Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
  • C25D3/38—Electroplating: Baths therefor from solutions of copper
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/02—Electroplating: Baths therefor from solutions
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D3/00—Electroplating: Baths therefor
  • C25D3/66—Electroplating: Baths therefor from melts
  • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

• the present invention relates to a plating solution. More specifically, the present invention relates to a plating solution capable of plating with high gloss.
• plating treatment is performed as one of the surface treatment techniques to impart appearance characteristics such as decoration and functionality such as corrosion resistance to base materials such as resins, metals, glass, and ceramics.
• electrolytic copper plating is used as a base plating because it has high ductility and can prevent cracks from occurring due to expansion and contraction of the material due to temperature changes.
• it is required to smooth out the surface of the base material roughened by etching and unevenness caused by the material, and to have high gloss.
• Patent Document 1 discloses an electrolytic copper plating solution that uses a basic dye such as Janus Green B as a smoothing agent in order to obtain a sufficiently glossy appearance.
• Patent Document 2 discloses an electrolytic copper plating solution using at least one aromatic reaction product of benzyl chloride and at least one polyethyleneimine.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a plating solution that enables plating with higher glossiness without using conventionally used basic dyes.
• the plating solution according to the present invention has a metal ion and a polyethyleneimine main skeleton, and has a structural part LX shown by the following formula (LX), a structural part LY shown by the following formula (LY), and a structural part LY shown by the following formula (LH).
• the plating solution in (1) has ⁇ i/(i+j+k) ⁇ 100 calculated based on i of the structural portion LX, j of the structural portion LY, and k of the structural portion LH from 20 to 90%. It is preferable that
• the metal ions include copper ions.
• a plating solution capable of plating with high gloss can be provided.
• the plating solution according to the present invention contains at least metal ions and a PEI compound (L).
• the plating solution according to the present invention can further contain an acid, a halide ion, a brightener, a surfactant, and the like.
• Metal ions constituting the plating solution of the present invention are not particularly limited, but include, for example, copper, tin, titanium, chromium, manganese, iron, nickel, cobalt, zinc, silver, gold, platinum, palladium, indium, molybdenum, and tungsten. , lead, rhenium, rhodium, ruthenium, osmium, iridium, bismuth, aluminum, and other ions. In the plating solution according to the present invention, it is preferable that the metal ions include copper ions.
• the metal ions of the plating solution according to the present invention are usually obtained by dissolving a metal salt in a solvent such as water.
• the plating solution according to the present invention is preferably one obtained by dissolving a copper-containing metal salt in water.
• Metal salts containing copper include, but are not particularly limited to, copper sulfate, copper pyrophosphate, copper acetate, and the like. Among these, copper sulfate is preferred.
• copper sulfate When copper sulfate is used, it is preferably copper sulfate pentahydrate, and the content of copper sulfate pentahydrate in the plating solution according to the present invention is not particularly limited, but is, for example, 50 to 300 g/L, preferably 100 g/L. ⁇ 280g/L.
• smoothing agent In the present invention, at least a PEI compound (L) is used as a smoothing agent. In the present invention, one or more known smoothing agents may be added in addition to the PEI compound (L).
• 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 includes a structural part LX shown in the following formula (LX), a structural part LY shown in the following formula (LY), and a structural part LY shown in the following formula (LH), which will be described later. It has a structural portion LH shown in FIG. The structural portion LX, structural portion LY, and structural portion LH will be described later, and each is a structural portion having at least a [-(CH 2 ) 2 -N-] skeleton.
• 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 with X and Y described below.
• the polyethyleneimine main skeleton is, for example, a network, branched, or linear polyethyleneimine main skeleton.
• network-like polyethyleneimine refers to polyethyleneimine in which part or all of the branched parts of branched polyethyleneimine are combined with other branched parts or the main skeleton to form a network-like polyethyleneimine.
• An example of mesh-like polyethyleneimine is shown in the following formula (NP).
• the PEI compound (L) preferably has a polyethyleneimine main skeleton that is network-like or branched.
• the PEI compound (L) is a compound in which 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, more preferably 1,100 to 1,800. It is preferable that the number average molecular weight of polyethyleneimine is within the above range because it is easy to obtain a metal plating film with high gloss.
• the polyethyleneimine having a polyethyleneimine main skeleton means polyethyleneimine in which the only atoms bonded to the polyethyleneimine main skeleton are hydrogen atoms H.
• the PEI compound (L) is often obtained by reacting polyethyleneimine having a polyethyleneimine main skeleton, the raw material for X in the structural part LX, and the raw material for Y in the structural part LY.
• the raw material X of the structural part LX and the raw material Y of the structural part LY are added to the polyethyleneimine raw material, the polyethyleneimine raw material does not polymerize and the PEI compound (L) is formed.
• the molecular weight of increases by the addition of the raw material for X in the structural part LX and the raw material for Y in the structural part LY.
• a portion of the PEI compound (L) in which the hydrogen atom H bonded to the polyethyleneimine main skeleton is replaced with X is referred to as a structural portion LX.
• a portion in which the hydrogen atom H bonded to the polyethyleneimine main skeleton is replaced with Y is referred to as a structural portion LY.
• the portion of the PEI compound (L) in which the hydrogen atom H bonded to the polyethyleneimine main skeleton exists as is is referred to as a structural portion LH.
• the PEI compound (L) includes at least a structural portion LX and a structural portion LY, and optionally a structural portion LH.
• the structural portion LX is a structural portion represented by the following formula (LX).
• X is a structural moiety X1 shown in formula (X1) below, and i is an integer of 1 or more.
• A is C or S
• E is a monovalent metal ion, H, a methyl group, an ethyl group, or an allyl group
• l is an integer of 1 to 6
• m is 1 or 2.
• E is preferably a monovalent metal ion, H, or an allyl group.
• l is preferably an integer of 3 to 4.
• monovalent metal ions 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 represented by the structural moieties X111, X112, X113, and X114 shown in the following formula (X11).
• the upper end portions of the structural portions X111, X112, and X114 correspond to the left end portion of the structural portion X1.
• the left end portion of the structural portion X113 corresponds to the left end portion of the structural portion X1.
• the structural portion LY is a structural portion represented by the following formula (LY).
• Y is a structural moiety Y1 shown in formula (Y1) below, and j is an integer of 1 or more.
• G is CH 2 or CH(OH)
• n is 0 or 4
• Q 1 and Q 2 are each H, an electron-withdrawing group or an electron-donating group.
• n is 0, the aryl group of structural moiety Y1 has a structure containing one benzene ring.
• n is 4, the aryl group of structural moiety Y1 has a structure containing one naphthalene ring.
• Q 1 and Q 2 of the aryl group of structural moiety Y1 are each H, an electron-withdrawing group, or an electron-donating group, and are not particularly limited.
• the electron-withdrawing group include a chloro group -Cl, a fluoro group -F, a nitro group -NO 2 and a hydroxy group -OH.
• the electron-donating group include methyl group -CH 3 and methoxy group -OCH 3 .
• Preferred embodiments of the structural moiety represented by the structural moiety Y1 include, for example, structural moieties represented by the structural moieties Y111, Y112, Y113, and Y114 shown in the following formula (Y11).
• the upper end portions of structural portions Y111, Y112, and Y113 correspond to the upper end portion of structural portion Y1.
• the upper right end portion of the structural portion Y114 corresponds to the upper end portion of the structural portion Y1.
• the aryl groups of structural moieties Y111, Y112, Y113 and Y114 shown in formula (Y11) may be bonded with a substituent other than the hydrogen atom H.
• Q 1 and Q 2 of the aryl group of structural moieties Y111, Y112, Y113, and Y114 are substituents other than hydrogen atom H, there are no particular restrictions on the type, number, and position of the substituents. Examples include Cl, fluoro group -F, methyl group -CH 3 , methoxy group -OCH 3 and the like.
• Preferred embodiments of the structural moiety in which Q 1 and Q 2 in formula (Y1) are substituents other than hydrogen atom H include, for example, each structural moiety shown in formula (Y11A) below.
• 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.
• structural portions Y111-oCl, Y111-pF, Y111-mCH3, and Y111-mOCH3 correspond to the upper end portion of structural portion Y1.
• Structural moiety Y111-oCl (-CH 2 C 6 H 4 Cl), structural moiety Y111-pF (-CH 2 C 6 H 4 F), structural moiety Y111-mCH3 (-CH 2 C 6 H 4 CH 3 ), and Structural moiety Y111-mOCH3 (-CH 2 C 6 H 4 OCH 3 ) has a structure in which one of Q 1 and Q 2 in formula (Y1) is H and the other is ortho in the aryl group (benzyl group) of structural moiety Y111. Cl at the position, F at the para position, CH 3 at the meta position, and OCH 3 at the meta position.
• Structural portion LH is a structural portion represented by the following formula (LH).
• k is 0 or an integer of 1 or more. Note that when k is 0, the PEI compound (L) becomes a compound that does not contain the structural moiety LH.
• the PEI compound (L) has ⁇ i/(i+j+k) ⁇ 100 calculated based on i of the structural portion LX, j of the structural portion LY, and k of the structural portion LH from 20 to 90%, preferably 30%. ⁇ 80%. It is preferable that ⁇ i/(i+j+k) ⁇ 100 is within the above range because it is easy to obtain a metal plating film with high gloss. Note that the above ⁇ i/(i+j+k) ⁇ 100 can be measured, for example, by NMR or the like.
• the plating solution according to the present invention contains a PEI compound (L), for example, 0.5 to 50 mg/L, preferably 1 to 30 mg/L. It is preferable that the concentration of the PEI compound (L) in the plating solution is within the above range because it is easy to obtain a metal plating film with high gloss.
• the plating solution according to the present invention may contain an acid.
• the acid is not particularly limited, but for example, a desired inorganic acid and/or organic acid can be used depending on the composition of the plating solution and the object to be plated.
• inorganic acids include hydrohalic acids such as sulfuric acid, nitric acid, and hydrochloric acid, and oxoacids such as phosphoric acid and chloric acid.
• organic acids examples include alkanesulfonic acids such as methanesulfonic acid and propanesulfonic acid, alkanolsulfonic acids such as isethionic acid and propanolsulfonic acid, aliphatic or aromatic carboxylic acids such as citric acid, tartaric acid, and formic acid. It will be done. Among these, when the raw material for metal ions in the plating solution is copper sulfate, it is preferable to include sulfuric acid as the acid.
• the content of sulfuric acid is not particularly limited, but is, for example, 20 to 200 g/L, preferably 30 to 150 g/L.
• the plating solution according to the present invention may contain halide ions for the purpose of bright metal plating and leveling.
• Halide ions are not particularly limited, but include, for example, chlorine, bromine, and iodine. Among these, chloride ions are preferred.
• the content of the chloride ion is not particularly limited, but is, for example, 10 to 120 mg/L, preferably 20 to 100 mg/L.
• the plating solution according to the present invention may contain a brightener.
• Brighteners are not particularly limited, but include, for example, benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, furfural, 1-naphthaldehyde, 2 - Naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 3-acenaphthaldehyde, benzylidene acetone, pyrididene acetone, furfuryldene acetone, cinnamaldehyde, anisaldehyde, salicylaldehyde, crotonaldehyde, acrolein, glutaraldehyde, paraldehyde , various aldehydes such as vanillin, tria
• the content of the brightener is not particularly limited, but is, for example, 1 to 50 mg/L, preferably 3 to 30 mg/L.
• the plating solution according to the present invention may contain a surfactant.
• the surfactant is not particularly limited, but includes, for example, nonionic surfactants and amphoteric surfactants.
• the nonionic surfactant is not particularly limited, but includes, for example, polyether compounds.
• the polyether compound is not particularly limited, but includes, for example, polyalkylene glycol, a polyether compound having an alkyl group, and a surface-active polyether compound consisting of a triblock copolymer of a hydrophilic ethylene oxide unit, a hydrophobic propylene oxide unit, and an ethylene oxide unit. agents, etc.
• the content of the surfactant is not particularly limited, but is, for example, 1 to 300 mg/L, preferably 5 to 200 mg/L.
• the PEI compound (L) contained in the plating solution according to the present invention undergoes nucleophilic addition of polyethyleneimine having a polyethyleneimine main skeleton, the raw material for X in the structural part LX, and the raw material for Y in the structural part LY. Obtained by reaction.
• the plating solution according to the present invention can be produced by a known method using the above PEI compound (L) as a smoothing agent.
• plating method a plating method using the plating solution according to the present invention will be explained.
• electroplating is performed on a substrate using the plating solution according to the present invention.
• the base material is not particularly limited, but includes, for example, a base material such as brass, copper, nickel, iron, zinc, zinc alloy, steel, resin, etc., on which a conductive layer of metal or the like is formed.
• the solution temperature during electroplating may be, for example, about 15 to 45°C, preferably about 20 to 35°C.
• the plating solution according to the present invention may have a current density during electroplating of, for example, about 0.5 to 15 A/dm 2 , preferably about 1 to 10 A/dm 2 .
• the plating time during electroplating may be, for example, 5 minutes or more, preferably 15 minutes or more.
• a plating solution capable of plating with high gloss can be obtained.
• PEI compound (sample No. A1)> 100 parts by weight of the above polyethyleneimine-sodium chloroacetate adduct aqueous solution (Int. 1) and 76 parts by weight of a caustic soda aqueous solution (8.5M) were heated to 90°C, 20 parts by weight of benzyl chloride was added little by little, and the mixture was reacted for 2 hours. I let it happen. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A1) was obtained. Table 1 shows details of the PEI compound (sample No. A1). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• An evaluation sample (sample No. S1) was set in a Micro Trigloss gloss meter manufactured by BYK-Gardner Co., Ltd. Glossiness was measured by irradiating light at an incident angle of 20° onto a portion of the evaluation sample at a current density of 3 A/dm 2 . Table 1 shows the glossiness.
• Example 2 (PEI compound) ⁇ Production of PEI compound (sample No. A2)> 100 parts by weight of the aqueous solution (Int. 1) of the polyethyleneimine-sodium chloroacetate adduct produced in Example 1 and 83 parts by weight of a caustic soda aqueous solution (7.5M) were heated to 90°C, and 25 parts by weight of 2-chlorobenzyl chloride were added. was added little by little and allowed to react for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A2) was obtained. Table 1 shows details of the PEI compound (sample No. A2). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• ⁇ Production of PEI compound (sample No. A3)> 100 parts by weight of the aqueous solution (Int. 2) of the above polyethyleneimine-sodium chloroacetate adduct and 29 parts by weight of a caustic soda aqueous solution (7.8M) were heated to 90°C, 6 parts by weight of benzyl chloride was added little by little, and the mixture was reacted for 2 hours. I let it happen. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A3) was obtained. Table 1 shows details of the PEI compound (sample No. A3). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A4)> 100 parts by weight of the above polyethyleneimine-sodium chloroacetate adduct aqueous solution (Int. 3) and 90 parts by weight of a caustic soda aqueous solution (6.6M) were heated to 90°C, 70 parts by weight of benzyl chloride was added little by little, and the mixture was reacted for 2 hours. I let it happen. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A4) was obtained. Table 1 shows details of the PEI compound (sample No. A4). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 5 (PEI compound) ⁇ Production of PEI compound (sample No. A5)> 100 parts by weight of the aqueous solution (Int. 3) of the polyethyleneimine-sodium chloroacetate adduct produced in Example 4 and 68 parts by weight of the caustic soda aqueous solution (9.6M) were heated to 90°C, and 23 parts by weight of 4-fluorobenzyl chloride were added. was added little by little and allowed to react for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A5) was obtained. Table 1 shows details of the PEI compound (sample No. A5). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 6 (PEI compound) ⁇ Production of PEI compound (sample No. A6)> 100 parts by weight of the aqueous solution (Int. 3) of the polyethyleneimine-sodium chloroacetate adduct produced in Example 4 and 68 parts by weight of the caustic soda aqueous solution (9.6M) were heated to 90°C, and 22 parts by weight of 3-methylbenzyl chloride were added. was added little by little and allowed to react for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A6) was obtained. Table 1 shows details of the PEI compound (sample No. A6). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 7 (PEI compound) ⁇ Production of PEI compound (sample No. A7)> 100 parts by weight of the aqueous solution (Int. 3) of the polyethyleneimine-sodium chloroacetate adduct produced in Example 4 and 69 parts by weight of the caustic soda aqueous solution (9.6M) were heated to 90°C, and 25 parts by weight of 3-methoxybenzyl chloride were added. was added little by little and allowed to react for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A7) was obtained. Table 1 shows details of the PEI compound (sample No. A7). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 8 (PEI compound) ⁇ Production of PEI compound (sample No. A8)> 100 parts by weight of the aqueous solution (Int. 3) of the polyethyleneimine-sodium chloroacetate adduct produced in Example 4 and 54 parts by weight of the caustic soda aqueous solution (13.3M) were heated to 90°C, and 28 parts by weight of 2-(chloromethyl)naphthalene was heated. Parts by weight were added and reacted for 2 hours. When the temperature was returned to room temperature and 168 parts by weight of pure water was added, an aqueous solution of a PEI compound (sample No. A8) was obtained. Table 1 shows details of the PEI compound (sample No. A8). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 9 (PEI compound) ⁇ Production of PEI compound (sample No. A9)> 100 parts by weight of the aqueous solution (Int. 3) of the polyethyleneimine-sodium chloroacetate adduct produced in Example 4 and 75 parts by weight of the caustic soda aqueous solution (8.4M) were heated to 90°C, and 27 parts by weight of 4-nitrobenzyl chloride were added. was added and reacted for 2 hours. When the temperature was returned to room temperature and 169 parts by weight of pure water was added, an aqueous solution of a PEI compound (sample No. A9) was obtained. Table 1 shows details of the PEI compound (sample No. A9). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 10 (PEI compound) ⁇ Production of PEI compound (sample No. A10)> 100 parts by weight of the aqueous solution of polyethyleneimine-sodium chloroacetate adduct (Int. 3) prepared in Example 4 and 5 parts by weight of vanillin were heated to 80 to 90°C and reacted for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A10) was obtained. Table 1 shows details of the PEI compound (sample No. A10). The progress of the reaction was confirmed by 13 CNMR by the disappearance of the signal around 191 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A11)> 100 parts by weight of the above polyethyleneimine-sodium chloroacetate adduct aqueous solution (Int. 4) and 66 parts by weight of a caustic soda aqueous solution (10.2M) were heated to 90°C, 20 parts by weight of benzyl chloride was added little by little, and the mixture was reacted for 2 hours. I let it happen. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A11) was obtained. Table 1 shows details of the PEI compound (sample No. A11). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A12)> 100 parts by weight of the aqueous solution of the polyethyleneimine-sodium chloroacetate adduct (Int. 5) and 130 parts by weight of a caustic soda aqueous solution (2.8M) were heated to 90°C, and 5 parts by weight of 2-chlorobenzyl chloride were added little by little. The reaction was allowed to proceed for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A12) was obtained. Table 1 shows details of the PEI compound (sample No. A12). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A13)> 100 parts by weight of the aqueous solution of the polyethyleneimine-1,3-propanesultone 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. . When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A13) was obtained. Table 1 shows details of the PEI compound (sample No. A13). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 14 (PEI compound) ⁇ Production of PEI compound (sample No. A14)> 100 parts by weight of the aqueous solution (Int. 6) of the polyethyleneimine-1,3-propane sultone adduct produced in Example 13, 150 parts by weight of pure water, and 22 parts by weight of 3-methoxybenzyl chloride were heated to 90°C, The reaction was allowed to proceed for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A14) was obtained. Table 1 shows details of the PEI compound (sample No. A14). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 15 (PEI compound) ⁇ Production of PEI compound (sample No. A15)> 100 parts by weight of the aqueous solution (Int. 6) of the polyethyleneimine-1,3-propane sultone adduct produced in Example 13, 200 parts by weight of pure water, and 23 parts by weight of 4-nitrobenzyl chloride were heated to 90°C, The reaction was allowed to proceed for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A15) was obtained. Table 1 shows details of the PEI compound (sample No. A15). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A16)> 100 parts by weight of the aqueous solution of the polyethyleneimine-1,3-propanesultone adduct (Int. 7) and 6 parts by weight of benzyl chloride were heated to 80 to 90°C and reacted for 3 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A16) was obtained. Table 1 shows details of the PEI compound (sample No. A16). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A17)> 100 parts by weight of the aqueous solution of the polyethyleneimine-allyl chloroacetate adduct (Int. 8) and 23 parts by weight of a caustic soda aqueous solution (1.9M) were heated to 90°C, 6 parts by weight of benzyl chloride was added little by little, and the mixture was reacted for 2 hours. I let it happen. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A17) was obtained. Table 2 shows details of the PEI compound (sample No. A17). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A18)> 100 parts by weight of the aqueous solution of the polyethyleneimine-allyl chloroacetate adduct (Int. 9) and 19 parts by weight of a caustic soda aqueous solution (4.4M) were heated to 90°C, 5 parts by weight of benzyl chloride was added little by little, and the mixture was reacted for 2 hours. I let it happen. When the temperature was returned to room temperature and 107 parts by weight of pure water was added, an aqueous solution of a PEI compound (sample No. A18) was obtained. Table 2 shows details of the PEI compound (sample No. A18). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A19)> 100 parts by weight of the aqueous solution of the polyethyleneimine-allyl chloroacetate adduct (Int. 10) and 80 parts by weight of a caustic soda aqueous solution (0.8M) were heated to 90°C, and 10 parts by weight of 2-chlorobenzyl chloride was added little by little. The reaction was allowed to proceed for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A19) was obtained. Table 2 shows details of the PEI compound (sample No. A19). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 20 (PEI compound) ⁇ Production of PEI compound (sample No. A20)> 100 parts by weight of the aqueous solution of the polyethyleneimine-allyl chloroacetate adduct produced in Example 19 (Int. 10) and 76 parts by weight of a caustic soda aqueous solution (1.7M) were heated to 90°C, and 9 parts by weight of 4-fluorobenzyl chloride were added. was allowed to react for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A20) was obtained. Table 2 shows details of the PEI compound (sample No. A20). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 21 (PEI compound) ⁇ Production of PEI compound (sample No. A21)> 100 parts by weight of the aqueous solution of the polyethyleneimine-allyl chloroacetate adduct produced in Example 19 (Int. 10) and 86 parts by weight of a caustic soda aqueous solution (1.4M) were heated to 90°C, and 8 parts by weight of 3-methylbenzyl chloride were added. was allowed to react for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A21) was obtained. Table 2 shows details of the PEI compound (sample No. A21). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 22 (PEI compound) ⁇ Production of PEI compound (sample No. A22)> 100 parts by weight of the aqueous solution (Int. 10) of the polyethyleneimine-allyl chloroacetate adduct produced in Example 19 and 63 parts by weight of a caustic soda aqueous solution (2M) were heated to 90°C, and 10 parts by weight of 3-methoxybenzyl chloride was added to 2 parts by weight. Allowed time to react. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A22) was obtained. Table 2 shows details of the PEI compound (sample No. A22). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• Example 23 (PEI compound) ⁇ Production of PEI compound (sample No. A23)> 100 parts by weight of the aqueous solution of the polyethyleneimine-allyl chloroacetate adduct produced in Example 19 (Int. 10) and 42 parts by weight of a caustic soda aqueous solution (1.5M) were heated to 90°C, and 10 parts by weight of 4-nitrobenzyl chloride were added. was allowed to react for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A23) was obtained. Table 2 shows details of the PEI compound (sample No. A23). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A24)> 100 parts by weight of the above aqueous solution of polyethyleneimine-allyl chloroacetate adduct (Int. 11) was heated to 90°C, and 5 parts by weight of benzyl chloride was reacted for 2 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A24) was obtained. Table 2 shows details of the PEI compound (sample No. A24). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• PEI compound (sample No. A25)> 100 parts by weight of the aqueous solution of the polyethyleneimine-1,4-butanesultone adduct (Int. 12) and 7 parts by weight of benzyl chloride were heated to 80 to 90°C and reacted for 3 hours. When the temperature was returned to room temperature, an aqueous solution of a PEI compound (sample No. A25) was obtained. Table 2 shows details of the PEI compound (sample No. A25). The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.5 ppm.
• 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 the PEI compound (sample No. A1).
• 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 in place of polyethylene glycol 20000 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
• the copper plating solution (Sample No. E26) is the same as the copper plating solution (Sample No. E4) prepared in Example 4, except that only the surfactant was changed.
• Example 27 (Preparation of plating solution) A copper plating solution (sample No. E27) was prepared.
• the copper plating solution (Sample No. E27) is the same as the copper plating solution (Sample No. E4) prepared in Example 4, except that only the surfactant was changed.
• [Comparative example 1] (Preparation of plating solution) 220 g/L of copper sulfate pentahydrate, 70 g/L of sulfuric acid, 60 mg/L of chloride ion Cl - 100 mg/L of polyethylene glycol 20000 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. as a surfactant, and gloss.
• a copper plating solution (sample No. E28) containing 8.3 mg/L of bis(3-sodium sulfopropyl) disulfide (SPS) as an agent and 3.0 mg/L of Janus Green B as a smoothing agent was used. Prepared.
• [Comparative example 2] (Preparation of plating solution) 220 g/L of copper sulfate pentahydrate, 70 g/L of sulfuric acid, 60 mg/L of chloride ion Cl - 100 mg/L of polyethylene glycol 20000 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. as a surfactant, and gloss. Copper containing 8.3 mg/L of bis(3-sodium sulfopropyl) disulfide (SPS) as an agent and 3.0 mg/L of an aromatic reaction product of benzyl chloride and polyalkyleneimine as a leveling agent. A plating solution (sample No. E29) was prepared.
• SPS bis(3-sodium sulfopropyl) disulfide

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