Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D21/00—Processes for servicing or operating cells for electrolytic coating
  • C25D21/12—Process control or regulation
  • C25D21/14—Controlled addition of electrolyte components
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1646—Characteristics of the product obtained
  • C23C18/165—Multilayered product
  • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• • 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
  • C25D3/42—Electroplating: Baths therefor from solutions of light metals
  • C25D3/44—Aluminium
• • 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
  • C25D5/54—Electroplating of non-metallic surfaces
  • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

• the present invention relates to a method for producing an aluminum film, which is capable of producing an aluminum film having excellent surface smoothness and a mirror surface.
• Aluminum has many excellent characteristics, such as electrical conductivity, corrosion resistance, lightweight properties, and non-toxicity, and is widely used for plating on metal products and the like. However, since aluminum has a high affinity for oxygen and a lower oxidation-reduction potential than hydrogen, it is difficult to perform electroplating in an aqueous solution-based plating bath.
• the aluminum electroplating method a method using a molten salt bath is employed.
• the plating bath using an existing molten salt needs to be heated to high temperatures. Therefore, when an attempt is made to electroplate aluminum on a resin product, the resin is melted, and it is not possible to perform electroplating, which is a problem.
• Japanese Unexamined Patent Application Publication No. 2012-144763 (PTL 1) describes that an aluminum plating bath that is liquid at room temperature is prepared by mixing an organic chloride salt, such as 1-ethyl-3-methylimidazolium chloride (EMIC) or 1-butylpyridinium chloride (BPC), and aluminum chloride (AlCl 3 ), and using the plating bath, aluminum is electroplated on the surface of a resin molded body.
• an organic chloride salt such as 1-ethyl-3-methylimidazolium chloride (EMIC) or 1-butylpyridinium chloride (BPC)
• AlCl 3 aluminum chloride
• the EMIC-AlCl 3 -based plating solution described in PTL 1 exhibits good liquid characteristics and is very useful as an aluminum plating solution. Furthermore, PTL 1 describes that by adding 1,10-phenanthroline at a concentration of 0.25 to 7.0 g/L to the aluminum plating solution, a smooth aluminum film is formed.
• an aluminum porous body produced by the method described in PTL 1 is very promising, for example, in improving the capacity of the positive electrode in lithium ion batteries.
• aluminum has excellent characteristics, such as electrical conductivity, corrosion resistance, and lightweight properties
• the positive electrode using a porous body composed of aluminum, the surface area is increased and the inside of the aluminum porous body can also be filled with the active material.
• the active material utilization ratio does not decrease, and the active material utilization ratio per unit area is improved, enabling improvement in the capacity of the positive electrode.
• an aluminum porous body having a three-dimensional network structure is very useful, and the present inventors have conducted studies on continuous mass production of aluminum porous bodies. As a result, it has been found that although a very good aluminum porous body is obtained by the method according to PTL 1, it has been observed that, in some cases, smoothness of the aluminum film may be degraded by continuous production, which requires a need to replace the plating solution with a new one.
• the present inventors have performed thorough studies in order to solve the problems described above. As a result, it has been conceivable that, when an aluminum plating film is continuously formed on the surface of a resin molded body subjected to conductivity-imparting treatment, the amount of 1,10-phenanthroline, which is effective for imparting smoothness, in the plating solution decreases.
• the 1,10-phenanthroline has two forms: anhydride and monohydrate, and PTL 1 does not particularly describe which form is better.
• PTL 1 does not particularly describe which form is better.
• it has been common general technical knowledge to use 1,10-phenanthroline anhydride instead of 1,10-phenanthroline monohydrate because aluminum chloride (AlCl 3 ) included in the plating solution reacts with water to generate hydrogen chloride. The reason for this is that generation of hydrogen chloride will cause corrosion of surrounding equipment and a problem of safety for the human body due to inhalation of hydrogen chloride.
• 1,10-phenanthroline monohydrate is effective for imparting smoothness to the plating film.
• 1,10-phenanthroline anhydride is also partially hydrated by moisture in the air, it is difficult to obtain 1,10-phenanthroline in the form of anhydride only. Therefore, in the case where 1,10-phenanthroline anhydride is added, 1,10-phenanthroline monohydrate is also mixed in the plating solution.
• the reason for the decrease in the smoothness of the aluminum film when the aluminum film is continuously formed by an existing method is believed to be that monohydrate included in 1,10-phenanthroline anhydride is consumed by continuous operation and the concentration of 1,10-phenanthroline monohydrate in the plating solution is decreased.
• the present invention employs the following features.
• a method for producing an aluminum film includes electrodepositing aluminum on a surface of a substrate in an electrolyte solution, in which the electrolyte solution contains, as components, (A) an aluminum halide, (B) at least one compound selected from the group consisting of an alkyl pyridinium halide, an alkyl imidazolium halide, and a urea compound, and (C) 1,10-phenanthroline monohydrate; in which the mixing ratio (molar ratio) of the component (A) to the component (B) is in the range of 1:1 to 3:1; and in which the concentration of the 1,10-phenanthroline monohydrate in the electrolyte solution is controlled to be in the range of 0.05 to 7.5 g/L.
• the concentration of the 1,10-phenanthroline monohydrate in the electrolyte solution is controlled by measuring an overvoltage caused by deposition of aluminum in the electrolyte solution and by adjusting the amount of 1,10-phenanthroline monohydrate added to the electrolyte solution such that the measured value of the overvoltage is within a set range.
• the concentration of 1,10-phenanthroline monohydrate in the electrolyte solution since it is possible to know the concentration of 1,10-phenanthroline monohydrate in the electrolyte solution, the concentration of 1,10-phenanthroline monohydrate in the electrolyte solution can be easily controlled.
• the component (A) is aluminum chloride and the component (B) is 1-ethyl-3-methylimidazolium chloride.
• the substrate is a resin molded body having a three-dimensional network structure which has been subjected to conductivity-imparting treatment.
• a method for producing an aluminum film according to the present invention includes electrodepositing aluminum on a surface of a substrate in an electrolyte solution, in which the electrolyte solution contains, as components, (A) an aluminum halide, (B) at least one compound selected from the group consisting of an alkyl pyridinium halide, an alkyl imidazolium halide, and a urea compound, and (C) 1,10-phenanthroline monohydrate; in which the mixing ratio (molar ratio) of the component (A) to the component (B) is in the range of 1:1 to 3:1; and in which the concentration of the 1,10-phenanthroline monohydrate in the electrolyte solution is controlled to be in the range of 0.05 to 7.5 g/L.
• the electrolyte solution contains, as components, (A) an aluminum halide, (B) at least one compound selected from the group consisting of an alkyl pyridinium halide, an alkyl imidazolium halide, and a
• the electrolyte solution used in the present invention is obtained by mixing at least the component (A), the component (B), and the component (C). Each of these components will be specifically described below.
• any aluminum halide that forms a molten salt at about 110° C. or lower when mixed with the component (B) can be satisfactorily used.
• examples thereof include aluminum chloride (AlCl 3 ), aluminum bromide (AlBr 3 ), and aluminum iodide (AlI 3 ), and among these, aluminum chloride is most preferable.
• any alkyl pyridinium halide that forms a molten salt at about 110° C. or lower when mixed with the component (A) can be satisfactorily used.
• Examples thereof include 1-butylpyridinium chloride (BPC), 1-ethylpyridinium chloride (EPC), and 1-butyl-3-methylpyridinium chloride (BMPC), and among these, 1-butylpyridinium chloride is most preferable.
• any alkyl imidazolium halide that forms a molten salt at about 110° C. or lower when mixed with the component (A) can be satisfactorily used.
• Examples thereof include imidazolium chloride having alkyl groups (having 1 to 5 carbon atoms) at the 1- and 3-positions, imidazolium chloride having alkyl groups (having 1 to 5 carbon atoms) at the 1-, 2-, and 3-positions, and imidazolium iodide having alkyl groups (having 1 to 5 carbon atoms) at the 1- and 3-positions.
• EMIC 1-ethyl-3-methylimidazolium chloride
• BMIC 1-butyl-3-methylimidazolium chloride
• MPIC 1-methyl-3-propylimidazolium chloride
• EMIC 1-ethyl-3-methylimidazolium chloride
• the urea compound which is the component (B), means urea or a derivative thereof, and any urea compound that forms a molten salt at about 110° C. or lower when mixed with the component (A) can be satisfactorily used.
• a compound represented by the formula (1) below may be preferably used.
• R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group and two Rs may be the same or different.
• urea compound among these, urea or dimethylurea can be particularly preferably used.
• the mixing ratio (molar ratio) of the component (A) to the component (B) is in the range of 1:1 to 3:1 in the electrolyte solution, it is possible to obtain an electrolyte solution that is suitable for electrodepositing an aluminum film on the surface of the substrate.
• 1,10-phenanthroline monohydrate which is the component (C)
• the electrolyte solution it is possible to smooth the surface of an aluminum film formed on the surface of the substrate such that the surface of the aluminum film is in the mirror surface state.
• the expression “the surface of the aluminum film is in the mirror surface state” refers to that the arithmetic mean roughness Ra of the surface of the aluminum film measured using a laser microscope is 0.10 ⁇ m or less.
• the concentration of 1,10-phenanthroline monohydrate in the electrolyte solution is set to be 0.05 to 7.5 g/L.
• the concentration of 1,10-phenanthroline monohydrate in the electrolyte solution is within the range described above, an aluminum film having excellent smoothness can be obtained.
• an optimum concentration range is selected depending on the type of substrate.
• the concentration range is preferably set to be 0.1 to 2.0 g/L.
• the concentration range is set to be 0.3 to 1.0 g/L.
• 1,10-Phenanthroline monohydrate is incorporated into aluminum when aluminum is electrodeposited on the surface of the substrate, and thus the concentration of 1,10-phenanthroline monohydrate in the electrolyte solution decreases as the operation proceeds. Therefore, it is necessary to control the concentration to be within the range described above by appropriately adding 1,10-phenanthroline monohydrate to the electrolyte solution.
• the concentration of the 1,10-phenanthroline monohydrate in the electrolyte solution is controlled by measuring an overvoltage in the electrolyte solution when aluminum is deposited and by adjusting the amount of 1,10-phenanthroline monohydrate added to the electrolyte solution such that the measured value of the overvoltage is within a set range.
• the concentration of 1,10-phenanthroline monohydrate in the electrolyte solution correlates with the overvoltage caused by the aluminum deposition reaction.
• the set range of the overvoltage may be appropriately determined depending on the composition of the electrolyte solution.
• the overvoltage may be set to be 105 to 170 mV.
• the overvoltage may be set to be 120 to 180 mV.
• the measurement of the overvoltage may be performed continuously or periodically with an interval between successive measurements. Furthermore, at the time of measurement of the overvoltage, the electrolyte solution may be taken out from the system and measured, or measurement may be performed by providing electrodes in the electrolyte solution in the plating tank in which the aluminum film is produced.
• overvoltage refers to the absolute value of the difference between the theoretical deposition potential of aluminum and the potential at which deposition of aluminum actually starts.
• an anode and a cathode are provided in the electrolyte solution, a voltage is applied between the two, and the potential at which aluminum starts to deposit, i.e., the voltage at which current starts to flow, is measured.
• the potential difference between the potential at that time and the theoretical potential (equilibrium electrode potential) is calculated as the overvoltage.
• aluminum aluminum may be used, and as the cathode, for example, platinum, glassy carbon, or the like may be used.
• 1,10-Phenanthroline has two forms: monohydrate and anhydride.
• the concentration of the 1,10-phenanthroline monohydrate in the electrolyte solution is controlled to be in the range of 0.05 to 7.5 g/L.
• the electrolyte solution may contain 1,10-phenanthroline anhydride.
• the ratio of 1,10-phenanthroline monohydrate relative to the total amount of 1,10-phenanthroline monohydrate and 1,10-phenanthroline anhydride is preferably set to be 1% to 100% by mass, more preferably 10% to 60% by mass, and still more preferably 20% to 30% by mass.
• the electrolyte solution may contain an addition agent and the like in addition to the component (A), the component (B), and the component (C).
• the electrolyte solution contains, as a brightener, at least one selected from the group consisting of an organic solvent, a nitrogen-containing heterocyclic compound, and a sulfur-containing heterocyclic compound, it is possible to enhance the surface glossiness of the aluminum film, which is preferable.
• the concentration of the brightener in the electrolyte solution is preferably set to be 0.01 to 10.0 g/L, more preferably 0.5 to 7.5 g/L, and still more preferably 2.5 to 5.0 g/L.
• organic solvent for example, benzene, xylene, toluene, tetralin, or the like can be preferably used.
• nitrogen-containing heterocyclic compound a compound having 3 to 14 carbon atoms is preferable.
• benzotriazole, pyridine, pyrazine, bipyridine, or the like can be preferably used.
• sulfur-containing heterocyclic compound for example, thiourea, ethylene thiourea, phenothiazine, or the like can be preferably used.
• the method for producing an aluminum film according to the present invention preferably, aluminum is electrodeposited on the surface of the substrate while controlling the temperature of the electrolyte solution to be 15° C. to 110° C.
• the temperature of the electrolyte solution is more preferably 30° C. to 60° C., and still more preferably 40° C. to 50° C.
• an aluminum electrode is provided in the electrolyte solution and electrically connected to the substrate in the electrolyte solution such that the substrate serves as a cathode, and a current is applied.
• aluminum is electrodeposited on the surface of the substrate at a current density of 2.0 to 10.0 A/dm 2 .
• the current density is more preferably 2.0 to 6.0 A/dm 2 , and still more preferably 2.5 to 4.0 A/dm 2 .
• the electrolyte solution may or may not be stirred.
• the substrate is not particularly limited as long as it needs to have an aluminum film on the surface thereof.
• a copper plate, a steel strip, a copper wire, a steel wire, a resin subjected to conductivity-imparting treatment, or the like can be used as the substrate.
• a resin subjected to conductivity-imparting treatment for example, polyurethane, a melamine resin, polypropylene, polyethylene, or the like which has been subjected to conductivity-imparting treatment can be used.
• the resin serving as the substrate may have any shape.
• a resin molded body having a three-dimensional network structure it is possible to eventually produce an aluminum porous body having a three-dimensional network structure that exhibits excellent characteristics for use in various filters, catalyst carriers, electrodes for batteries, and the like, which is preferable.
• a resin having a nonwoven fabric shape it is also possible to eventually produce an aluminum porous body having a porous structure.
• the aluminum porous body having a nonwoven fabric shape thus produced can be suitably used for various filters, catalyst carriers, electrodes for batteries, and the like.
• the resin molded body having the three-dimensional network structure for example, a foamed resin molded body produced using polyurethane, a melamine resin, or the like can be used.
• a resin molded body having any shape can be selected as long as it has pores connecting with each other (interconnecting pores).
• a body having a nonwoven fabric-like shape in which resin fibers of polypropylene, polyethylene, or the like are entangled with each other can be used instead of the foamed resin molded body.
• porous body having a three-dimensional network structure may also be simply described as the “porous body”.
• the porous body has a porosity of 80% to 98% and a pore size of 50 to 500 ⁇ m.
• a polyurethane foam or foamed melamine resin has a high porosity, an interconnecting property of pores, and excellent heat decomposability, and therefore can be suitably used as a foamed resin molded body.
• a polyurethane foam is preferable in terms of uniformity of pores, easy availability, and the like, and a foamed melamine resin is preferable from the standpoint that a foamed resin molded body having a small pore size can be obtained.
• a foamed resin molded body such as a polyurethane foam or foamed melamine resin
• residues such as a foaming agent and unreacted monomers, in the foam production process, and it is preferable to carry out cleaning treatment.
• the porosity of the porous body is defined by the following formula:
• Porosity (1 ⁇ (weight of porous material [g]/(volume of porous material [cm 3 ] ⁇ material density))) ⁇ 100 [%]
• the resin molded body having a three-dimensional network structure is subjected to conductivity-imparting treatment before use.
• any method including any known method, may be selected.
• a method in which a metal layer of nickel or the like is formed by electroless plating or a vapor phase method, or a method in which a metal or carbon layer is formed by application of a conductive coating material can be used.
• the conductivity of the surface of the resin can be increased.
• the method in which conductivity is imparted to the surface of the resin by application of carbon although which is slightly inferior, an aluminum structure produced after forming an aluminum film can be obtained without mixing a metal other than aluminum thereinto. Therefore, it is possible to produce a structure substantially composed of aluminum alone as a metal. It is also advantageous from the standpoint that conductivity can be imparted inexpensively.
• a carbon coating material as a conductive coating material is prepared.
• a suspension as the carbon coating material preferably contains, in addition to carbon particles, a binder, a dispersant, and a dispersing medium.
• the suspension in order to perform application of carbon particles uniformly in the porous body, the suspension needs to maintain a uniformly suspended state.
• the suspension is preferably maintained at 20° C. to 40° C.
• the temperature of the suspension is 40° C. or lower, evaporation of the dispersant can be suppressed, and therefore, the suspension becomes unlikely to be concentrated as the application treatment time passes.
• the particle size of carbon particles is 0.01 to 5 ⁇ m, and preferably 0.01 to 0.5 ⁇ m.
• the particle size is large, particles may clog pores of the porous resin molded body or block smooth plating.
• the particle size is excessively small, it is difficult to secure sufficient electrical conductivity.
• a molten salt was prepared by mixing aluminum chloride (AlCl 3 ) and 1-ethyl-3-methylimidazolium chloride (EMIC) at a mixing ratio (molar ratio) of 2:1. 1,10-Phenanthroline monohydrate was added to the molten salt at a concentration of 3.0 g/L to thereby obtain an electrolyte solution.
• AlCl 3 aluminum chloride
• EMIC 1-ethyl-3-methylimidazolium chloride
• an aluminum film was electrodeposited on a surface of a substrate.
• a copper (Cu) plate (20 mm ⁇ 40 mm ⁇ 1 mm) was used as the substrate.
• the substrate was connected to the negative side of a rectifier, and an aluminum plate (purity 99.99%) as a counter electrode was connected to the positive side.
• the temperature of the electrolyte solutions was set to be 45° C., and the current density was controlled to be 3.0 A/dm 2 .
• An aluminum electrode (anode) and a platinum electrode (cathode) were provided in the electrolyte solution, and the overvoltage was measured.
• the concentration of 1,10-phenanthroline monohydrate was controlled by appropriately adding 1,10-phenanthroline monohydrate to the electrolyte solution such that the overvoltage is in the range of 105 to 170 mV.
• the arithmetic mean roughness Ra of the surface of the aluminum film formed on the 50th copper plate was measured using a laser microscope.
• the measured value was 0.055 ⁇ m, which confirmed a very good mirror surface state.
• Example 2 An aluminum film was formed as in Example 1 except that a resin molded body having a three-dimensional network structure subjected to conductivity-imparting treatment was used as the substrate.
• a resin molded body As the resin molded body, a polyurethane foam (100 mm ⁇ 30 mm rectangle) with a thickness of 1 mm and a porosity of 95%, in which the number of pores (number of cells) per inch was about 50, was used.
• Conductivity-imparting treatment was performed by immersing the polyurethane foam in a carbon suspension, followed by drying.
• the carbon suspension contained, as components, 25% of graphite and carbon black, and also contained a resin binder, a penetrating agent, and an anti-foaming agent.
• the particle size of carbon black was set to be 0.5 ⁇ m.
• the arithmetic mean roughness Ra of the surface of the aluminum film formed on the 50th polyurethane foam was measured using a laser microscope. The measured value was 0.10 ⁇ m, which confirmed a very good mirror surface state.
• An aluminum film was formed on the surface of a copper plate as in Example 1 except that 1,10-phenanthroline anhydride was used instead of the 1,10-phenanthroline monohydrate.
• Example 1 the arithmetic mean roughness Ra of the surface of the aluminum film formed on the surface of the 50th copper plate was measured using a laser microscope. The measured value was 0.75 ⁇ m, which confirmed that surface smoothness was not good.

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• 2012
  • 2012-09-18 JP JP2012203815A patent/JP5950162B2/ja active Active
• 2013
  • 2013-08-23 DE DE112013004530.3T patent/DE112013004530T5/de not_active Withdrawn
  • 2013-08-23 US US14/428,645 patent/US20150233012A1/en not_active Abandoned
  • 2013-08-23 WO PCT/JP2013/072554 patent/WO2014045798A1/ja active Application Filing
  • 2013-08-23 CN CN201380048581.XA patent/CN104641022B/zh active Active
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