacrylamide (Mw2000~60
00) and polyacrylamide (Mw700000~1
000000) is 0. Ig/7 was added individually.

A plating sample was prepared in the same manner as in Example 1, and its tensile strength and elongation were measured. As a result, no matter which additive component (A) was used, within the pH range of 6 to 10, the tensile strength was 50 to 80 kg/m1I12, and the elongation rate was 2.
．． A plating film of 5 to 4.0% was formed.

Example 4 A plating solution having the following composition was prepared.

0CuC72-2H200, 25 mol/l0 ethylenediaminetetraacetic acid 0.4 mol/lO formaldehyde
0.05 mol/ItO additive component (B) shrimp
0.03 mol/l* As the additive component (B), alanine, N-methylglycine, lysine, valine, leucine, and glutamic acid were each used alone.

A plating sample was prepared in the same manner as in Example 1, and its tensile strength and elongation were measured. As a result, no matter which additive component (B) was used, within the pH range of 6 to 10, the tensile strength was 50 to 80'g/mm2, and the elongation rate was 2.5.
~4.0% plating film was formed.

Example 5 A plating solution having the following composition was prepared.

C bath D bath Mol/l Mol/l oCuC12・2H20 0 Ethylenediaminetetraacetic acid O Formaldehyde 0 Glycine xcz 0, 25 0. 25 0.4 0.4 0, 05 0. 05 0, 03 0.03 Using the above C bath and D bath, under the conditions of bath temperature 50 ° C., pH 8, and cathode current density 2 and 3 A/dm2, respectively,
Plating films with a thickness of 30 μm were formed on printed circuit boards of different aspect ratios, each having a size of 60 mm×100 mm. Thereafter, the thickness of the plating film on the round part and through-hole part of the printed circuit board was measured, and the uniform electrodeposition was determined from the ratio of the two. The results are shown in Figure 3.

FIG. 3 also shows the results of similarly measuring uniform electrodeposition using a conventional copper pyrophosphate plating solution (hereinafter referred to as conventional bath).

From FIG. 3, it can be seen that both C bath and D bath are superior in uniform electrodeposition compared to the conventional bath.

In particular, bath D containing KCI showed excellent uniform electrodeposition.

[Brief explanation of drawings]

Fig. 1 is a graph of the measurement results of the tensile strength of the plating film of Example 1, Fig. 2 is a graph of the measurement results of the elongation rate of the plating film of Example 1, and Fig. 3 is a graph of the measurement results of the plating film of Example 5. It is a graph of the uniform electrodeposition test result of a liquid. (Above) Figure 1, dQpH Figure basis aspect ratio procedure amendment letter) □. May 2, 1991 Koda Commissioner of the Patent Office Satoshi Uematsu Display of the case 1990 Patent Application No. 46991, Name of the invention Relationship to the case of person amending electrolytic copper plating solution Patent applicant Ishihara Pharmaceutical Co., Ltd.

Claims (3)

[Claims] (1) a) Copper compound 0.01 to 1 mol/l b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X_1 is a hydrogen atom or group -COOM_4, X_
2 is a group -COOM_5 or a group -CH_2CH_2OH,
n represents an integer from 0 to 2, M_1, M_2, M_3, M
_4 and M_5 are the same or different and each represents a hydrogen atom, K,
There are compounds represented by Na or NH_4), and general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, X_3 is a hydrogen atom, the group -CH_2COOM_6
, group -CH_2CH_2COOM_7 or group -CH_2CH_2OH, X_4 is group -CH_2CO
OM_8, group -CH_2CH_2COOM_9 or group -
CH_2CH_2OH, X_5 is a group -CH_2COOM
_1_0, represents the group -CH_2CH_2COOM_1_1 or the group -CH_2CH_2OH, M_6, M_7, M
_8, M_9, M_1_0 and M_1_1 are the same or different and each is a hydrogen atom, K, Na or NH_4) chelating agent 0.01 to 2 mol/l, and c) formaldehyde An aqueous solution containing at least one of 0.01 to 1 mol/l, formaldehyde polymer 0.3 to 30 g/l, hydrazine compound 0.0005 to 0.1 mol/l, and polyacrylamide 0.005 to 10 g/l. An electrolytic copper plating solution consisting of (2) a) Copper compound 0.01-1 mol/l b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X_1 is a hydrogen atom or a group -COOM_4, X_
2 is a group -COOM_5 or a group -CH_2CH_2OH,
n represents an integer from 0 to 2, M_1, M_2, M_3, M
_4 and M_5 are the same or different and each represents a hydrogen atom, K,
There are compounds represented by Na or NH_4), and general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, X_3 is a hydrogen atom, the group -CH_2COOM_6
, group -CH_2CH_2COOM_7 or group -CH_2CH_2OH, X_4 is group -CH_2CO
OM_8, group -CH_2CH_2COOM_9 or group -
CH_2CH_2OH, X_5 is a group -CH_2COOM
_1_0, represents the group -CH_2CH_2COOM_1_1 or the group -CH_2CH_2OH, M_6, M_7, M
_8, M_9, M_1_0 and M_1_1 are the same or different and each is a hydrogen atom, K, Na or NH_4) A chelating agent consisting of at least one compound represented by 0.01 to 2 mol/l, c) Formaldehyde 0 .01 to 1 mol/l, formaldehyde polymer 0.3 to 30 g/l, hydrazine compound 0.0005 to 0.1 mol/l, and at least one of polyacrylamide 0.005 to 10 g/l, and d) General Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z_1, Z_2, Z_3 and Z_4 are the same or different and each is a hydrogen atom or a methyl group, Q_1 is a hydrogen atom, K, Na or NH_4, m is 1 to 15 ), as well as general formulas ▲mathematical formulas, chemical formulas, tables, etc. N
H_2-C-NH-, group CH_3CH_2S- or NH group NH_2CONH-, Z_5, Z_6 and Z_7 are the same or different and are each a hydrogen atom, a methyl group or an ethyl group,
l is an integer from 0 to 4, k is 0 or 1, Q_2 and Q
_3 are the same or different and each is a hydrogen atom, K, Na or N
H_4) at least one compound represented by 0
．． An electrolytic copper plating solution consisting of an aqueous solution containing 0.006 to 1 mol/l. (3) At least one of alkali metal halides and sulfates, alkaline earth metal halides and sulfates, and ammonium halides and sulfates: 0.01
The electrolytic copper plating solution according to claim 1 or 2, wherein the electrolytic copper plating solution contains up to 3 mol/l.