WO2024048039A1 - Plating solution - Google Patents

Plating solution Download PDF

Info

Publication number
WO2024048039A1
WO2024048039A1 PCT/JP2023/023544 JP2023023544W WO2024048039A1 WO 2024048039 A1 WO2024048039 A1 WO 2024048039A1 JP 2023023544 W JP2023023544 W JP 2023023544W WO 2024048039 A1 WO2024048039 A1 WO 2024048039A1
Authority
WO
WIPO (PCT)
Prior art keywords
sample
plating solution
pei compound
copper plating
formula
Prior art date
Application number
PCT/JP2023/023544
Other languages
French (fr)
Japanese (ja)
Inventor
由実 谷本
峻 辻野
和男 衣幡
千香子 横山
Original Assignee
株式会社Jcu
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社Jcu filed Critical 株式会社Jcu
Publication of WO2024048039A1 publication Critical patent/WO2024048039A1/en

Links

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

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

Abstract

The present invention provides a plating solution which enables the achievement of plating with high degree of gloss. The plating solution contains metal ions and a PEI compound (L) which has a polyethyleneimine main backbone, while having a structural portion LX represented by formula (LX), a structural portion LY represented by formula (LY) and a structural portion LH represented by formula (LH). (In formula (LX), X represents a structural portion X1 represented by formula (X1); and i represents an integer of 1 or more.) (In formula (LY), Y represents a structural portion Y1 represented by formula (Y1); and j represents an integer of 1 or more.) (In formula (LH), k represents 0 or an integer of 1 or more.) (In formula (X1), A represents C or S; E represents a monovalent metal ion, H, a methyl group, an ethyl group or an allyl group; l represents an integer of 1 to 6; and m represents 1 or 2.) (In formula (Y1), G represents CH2 or CH(OH); n represents 0 or 4; and each of Q1 and Q2 represents H, an electron-withdrawing group or an electron-donating group.)

Description

めっき液Plating solution
　本発明は、めっき液に関する。より具体的には、光沢度の高いめっきが可能なめっき液に関する。 The present invention relates to a plating solution. More specifically, the present invention relates to a plating solution capable of plating with high gloss.
　一般的に、樹脂、金属、ガラス、セラミックス等の基材に装飾性等の外観特性や耐食性等の機能性を付与するために、表面処理技術の一つとしてめっき処理が行われている。その中でも電気銅めっきは高延性で、温度変化に伴う素材の伸縮によるクラック発生を防止することができるため、下地めっきとして用いられる。装飾用途では、エッチングで粗化された基材表面や素材由来の凹凸を平滑にすることや、高い光沢性が求められる。 In general, 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. Among these, 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. For decorative purposes, 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.
　例えば、特許文献１には、十分な光沢外観を得るために、平滑剤としてヤヌスグリーンＢ等の塩基性染料を用いる電気銅めっき液が開示されている。また、特許文献２のような、平滑剤として塩基性染料を用いない電気銅めっき液も開示されている。特許文献２には、塩化ベンジルと少なくとも１種のポリエチレンイミンとの少なくとも１種の芳香族反応生成物を用いる電気銅めっき液が開示されている。 For example, 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. Moreover, an electrolytic copper plating solution that does not use a basic dye as a smoothing agent is also disclosed, as in Patent Document 2. Patent Document 2 discloses an electrolytic copper plating solution using at least one aromatic reaction product of benzyl chloride and at least one polyethyleneimine.
特表２０２０－５３６１６８号公報Special Publication No. 2020-536168 特表２０２０－５２３４８１号公報Special Publication No. 2020-523481
　しかし、装飾用めっき製品では、より光沢度の高いめっきが望まれている。本発明はこのような実状に鑑みてなされたものであり、従来から用いられる塩基性染料を用いずに、より光沢度の高いめっきが可能なめっき液を提供することを目的とする。 However, for decorative plated products, plating with higher gloss is desired. 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.
　本発明者等は、鋭意研究を行った結果、平滑剤として特定の化合物を含むことにより、光沢度の高いめっきが可能であることを見出し、本発明を完成するに至った。 As a result of extensive research, the present inventors have discovered that plating with high gloss is possible by including a specific compound as a smoothing agent, and have completed the present invention.
　（１）　本発明に係るめっき液は、金属イオンと、ポリエチレンイミン主骨格を有し、下記式（ＬＸ）に示す構造部分ＬＸ、下記式（ＬＹ）に示す構造部分ＬＹ及び下記式（ＬＨ）に示す構造部分ＬＨを有するＰＥＩ化合物（Ｌ）と、
Figure JPOXMLDOC01-appb-C000006
 （式（ＬＸ）中、Ｘは下記式（Ｘ１）に示す構造部分Ｘ１、ｉは１以上の整数である。）
Figure JPOXMLDOC01-appb-C000007
 （式（ＬＹ）中、Ｙは下記式（Ｙ１）に示す構造部分Ｙ１、ｊは１以上の整数である。）
Figure JPOXMLDOC01-appb-C000008
 （式（ＬＨ）中、ｋは０又は１以上の整数である。）
Figure JPOXMLDOC01-appb-C000009
 （式（Ｘ１）中、ＡはＣ又はＳ、Ｅは一価の金属イオン、Ｈ、メチル基、エチル基又はアリル基、ｌは１～６の整数、ｍは１又は２である。）
Figure JPOXMLDOC01-appb-C000010
 （式（Ｙ１）中、ＧはＣＨ２又はＣＨ（ＯＨ）、ｎは０又は４、Ｑ１及びＱ２はそれぞれＨ、電子求引性基又は電子供与性基である。）
を含むめっき液である。 (1) 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). A PEI compound (L) having a structural moiety LH shown in
Figure JPOXMLDOC01-appb-C000006
 (In formula (LX), X is the structural moiety X1 shown in formula (X1) below, and i is an integer of 1 or more.)
Figure JPOXMLDOC01-appb-C000007
 (In formula (LY), Y is the structural moiety Y1 shown in formula (Y1) below, and j is an integer of 1 or more.)
Figure JPOXMLDOC01-appb-C000008
 (In formula (LH), k is 0 or an integer of 1 or more.)
Figure JPOXMLDOC01-appb-C000009
 (In formula (X1), A is C or S, E is a monovalent metal ion, H, methyl group, ethyl group, or allyl group, l is an integer of 1 to 6, and m is 1 or 2.)
Figure JPOXMLDOC01-appb-C000010
 (In formula (Y1), 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.)
It is a plating solution containing
　（２）　（１）のめっき液は、前記構造部分ＬＸのｉと前記構造部分ＬＹのｊと前記構造部分ＬＨのｋとに基づき算出した｛ｉ／（ｉ＋ｊ＋ｋ）｝×１００が２０～９０％であることが好ましい。 (2) 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
　（３）　（１）又は（２）のめっき液は、前記金属イオンが銅イオンを含むことが好ましい。 (3) In the plating solution of (1) or (2), it is preferable that the metal ions include copper ions.
　本発明によれば、光沢度の高いめっきが可能なめっき液を提供することができる。 According to the present invention, a plating solution capable of plating with high gloss can be provided.
　以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
［めっき液］
　本発明に係るめっき液は、少なくとも金属イオンとＰＥＩ化合物（Ｌ）とを含む。本発明に係るめっき液は、酸、ハロゲン化物イオン、光沢剤、界面活性剤等をさらに含むことができる。 [Plating solution]
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.
　（金属イオン）
　本発明のめっき液を構成する金属イオンとしては特に限定されないが、例えば、銅、錫、チタン、クロム、マンガン、鉄、ニッケル、コバルト、亜鉛、銀、金、白金、パラジウム、インジウム、モリブデン、タングステン、鉛、レニウム、ロジウム、ルテニウム、オスミウム、イリジウム、ビスマス、アルミニウム等のイオンが挙げられる。本発明に係るめっき液では、金属イオンが銅イオンを含むと好ましい。 (Metal ions)
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.
　本発明に係るめっき液の金属イオンは、通常、金属塩を水等の溶媒に溶解して得られる。本発明に係るめっき液は、銅を含む金属塩を水に溶解して得られるものが好ましい。銅を含む金属塩としては特に限定されないが、例えば、硫酸銅、ピロリン酸銅、酢酸銅等が挙げられる。これらの中でも硫酸銅が好ましい。 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.
　硫酸銅を用いる場合は硫酸銅五水和物である場合が好ましく、本発明に係るめっき液における硫酸銅五水和物の含有量は特に限定されないが、例えば５０～３００ｇ／Ｌ、好ましくは１００～２８０ｇ／Ｌである。 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.
　（平滑剤）
　本発明では、平滑剤として少なくともＰＥＩ化合物（Ｌ）を用いる。本発明は、ＰＥＩ化合物（Ｌ）に加えて公知の平滑剤を１種以上加えてもよい。 (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).
　　＜ＰＥＩ化合物＞
　ＰＥＩ化合物（Ｌ）は、ポリエチレンイミン主骨格を有し、特定の構造部分を有する。具体的には、ＰＥＩ化合物（Ｌ）は、ポリエチレンイミン主骨格を有し、後述の、下記式（ＬＸ）に示す構造部分ＬＸ、下記式（ＬＹ）に示す構造部分ＬＹ及び下記式（ＬＨ）に示す構造部分ＬＨを有する。構造部分ＬＸ、構造部分ＬＹ及び構造部分ＬＨについては後述するが、それぞれが、少なくとも［－（ＣＨ２）２－Ｎ－］の骨格を有する構造部分である。 <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 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.
　ここで、ポリエチレンイミン主骨格とは、ポリエチレンイミン（ＰＥＩ）の主骨格を意味する。ＰＥＩ化合物（Ｌ）は、ポリエチレンイミン主骨格に結合する水素原子Ｈが後述のＸ及びＹで置換された構造を有する。ポリエチレンイミン主骨格は、例えば、網目状、分岐状又は直鎖状のポリエチレンイミンの主骨格である。ここで、網目状のポリエチレンイミンとは、分岐状のポリエチレンイミンにおいて、分岐した部分の一部又は全部が、他の分岐した部分又は主骨格と結合することにより、網目状になっているポリエチレンイミンを意味する。網目状のポリエチレンイミンの一例を下記式（ＮＰ）に示す。 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 with X and Y described below. The polyethyleneimine main skeleton is, for example, a network, branched, or linear polyethyleneimine main skeleton. Here, 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. means. An example of mesh-like polyethyleneimine is shown in the following formula (NP).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　ＰＥＩ化合物（Ｌ）は、ポリエチレンイミン主骨格が網目状又は分岐状のポリエチレンイミンの主骨格であると好ましい。 The PEI compound (L) preferably has a polyethyleneimine main skeleton that is network-like or branched.
　ＰＥＩ化合物（Ｌ）は、ポリエチレンイミン主骨格を有するポリエチレンイミンの数平均分子量が、例えば３００～７００００、好ましくは１１００～１００００、より好ましくは１１００～１８００となる化合物である。ポリエチレンイミンの数平均分子量が上記範囲内にあると、光沢度の高い金属めっき皮膜を得やすいため好ましい。ここで、ポリエチレンイミン主骨格を有するポリエチレンイミンとは、ポリエチレンイミン主骨格に結合する原子が水素原子Ｈのみである場合のポリエチレンイミンを意味する。 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. Here, the polyethyleneimine having a polyethyleneimine main skeleton means polyethyleneimine in which the only atoms bonded to the polyethyleneimine main skeleton are hydrogen atoms H.
　ＰＥＩ化合物（Ｌ）は、ポリエチレンイミン主骨格を有するポリエチレンイミンと、構造部分ＬＸのＸの原料と、構造部分ＬＹのＹの原料と、を反応させることにより得られることが多い。この場合、原料であるポリエチレンイミンに対して、構造部分ＬＸのＸの原料と、構造部分ＬＹのＹの原料を付加した際に、原料であるポリエチレンイミンが重合することなく、ＰＥＩ化合物（Ｌ）の分子量は、構造部分ＬＸのＸの原料と、構造部分ＬＹのＹの原料を付加した分増加する。 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. In this case, when 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.
　本発明では、ＰＥＩ化合物（Ｌ）のうち、ポリエチレンイミン主骨格に結合する水素原子ＨがＸで置換された部分を構造部分ＬＸという。また、ＰＥＩ化合物（Ｌ）のうち、ポリエチレンイミン主骨格に結合する水素原子ＨがＹで置換された部分を構造部分ＬＹという。さらに、ＰＥＩ化合物（Ｌ）のうちポリエチレンイミン主骨格に結合する水素原子Ｈがそのまま存在する部分を構造部分ＬＨという。なお、ＰＥＩ化合物（Ｌ）は、少なくとも構造部分ＬＸ及び構造部分ＬＹを含み、必要により構造部分ＬＨを含む。 In the present invention, 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. Further, in the PEI compound (L), 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. Furthermore, 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. Note that the PEI compound (L) includes at least a structural portion LX and a structural portion LY, and optionally a structural portion LH.
　　　［構造部分ＬＸ］
　構造部分ＬＸは、下記式（ＬＸ）に示す構造部分である。 [Structural part LX]
The structural portion LX is a structural portion represented by the following formula (LX).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（ＬＸ）中、Ｘは下記式（Ｘ１）に示す構造部分Ｘ１、ｉは１以上の整数である。 In formula (LX), X is a structural moiety X1 shown in formula (X1) below, and i is an integer of 1 or more.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（Ｘ１）中、ＡはＣ又はＳ、Ｅは一価の金属イオン、Ｈ、メチル基、エチル基又はアリル基、ｌは１～６の整数、ｍは１又は２である。Ｅは好ましくは一価の金属イオン、Ｈ、又はアリル基である。ｌは好ましくは３～４の整数である。一価の金属イオンとしては、例えばＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｆｒ等が挙げられる。 In formula (X1), 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, and 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. Examples of monovalent metal ions include Li, Na, K, Rb, Cs, and Fr.
　構造部分Ｘ１で表される構造部分の好ましい実施形態としては、例えば、下記式（Ｘ１１）に示す構造部分Ｘ１１１、Ｘ１１２、Ｘ１１３及びＸ１１４で表される構造部分が挙げられる。 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).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　構造部分Ｘ１１１、Ｘ１１２及びＸ１１４の上端部分が、構造部分Ｘ１の左端部分に対応する。構造部分Ｘ１１３の左端部分が、構造部分Ｘ１の左端部分に対応する。 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.
　　　［構造部分ＬＹ］
　構造部分ＬＹは、下記式（ＬＹ）に示す構造部分である。 [Structural part LY]
The structural portion LY is a structural portion represented by the following formula (LY).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（ＬＹ）中、Ｙは下記式（Ｙ１）に示す構造部分Ｙ１、ｊは１以上の整数である。 In formula (LY), Y is a structural moiety Y1 shown in formula (Y1) below, and j is an integer of 1 or more.
Figure JPOXMLDOC01-appb-C000016
 　式（Ｙ１）中、ＧはＣＨ２又はＣＨ（ＯＨ）、ｎは０又は４、Ｑ１及びＱ２はそれぞれＨ、電子求引性基又は電子供与性基である。ｎが０の場合、構造部分Ｙ１のアリール基は、ベンゼン環１個を含む構造となる。ｎが４の場合、構造部分Ｙ１のアリール基は、ナフタレン環１個を含む構造となる。
Figure JPOXMLDOC01-appb-C000016
 In formula (Y1), 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. When n is 0, the aryl group of structural moiety Y1 has a structure containing one benzene ring. When n is 4, the aryl group of structural moiety Y1 has a structure containing one naphthalene ring.
　なお、式（Ｙ１）中、構造部分Ｙ１のアリール基のＱ１及びＱ２は、それぞれＨ、電子求引性基又は電子供与性基であり、特に限定されるものではない。電子求引性基としては、例えば、クロロ基－Ｃｌ、フルオロ基－Ｆ、ニトロ基－ＮＯ２、ヒドロキシ基－ＯＨ等が挙げられる。電子供与性基としては、例えば、メチル基－ＣＨ３、メトキシ基－ＯＣＨ３等が挙げられる。Ｑ１及びＱ２が水素原子Ｈ以外の置換基である場合、ポリエチレンイミン主骨格に結合する部分から見た置換基の置換位置としては、例えば、オルト位、メタ位、パラ位等が挙げられる。 In addition, in formula (Y1), 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. Examples of the electron-withdrawing group include a chloro group -Cl, a fluoro group -F, a nitro group -NO 2 and a hydroxy group -OH. Examples of the electron-donating group include methyl group -CH 3 and methoxy group -OCH 3 . When Q 1 and Q 2 are substituents other than the hydrogen atom H, the substitution position of the substituent viewed from the part bonded to the polyethyleneimine main skeleton includes, for example, ortho position, meta position, para position, etc. .
　構造部分Ｙ１で表される構造部分の好ましい実施形態としては、例えば、下記式（Ｙ１１）に示す構造部分Ｙ１１１、Ｙ１１２、Ｙ１１３及びＹ１１４で表される構造部分が挙げられる。 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).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　構造部分Ｙ１１１、Ｙ１１２及びＹ１１３の上端部分が、構造部分Ｙ１の上端部分に対応する。構造部分Ｙ１１４の右側上端部分が、構造部分Ｙ１の上端部分に対応する。 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.
　式（Ｙ１）中のＱ１及びＱ２は、それぞれ、Ｈ、電子求引性基又は電子供与性基であるから、式（Ｙ１１）に示す構造部分Ｙ１１１、Ｙ１１２、Ｙ１１３及びＹ１１４のアリール基には水素原子Ｈ以外の置換基が結合していてもよい。構造部分Ｙ１１１、Ｙ１１２、Ｙ１１３及びＹ１１４のアリール基のＱ１及びＱ２が水素原子Ｈ以外の置換基である場合、置換基の種類、数、及び位置に特に制限はなく、例えば、クロロ基－Ｃｌ、フルオロ基－Ｆ、メチル基－ＣＨ３、メトキシ基－ＯＣＨ３等が挙げられる。 Since Q 1 and Q 2 in formula (Y1) are H, an electron-withdrawing group or an electron-donating group, respectively, 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. When 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.
　式（Ｙ１）中のＱ１及びＱ２が水素原子Ｈ以外の置換基である構造部分の好ましい実施形態としては、例えば、下記式（Ｙ１１Ａ）に示す各構造部分が挙げられる。 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.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　構造部分Ｙ１１１－Ｃｌ、Ｙ１１１－Ｆ、Ｙ１１１－ＣＨ３及びＹ１１１－ＯＣＨ３の上端部分が、構造部分Ｙ１の上端部分に対応する。 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.
　式（Ｙ１）中のＱ１及びＱ２が水素原子Ｈ以外の置換基である構造部分の特に好ましい実施形態としては、例えば、下記式（Ｙ１１Ｂ）に示す各構造部分が挙げられる。 Particularly 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 (Y11B) below.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　構造部分Ｙ１１１－ｏＣｌ、Ｙ１１１－ｐＦ、Ｙ１１１－ｍＣＨ３及びＹ１１１－ｍＯＣＨ３の上端部分が、構造部分Ｙ１の上端部分に対応する。 The upper end portions of structural portions Y111-oCl, Y111-pF, Y111-mCH3, and Y111-mOCH3 correspond to the upper end portion of structural portion Y1.
　構造部分Ｙ１１１－ｏＣｌ（－ＣＨ２Ｃ６Ｈ４Ｃｌ）、構造部分Ｙ１１１－ｐＦ（－ＣＨ２Ｃ６Ｈ４Ｆ）、構造部分Ｙ１１１－ｍＣＨ３（－ＣＨ２Ｃ６Ｈ４ＣＨ３）、及び構造部分Ｙ１１１－ｍＯＣＨ３（－ＣＨ２Ｃ６Ｈ４ＯＣＨ３）は、それぞれ、構造部分Ｙ１１１のアリール基（ベンジル基）において式（Ｙ１）中のＱ１及びＱ２の一方がＨで他方がオルト位のＣｌ、パラ位のＦ、メタ位のＣＨ３、メタ位のＯＣＨ３になっている。 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.
　　　［構造部分ＬＨ］
　構造部分ＬＨは、下記式（ＬＨ）に示す構造部分である。 [Structural part LH]
Structural portion LH is a structural portion represented by the following formula (LH).
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　式（ＬＨ）中、ｋは０又は１以上の整数である。なお、ｋが０の場合、ＰＥＩ化合物（Ｌ）は構造部分ＬＨを含まない化合物になる。 In 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.
　ＰＥＩ化合物（Ｌ）は、前記構造部分ＬＸのｉと前記構造部分ＬＹのｊと前記構造部分ＬＨのｋとに基づき算出した｛ｉ／（ｉ＋ｊ＋ｋ）｝×１００が２０～９０％、好ましくは３０～８０％である。｛ｉ／（ｉ＋ｊ＋ｋ）｝×１００が上記範囲内にあると、光沢度の高い金属めっき皮膜を得やすいため好ましい。なお、前記｛ｉ／（ｉ＋ｊ＋ｋ）｝×１００は、例えばＮＭＲ等により測定することができる。 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.
　本発明に係るめっき液は、ＰＥＩ化合物（Ｌ）を、例えば０．５～５０ｍｇ／Ｌ、好ましくは１～３０ｍｇ／Ｌ含む。めっき液中のＰＥＩ化合物（Ｌ）の濃度が上記範囲内にあると、光沢度の高い金属めっき皮膜を得やすいため好ましい。 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.
　（酸）
　本発明に係るめっき液は、酸を含んでいてもよい。酸としては特に限定されないが、例えば、無機酸及び／又は有機酸の内の所望のものを、めっき液の組成やめっき対象に合わせて使用することができる。無機酸としては、例えば、硫酸、硝酸、塩酸を始めとするハロゲン化水素酸、リン酸、塩素酸を始めとするオキソ酸等が挙げられる。有機酸としては、例えば、メタンスルホン酸、プロパンスルホン酸等のアルカンスルホン酸類、イセチオン酸、プロパノールスルホン酸等のアルカノールスルホン酸類、クエン酸、酒石酸、ギ酸等の脂肪族又は芳香族カルボン酸等が挙げられる。このうち、めっき液の金属イオンの原料が硫酸銅である場合は、酸として硫酸を含むことが好ましい。 (acid)
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. Examples of inorganic acids include hydrohalic acids such as sulfuric acid, nitric acid, and hydrochloric acid, and oxoacids such as phosphoric acid and chloric acid. Examples of organic acids 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.
　酸が硫酸である場合、硫酸の含有量は特に限定されないが、例えば２０～２００ｇ／Ｌ、好ましくは３０～１５０ｇ／Ｌである。 When the acid is sulfuric 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.
　（ハロゲン化物イオン）
　本発明に係るめっき液は、光沢金属めっきやレベリングを行う目的からハロゲン化物イオンを含んでいてもよい。ハロゲン化物イオンとしては特に限定されないが、例えば、塩素、臭素、ヨウ素等が挙げられる。このうち、塩化物イオンが好ましい。 (halide ion)
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.
　ハロゲン化物イオンが塩化物イオンである場合、塩化物イオンの含有量は特に限定されないが、例えば１０～１２０ｍｇ／Ｌ、好ましくは２０～１００ｍｇ／Ｌである。 When the halide ion is a chloride ion, 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.
　（光沢剤）
　本発明に係るめっき液は、光沢剤を含んでいてもよい。光沢剤としては特に限定されないが、例えば、ベンズアルデヒド、ｏ－クロロベンズアルデヒド、２,４,６－トリクロロベンズアルデヒド、ｍ－クロロベンズアルデヒド、ｐ－ニトロベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒド、フルフラール、１－ナフトアルデヒド、２－ナフトアルデヒド、２－ヒドロキシ－１－ナフトアルデヒド、３－アセナフトアルデヒド、ベンジリデンアセトン、ピリジデンアセトン、フルフリルデンアセトン、シンナムアルデヒド、アニスアルデヒド、サリチルアルデヒド、クロトンアルデヒド、アクロレイン、グルタルアルデヒド、パラアルデヒド、バニリン等の各種アルデヒド、トリアジン、イミダゾール、インドール、キノリン、２－ビニルピリジン、アニリン、フェナントロリン、ネオクプロイン、ピコリン酸、チオ尿素類、Ｎ－（３－ヒドロキシブチリデン）－ｐ－スルファニル酸、Ｎ－ブチリデンスルファニル酸、Ｎ－シンナモイリデンスルファニル酸、２，４－ジアミノ－６－（２’－メチルイミダゾリル（１’））エチル－１，３，５－トリアジン、２，４－ジアミノ－６－（２’－エチル－４－メチルイミダゾリル（１’））エチル－１，３，５－トリアジン、２，４－ジアミノ－６－（２’－ウンデシルイミダゾリル（１’））エチル－１，３，５－トリアジン、サリチル酸フェニル、あるいは、ベンゾチアゾール、２－メルカトプトベンゾチアゾール、２－メチルベンゾチアゾール、２－アミノベンゾチアゾール、２－アミノ－６－メトキシベンゾチアゾール、２－メチル－５－クロロベンゾチアゾール、２－ヒドロキシベンゾチアゾール、２－アミノ－６－メチルベンゾチアゾール、２－クロロベンゾチアゾール、２，５－ジメチルベンゾチアゾール、５－ヒドロキシ－２－メチルベンゾチアゾール等のベンゾチアゾール類、ビス（３－ナトリウムスルホプロピル）ジスルフィド（ＳＰＳ）及びその塩等のスルフィド類等が挙げられる。 (brightener)
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, triazine, imidazole, indole, quinoline, 2-vinylpyridine, aniline, phenanthroline, neocuproine, picolinic acid, thioureas, N-(3-hydroxybutylidene)-p-sulfanilic acid, N- Butylidenesulfanilic acid, N-cinnamoylidenesulfanilic 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-mercatoptobenzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole, 2-methyl-5-chloro Benzothiazoles such as benzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-chlorobenzothiazole, 2,5-dimethylbenzothiazole, 5-hydroxy-2-methylbenzothiazole, bis( Examples include sulfides such as 3-sodium sulfopropyl) disulfide (SPS) and its salts.
　光沢剤の含有量は特に限定されないが、例えば１～５０ｍｇ／Ｌ、好ましくは３～３０ｍｇ／Ｌである。 The content of the brightener is not particularly limited, but is, for example, 1 to 50 mg/L, preferably 3 to 30 mg/L.
　（界面活性剤）
　本発明に係るめっき液は、界面活性剤を含んでいてもよい。界面活性剤としては特に限定されないが、例えば、非イオン性界面活性剤や両性界面活性剤等が挙げられる。非イオン性界面活性剤としては特に限定されないが、例えば、ポリエーテル化合物等が挙げられる。ポリエーテル化合物としては特に限定されないが、例えば、ポリアルキレングリコール、アルキル基を有するポリエーテル化合物、親水性のエチレンオキシドユニットと疎水性のプロピレンオキシドユニットとエチレンオキシドユニットとのトリブロック共重合体からなる界面活性剤等が挙げられる。 (surfactant)
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.
　界面活性剤の含有量は特に限定されないが、例えば１～３００ｍｇ／Ｌ、好ましくは５～２００ｍｇ／Ｌである。 The content of the surfactant is not particularly limited, but is, for example, 1 to 300 mg/L, preferably 5 to 200 mg/L.
　（製造方法）
　本発明に係るめっき液に含まれるＰＥＩ化合物（Ｌ）は、例えば、ポリエチレンイミン主骨格を有するポリエチレンイミンと、構造部分ＬＸのＸの原料と、構造部分ＬＹのＹの原料と、を求核付加反応させることにより得られる。 (Production method)
The PEI compound (L) contained in the plating solution according to the present invention, for example, 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.
　本発明に係るめっき液は、平滑剤として上記ＰＥＩ化合物（Ｌ）を用い、公知の方法で製造することができる。 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.
［めっき方法］
　以下、本発明に係るめっき液を用いためっき方法について説明する。本めっき方法では、本発明に係るめっき液を用いて、素地の上に電気めっきを行う。 [Plating method]
Hereinafter, a plating method using the plating solution according to the present invention will be explained. In this plating method, electroplating is performed on a substrate using the plating solution according to the present invention.
　（素地）
　素地としては、特に限定されないが、例えば、真鍮、銅、ニッケル、鉄、亜鉛、亜鉛合金、鉄鋼、樹脂等の基材に金属等の導電層を形成したもの等が挙げられる。 (base material)
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.
　（温度）
　本発明に係るめっき液は、電気めっき時の液温を、例えば１５～４５℃、好ましくは２０～３５℃程度とすればよい。 (temperature)
In the plating solution according to the present invention, the solution temperature during electroplating may be, for example, about 15 to 45°C, preferably about 20 to 35°C.
　（電流密度）
　本発明に係るめっき液は、電気めっき時の電流密度を、例えば０．５～１５Ａ／ｄｍ２、好ましくは１～１０Ａ／ｄｍ２程度とすればよい。 (Current density)
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 .
　（めっき時間）
　本発明に係るめっき液は、電気めっき時のめっき時間を、例えば５分以上、好ましくは１５分以上とすればよい。 (Plating time)
With the plating solution according to the present invention, the plating time during electroplating may be, for example, 5 minutes or more, preferably 15 minutes or more.
　本発明によれば、光沢度の高いめっきが可能なめっき液が得られる。 According to the present invention, a plating solution capable of plating with high gloss can be obtained.
　以下に、実施例により本発明をさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.
［実施例１］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．１）の製造＞
　ポリエチレンイミン（数平均分子量３００）水溶液（０．９０Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．６当量のクロロ酢酸ナトリウムを少しずつ加え、２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸ナトリウム付加物の４０重量％水溶液（Ｉｎｔ．１）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [Example 1]
(PEI compound)
<Production of intermediate (Int.1)>
An aqueous solution (0.90 M) of polyethyleneimine (number average molecular weight 300) was heated to 70 to 90°C, and sodium chloroacetate in an amount of 0.6 equivalent based on the amine value was added little by little and reacted for 2 hours. The temperature was returned to room temperature, and a 40% by weight aqueous solution (Int. 1) of polyethyleneimine-sodium chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１）の製造＞
　上記ポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．１）１００重量部及び苛性ソーダ水溶液（８．５Ｍ）７６重量部を９０℃に加熱し、塩化ベンジル２０重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ１）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
　（めっき液の調製）
　硫酸銅五水和物２２０ｇ／Ｌと、硫酸７０ｇ／Ｌと、塩化物イオンＣｌ－６０ｍｇ／Ｌと、界面活性剤としての富士フイルム和光純薬株式会社製ポリエチレングリコール２００００の１００ｍｇ／Ｌと、光沢剤としてのビス（３－ナトリウムスルホプロピル）ジスルフィド（ＳＰＳ）の８．３ｍｇ／Ｌと、平滑剤としてのＰＥＩ化合物（試料Ｎｏ．Ａ１）の３．０ｍｇ／Ｌと、を含む銅めっき液（試料Ｎｏ．Ｅ１）を調製した。 (Preparation of plating solution)
Copper sulfate pentahydrate 220g/L, sulfuric acid 70g/L, chloride ion Cl - 60mg/L, 100mg/L of polyethylene glycol 20000 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. as a surfactant, and gloss. A copper plating solution (sample) containing 8.3 mg/L of bis(3-sodium sulfopropyl) disulfide (SPS) as an agent and 3.0 mg/L of a PEI compound (sample No. No.E1) was prepared.
　（電気めっき試験）
　　＜前処理＞
　はじめに、ハルセル真鍮板を、株式会社ＪＣＵ製ＥＢＡＰＲＥＰ　ＳＫ－１４４（脱脂）を用いて５５℃で５分間浸漬した後、株式会社ＪＣＵ製ＥＢＡＶＡＴＥ　Ｖ－３４５（酸活性）を用いて常温で０．５分間浸漬した。 (Electroplating test)
<Pretreatment>
First, a Hull Cell brass plate was immersed for 5 minutes at 55°C using EBAPREP SK-144 (degreased) manufactured by JCU Co., Ltd., and then soaked at room temperature using EBAVATE V-345 (acid active) manufactured by JCU Co., Ltd. Soaked for minutes.
　　＜電気めっき＞
　前処理後のハルセル真鍮板と、銅めっき液（試料Ｎｏ．Ｅ１）とを用い、ハルセル試験にて常温で陰極電解（全電流２Ａ）を１０分間行った。その後、株式会社ＪＣＵ製ＥＢＡＦＩＮ　Ｇ－８００にて常温で０．５分間防錆処理したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１）が得られた。 <Electroplating>
Using the pretreated Hull Cell brass plate and the copper plating solution (sample No. E1), cathode electrolysis (total current 2 A) was performed for 10 minutes at room temperature in the Hull Cell test. Thereafter, when antirust treatment was performed for 0.5 minutes at room temperature using EBAFIN G-800 manufactured by JCU Co., Ltd., an evaluation sample (sample No. S1) in which a copper plating film was formed on the surface of the brass plate was obtained.
　（評価）
　ＢＹＫ－ガードナー株式会社製マイクロトリグロス光沢計に評価サンプル（試料Ｎｏ．Ｓ１）をセットした。評価サンプルの電流密度３Ａ／ｄｍ２の部分に入射角２０°で光を照射して光沢度を測定した。表１に光沢度を示す。 (evaluation)
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.
［実施例２］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ２）の製造＞
　実施例１で製造したポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．１）１００重量部及び苛性ソーダ水溶液（７．５Ｍ）８３重量部を９０℃に加熱し、２－クロロベンジルクロリド２５重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ２）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ２）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ２）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E2) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S2) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例３］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．２）の製造＞
　ポリエチレンイミン（数平均分子量１１００）水溶液（０．２２Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．６当量のクロロ酢酸ナトリウムを少しずつ加え、２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸ナトリウム付加物の３２．９重量％水溶液（Ｉｎｔ．２）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [Example 3]
(PEI compound)
<Production of intermediate (Int.2)>
An aqueous solution (0.22M) of polyethyleneimine (number average molecular weight 1100) was heated to 70 to 90°C, and sodium chloroacetate in an amount of 0.6 equivalent based on the amine value was added little by little, and the mixture was allowed to react for 2 hours. The temperature was returned to room temperature, and a 32.9% by weight aqueous solution (Int. 2) of polyethyleneimine-sodium chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ３）の製造＞
　上記ポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．２）１００重量部及び苛性ソーダ水溶液（７.８Ｍ）２９重量部を９０℃に加熱し、塩化ベンジル６重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ３）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ３）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ３）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ３）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ３）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ３）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E3) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S3) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例４］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．３）の製造＞
　ポリエチレンイミン（数平均分子量１８００）水溶液（０．３０Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．６当量のクロロ酢酸ナトリウム（７．０Ｍ）を少しずつ加え、２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸ナトリウム付加物の４０重量％水溶液（Ｉｎｔ．３）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [Example 4]
(PEI compound)
<Production of intermediate (Int.3)>
Polyethyleneimine (number average molecular weight 1800) aqueous solution (0.30M) was heated to 70 to 90°C, 0.6 equivalent of sodium chloroacetate (7.0M) was added little by little based on the amine value, and the mixture was allowed to react for 2 hours. Ta. The temperature was returned to room temperature, and a 40% by weight aqueous solution (Int. 3) of polyethyleneimine-sodium chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ４）の製造＞
　上記ポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．３）１００重量部及び苛性ソーダ水溶液（６.６Ｍ）９０重量部を９０℃に加熱し、塩化ベンジル７０重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ４）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ４）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ４）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ４）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ４）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ４）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E4) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S4) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例５］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ５）の製造＞
　実施例４で製造したポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．３）１００重量部及び苛性ソーダ水溶液（９．６Ｍ）６８重量部を９０℃に加熱し、４－フルオロベンジルクロリド２３重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ５）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ５）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ５）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ５）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ５）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ５）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E5) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S5) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例６］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ６）の製造＞
　実施例４で製造したポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．３）１００重量部及び苛性ソーダ水溶液（９．６Ｍ）６８重量部を９０℃に加熱し、３－メチルベンジルクロリド２２重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ６）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ６）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ６）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ６）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ６）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ６）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E6) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S6) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例７］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ７）の製造＞
　実施例４で製造したポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．３）１００重量部及び苛性ソーダ水溶液（９．６Ｍ）６９重量部を９０℃に加熱し、３－メトキシベンジルクロリド２５重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ７）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ７）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ７）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ７）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ７）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ７）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E7) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S7) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例８］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ８）の製造＞
　実施例４で製造したポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．３）１００重量部及び苛性ソーダ水溶液（１３．３Ｍ）５４重量部を９０℃に加熱し、２－（クロロメチル）ナフタレン２８重量部を加え、２時間反応させた。室温に戻し、純水１６８重量部を加えたところＰＥＩ化合物（試料Ｎｏ．Ａ８）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ８）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ８）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ８）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ８）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ８）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E8) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S8) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例９］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ９）の製造＞
　実施例４で製造したポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．３）１００重量部及び苛性ソーダ水溶液（８．４Ｍ）７５重量部を９０℃に加熱し、４－ニトロベンジルクロリド２７重量部を加え、２時間反応させた。室温に戻し、純水１６９重量部を加えたところＰＥＩ化合物（試料Ｎｏ．Ａ９）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ９）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ９）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ９）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ９）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ９）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E9) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S9) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例１０］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１０）の製造＞
　実施例４で製造したポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．３）１００重量部及びバニリン５重量部を８０～９０℃に加熱し、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１０）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ１０）の詳細を示す。なお、反応の進行は１３ＣＮＭＲにより、１９１ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１０）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１０）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１０）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１０）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E10) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S10) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例１１］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．４）の製造＞
　ポリエチレンイミン（数平均分子量１００００）水溶液（０．０１７Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．６当量のクロロ酢酸ナトリウムを少しずつ加え、２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸ナトリウム付加物の４０重量％水溶液（Ｉｎｔ．４）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [Example 11]
(PEI compound)
<Production of intermediate (Int.4)>
An aqueous solution (0.017M) of polyethyleneimine (number average molecular weight 10,000) was heated to 70 to 90°C, and sodium chloroacetate in an amount of 0.6 equivalent based on the amine value was added little by little and reacted for 2 hours. The temperature was returned to room temperature, and a 40% by weight aqueous solution (Int. 4) of polyethyleneimine-sodium chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１１）の製造＞
　上記ポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．４）１００重量部及び苛性ソーダ水溶液（１０.２Ｍ）６６重量部を９０℃に加熱し、塩化ベンジル２０重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１１）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ１１）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１１）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１１）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１１）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１１）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E11) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S11) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例１２］
（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．５）の製造＞
　ポリエチレンイミン（数平均分子量７００００）水溶液（０．００４Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．６当量のクロロ酢酸ナトリウムを少しずつ加え、２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸ナトリウム付加物の１７重量％水溶液（Ｉｎｔ．５）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [Example 12]
(PEI compound)
<Production of intermediate (Int.5)>
An aqueous solution (0.004 M) of polyethyleneimine (number average molecular weight 70,000) was heated to 70 to 90°C, and sodium chloroacetate in an amount of 0.6 equivalent based on the amine value was added little by little, and the mixture was allowed to react for 2 hours. The temperature was returned to room temperature, and a 17% by weight aqueous solution (Int. 5) of a polyethyleneimine-sodium chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１２）の製造＞
　上記ポリエチレンイミン－クロロ酢酸ナトリウム付加物の水溶液（Ｉｎｔ．５）１００重量部及び苛性ソーダ水溶液（２．８Ｍ）１３０重量部を９０℃に加熱し、２－クロロベンジルクロリド５重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１２）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ１２）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１２）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１２）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１２）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１２）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E12) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S12) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例１３］
　（ＰＥＩ化合物）
　＜中間体（Ｉｎｔ．６）の製造＞
　ポリエチレンイミン（数平均分子量１８００）水溶液（０．１７Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．３当量の１，３－プロパンスルトンを２時間反応させた。室温に戻し、ポリエチレンイミン－１，３－プロパンスルトン付加物の３４質量％水溶液（Ｉｎｔ．６）を得た。なお、反応の進行は１ＨＮＭＲにより、４．４９ｐｐｍ付近のシグナルの消失で確認した。 [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 to 90°C, and 1,3-propane sultone in an amount of 0.3 equivalent based on the amine value was reacted for 2 hours. The temperature was returned to room temperature, and a 34% by mass aqueous solution (Int. 6) of a polyethyleneimine-1,3-propane sultone adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of the signal around 4.49 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１３）の製造＞
　上記ポリエチレンイミン－１，３－プロパンスルトン付加物の水溶液（Ｉｎｔ．６）１００重量部、純水１５０重量部、及び４－フルオロベンジルクロリド２０重量部を９０℃に加熱し、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１３）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ１３）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１３）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１３）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１３）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１３）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E13) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S13) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例１４］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１４）の製造＞
　実施例１３で製造したポリエチレンイミン－１，３－プロパンスルトン付加物の水溶液（Ｉｎｔ．６）１００重量部、純水１５０重量部、及び３－メトキシベンジルクロリド２２重量部を９０℃に加熱し、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１４）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ１４）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１４）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１４）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１４）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１４）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E14) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S14) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例１５］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１５）の製造＞
　実施例１３で製造したポリエチレンイミン－１，３－プロパンスルトン付加物の水溶液（Ｉｎｔ．６）１００重量部、純水２００重量部、及び４－ニトロベンジルクロリド２３重量部を９０℃に加熱し、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１５）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ１５）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１５）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１５）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１５）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１５）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E15) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S15) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例１６］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．７）の製造＞
　ポリエチレンイミン（数平均分子量１００００）水溶液（０．０１５Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．３当量の１，３－プロパンスルトンを２時間反応させた。室温に戻し、ポリエチレンイミン－１，３－プロパンスルトン付加物の２３重量％水溶液（Ｉｎｔ．７）を得た。なお、反応の進行は１ＨＮＭＲにより、４．４９ｐｐｍ付近のシグナルの消失で確認した。 [Example 16]
(PEI compound)
<Production of intermediate (Int.7)>
An aqueous solution (0.015M) of polyethyleneimine (number average molecular weight 10,000) was heated to 70 to 90°C, and 0.3 equivalent of 1,3-propane sultone was reacted with the amine value for 2 hours. The temperature was returned to room temperature, and a 23% by weight aqueous solution (Int. 7) of a polyethyleneimine-1,3-propane sultone adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of the signal around 4.49 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１６）の製造＞
　上記ポリエチレンイミン－１，３－プロパンスルトン付加物の水溶液（Ｉｎｔ．７）１００重量部及び塩化ベンジル６重量部を８０～９０℃に加熱し、３時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１６）の水溶液が得られた。表１にＰＥＩ化合物（試料Ｎｏ．Ａ１６）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１６）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１６）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１６）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１６）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E16) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S16) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表１に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 1 shows the glossiness.
［実施例１７］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．８）の製造＞
　ポリエチレンイミン（数平均分子量１１００）水溶液（０．１２Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．２当量のクロロ酢酸アリルを２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸アリル付加物の１７重量％水溶液（Ｉｎｔ．８）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [Example 17]
(PEI compound)
<Production of intermediate (Int.8)>
An aqueous solution (0.12M) of polyethyleneimine (number average molecular weight 1100) was heated to 70 to 90°C, and 0.2 equivalents of allyl chloroacetate based on the amine value were reacted for 2 hours. The temperature was returned to room temperature, and a 17% by weight aqueous solution (Int. 8) of polyethyleneimine-allyl chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１７）の製造＞
　上記ポリエチレンイミン－クロロ酢酸アリル付加物の水溶液（Ｉｎｔ．８）１００重量部、苛性ソーダ水溶液（１．９Ｍ）２３重量部を９０℃に加熱し、塩化ベンジル６重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１７）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ１７）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１７）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１７）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１７）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１７）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E17) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S17) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例１８］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．９）の製造＞
　ポリエチレンイミン（数平均分子量１８００）水溶液（０．１０Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．４当量のクロロ酢酸アリルを２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸アリル付加物の１９重量％水溶液（Ｉｎｔ．９）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [Example 18]
(PEI compound)
<Production of intermediate (Int.9)>
An aqueous solution (0.10M) of polyethyleneimine (number average molecular weight 1800) was heated to 70 to 90°C, and 0.4 equivalent of allyl chloroacetate based on the amine value was reacted for 2 hours. The temperature was returned to room temperature, and a 19% by weight aqueous solution (Int. 9) of polyethyleneimine-allyl chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１８）の製造＞
　上記ポリエチレンイミン－クロロ酢酸アリル付加物の水溶液（Ｉｎｔ．９）１００重量部、苛性ソーダ水溶液（４．４Ｍ）１９重量部を９０℃に加熱し、塩化ベンジル５重量部を少しずつ加え、２時間反応させた。室温に戻し、純水１０７重量部を加えたところＰＥＩ化合物（試料Ｎｏ．Ａ１８）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ１８）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１８）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１８）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１８）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１８）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E18) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S18) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例１９］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．１０）の製造＞
　ポリエチレンイミン（数平均分子量１８００）水溶液（０．１０Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．２当量のクロロ酢酸アリルを２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸アリル付加物の１５重量％水溶液（Ｉｎｔ．１０）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [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 to 90°C, and 0.2 equivalent of allyl chloroacetate based on the amine value was reacted for 2 hours. The temperature was returned to room temperature, and a 15% by weight aqueous solution (Int. 10) of polyethyleneimine-allyl chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ１９）の製造＞
　上記ポリエチレンイミン－クロロ酢酸アリル付加物の水溶液（Ｉｎｔ．１０）１００重量部及び苛性ソーダ水溶液（０．８Ｍ）８０重量部を９０℃に加熱し、２－クロロベンジルクロリド１０重量部を少しずつ加え、２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ１９）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ１９）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ１９）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ１９）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ１９）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ１９）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E19) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S19) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例２０］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ２０）の製造＞
　実施例１９で製造したポリエチレンイミン－クロロ酢酸アリル付加物の水溶液（Ｉｎｔ．１０）１００重量部、苛性ソーダ水溶液（１．７Ｍ）７６重量部を９０℃に加熱し、４－フルオロベンジルクロリド９重量部を２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ２０）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ２０）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ２０）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２０）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２０）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２０）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E20) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S20) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例２１］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ２１）の製造＞
　実施例１９で製造したポリエチレンイミン－クロロ酢酸アリル付加物の水溶液（Ｉｎｔ．１０）１００重量部、苛性ソーダ水溶液（１．４Ｍ）８６重量部を９０℃に加熱し、３－メチルベンジルクロリド８重量部を２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ２１）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ２１）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ２１）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２１）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２１）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２１）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E21) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S21) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例２２］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ２２）の製造＞
　実施例１９で製造したポリエチレンイミン－クロロ酢酸アリル付加物の水溶液（Ｉｎｔ．１０）１００重量部、苛性ソーダ水溶液（２Ｍ）６３重量部を９０℃に加熱し、３－メトキシベンジルクロリド１０重量部を２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ２２）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ２２）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ２２）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２２）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２２）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２２）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E22) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S22) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例２３］
　（ＰＥＩ化合物）
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ２３）の製造＞
　実施例１９で製造したポリエチレンイミン－クロロ酢酸アリル付加物の水溶液（Ｉｎｔ．１０）１００重量部、苛性ソーダ水溶液（１．５Ｍ）４２重量部を９０℃に加熱し、４－ニトロベンジルクロリド１０重量部を２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ２３）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ２３）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 [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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ２３）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２３）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２３）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２３）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E23) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S23) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例２４］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．１１）の製造＞
　ポリエチレンイミン（数平均分子量１００００）水溶液（０．１１Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．２当量のクロロ酢酸アリルを２時間反応させた。室温に戻し、ポリエチレンイミン－クロロ酢酸アリル付加物の１２重量％水溶液（Ｉｎｔ．１１）を得た。なお、反応の進行は１ＨＮＭＲにより、４．１ｐｐｍ付近のシグナルの消失で確認した。 [Example 24]
(PEI compound)
<Production of intermediate (Int.11)>
An aqueous solution (0.11M) of polyethyleneimine (number average molecular weight 10,000) was heated to 70 to 90°C, and 0.2 equivalent of allyl chloroacetate based on the amine value was reacted for 2 hours. The temperature was returned to room temperature, and a 12% by weight aqueous solution (Int. 11) of polyethyleneimine-allyl chloroacetate adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of a signal around 4.1 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ２４）の製造＞
　上記ポリエチレンイミン－クロロ酢酸アリル付加物の水溶液（Ｉｎｔ．１１）１００重量部を９０℃に加熱し、塩化ベンジル５重量部を２時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ２４）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ２４）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ２４）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２４）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２４）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２４）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E24) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S24) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例２５］
　（ＰＥＩ化合物）
　　＜中間体（Ｉｎｔ．１２）の製造＞
　ポリエチレンイミン（数平均分子量１８００）水溶液（０．１３Ｍ）を７０～９０℃に加熱し、アミン価に対し、０．６当量の１，４－ブタンスルトンを２時間反応させた。室温に戻し、ポリエチレンイミン－１，４－ブタンスルトン付加物の３８重量％水溶液（Ｉｎｔ．１２）を得た。なお、反応の進行は１ＨＮＭＲにより、４．４９ｐｐｍ付近のシグナルの消失で確認した。 [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 to 90°C, and 1,4-butane sultone in an amount of 0.6 equivalent based on the amine value was reacted for 2 hours. The temperature was returned to room temperature, and a 38% by weight aqueous solution (Int. 12) of a polyethyleneimine-1,4-butanesultone adduct was obtained. The progress of the reaction was confirmed by 1 H NMR by the disappearance of the signal around 4.49 ppm.
　　＜ＰＥＩ化合物（試料Ｎｏ．Ａ２５）の製造＞
　上記ポリエチレンイミン－１，４－ブタンスルトン付加物の水溶液（Ｉｎｔ．１２）１００重量部及び塩化ベンジル７重量部を８０～９０℃に加熱し、３時間反応させた。室温に戻したところＰＥＩ化合物（試料Ｎｏ．Ａ２５）の水溶液が得られた。表２にＰＥＩ化合物（試料Ｎｏ．Ａ２５）の詳細を示す。なお、反応の進行は１ＨＮＭＲにより、４．５ｐｐｍ付近のシグナルの消失で確認した。 <Production of 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.
　（めっき液の調製）
　ＰＥＩ化合物（試料Ｎｏ．Ａ１）に代えてＰＥＩ化合物（試料Ｎｏ．Ａ２５）を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２５）を調製した。 (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 the PEI compound (sample No. A1).
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２５）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２５）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E25) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S25) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例２６］
　（めっき液の調製）
　富士フイルム和光純薬株式会社製ポリエチレングリコール２００００に代えて富士フイルム和光純薬株式会社製ポリエチレングリコール４０００を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２６）を調製した。
　銅めっき液（試料Ｎｏ．Ｅ２６）は、実施例４で調製した銅めっき液（試料Ｎｏ．Ｅ４）において界面活性剤のみを変更したものである。 [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.
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２６）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２６）が得られた。 (Electroplating test)
Evaluation: A copper plating film was formed on the surface of the brass plate when cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E26) was used instead of the copper plating solution (sample No. E1). A sample (sample No. S26) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［実施例２７］
　（めっき液の調製）
　富士フイルム和光純薬株式会社製ポリエチレングリコール２００００に代えて株式会社アデカ製非イオン性界面活性剤アデカプルロニック（登録商標）Ｌ－６４を用いた以外は実施例１と同様にして銅めっき液（試料Ｎｏ．Ｅ２７）を調製した。
　銅めっき液（試料Ｎｏ．Ｅ２７）は、実施例４で調製した銅めっき液（試料Ｎｏ．Ｅ４）において界面活性剤のみを変更したものである。 [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.
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２７）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２７）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E27) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S27) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［比較例１］
　（めっき液の調製）
　硫酸銅５水和物２２０ｇ／Ｌと、硫酸７０ｇ／Ｌと、塩化物イオンＣｌ－６０ｍｇ／Ｌと、界面活性剤としての富士フイルム和光純薬株式会社製ポリエチレングリコール２００００の１００ｍｇ／Ｌと、光沢剤としてのビス（３－ナトリウムスルホプロピル）ジスルフィド（ＳＰＳ）の８．３ｍｇ／Ｌと、平滑剤としてのヤヌスグリーンＢの３．０ｍｇ／Ｌと、を含む銅めっき液（試料Ｎｏ．Ｅ２８）を調製した。 [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.
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２８）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２８）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E28) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S28) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
［比較例２］
　（めっき液の調製）
　硫酸銅５水和物２２０ｇ／Ｌと、硫酸７０ｇ／Ｌと、塩化物イオンＣｌ－６０ｍｇ／Ｌと、界面活性剤としての富士フイルム和光純薬株式会社製ポリエチレングリコール２００００の１００ｍｇ／Ｌと、光沢剤としてのビス（３－ナトリウムスルホプロピル）ジスルフィド（ＳＰＳ）の８．３ｍｇ／Ｌと、平滑剤としての塩化ベンジルとポリアルキレンイミンの芳香族反応生成物の３．０ｍｇ／Ｌと、を含む銅めっき液（試料Ｎｏ．Ｅ２９）を調製した。 [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.
　（電気めっき試験）
　銅めっき液（試料Ｎｏ．Ｅ１）に代えて銅めっき液（試料Ｎｏ．Ｅ２９）を用いた以外は実施例１と同様にして陰極電解したところ、真鍮板表面に銅めっき皮膜が形成された評価サンプル（試料Ｎｏ．Ｓ２９）が得られた。 (Electroplating test)
Evaluation: When cathodic electrolysis was performed in the same manner as in Example 1 except that a copper plating solution (sample No. E29) was used instead of the copper plating solution (sample No. E1), a copper plating film was formed on the surface of the brass plate. A sample (sample No. S29) was obtained.
　（評価）
　実施例１と同様にして光沢度を測定した。表２に光沢度を示す。 (evaluation)
Glossiness was measured in the same manner as in Example 1. Table 2 shows the glossiness.
　表１及び表２より、実施例（試料Ｎｏ．Ｅ１～Ｅ２７）で作製した評価サンプルは、比較例（試料Ｎｏ．Ｅ２８及びＥ２９）と比較して光沢度が高くなることが分かった。 From Tables 1 and 2, it was found that the evaluation samples prepared in the Examples (Sample Nos. E1 to E27) had higher glossiness than the Comparative Examples (Samples No. E28 and E29).

Claims (3)

  1. 　金属イオンと、
    　ポリエチレンイミン主骨格を有し、下記式（ＬＸ）に示す構造部分ＬＸ、下記式（ＬＹ）に示す構造部分ＬＹ及び下記式（ＬＨ）に示す構造部分ＬＨを有するＰＥＩ化合物（Ｌ）と、
    Figure JPOXMLDOC01-appb-C000001
     （式（ＬＸ）中、Ｘは下記式（Ｘ１）に示す構造部分Ｘ１、ｉは１以上の整数である。）
    Figure JPOXMLDOC01-appb-C000002
     （式（ＬＹ）中、Ｙは下記式（Ｙ１）に示す構造部分Ｙ１、ｊは１以上の整数である。）
    Figure JPOXMLDOC01-appb-C000003
     （式（ＬＨ）中、ｋは０又は１以上の整数である。）
    Figure JPOXMLDOC01-appb-C000004
     （式（Ｘ１）中、ＡはＣ又はＳ、Ｅは一価の金属イオン、Ｈ、メチル基、エチル基又はアリル基、ｌは１～６の整数、ｍは１又は２である。）
    Figure JPOXMLDOC01-appb-C000005
     （式（Ｙ１）中、ＧはＣＨ２又はＣＨ（ＯＨ）、ｎは０又は４、Ｑ１及びＱ２はそれぞれＨ、電子求引性基又は電子供与性基である。）
    を含むめっき液。     metal ions and
    A PEI compound (L) having a polyethyleneimine main skeleton and having a structural moiety LX represented by the following formula (LX), a structural moiety LY represented by the following formula (LY), and a structural moiety LH represented by the following formula (LH),
    Figure JPOXMLDOC01-appb-C000001
     (In formula (LX), X is the structural moiety X1 shown in formula (X1) below, and i is an integer of 1 or more.)
    Figure JPOXMLDOC01-appb-C000002
     (In formula (LY), Y is the structural moiety Y1 shown in formula (Y1) below, and j is an integer of 1 or more.)
    Figure JPOXMLDOC01-appb-C000003
     (In formula (LH), k is 0 or an integer of 1 or more.)
    Figure JPOXMLDOC01-appb-C000004
     (In formula (X1), A is C or S, E is a monovalent metal ion, H, methyl group, ethyl group, or allyl group, l is an integer of 1 to 6, and m is 1 or 2.)
    Figure JPOXMLDOC01-appb-C000005
     (In formula (Y1), 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.)
    plating solution containing
  2. 　前記構造部分ＬＸのｉと前記構造部分ＬＹのｊと前記構造部分ＬＨのｋとに基づき算出した｛ｉ／（ｉ＋ｊ＋ｋ）｝×１００が２０～９０％である、請求項１に記載のめっき液。 The plating solution according to claim 1, wherein {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 is 20 to 90%. .
  3. 　前記金属イオンが銅イオンを含む、請求項１又は２に記載のめっき液。 The plating solution according to claim 1 or 2, wherein the metal ions include copper ions.
PCT/JP2023/023544 2022-08-31 2023-06-26 Plating solution WO2024048039A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022138480 2022-08-31
JP2022-138480 2022-08-31

Publications (1)

Publication Number Publication Date
WO2024048039A1 true WO2024048039A1 (en) 2024-03-07

Family

ID=90099390

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/023544 WO2024048039A1 (en) 2022-08-31 2023-06-26 Plating solution

Country Status (1)

Country Link
WO (1) WO2024048039A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001279228A (en) * 2000-03-31 2001-10-10 Ajinomoto Co Inc New chelating agent
JP2004043957A (en) * 2002-03-05 2004-02-12 Enthone Inc Reduction of defect in electrodeposition copper for semiconductor application
JP2005536579A (en) * 2002-06-19 2005-12-02 ビーエーエスエフ アクチェンゲゼルシャフト Complexing agents for the treatment of metal and plastic surfaces
CN110117801A (en) * 2019-06-21 2019-08-13 郑州知淘信息科技有限责任公司 A kind of printed circuit board blind hole fills out copper copper plating additive and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001279228A (en) * 2000-03-31 2001-10-10 Ajinomoto Co Inc New chelating agent
JP2004043957A (en) * 2002-03-05 2004-02-12 Enthone Inc Reduction of defect in electrodeposition copper for semiconductor application
JP2005536579A (en) * 2002-06-19 2005-12-02 ビーエーエスエフ アクチェンゲゼルシャフト Complexing agents for the treatment of metal and plastic surfaces
CN110117801A (en) * 2019-06-21 2019-08-13 郑州知淘信息科技有限责任公司 A kind of printed circuit board blind hole fills out copper copper plating additive and preparation method thereof

Similar Documents

Publication Publication Date Title
TWI486490B (en) Polymers having terminal amino groups and use thereof as additives for zinc and zinc alloy electrodeposition baths
JP2009541580A (en) Cyanide-free aqueous alkaline bath for electrodeposition of zinc and zinc alloy coatings
JP6227722B2 (en) Electroplating method for uniform copper layer
CA1078323A (en) Acid copper plating baths
JP5103372B2 (en) Polyvinylammonium compound, method for producing polyvinylammonium compound, acidic solution containing polyvinylammonium compound and method for electrolytically depositing copper plating
JP5586587B2 (en) Pd electrolyte bath and Pd-Ni electrolyte bath
TWI359880B (en) Method to electrodeposit metals using ionic liquid
KR101609171B1 (en) Pyrophosphate-containing bath for cyanide-free deposition of copper-tin alloys
JPS6056084A (en) Zinc and zinc alloy electrodeposition bath and process
KR102001322B1 (en) Copper-nickel alloy electroplating bath
TW200949021A (en) Pyrophosphate-based bath for plating of tin alloy layers
US20210262105A1 (en) Acidic aqueous composition for electrolytic copper plating
JPS6012432B2 (en) Bright galvanizing bath
JP4352004B2 (en) Acid bath for electrolytic deposition of mixtures of phenazinium compound oligomers and copper deposits
WO2024048039A1 (en) Plating solution
JPH0363542B2 (en)
JPS5815553B2 (en) Acidic tin bath for electrodepositing tin gloss coatings
JP4855631B2 (en) Zinc and zinc alloy electroplating additive and electroplating method
WO2023241905A1 (en) Stable alkaline electroplating bath with a diacid
TW202409351A (en) Stable alkaline electroplating bath with a diacid
PL168375B1 (en) Method of obtaining a brightening agent for use in ellectroplating processes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23859809

Country of ref document: EP

Kind code of ref document: A1