TWI878013B - Plating solution - Google Patents

Abstract

The present invention provides a coating solution capable of achieving high gloss coating. The present invention is a coating solution comprising: metal ions; and a PEI compound (L) having a polyethyleneimine main skeleton and having a structural part LX represented by the following formula (LX), a structural part LY represented by the following formula (LY), and a structural part LH represented by the following formula (LH), [Chemical 1] (In formula (LX), X is a structural part X1 represented by the following formula (X1), and i is an integer greater than or equal to 1) (In formula (LY), Y is a structural part Y1 represented by the following formula (Y1), and j is an integer greater than or equal to 1) (In formula (LH), k is an integer greater than 0 or 1) [Formula 4] (In formula (X1), A is C or S, E is a monovalent metal ion, H, methyl, ethyl or allyl, l is an integer from 1 to 6, and m is 1 or 2) [Chemistry 5] (In formula (Y1), G is _CH2 or CH(OH), n is 0 or 4, _Q1 and _Q2 are H, an electron-withdrawing group or an electron-donating group, respectively).

Description

Plating solution

The present invention relates to a coating liquid, and more particularly to a coating liquid capable of achieving high gloss coating.

Generally speaking, plating is used as one of the surface treatment technologies to give decorative appearance or corrosion resistance to substrates such as resins, metals, glass, and ceramics. Among them, electrolytic copper has high ductility and can prevent cracks caused by the expansion and contraction of the material due to temperature changes, so it is used as a base plating. In decorative applications, it is required to make the roughened substrate surface or the unevenness caused by the material smooth by etching, or high gloss is required.

For example, Patent Document 1 discloses an electrolytic copper plating solution that uses an alkaline dye such as Janus Green B as a lubricant in order to obtain a sufficient glossy appearance. In addition, an electrolytic copper plating solution that does not use an alkaline dye as a lubricant, such as Patent Document 2, is also disclosed. Patent Document 2 discloses an electrolytic copper plating solution that uses at least one aromatic reaction product of benzyl chloride and at least one polyethyleneimine. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent List No. 2020-536168 [Patent Document 2] Japanese Patent List No. 2020-523481

[The problem the invention is trying to solve]

However, in decorative coated products, a coating with a higher gloss is desired. The present invention is completed in view of this actual situation, and its purpose is to provide a coating liquid that can achieve a coating with a higher gloss without using the alkaline dye used previously. [Technical means to solve the problem]

The inventors of the present invention have conducted intensive research and found that a coating with high gloss can be achieved by including a specific compound as a smoothing agent, thereby completing the present invention.

(1) The coating solution of the present invention comprises: metal ions; and a PEI compound (L) having a polyethyleneimine main skeleton and having a structural portion LX represented by the following formula (LX), a structural portion LY represented by the following formula (LY) and a structural portion LH represented by the following formula (LH), [Chemical 1] (In formula (LX), X is a structural part X1 represented by the following formula (X1), and i is an integer greater than or equal to 1) (In formula (LY), Y is a structural part Y1 represented by the following formula (Y1), and j is an integer greater than or equal to 1) (In formula (LH), k is an integer greater than 0 or 1) [Formula 4] (In formula (X1), A is C or S, E is a monovalent metal ion, H, methyl, ethyl or allyl, l is an integer from 1 to 6, and m is 1 or 2) [Chemistry 5] (In formula (Y1), G is _CH2 or CH(OH), n is 0 or 4, _Q1 and _Q2 are H, an electron-withdrawing group or an electron-donating group, respectively).

(2) The coating solution of (1) is preferably such that [i/(i+j+k)]×100 calculated based on i of the structure portion LX, j of the structure portion LY and k of the structure portion LH is 20 to 90%.

(3) The plating solution of (1) or (2) is preferably such that the metal ions mentioned above include copper ions. [Effect of the invention]

According to the present invention, a coating liquid capable of achieving high gloss coating can be provided.

The following describes the implementation of the present invention.

[Coating solution] The coating solution of the present invention contains at least metal ions and PEI compound (L). The coating solution of the present invention may further contain acid, halogenide ions, brightener, surfactant, etc.

(Metal ions) The metal ions constituting the plating solution of the present invention are not particularly limited, and examples thereof include ions of copper, tin, titanium, chromium, manganese, iron, nickel, cobalt, zinc, silver, gold, platinum, palladium, indium, molybdenum, tungsten, lead, ruthenium, rhodium, ruthenium, nirconium, iridium, bismuth, and aluminum. In the plating solution of the present invention, it is preferred that the metal ions include copper ions.

The metal ions of the plating solution of the present invention are usually obtained by dissolving a metal salt in a solvent such as water. The plating solution of the present invention is preferably obtained by dissolving a metal salt containing copper in water. The metal salt containing copper is not particularly limited, and examples thereof include copper sulfate, copper pyrophosphate, copper acetate, etc. Among these, copper sulfate is preferred.

When copper sulfate is used, copper sulfate pentahydrate is preferred. The content of copper sulfate pentahydrate in the plating solution of the present invention is not particularly limited, and is, for example, 50 to 300 g/L, preferably 100 to 280 g/L.

(Smoothing agent) In the present invention, at least PEI compound (L) is used as a smoothing agent. In addition to PEI compound (L), the present invention may also add one or more known smoothing agents.

<PEI compound> The PEI compound (L) has a polyethyleneimine main skeleton and has a specific structural part. Specifically, the PEI compound (L) has a polyethyleneimine main skeleton and has a structural part LX represented by the following formula (LX), a structural part LY represented by the following formula (LY), and a structural part LH represented by the following formula (LH). The structural part LX, the structural part LY, and the structural part LH will be described below, and are structural parts having at least a [-(CH ₂ ) ₂ -N-] skeleton.

Here, the polyethyleneimine main skeleton means the main skeleton of polyethyleneimine (PEI). The PEI compound (L) has a structure in which the hydrogen atom H bonded to the polyethyleneimine main skeleton is substituted by the following X and Y. The polyethyleneimine main skeleton is, for example, a main skeleton of polyethyleneimine in a network, branched chain or straight chain. Here, the network polyethyleneimine means a polyethyleneimine in which a part or all of the branch parts in the branched chain polyethyleneimine are bonded to other branch parts or the main skeleton, thereby becoming a network. An example of a network polyethyleneimine is shown in the following formula (NP).

[Chemistry 66]

The PEI compound (L) is preferably a polyethyleneimine main skeleton having a network or branched structure.

The PEI compound (L) is a compound as follows: the number average molecular weight of polyethyleneimine having a polyethyleneimine main skeleton is, for example, 300 to 70,000, preferably 1,100 to 10,000, and more preferably 1,100 to 1,800. When the number average molecular weight of polyethyleneimine is within the above range, it is easy to obtain a metal plating film with a higher gloss, so it is preferred. Here, polyethyleneimine having a polyethyleneimine main skeleton means polyethyleneimine in which the atoms bonded to the polyethyleneimine main skeleton are only hydrogen atoms H.

PEI compound (L) is often obtained by reacting polyethyleneimine having a polyethyleneimine main skeleton, a raw material of X of the structural part LX, and a raw material of Y of the structural part LY. In this case, when the raw material of X of the structural part LX and the raw material of Y of the structural part LY are added to the polyethyleneimine as a raw material, the polyethyleneimine as a raw material does not polymerize, and the molecular weight of the PEI compound (L) increases accordingly by the amount of the raw material of X of the structural part LX and the raw material of Y of the structural part LY added.

In the present invention, the portion of the PEI compound (L) in which the hydrogen atom H bonded to the polyethyleneimine main skeleton is replaced by X is referred to as the structural portion LX. In addition, the portion of the PEI compound (L) in which the hydrogen atom H bonded to the polyethyleneimine main skeleton is replaced by Y is referred to as the structural portion LY. Furthermore, the portion of the PEI compound (L) in which the hydrogen atom H bonded to the polyethyleneimine main skeleton remains intact is referred to as the structural portion LH. Furthermore, the PEI compound (L) comprises at least the structural portion LX and the structural portion LY, and optionally comprises the structural portion LH.

[Structural part LX] The structural part LX is a structural part represented by the following formula (LX).

[Chemistry 77]

In the formula (LX), X is a structural part X1 represented by the following formula (X1), and i is an integer greater than or equal to 1.

[Chemistry 88]

In formula (X1), A is C or S, E is a monovalent metal ion, H, methyl, ethyl or allyl, l is an integer of 1 to 6, and m is 1 or 2. E is preferably a monovalent metal ion, H or allyl. l is preferably an integer of 3 to 4. Examples of the monovalent metal ion include Li, Na, K, Rb, Cs, and Fr.

Preferred embodiments of the structural moiety represented by the structural moiety X1 include, for example, structural moieties X111, X112, X113, and X114 represented by the following formula (X11).

[Chemistry 99]

The upper ends of the structural parts X111, X112 and X114 correspond to the left end of the structural part X1. The left end of the structural part X113 corresponds to the left end of the structural part X1.

[Structural part LY] The structural part LY is a structural part represented by the following formula (LY).

[Chemical 1010]

In the formula (LY), Y is a structural part Y1 represented by the following formula (Y1), and j is an integer greater than or equal to 1.

[Chemistry 11] In formula (Y1), G is _CH2 or CH(OH), n is 0 or 4, _Q1 and _Q2 are H, an electron-withdrawing group or an electron-donating group, respectively. When n is 0, the aryl group of the structural part Y1 is a structure containing one benzene ring. When n is 4, the aryl group of the structural part Y1 is a structure containing one naphthyl ring.

Furthermore, in formula (Y1), _Q1 and _Q2 of the aryl group of the structural part Y1 are H, an electron-withdrawing group or an electron-pushing group, respectively, and are not particularly limited. Examples of the electron-withdrawing group include chloro -Cl, fluoro -F, nitro _-NO2 , hydroxyl -OH, etc. Examples of the electron-pushing group include methyl _-CH3 , methoxy _-OCH3 , etc. When _Q1 and _Q2 are substituents other than hydrogen atom H, the substitution position of the substituent observed from the portion bonded to the polyethyleneimine main skeleton may include ortho, meta, para, etc.

Preferred embodiments of the structural moiety represented by the structural moiety Y1 include, for example, structural moieties Y111, Y112, Y113, and Y114 represented by the following formula (Y11).

[Chemistry 1112]

The upper end portions of the structural portions Y111, Y112 and Y113 correspond to the upper end portion of the structural portion Y1. The upper end portion of the right side of the structural portion Y114 corresponds to the upper end portion of the structural portion Y1.

Since _Q1 and _Q2 in formula (Y1) are H, an electron-withdrawing group or an electron-donating group, respectively, the aryl groups of the structural moieties Y111, Y112, Y113 and Y114 represented by formula (Y11) may be bonded with a substituent other than hydrogen atom H. When _Q1 and _Q2 of the aryl groups of the structural moieties Y111, Y112, Y113 and Y114 are substituents other than hydrogen atom H, the type, amount and position of the substituent are not particularly limited, and examples thereof include chloro -Cl, fluoro -F, methyl -CH ₃ , methoxy -OCH ₃ and the like.

Preferred embodiments in which _Q1 and _Q2 in formula (Y1) are structural moieties that are substituents other than hydrogen atom H include, for example, the structural moieties represented by the following formula (Y11A).

[Chemistry 13]

The upper end portions of the structural portions Y111-Cl, Y111-F, Y111-CH3 and Y111-OCH3 correspond to the upper end portion of the structural portion Y1.

As a particularly preferred embodiment in which _Q1 and _Q2 in formula (Y1) are a structural moiety that is a substituent other than a hydrogen atom H, for example, each structural moiety represented by the following formula (Y11B) can be exemplified.

[Chemistry 1214]

The upper end portions of the structural portions Y111-oCl, Y111-pF, Y111-mCH3 and Y111-mOCH3 correspond to the upper end portion of the structural portion Y1.

The structural portion Y111-oCl (-CH ₂ C ₆ H ₄ Cl), the structural portion Y111-pF (-CH ₂ C ₆ H ₄ F), the structural portion Y111-mCH3 (-CH ₂ C ₆ H ₄ CH ₃ ), and the structural portion Y111-mOCH3 (-CH ₂ C ₆ H ₄ OCH ₃ ) are respectively as follows: in the aryl group (benzyl group) of the structural portion Y111, one of Q ₁ and Q ₂ in the formula (Y1) is H, and the other is Cl at the ortho position, F at the para position, CH ₃ at the meta position, or OCH ₃ at the meta position.

[Structural part LH] The structural part LH is a structural part represented by the following formula (LH).

[Chemistry 1315]

In formula (LH), k is an integer greater than or equal to 0 or 1. When k is 0, the PEI compound (L) is a compound that does not contain the structural part LH.

Regarding the PEI compound (L), [i/(i+j+k)]×100 calculated based on i of the above structural part LX, j of the above structural part LY, and k of the above structural part LH is 20 to 90%, preferably 30 to 80%. When [i/(i+j+k)]×100 is within the above range, it is easy to obtain a metal plating film with higher gloss, which is preferred. Furthermore, the above [i/(i+j+k)]×100 can be measured by, for example, NMR (Nuclear Magnetic Resonance) or the like.

The coating solution of the present invention contains, for example, 0.5-50 mg/L of PEI compound (L), preferably 1-30 mg/L. When the concentration of PEI compound (L) in the coating solution is within the above range, it is easy to obtain a metal coating film with higher gloss, which is preferred.

(Acid) The plating solution of the present invention may contain an acid. The acid is not particularly limited. For example, inorganic acids and/or organic acids may be used in accordance with the composition of the plating solution or the plating object. Examples of inorganic acids include: hydrohalogen acids represented by sulfuric acid, nitric acid, and hydrochloric acid; oxygen-containing acids represented by phosphoric acid and chloric acid. Examples of organic acids include: alkanesulfonic acids such as methanesulfonic acid and propanesulfonic acid; alkanolsulfonic acids such as hydroxyethanesulfonic acid and propanolsulfonic acid; aliphatic or aromatic carboxylic acids such as citric acid, tartaric acid, and formic acid. Among them, when the raw material of the metal ion of the plating solution is copper sulfate, it is preferred to include sulfuric acid as the acid.

When the acid is sulfuric acid, the content of the sulfuric acid is not particularly limited, and is, for example, 20 to 200 g/L, preferably 30 to 150 g/L.

(Halide ions) In order to perform glossy metal plating or leveling, the plating solution of the present invention may also contain halide ions. The halide ions are not particularly limited, and examples thereof include chlorine, bromine, iodine, etc. Among them, chloride ions are preferred.

When the halogenide ions are chloride ions, the content of chloride ions is not particularly limited, and is, for example, 10 to 120 mg/L, preferably 20 to 100 mg/L.

(Glossing agent) The coating solution of the present invention may contain a glossing agent. The glossing agent is not particularly limited, and examples thereof include: benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 3-acenaphthaldehyde, benzylideneacetone, pyridylideneacetone, furfurylideneacetone, cinnamaldehyde, anisaldehyde, salicylic aldehyde, crotonaldehyde , acrolein, glutaraldehyde, paraldehyde, vanillin and other aldehydes; tris(III), imidazole, indole, quinoline, 2-vinylpyridine, aniline, phenanthroline, dimethylphenanthroline, picolinic acid, thioureas, N-(3-hydroxybutylene)-p-sulfanilic acid, N-butylenesulfanilic acid, N-cinnamylsulfanilic acid, 2,4-diamino-6-(2'-methylimidazolyl (1')) ethyl-1,3,5-triazine, 2,4-diamino-6-(2'-ethyl-4-methylimidazolyl (1'))ethyl-1,3,5-triazine, 2,4-diamino-6-(2'-undecylimidazolyl (1'))ethyl-1,3,5-triazine, phenyl salicylate; or benzothiazole, 2-hydroxybenzothiazole, 2-methylbenzothiazole, 2-amino Benzothiazoles such as benzothiazole, 2-amino-6-methoxybenzothiazole, 2-methyl-5-chlorobenzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-chlorobenzothiazole, 2,5-dimethylbenzothiazole, and 5-hydroxy-2-methylbenzothiazole; sulfides such as bis(sodium sulfopropyl)disulfide (SPS) and its salts, etc.

The content of the glossing agent is not particularly limited, and is, for example, 1 to 50 mg/L, preferably 3 to 30 mg/L.

(Surfactant) The coating solution of the present invention may contain a surfactant. The surfactant is not particularly limited, and examples thereof include non-ionic surfactants or amphoteric surfactants. The non-ionic surfactant is not particularly limited, and examples thereof include polyether compounds. The polyether compound is not particularly limited, and examples thereof include: polyalkylene glycol, polyether compounds having alkyl groups, and surfactants of triblock copolymers containing hydrophilic ethylene oxide units, hydrophobic propylene oxide units, and ethylene oxide units.

The content of the surfactant is not particularly limited, and is, for example, 1 to 300 mg/L, preferably 5 to 200 mg/L.

(Manufacturing method) The PEI compound (L) contained in the coating solution of the present invention is obtained by, for example, subjecting polyethyleneimine having a polyethyleneimine main skeleton, a raw material of X in the structural part LX, and a raw material of Y in the structural part LY to a nucleophilic addition reaction.

The coating solution of the present invention can be produced by a known method using the above-mentioned PEI compound (L) as a lubricant.

[Plating method] The following is a description of a plating method using the plating solution of the present invention. In this plating method, electroplating is performed on a substrate using the plating solution of the present invention.

(Substrate) The substrate is not particularly limited, and examples thereof include a substrate such as brass, copper, nickel, iron, zinc, zinc alloy, steel, resin, etc., on which a conductive layer such as a metal is formed.

(Temperature) The plating liquid of the present invention can set the liquid temperature during electroplating to, for example, 15 to 45°C, preferably about 20 to 35°C.

(Current Density) The plating solution of the present invention can set the current density during electroplating to, for example, 0.5 to 15 A/dm ² , preferably about 1 to 10 A/dm ² .

(Coating time) The coating liquid of the present invention can set the coating time during electroplating to, for example, more than 5 minutes, preferably more than 15 minutes.

According to the present invention, a coating liquid capable of achieving high gloss coating can be obtained. [Example]

The present invention is described in further detail below by way of embodiments, but the present invention is not limited to these embodiments.

[Example 1] (PEI compound) <Production of intermediate (Int.1)> Heat a polyethyleneimine (number average molecular weight 300) aqueous solution (0.90 M) to 70-90°C, add sodium chloroacetate in small amounts corresponding to 0.6 equivalents of the amine value, and react for 2 hours. Return to room temperature to obtain a 40 wt% aqueous solution of polyethyleneimine-sodium chloroacetate adduct (Int.1). Furthermore, ¹ HNMR (Hydrogen-1 Nuclear Magnetic Resonance) is used to confirm the progress of the reaction by the disappearance of the signal near 4.1 ppm.

<Preparation of PEI compound (sample No. A1)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-sodium chloroacetate adduct (Int. 1) and 76 parts by weight of a caustic sodium aqueous solution (8.5 M) were heated to 90°C, 20 parts by weight of benzyl chloride were added in small amounts gradually, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of the PEI compound (sample No. A1). The details of the PEI compound (sample No. A1) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

[Table 1] Experimental Example No. PEI compounds Plating solution Evaluation samples Sample No. The number average molecular weight Mn of the raw material polyethyleneimine Structure part LX Structure Sample No. Glossiness X Y Structural part name Structure Structural part name Structure Substituents of the aryl group of Y Type Location Embodiment 1 A1 300 X111 _-CH2COONa Y111 _{-CH2C6H5 ​ ​} - - E1 704 Embodiment 2 A2 300 X111 _-CH2COONa Y111-oCl -CH ₂ C ₆ H ₄ Cl -Cl Neighborhood E2 715 Embodiment 3 A3 1100 X111 _-CH2COONa Y111 _{-CH2C6H5 ​ ​} - - E3 1126 Embodiment 4 A4 1800 X111 _-CH2COONa Y111 _{-CH2C6H5 ​ ​} - - E4 1065 Embodiment 5 A5 1800 X111 _-CH2COONa Y111-pF _{-CH2C6H4F ​ ​} -F Counterpoint E5 893 Embodiment 6 A6 1800 X111 _-CH2COONa Y111-mCH3 -CH ₂ C ₆ H ₄ CH _{3 -CH3} Intermediate E6 1133 Embodiment 7 A7 1800 X111 _-CH2COONa Y111-mOCH3 -CH ₂ C ₆ H ₄ OCH ₃ -OCH ₃ Intermediate E7 967 Embodiment 8 A8 1800 X111 _-CH2COONa Y112 _{-CH2C10H7 ​ ​} - - E8 951 Embodiment 9 A9 1800 X111 _-CH2COONa Y113 _{-CH2C6H4NO2 ​ ​ ​} -NO ₂ Counterpoint E9 654 Embodiment 10 A10 1800 X111 _-CH2COONa Y114 -CHOHC ₆ H ₃ OCH ₃ OH -OCH ₃ /-OH Intermediate/opposite E10 494 Embodiment 11 A11 10000 X111 _-CH2COONa Y111 _{-CH2C6H5 ​ ​} - - E11 593 Embodiment 12 A12 70000 X111 _-CH2COONa Y111-oCl -CH ₂ C ₆ H ₄ Cl -Cl Neighborhood E12 562 Embodiment 13 A13 1800 X112 -(CH ₂ ) ₃ SO ₃ H Y111-pF _{-CH2C6H4F ​ ​} -F Counterpoint E13 490 Embodiment 14 A14 1800 X112 -(CH ₂ ) ₃ SO ₃ H Y111-mOCH3 -CH ₂ C ₆ H ₄ OCH ₃ -OCH ₃ Intermediate E14 692 Embodiment 15 A15 1800 X112 -(CH ₂ ) ₃ SO ₃ H Y113 _{-CH2C6H4NO2 ​ ​ ​} -NO ₂ Counterpoint E15 564 Embodiment 16 A16 10000 X112 -(CH ₂ ) ₃ SO ₃ H Y111 _{-CH2C6H5 ​ ​} - - E16 978

(Preparation of plating solution) A copper plating solution (Sample No. E1) containing 220 g/L of copper sulfate pentahydrate, 70 g/L of sulfuric acid, 60 mg/L of chloride ions Cl ^- , 100 mg/L of polyethylene glycol 20000 manufactured by Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd. as a surfactant, 8.3 mg/L of bis(sulfopropyl sodium)-disulfide (SPS) as a glossing agent, and 3.0 mg/L of PEI compound (Sample No. A1) as a smoothing agent was prepared.

(Electroplating test) ＜Pretreatment＞ First, the Hull Cell brass plate was immersed in EBAPREP SK-144 (degreased) manufactured by JCU Co., Ltd. at 55°C for 5 minutes, and then immersed in EBAVATE V-345 (acid activated) manufactured by JCU Co., Ltd. at room temperature for 0.5 minutes.

＜Electroplating＞ Using the pre-treated Hull cell brass plate and copper plating solution (sample No. E1), the Hull cell test was conducted for 10 minutes of cathodic electrolysis (total current 2 A) at room temperature. Afterwards, 0.5 minutes of anti-rust treatment was performed at room temperature using EBAFIN G-800 manufactured by JCU Co., Ltd., and an evaluation sample (sample No. S1) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The evaluation sample (sample No. S1) was placed in a Micro-Tri-Gloss gloss meter manufactured by BYK-Gardner Co., Ltd. The gloss was measured by irradiating light at an incident angle of 20° to the portion of the evaluation sample where the current density was 3 A/dm ^2. The gloss is shown in Table 1.

[Example 2] (PEI compound) ＜Preparation of PEI compound (Sample No. A2)＞ 100 parts by weight of the aqueous solution of the polyethyleneimine-sodium chloroacetate adduct prepared in Example 1 (Int. 1) and 83 parts by weight of a caustic sodium aqueous solution (7.5 M) were heated to 90°C, 25 parts by weight of 2-chlorobenzyl chloride were added in small amounts gradually, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (Sample No. A2). The details of the PEI compound (Sample No. A2) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E2) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A2) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except for using copper plating solution (sample No. E2) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S2) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 3] (PEI compound) <Production of intermediate (Int.2)> Heat a polyethyleneimine (number average molecular weight 1100) aqueous solution (0.22 M) to 70-90°C, add sodium chloroacetate in small amounts to 0.6 equivalents relative to the amine value, and react for 2 hours. Return to room temperature to obtain a 32.9 wt% aqueous solution of polyethyleneimine-sodium chloroacetate adduct (Int.2). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.1 ppm using ¹ HNMR.

<Preparation of PEI compound (sample No. A3)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-sodium chloroacetate adduct (Int. 2) and 29 parts by weight of a caustic sodium aqueous solution (7.8 M) were heated to 90°C, 6 parts by weight of benzyl chloride were added in small amounts, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (sample No. A3). The details of the PEI compound (sample No. A3) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E3) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A3) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E3) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S3) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 4] (PEI compound) <Production of intermediate (Int.3)> Heat a polyethyleneimine (number average molecular weight 1800) aqueous solution (0.30 M) to 70-90°C, add sodium chloroacetate (7.0 M) in small amounts with respect to the amine value of 0.6 equivalents, and react for 2 hours. Return to room temperature to obtain a 40 wt% aqueous solution of polyethyleneimine-sodium chloroacetate adduct (Int.3). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.1 ppm using ¹ HNMR.

<Preparation of PEI compound (sample No. A4)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-sodium chloroacetate adduct (Int. 3) and 90 parts by weight of a caustic sodium aqueous solution (6.6 M) were heated to 90°C, 70 parts by weight of benzyl chloride were added in small amounts gradually, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (sample No. A4). The details of the PEI compound (sample No. A4) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E4) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A4) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except for using copper plating solution (sample No. E4) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S4) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 5] (PEI compound) ＜Preparation of PEI compound (Sample No. A5)＞ 100 parts by weight of the aqueous solution of the polyethyleneimine-sodium chloroacetate adduct prepared in Example 4 (Int. 3) and 68 parts by weight of a caustic sodium aqueous solution (9.6 M) were heated to 90°C, 23 parts by weight of 4-fluorobenzyl chloride were added in small amounts gradually, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (Sample No. A5). The details of the PEI compound (Sample No. A5) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E5) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A5) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except for using copper plating solution (sample No. E5) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S5) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 6] (PEI compound) ＜Preparation of PEI compound (Sample No. A6)＞ 100 parts by weight of the aqueous solution of the polyethyleneimine-sodium chloroacetate adduct prepared in Example 4 (Int. 3) and 68 parts by weight of a caustic sodium aqueous solution (9.6 M) were heated to 90°C, 22 parts by weight of 3-methylbenzyl chloride were added in small amounts gradually, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (Sample No. A6). The details of the PEI compound (Sample No. A6) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E6) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A6) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except for using copper plating solution (sample No. E6) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S6) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 7] (PEI compound) <Preparation of PEI compound (Sample No. A7)> 100 parts by weight of the aqueous solution of the polyethyleneimine-sodium chloroacetate adduct prepared in Example 4 (Int. 3) and 69 parts by weight of a caustic sodium aqueous solution (9.6 M) were heated to 90°C, 25 parts by weight of 3-methoxybenzyl chloride were added in small amounts gradually, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (Sample No. A7). The details of the PEI compound (Sample No. A7) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E7) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A7) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E7) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S7) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 8] (PEI compound) <Preparation of PEI compound (Sample No. A8)> 100 parts by weight of the aqueous solution of the polyethyleneimine-sodium chloroacetate adduct prepared in Example 4 (Int. 3) and 54 parts by weight of an aqueous caustic sodium solution (13.3 M) were heated to 90°C, 28 parts by weight of 2-(chloromethyl)naphthalene were added, and the mixture was reacted for 2 hours. The mixture was returned to room temperature and 168 parts by weight of pure water were added to obtain an aqueous solution of a PEI compound (Sample No. A8). The details of the PEI compound (Sample No. A8) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E8) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A8) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except for using copper plating solution (sample No. E8) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S8) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 9] (PEI compound) <Preparation of PEI compound (Sample No. A9)> 100 parts by weight of the aqueous solution of the polyethyleneimine-sodium chloroacetate adduct prepared in Example 4 (Int. 3) and 75 parts by weight of an aqueous caustic sodium solution (8.4 M) were heated to 90°C, 27 parts by weight of 4-nitrobenzyl chloride were added, and the mixture was reacted for 2 hours. The mixture was returned to room temperature and 169 parts by weight of pure water were added to obtain an aqueous solution of a PEI compound (Sample No. A9). The details of the PEI compound (Sample No. A9) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E9) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A9) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E9) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S9) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 10] (PEI compound) <Preparation of PEI compound (Sample No. A10)> Heat 100 parts by weight of the aqueous solution of polyethyleneimine-sodium chloroacetate adduct prepared in Example 4 (Int. 3) and 5 parts by weight of vanillin to 80-90°C and react for 2 hours. Return to room temperature to obtain an aqueous solution of PEI compound (Sample No. A10). The details of the PEI compound (Sample No. A10) are shown in Table 1. Furthermore, using ¹³ CNMR (Carbon-13 Nuclear Magnetic Resonance, 13 carbon nuclear magnetic resonance), the progress of the reaction is confirmed by the disappearance of the signal near 191 ppm.

(Preparation of plating solution) A copper plating solution (sample No. E10) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A10) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E10) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S10) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 11] (PEI compound) <Production of intermediate (Int.4)> Heat a polyethyleneimine (number average molecular weight 10000) aqueous solution (0.017 M) to 70-90°C, add sodium chloroacetate in small amounts corresponding to 0.6 equivalents of the amine value, and react for 2 hours. Return to room temperature to obtain a 40 wt% aqueous solution of polyethyleneimine-sodium chloroacetate adduct (Int.4). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.1 ppm using ¹ HNMR.

<Production of PEI compound (sample No. A11)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-sodium chloroacetate adduct (Int. 4) and 66 parts by weight of a caustic sodium aqueous solution (10.2 M) were heated to 90°C, 20 parts by weight of benzyl chloride were added in small amounts, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (sample No. A11). The details of the PEI compound (sample No. A11) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E11) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A11) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E11) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S11) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 12] (PEI compound) <Production of intermediate (Int.5)> A 0.004 M aqueous solution of polyethyleneimine (number average molecular weight 70000) was heated to 70-90°C, and sodium chloroacetate was added in small amounts in an amount of 0.6 equivalents relative to the amine value, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain a 17 wt% aqueous solution of polyethyleneimine-sodium chloroacetate adduct (Int.5). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.1 ppm using ¹ HNMR.

<Preparation of PEI compound (sample No. A12)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-sodium chloroacetate adduct (Int. 5) and 130 parts by weight of a caustic sodium aqueous solution (2.8 M) were heated to 90°C, 5 parts by weight of 2-chlorobenzyl chloride were added in small amounts, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (sample No. A12). The details of the PEI compound (sample No. A12) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E12) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A12) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except for using copper plating solution (sample No. E12) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S12) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 13] (PEI compound) <Production of intermediate (Int.6)> An aqueous solution (0.17 M) of polyethyleneimine (number average molecular weight 1800) was heated to 70-90°C and reacted with 1,3-propane sultone having an amine value of 0.3 equivalents for 2 hours. The mixture was returned to room temperature to obtain a 34% aqueous solution (Int.6) of polyethyleneimine-1,3-propane sultone adduct. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.49 ppm using ¹ HNMR.

<Production of PEI compound (sample No. A13)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-1,3-propane sultone adduct (Int. 6), 150 parts by weight of pure water, and 20 parts by weight of 4-fluorobenzyl chloride were heated to 90°C and reacted for 2 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (sample No. A13). The details of the PEI compound (sample No. A13) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E13) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A13) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E13) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S13) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 14] (PEI compound) ＜Preparation of PEI compound (Sample No. A14)＞ 100 parts by weight of the aqueous solution of polyethyleneimine-1,3-propane sultone adduct prepared in Example 13 (Int. 6), 150 parts by weight of pure water, and 22 parts by weight of 3-methoxybenzyl chloride were heated to 90°C and reacted for 2 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (Sample No. A14). The details of the PEI compound (Sample No. A14) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E14) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A14) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E14) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S14) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 15] (PEI compound) ＜Preparation of PEI compound (Sample No. A15)＞ 100 parts by weight of the aqueous solution of polyethyleneimine-1,3-propane sultone adduct prepared in Example 13 (Int. 6), 200 parts by weight of pure water, and 23 parts by weight of 4-nitrobenzyl chloride were heated to 90°C and reacted for 2 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (Sample No. A15). The details of the PEI compound (Sample No. A15) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E15) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A15) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E15) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S15) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 16] (PEI compound) <Production of intermediate (Int.7)> An aqueous solution (0.015 M) of polyethyleneimine (number average molecular weight 10000) was heated to 70-90°C and reacted with 1,3-propane sultone having an amine value of 0.3 equivalents for 2 hours. The mixture was returned to room temperature to obtain a 23 wt% aqueous solution of polyethyleneimine-1,3-propane sultone adduct (Int.7). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.49 ppm using ¹ HNMR.

<Production of PEI compound (Sample No. A16)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-1,3-propane sultone adduct (Int. 7) and 6 parts by weight of benzyl chloride were heated to 80-90°C and reacted for 3 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (Sample No. A16). The details of the PEI compound (Sample No. A16) are shown in Table 1. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 PPM using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E16) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A16) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E16) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S16) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 1.

[Example 17] (PEI compound) <Production of intermediate (Int.8)> An aqueous solution (0.12 M) of polyethyleneimine (number average molecular weight 1100) was heated to 70-90°C and reacted with 0.2 equivalents of allyl chloroacetate relative to the amine value for 2 hours. The mixture was returned to room temperature to obtain a 17 wt% aqueous solution of polyethyleneimine-allyl chloroacetate adduct (Int.8). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.1 ppm using ¹ HNMR.

<Preparation of PEI compound (sample No. A17)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-allyl chloroacetate adduct (Int. 8) and 23 parts by weight of a caustic sodium aqueous solution (1.9M) were heated to 90°C, 6 parts by weight of benzyl chloride were added in small amounts, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of a PEI compound (sample No. A17). The details of the PEI compound (sample No. A17) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

[Table 2] Experimental Example No. PEI compounds Plating solution Evaluation samples Sample No. The number average molecular weight Mn of the raw material polyethyleneimine Structure part LX Structure Sample No. Glossiness X Y Structural part name Structure Structural part name Structure Substituents of the aryl group of Y Type Location Embodiment 17 A17 1100 X113 -CH ₂ COOCH ₂ CH=CH ₂ Y111 _{-CH2C6H5 ​ ​} - - E17 595 Embodiment 18 A18 1800 X113 -CH ₂ COOCH ₂ CH=CH ₂ Y111 _{-CH2C6H5 ​ ​} - - E18 1126 Embodiment 19 A19 1800 X113 -CH ₂ COOCH ₂ CH=CH ₂ Y111-oCl -CH ₂ C ₆ H ₄ Cl -CI Neighborhood E19 610 Embodiment 20 A20 1800 X113 -CH ₂ COOCH ₂ CH=CH ₂ Y111-pF _{-CH2C6H4F ​ ​} -F Counterpoint E20 645 Embodiment 21 A21 1800 X113 -CH ₂ COOCH ₂ CH=CH ₂ Y111-mCH3 -CH ₂ C ₆ H ₄ CH _{3 -CH3} Intermediate E21 528 Embodiment 22 A22 1800 X113 -CH ₂ COOCH ₂ CH=CH ₂ Y111-mOCH3 -CH ₂ C ₆ H ₄ OCH ₃ -OCH ₃ Intermediate E22 864 Embodiment 23 A23 1800 X113 -CH ₂ COOCH ₂ CH=CH ₂ Y113 _{-CH2C6H4NO2 ​ ​ ​} -NO ₂ Counterpoint E23 536 Embodiment 24 A24 10000 X113 -CH ₂ COOCH ₂ CH=CH ₂ Y111 _{-CH2C6H5 ​ ​} - - E24 756 Embodiment 25 A25 1800 X114 -(CH ₂ ) ₄ SO ₃ H Y111 _{-CH2C6H5 ​ ​} - - E25 526 Embodiment 26 A4 1800 X111 _-CH2COONa Y111 _{-CH2C6H5 ​ ​} - - E26 1249 Embodiment 27 A4 1800 X111 _-CH2COONa Y111 _{-CH2C6H5 ​ ​} - - E27 1215 Comparison Example 1 - - - - - - - - E28 468 Comparison Example 2 - - - - - - - - E29 389

(Preparation of plating solution) A copper plating solution (sample No. E17) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A17) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E17) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S17) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 18] (PEI compound) <Production of intermediate (Int.9)> An aqueous solution (0.10 M) of polyethyleneimine (number average molecular weight 1800) was heated to 70-90°C and reacted with 0.4 equivalents of allyl chloroacetate relative to the amine value for 2 hours. The mixture was returned to room temperature to obtain a 19 wt% aqueous solution of polyethyleneimine-allyl chloroacetate adduct (Int.9). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.1 ppm using ¹ HNMR.

<Preparation of PEI compound (sample No. A18)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-allyl chloroacetate adduct (Int. 9) and 19 parts by weight of a caustic sodium aqueous solution (4.4 M) were heated to 90°C, 5 parts by weight of benzyl chloride were added in small amounts, and the mixture was reacted for 2 hours. The mixture was returned to room temperature and 107 parts by weight of pure water were added to obtain an aqueous solution of a PEI compound (sample No. A18). The details of the PEI compound (sample No. A18) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E18) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A18) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E18) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S18) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 19] (PEI compound) <Production of intermediate (Int.10)> An aqueous solution (0.10 M) of polyethyleneimine (number average molecular weight 1800) was heated to 70-90°C and reacted with 0.2 equivalents of allyl chloroacetate relative to the amine value for 2 hours. The mixture was returned to room temperature to obtain a 15 wt% aqueous solution of polyethyleneimine-allyl chloroacetate adduct (Int.10). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.1 ppm using ¹ HNMR.

<Preparation of PEI compound (sample No. A19)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-allyl chloroacetate adduct (Int. 10) and 80 parts by weight of a caustic sodium aqueous solution (0.8 M) were heated to 90°C, 10 parts by weight of 2-chlorobenzyl chloride were added in small amounts, and the mixture was reacted for 2 hours. The mixture was returned to room temperature to obtain an aqueous solution of PEI compound (sample No. A19). The details of the PEI compound (sample No. A19) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E19) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A19) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E19) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S19) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 20] (PEI compound) ＜Preparation of PEI compound (Sample No. A20)＞ 100 parts by weight of the aqueous solution of polyethyleneimine-allyl chloroacetate adduct prepared in Example 19 (Int. 10) and 76 parts by weight of caustic sodium aqueous solution (1.7 M) were heated to 90°C and reacted with 9 parts by weight of 4-fluorobenzyl chloride for 2 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (Sample No. A20). The details of the PEI compound (Sample No. A20) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E20) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A20) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except for using copper plating solution (sample No. E20) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S20) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 21] (PEI compound) ＜Preparation of PEI compound (Sample No. A21)＞ 100 parts by weight of the aqueous solution of polyethyleneimine-allyl chloroacetate adduct prepared in Example 19 (Int. 10) and 86 parts by weight of caustic sodium aqueous solution (1.4 M) were heated to 90°C and reacted with 8 parts by weight of 3-methylbenzyl chloride for 2 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (Sample No. A21). The details of the PEI compound (Sample No. A21) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E21) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A21) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E21) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S21) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 22] (PEI compound) ＜Preparation of PEI compound (Sample No. A22)＞ 100 parts by weight of the aqueous solution of polyethyleneimine-allyl chloroacetate adduct prepared in Example 19 (Int. 10) and 63 parts by weight of an aqueous solution of caustic sodium (2 M) were heated to 90°C and reacted with 10 parts by weight of 3-methoxybenzyl chloride for 2 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (Sample No. A22). The details of the PEI compound (Sample No. A22) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E22) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A22) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E22) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S22) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 23] (PEI compound) ＜Preparation of PEI compound (Sample No. A23)＞ 100 parts by weight of the aqueous solution of polyethyleneimine-allyl chloroacetate adduct prepared in Example 19 (Int. 10) and 42 parts by weight of a caustic sodium aqueous solution (1.5 M) were heated to 90°C and reacted with 10 parts by weight of 4-nitrobenzyl chloride for 2 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (Sample No. A23). The details of the PEI compound (Sample No. A23) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E23) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A23) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E23) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S23) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 24] (PEI compound) <Production of intermediate (Int.11)> An aqueous solution (0.11 M) of polyethyleneimine (number average molecular weight 10000) was heated to 70-90°C and reacted with 0.2 equivalents of allyl chloroacetate relative to the amine value for 2 hours. The mixture was returned to room temperature to obtain a 12 wt% aqueous solution of polyethyleneimine-allyl chloroacetate adduct (Int.11). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.1 ppm using ¹ HNMR.

<Production of PEI compound (Sample No. A24)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-allyl chloroacetate adduct (Int. 11) was heated to 90°C and reacted with 5 parts by weight of benzyl chloride for 2 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (Sample No. A24). The details of the PEI compound (Sample No. A24) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E24) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A24) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except for using copper plating solution (sample No. E24) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S24) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 25] (PEI compound) <Production of intermediate (Int.12)> An aqueous solution (0.13 M) of polyethyleneimine (number average molecular weight 1800) was heated to 70-90°C and reacted with 1,4-butane sultone having an amine value of 0.6 equivalents for 2 hours. The mixture was returned to room temperature to obtain a 38 wt% aqueous solution of polyethyleneimine-1,4-butane sultone adduct (Int.12). Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.49 ppm using ¹ HNMR.

<Preparation of PEI compound (sample No. A25)> 100 parts by weight of the aqueous solution of the above-mentioned polyethyleneimine-1,4-butane sultone adduct (Int. 12) and 7 parts by weight of benzyl chloride were heated to 80-90°C and reacted for 3 hours. The solution was returned to room temperature to obtain an aqueous solution of PEI compound (sample No. A25). The details of the PEI compound (sample No. A25) are shown in Table 2. Furthermore, the progress of the reaction was confirmed by the disappearance of the signal near 4.5 ppm using ¹ HNMR.

(Preparation of plating solution) A copper plating solution (sample No. E25) was prepared in the same manner as in Example 1 except that a PEI compound (sample No. A25) was used instead of a PEI compound (sample No. A1).

(Electroplating test) Except that copper plating solution (sample No. E25) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S25) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 26] (Preparation of plating solution) A copper plating solution (sample No. E26) was prepared in the same manner as in Example 1, except that polyethylene glycol 4000 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. was used instead of polyethylene glycol 20000 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. The copper plating solution (sample No. E26) was obtained by changing only the surfactant in the copper plating solution (sample No. E4) prepared in Example 4.

(Electroplating test) Except that copper plating solution (sample No. E26) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S26) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Example 27] (Preparation of plating solution) A copper plating solution (sample No. E27) was prepared in the same manner as in Example 1, except that the non-ionic surfactant Adeka Pluronic (registered trademark) L-64 manufactured by ADEKA Co., Ltd. was used instead of polyethylene glycol 20000 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. The copper plating solution (sample No. E27) was obtained by changing only the surfactant in the copper plating solution (sample No. E4) prepared in Example 4.

(Electroplating test) Except that copper plating solution (sample No. E27) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S27) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Comparative Example 1] (Preparation of plating solution) A copper plating solution containing 220 g/L of copper sulfate pentahydrate, 70 g/L of sulfuric acid, 60 mg/L of chloride ions Cl ^- , 100 mg/L of polyethylene glycol 20000 manufactured by Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd. as a surfactant, 8.3 mg/L of bis(sulfopropyl sodium)-disulfide (SPS) as a brightener, and 3.0 mg/L of Janus Green B as a smoothing agent was prepared (Sample No. E28).

(Electroplating test) Except that copper plating solution (sample No. E28) was used instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1. As a result, an evaluation sample (sample No. S28) having a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

[Comparative Example 2] (Preparation of plating solution) A copper plating solution containing 220 g/L of copper sulfate pentahydrate, 70 g/L of sulfuric acid, 60 mg/L of chloride ions Cl ^- , 100 mg/L of polyethylene glycol 20000 manufactured by Fuji Film Co., Ltd. Wako Pure Chemical Industries, Ltd. as a surfactant, 8.3 mg/L of bis(sulfopropyl sodium)-disulfide (SPS) as a brightener, and 3.0 mg/L of an aromatic reaction product of benzyl chloride and polyalkylene imine as a lubricant was prepared (Sample No. E29).

(Electroplating test) Except for using copper plating solution (sample No. E29) instead of copper plating solution (sample No. E1), cathodic electrolysis was performed in the same manner as in Example 1, and an evaluation sample (sample No. S29) with a copper-plated film formed on the surface of the brass plate was obtained.

(Evaluation) The gloss was measured in the same manner as in Example 1. The gloss is shown in Table 2.

As can be seen from Tables 1 and 2, the evaluation samples prepared in the embodiments (samples No. E1 to E27) have higher gloss than the comparative examples (samples No. E28 and E29).

Claims (2)

A plating solution comprising: metal ions including copper ions; and a PEI compound (L) having a polyethyleneimine main skeleton and having a structural portion LX represented by the following formula (LX), a structural portion LY represented by the following formula (LY), and a structural portion LH represented by the following formula (LH),

(In formula (LX), X is the structural part X1 represented by the following formula (X1), and i is an integer greater than or equal to 1)

(In formula (LY), Y is the structural part Y1 represented by the following formula (Y1), and j is an integer greater than or equal to 1)

(In formula (LH), k is an integer greater than 0 or 1)

(In formula (X1), A is C or S, E is a monovalent metal ion, H, methyl, ethyl or allyl, l is an integer of 1 to 6, and m is 1 or 2) [Chemical 5]

(In formula (Y1), G is _CH2 or CH(OH), n is 0 or 4, _Q1 and _Q2 are H, an electron-withdrawing group or an electron-donating group, respectively). For example, the coating solution of claim 1, wherein [i/(i+j+k)]×100 calculated based on i of the above-mentioned structural part LX, j of the above-mentioned structural part LY and k of the above-mentioned structural part LH is 20~90%.