Classifications

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

Definitions

• the present invention relates to a plating solution. More specifically, the present invention relates to a plating solution that enables plating with high gloss.
• Plating treatments are generally applied as one of surface treatment techniques in order to confer appearance characteristics such as decoration and functionalities such as corrosion resistance to a base material such as a resin, a metal, a glass material, or a ceramic material.
• a base material such as a resin, a metal, a glass material, or a ceramic material.
• electrolytic copper plating is used as a base plating because it yields a highly ductile plating film and can prevent cracks from being caused by expansion and contraction of the material due to temperature changes.
• smoothing of a substrate surface roughened due to etching and intrinsic unevenness of a material as well as high gloss are required.
• Patent Document 1 discloses an electrolytic copper plating solution containing a basic dye such as janus green B as a leveler in order to achieve a sufficiently glossy appearance.
• An electrolytic copper plating solution free of a basic dye as a leveler is also disclosed in, for example, Patent Document 2.
• Patent Document 2 discloses an electrolytic copper plating solution containing at least one aromatic reaction product of benzyl chloride and at least one polyethylenimine.
• 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 is free of a basic dye conventionally used and enables plating with higher gloss.
• a first aspect of the present invention relates to a plating solution comprising: a metal ion; and a polyethylenimine (PEI) compound (L) having a polyethylenimine 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), wherein in the formula (LX), X represents a structural moiety X1 represented by the following formula (X1), and i represents an integer of 1 or more, wherein in the formula (LY), Y represents a structural moiety Y1 represented by the following formula (Y1), and j represents an integer of 1 or more, wherein in the formula (LH), k represents 0 or an integer of 1 or more, wherein in the formula (X1), A represents C or S, E represents a monovalent metal ion, H, a methyl group, an ethyl group, or an allyl group,
• a third aspect of the present invention relates to the plating solution according to the first or second aspect, wherein the metal ion preferably comprises a copper ion.
• a plating solution that enables plating with high gloss can be provided.
• Copper sulfate pentahydrate is preferably used as the copper sulfate, and the content of copper sulfate pentahydrate in the plating solution according to the present invention is not limited, and is, for example, 50 to 300 g/L, and preferably 100 to 280 g/L.
• the PEI compound (L) is at least used as a leveler.
• one or more known levelers may be added in addition to the PEI compound (L).
• the polyethylenimine skeleton means the skeleton of polyethylenimine (PEI).
• PEI compound (L) has a structure in which hydrogen atoms H bonded to the polyethylenimine skeleton are substituted with X and Y described later.
• the polyethylenimine skeleton is, for example, a network, branched, or linear polyethylenimine skeleton.
• the network polyethylenimine as used herein, means a branched polyethylenimine in which a part or all of the branched portions of the branched polyethylenimine is bonded to another branched portion or the skeleton to form a network.
• An example of the network polyethylenimine is shown in the following formula (NP).
• the polyethylenimine skeleton of the PEI compound (L) is preferably the network or branched polyethylenimine skeleton.
• the PEI compound (L) is a compound in which polyethylenimine having a polyethylenimine skeleton has a number-average molecular weight of, for example, 300 to 70,000, preferably 1,100 to 10,000, and more preferably 1,100 to 1,800.
• the number-average molecular weight of the polyethylenimine falling within the above range is preferable, since a metal plating film having high gloss can be easily obtained.
• the polyethylenimine having a polyethylenimine skeleton as used herein, means polyethylenimine in which the atoms bonded to the polyethylenimine skeleton are only the hydrogen atoms H.
• the PEI compound (L) is often obtained by reacting polyethylenimine having a polyethylenimine skeleton with a source material of X in the structural moiety LX, and a source material of Y in the structural moiety LY.
• the molecular weight of the PEI compound (L) is increased by an amount commensurate with the addition of the source material of X in the structural moiety LX, and the source material of Y in the structural moiety LY, without the polymerization of the basic material polyethylenimine.
• a moiety of the PEI compound (L) in which the hydrogen atom H bonded to the polyethylenimine skeleton is substituted with X is referred to as a structural moiety LX.
• a moiety of the PEI compound (L) in which the hydrogen atom H bonded to the polyethylenimine skeleton is substituted with Y is referred to as a structural moiety LY.
• a moiety of the PEI compound (L) in which the hydrogen atom H bonded to the polyethylenimine skeleton is present and unsubstituted is referred to as a structural moiety LH.
• the PEI compound (L) includes at least the structural moiety LX and the structural moiety LY, and optionally includes the structural moiety LH.
• LX is a structural moiety represented by the following formula (LX).
• X represents a structural moiety X1 represented by the following formula (X1), and i represents an integer of 1 or more.
• 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
• m represents 1 or 2.
• E preferably represents a monovalent metal ion, H, or an allyl group.
• l preferably represents an integer of 3 to 4. Examples of the monovalent metal ion include Li, Na, K, Rb, Cs, Fr, etc.
• Preferred embodiments of the structural moiety represented by the structural moiety X1 include, for example, structural moieties represented by structural moieties X111, X112, X113, and X114 shown in the following formula (X11).
• LY is a structural moiety represented by the following formula (LY).
• Y represents a structural moiety Y1 represented by the following formula (Y1), and j represents an integer of 1 or more.
• G represents CH 2 or CH(OH)
• n represents 0 or 4
• Q 1 and Q 2 each independently represent H, an electron-withdrawing group, or an electron-donating group.
• n 0, the aryl group of the structural moiety Y1 has a structure containing one benzene ring.
• n is 4
• the aryl group of the structural moiety Y1 has a structure containing one naphthalene ring.
• Q 1 and Q 2 on the aryl group of the structural moiety Y1 each independently represent H, an electron-withdrawing group, or an electron-donating group, and are not limited to a particular group.
• the electron-withdrawing group include a chloro group -Cl, a fluoro group -F, a nitro group -NO 2 , a hydroxy group -OH, etc.
• the electron-donating group include a methyl group -CH 3 , a methoxy group -OCH 3 , etc.
• Q 1 and Q 2 are substituents other than the hydrogen atom H
• examples of the substitution position of the substituents with respect to the portion bonded to the polyethylenimine skeleton include an ortho position, a meta position, a para position, etc.
• Preferred embodiments of the structural moiety represented by the structural moiety Y1 include, for example, structural moieties represented by structural moieties Y111, Y112, Y113, and Y114 shown in the following formula (Y11).
• the upper end portions of the structural moieties Y111, Y112, and Y113 correspond to the upper end portion of the structural moiety Y1.
• the right upper end portion of the structural moiety Y114 corresponds to the upper end portion of the structural moiety Y1.
• Q 1 and Q 2 on the aryl group in the structural moieties Y111, Y112, Y113, and Y114 are substituents other than the hydrogen atom H
• the types, numbers and positions of the substituents are not limited, and examples of the substituents include a chloro group -Cl, a fluoro group -F, a methyl group -CH 3 , and a methoxy group -OCH 3 , etc.
• Preferred embodiments of the structural moiety in which Q 1 and Q 2 in the formula (Y1) are substituents other than the hydrogen atom H include, for example, structural moieties shown in the following formula (Y11A).
• Particularly preferred embodiments of the structural moiety in which Q 1 and Q 2 in the formula (Y1) are substituents other than the hydrogen atom H include, for example, structural moieties shown in the following formula (Y11B).
• the structural moiety LH is a structural moiety represented by the following formula (LH).
• a value of ⁇ i/(i+j+k) ⁇ 100 calculated based on i in the structural moiety LX, j in the structural moiety LY, and k in the structural moiety LH is 20 to 90%, and preferably 30 to 80%.
• the value of ⁇ i/(i+j+k) ⁇ 100 falling within the above range is preferable, since a metal plating film having high gloss can be easily obtained. It should be noted that the value of ⁇ i/(i+j+k) ⁇ 100 can be determined by, for example, NMR or the like.
• the plating solution according to the present invention may contain an acid.
• the acid is not limited, and, for example, any desired acid among inorganic and/or organic acids may be used in accordance with the composition of the plating solution or the plating target.
• the inorganic acids include sulfuric acid, nitric acid, hydrohalic acids including hydrochloric acid, phosphoric acid, oxo acids including chloric acid, etc.
• the organic acids include alkanesulfonic acids such as methanesulfonic acid and propanesulfonic acid, alkanolsulfonic acids such as isethionic acid and propanolsulfonic acid, and aliphatic or aromatic carboxylic acids such as citric acid, tartaric acid and formic acid, etc.
• the plating solution preferably contains sulfuric acid as an acid.
• the content of sulfuric acid is not limited, and is, for example, 20 to 200 g/L, and preferably 30 to 150 g/L.
• the plating solution according to the present invention may contain a halide ion for the purpose of achieving glossy metal plating or leveling.
• the halide ion is not limited, and examples thereof include a chloride ion, a bromide ion, an iodide ion, etc. Among them, a chloride ion is preferable.
• the content of the chloride ion is not limited, and is, for example, 10 to 120 mg/L, and preferably 20 to 100 mg/L.
• the plating solution according to the present invention may contain a brightener.
• the brightener is not limited to a particular brightener, and examples thereof include: various aldehydes such as benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 3-acenaphthaldehyde, benzylideneacetone, pyridydeneacetone, furfurylideneacetone, cinnamaldehyde, anisaldehyde, salicylaldehyde, crotonaldehyde, acrolein, glutaraldehyde, paraldehyde, and vanillin; tria
• the content of the brightener is not limited, and is, for example, 1 to 50 mg/L, and preferably 3 to 30 mg/L.
• the plating solution according to the present invention may contain a surfactant.
• the surfactant is not limited, and examples thereof include nonionic surfactants and amphoteric surfactants, etc.
• the nonionic surfactants are not limited, and examples thereof include polyether compounds, etc.
• the polyether compounds are not limited, and examples thereof include polyalkylene glycols, polyether compounds having an alkyl group, and surfactants composed of a triblock copolymer of a hydrophilic ethylene oxide unit, a hydrophobic propylene oxide unit, and an ethylene oxide unit.
• the content of the surfactant is not limited, and is, for example, 1 to 300 mg/L, and preferably 5 to 200 mg/L.
• the PEI compound (L) contained in the plating solution according to the present invention is obtained, for example, by nucleophilic addition reaction of polyethylenimine having a polyethylenimine skeleton, a source material of X in the structural moiety LX, and a source material of Y in the structural moiety LY.
• the plating solution according to the present invention can be produced by any known method using the PEI compound (L) as a leveler.
• a plating method using the plating solution according to the present invention will be described below.
• electroplating is performed on a substrate using the plating solution according to the present invention.
• the substrate is not limited, and examples thereof include substrates having a base material made of brass, copper, nickel, iron, zinc, zinc alloys, steel, resin, or the like, and having a conductive layer made of metal or the like and formed on the base material.
• a copper plating solution (Sample No. E1) containing 220 g/L of copper sulfate pentahydrate, 70 g/L of sulfuric acid, 60 mg/L of chloride ion Cl - , 100 mg/L of polyethylene glycol 20,000 from FUJIFILM Wako Pure Chemical Corporation as a surfactant, 8.3 mg/L of bis(3-sodium sulfopropyl) disulfide (SPS) as a brightener, and 3.0 mg/L of the PEI compound (Sample No. A1) as a leveler was prepared.
• SPS bis(3-sodium sulfopropyl) disulfide
• a Hull cell brass plate was immersed at 55°C for 5 minutes using EBAPREP SK-144 (degreasing) from JCU CORPORATION, and then immersed at room temperature for 0.5 minutes using EBAVATE V-345 (acid activation) from JCU CORPORATION.
• Example No. S1 Cathodic electrolysis (total current: 2 A) was performed for 10 minutes at room temperature in a Hull cell test using the pretreated Hull cell brass plate and the copper plating solution (Sample No. E1). Subsequently, a rust-proofing treatment was carried out using EBAFIN G-800 from JCU CORPORATION at room temperature for 0.5 minutes to obtain an evaluation sample (Sample No. S1), which was the brass plate having a copper plating film formed on the surface thereof.
• the evaluation sample (Sample No. S1) was set in a micro-TRI-gloss gloss meter from BYK-Gardner GmbH. A portion of the evaluation sample subjected to a current density of 3 A/dm 2 was irradiated with light at an incidence angle of 20° to measure gloss. The gloss is shown in Table 1.
• Example No. A2 One hundred parts by weight of the aqueous solution of the polyethylenimine-sodium chloroacetate adduct (Int. 1) produced in Example 1 and 83 parts by weight of an aqueous sodium hydroxide solution (7.5 M) were heated to 90°C, then 25 parts by weight of 2-chlorobenzyl chloride was added in portions, and the reaction was allowed to proceed for 2 hours. The mixture was cooled to room temperature, and an aqueous solution of a PEI compound (Sample No. A2) was obtained. The details of the PEI compound (Sample No. A2) are shown in Table 1. Incidentally, the progress of the reaction was confirmed by 1 H NMR based on 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 the PEI compound (Sample No. A2) was used instead of the PEI compound (Sample No. A1).
• Example No. E2 the copper plating solution (Sample No. E2) was used instead of the copper plating solution (Sample No. E1), and an evaluation sample (Sample No. S2), which was a brass plate having a copper plating film formed on the surface thereof, was obtained.
• a copper plating solution (Sample No. E3) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A3) was used instead of the PEI compound (Sample No. A1).
• Example No. E3 the copper plating solution (Sample No. E3) was used instead of the copper plating solution (Sample No. E1), and an evaluation sample (Sample No. S3), which was a brass plate having a copper plating film formed on the surface thereof, was obtained.
• a copper plating solution (Sample No. E4) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A4) was used instead of the PEI compound (Sample No. A1).
• Example No. E4 the copper plating solution (Sample No. E4) was used instead of the copper plating solution (Sample No. E1), and an evaluation sample (Sample No. S4), which was a brass plate having a copper plating film formed on the surface thereof, was obtained.
• a copper plating solution (Sample No. E5) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A5) was used instead of the PEI compound (Sample No. A1).
• a copper plating solution (Sample No. E7) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A7) was used instead of the PEI compound (Sample No. A1).
• a copper plating solution (Sample No. E8) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A8) was used instead of the PEI compound (Sample No. A1).
• Example No. A9 One hundred parts by weight of the aqueous solution of the polyethylenimine-sodium chloroacetate adduct (Int. 3) produced in Example 4 and 75 parts by weight of an aqueous sodium hydroxide solution (8.4 M) were heated to 90°C, then 27 parts by weight of 4-nitrobenzyl chloride was added, and the reaction was allowed to proceed for 2 hours. The mixture was cooled to room temperature, and 169 parts by weight of pure water was added to obtain an aqueous solution of a PEI compound (Sample No. A9). The details of the PEI compound (Sample No. A9) are shown in Table 1. Incidentally, the progress of the reaction was confirmed by 1 H NMR based on 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 the PEI compound (Sample No. A9) was used instead of the PEI compound (Sample No. A1).
• Example No. E14 the copper plating solution (Sample No. E14) was used instead of the copper plating solution (Sample No. E1), and an evaluation sample (Sample No. S14), which was a brass plate having a copper plating film formed on the surface thereof, was obtained.
• a copper plating solution (Sample No. E15) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A15) was used instead of the PEI compound (Sample No. A1).
• a copper plating solution (Sample No. E16) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A16) was used instead of the PEI compound (Sample No. A1).
• a copper plating solution (Sample No. E17) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A17) was used instead of the PEI compound (Sample No. A1).
• a copper plating solution (Sample No. E18) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A18) was used instead of the PEI compound (Sample No. A1).
• Example No. E18 the copper plating solution (Sample No. E18) was used instead of the copper plating solution (Sample No. E1), and an evaluation sample (Sample No. S18), which was a brass plate having a copper plating film formed on the surface thereof, was obtained.
• a copper plating solution (Sample No. E19) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A19) was used instead of the PEI compound (Sample No. A1).
• Example No. E19 the copper plating solution (Sample No. E19) was used instead of the copper plating solution (Sample No. E1), and an evaluation sample (Sample No. S19), which was a brass plate having a copper plating film formed on the surface thereof, was obtained.
• Example No. A20 One hundred parts by weight of the aqueous solution of the polyethylenimine-allyl chloroacetate adduct (Int. 10) produced in Example 19 and 76 parts by weight of an aqueous sodium hydroxide solution (1.7 M) were heated to 90°C, and 9 parts by weight of 4-fluorobenzyl chloride was reacted therewith for 2 hours. The mixture was cooled to room temperature, and an aqueous solution of a PEI compound (Sample No. A20) was obtained. The details of the PEI compound (Sample No. A20) are shown in Table 2. Incidentally, the progress of the reaction was confirmed by 1 H NMR based on the disappearance of a signal around 4.5 ppm.
• Example No. E20 the copper plating solution (Sample No. E20) was used instead of the copper plating solution (Sample No. E1), and an evaluation sample (Sample No. S20), which was a brass plate having a copper plating film formed on the surface thereof, was obtained.
• a copper plating solution (Sample No. E21) was prepared in the same manner as in Example 1 except that the PEI compound (Sample No. A21) was used instead of the PEI compound (Sample No. A1).
• Example No. E21 the copper plating solution (Sample No. E21) was used instead of the copper plating solution (Sample No. E1), and an evaluation sample (Sample No. S21), which was a brass plate having a copper plating film formed on the surface thereof, was obtained.

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• 2023
  • 2023-06-26 JP JP2024502553A patent/JP7553747B2/ja active Active
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