WO2015198819A1 - Alluminum plating solution, aluminum film manufacturing method, and porous aluminum object - Google Patents

Alluminum plating solution, aluminum film manufacturing method, and porous aluminum object Download PDF

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Publication number
WO2015198819A1
WO2015198819A1 PCT/JP2015/066132 JP2015066132W WO2015198819A1 WO 2015198819 A1 WO2015198819 A1 WO 2015198819A1 JP 2015066132 W JP2015066132 W JP 2015066132W WO 2015198819 A1 WO2015198819 A1 WO 2015198819A1
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WO
WIPO (PCT)
Prior art keywords
aluminum
component
plating solution
porous body
elongation
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PCT/JP2015/066132
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French (fr)
Japanese (ja)
Inventor
健吾 後藤
細江　晃久
西村　淳一
知陽 竹山
奥野　一樹
英彰 境田
弘太郎 木村
隼一 本村
Original Assignee
住友電気工業株式会社
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
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Application filed by 住友電気工業株式会社 filed Critical 住友電気工業株式会社
Priority to DE112015003017.4T priority Critical patent/DE112015003017T5/en
Priority to KR1020167035569A priority patent/KR20170021252A/en
Priority to US15/320,006 priority patent/US20170121835A1/en
Priority to CN201580033821.8A priority patent/CN106460216B/en
Publication of WO2015198819A1 publication Critical patent/WO2015198819A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/08—Perforated or foraminous objects, e.g. sieves
    • 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
    • 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
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode

Definitions

  • the present invention relates to an aluminum plating solution capable of producing an aluminum film having excellent surface smoothness and excellent flexibility. Furthermore, the present invention relates to an aluminum film manufacturing method using the aluminum plating solution and an aluminum porous body.
  • Aluminum has many excellent features such as conductivity, corrosion resistance, light weight, and non-toxicity, and is widely used for plating metal products. 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 plating bath.
  • Patent Document 1 discloses an organic chloride salt such as 1-ethyl-3-methylimidazolium chloride (EMIC) or 1-butylpyridinium chloride (BPC) and a chloride. It is described that aluminum (AlCl 3 ) is mixed to form a liquid aluminum plating bath at room temperature, and aluminum is electroplated on the surface of the resin molded body using this plating bath.
  • EMIC 1-ethyl-3-methylimidazolium chloride
  • BPC 1-butylpyridinium chloride
  • Patent Document 1 discloses that a smooth aluminum film can be formed by adding 1,10-phenanthroline to the aluminum plating solution so as to have a concentration of 0.25 g / L to 7.0 g / L. Are listed.
  • an aluminum porous body manufactured by the method described in Patent Document 1 is very promising, for example, for improving the capacity of a positive electrode of a lithium ion battery.
  • aluminum has excellent characteristics such as conductivity, corrosion resistance, and light weight
  • an aluminum foil whose surface is coated with an active material such as lithium cobaltate is used as a positive electrode of a lithium ion battery.
  • the positive electrode With a porous body made of aluminum, the surface area can be increased and the active material can be filled inside the aluminum. Thereby, even if the electrode is thickened, the utilization factor of the active material is not reduced, the utilization factor of the active material per unit area is improved, and the capacity of the positive electrode can be improved.
  • Patent Document 2 discloses that the concentration of 1,10-phenanthroline monohydrate in the aluminum plating solution is 0.05 g / L or more and 7.5 g / L. It is described that it is effective to control the following.
  • 1,10-phenanthroline monohydrate is added to the aluminum plating solution while controlling the concentration to be 0.05 g / L or more and 7.5 g / L or less.
  • concentration 0.05 g / L or more and 7.5 g / L or less.
  • the aluminum film may be required to have flexibility and elongation. Therefore, the present inventors apply heat to the aluminum porous body to make the aluminum flexible. It was investigated. In general, metals have the property of becoming soft when heat-treated, but in the case of an aluminum porous body obtained by the method described in Patent Document 1, it did not become flexible even when heat-treated.
  • an object of the present invention is to provide an aluminum plating solution capable of continuously producing an aluminum film having a smooth surface and excellent elongation.
  • the aluminum plating solution is: (1) An aluminum plating solution capable of electrodepositing aluminum on a substrate surface,
  • the aluminum plating solution is (A) an aluminum halide; (B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds; (C1) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound;
  • the component (C1) has a linear or branched alkyl group having 8 to 36 carbon atoms as at least one side chain,
  • the mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio,
  • An aluminum plating solution having a concentration of the component (C1) of 1.0 g / L or more and 45 g / L or less.
  • the aluminum plating solution is (A) an aluminum halide; (B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds; (C2) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound; (D) any one or more selected from the group consisting of alkyl halides, alkynes, alkenes and alkanes; As an ingredient,
  • the component (C2) has a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain,
  • the component (D) is a compound having 3 to 36 carbon atoms and having a linear or branched structure, The mixing ratio of the component (A) and the component
  • an aluminum plating solution capable of continuously producing an aluminum film having a smooth surface and excellent elongation can be provided.
  • the aluminum plating solution according to one aspect of the present invention is: An aluminum plating solution capable of electrodepositing aluminum on the substrate surface,
  • the aluminum plating solution is (A) an aluminum halide; (B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds; (C1) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound;
  • the component (C1) has a linear or branched alkyl group having 8 to 36 carbon atoms as at least one side chain,
  • the mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio,
  • the aluminum plating solution according to one aspect of the present invention is an aluminum plating solution capable of electrodepositing aluminum on the surface of a substrate,
  • the aluminum plating solution is (A) an aluminum halide; (B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds; (C2) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound; (D) any one or more selected from the group consisting of alkyl halides, alkynes, alkenes and alkanes;
  • the component (C2) has a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain,
  • the component (D) is a compound having 3 to 36 carbon atoms and having a linear or branched structure,
  • the component (A) is aluminum chloride
  • the component (B) is 1-ethyl-3-methylimidazolium chloride. It is preferable. According to the aspect of the invention described in the above (3), an aluminum plating solution capable of continuously and stably obtaining an aluminum film excellent in surface smoothness can be provided.
  • An aluminum porous body according to an aspect of the present invention is an aluminum porous body obtained using the aluminum plating solution according to any one of (1) and (3) above, and has a three-dimensional network.
  • the elongation of the aluminum porous body according to one embodiment of the present invention is affected by the weight of aluminum, the elongation is 100 g / m 2 or more and 180 g / m 2 or less of the aluminum weight of the aluminum porous body.
  • the elongation is in the case where the thickness is 0.95 mm or more and 1.05 mm or less.
  • the elongation refers to the elongation measured when a tensile test is performed according to JIS Z 2241, and refers to the ratio of the displacement amount to the distance between ratings (Gage Length: GL).
  • the porous aluminum body described in (5) above preferably has a crystal grain size of 1 ⁇ m or more and 50 ⁇ m or less in the cross section of the skeleton. Since the aluminum porous body described in (6) has a large crystal grain size, the aluminum porous body is soft and excellent in elongation.
  • the aluminum carbide content is preferably 0.8% by mass or less. Since the aluminum porous body described in the above (7) has a small amount of aluminum carbide contained in the aluminum film, recrystallization of aluminum proceeds by heat treatment, and the aluminum porous body is made of a softer aluminum film. Can do.
  • the present inventors tried heat-treating the aluminum porous body to give flexibility to the aluminum porous body obtained by using a conventional aluminum plating solution, but the characteristics of high strength and low elongation are maintained even after the heat treatment. It was found. When this reason was examined in detail, it was found that recrystallization did not proceed because aluminum carbide was formed at the grain boundaries of the aluminum crystals by the heat treatment. This aluminum carbide was caused by 1,10-phenanthroline incorporated into the aluminum film when it was formed.
  • the present inventors have found that the component (C1) is effective as an additive that contributes to the smoothness of the aluminum film. That is, the aluminum plating solution according to the embodiment of the present invention is an aluminum plating solution obtained by mixing at least the following components (A) to (C1) as described above.
  • the component (C1) is a linear or branched alkyl group having 8 to 36 carbon atoms. As at least one side chain.
  • the aluminum plating solution according to the embodiment of the present invention may contain other components as inevitable impurities. Moreover, you may contain other components intentionally in the range which does not impair the effect of the aluminum film which concerns on embodiment of this invention that can form the aluminum film excellent in smoothness and elongation.
  • the aluminum halide as the component (A) can be favorably used as long as it forms a molten salt at about 110 ° C. or less when mixed with the component (B).
  • aluminum chloride (AlCl 3 ), aluminum bromide (AlBr 3 ), aluminum iodide (AlI 3 ) and the like can be mentioned.
  • aluminum chloride is most preferable.
  • alkylimidazolium halide of the component (B) those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
  • EMIC 1-ethyl-3-methylimidazolium chloride
  • BMIC 1-butyl-3-methylimidazolium chloride
  • MPIC 1-methyl-3-propylimidazolium chloride
  • EMIC 1-ethyl-3-methylimidazolium chloride
  • alkylpyridinium halide of the component (B) those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
  • examples thereof include 1-butylpyridinium chloride (BPC), 1-ethylpyridinium chloride (EPC), 1-butyl-3-methylpyridinium chloride (BMPC), etc.
  • BPC 1-butylpyridinium chloride
  • EPC 1-ethylpyridinium chloride
  • BMPC 1-butyl-3-methylpyridinium chloride
  • 1-butylpyridinium chloride is most preferable.
  • the urea compound of the component (B) means urea and derivatives thereof, and those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
  • a compound represented by the following formula (1) can be preferably used.
  • R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, which may be the same or different.
  • urea and dimethylurea can be particularly preferably used.
  • the mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio, so that the aluminum film is formed on the substrate surface.
  • An aluminum plating solution suitable for electrodeposition is obtained.
  • the molar ratio of the component (A) is less than 1 when the component (B) is 1, no aluminum electrodeposition reaction occurs.
  • the molar ratio of the component (A) is more than 3 when the component (B) is 1, aluminum chloride is precipitated in the aluminum plating solution and taken into the aluminum film, and the quality of the film is improved. descend.
  • the component (C1) is at least one selected from the group consisting of ammonium salts, phosphonium salts, sulfonium salts, amine compounds, phosphine compounds, and sulfide compounds.
  • the component (C1) only needs to have a linear or branched alkyl group having 8 to 36 carbon atoms as at least one side chain, and the remaining side chains are particularly limited. It is not a thing. Examples of the remaining side chain include hydrogen, a group containing a benzene ring, and a linear or branched alkyl group having 1 to 36 carbon atoms.
  • the alkyl group that the (C1) component has as at least one side chain may be branched, but is preferably a straight chain. Further, when the alkyl group has 8 or more carbon atoms, it can contribute to the smoothness of the aluminum film, and when it is 36 or less, the viscosity of the aluminum plating solution can be prevented from becoming too high. From these viewpoints, the number of carbon atoms of the alkyl group which the component (C1) has as a side chain is preferably 8 or more and 22 or less, and more preferably 12 or more and 18 or less.
  • the component (C1) is a salt, it is preferably a halogen salt. Among these, a salt of chlorine ion (Cl ⁇ ), bromine ion (Br ⁇ ), or iodine ion (I ⁇ ) is preferable.
  • component (C1) examples include stearylamine, dimethylstearylamine, N-docosyl-N-methyl1-docosamine, dimethyldistearylammonium chloride, dodecyltrimethylammonium chloride, octyltrimethylammonium chloride, and tributyltetra Examples include decylphosphonium chloride.
  • the concentration of the component (C1) in the aluminum plating solution is 1.0 g / L or more and 45 g / L or less, a smooth aluminum film excellent in elongation can be formed. If the concentration of the component (C1) is less than 1.0 g / L, the aluminum film cannot be sufficiently smoothed, and if it exceeds 45 g / L, the component (C1) is taken into the aluminum film. However, the aluminum film becomes brittle and has little elongation.
  • the concentration of the component (C1) is preferably 5 g / L or more and 25 g / L or less, and more preferably 7.5 g / L or more and 20 g / L or less.
  • the concentration of the component (C1) in the aluminum plating solution is 1.0 g / L or more and 45 g / L or less as described above. Good.
  • the present inventors examined the reason why the component (C1) decreases from the aluminum plating solution. As a result, the side chain of the component (C1), that is, linear or branched having 8 to 36 carbon atoms. It has been found that the alkyl group is gradually decomposed. Furthermore, it was found that the cut alkyl group contributes to the smoothness of the aluminum film by being taken into the aluminum film.
  • the chain length of the alkyl group gradually decreases, and the component having an alkyl group having 7 or less carbon atoms in the side chain Will accumulate.
  • the following component (D) may be supplemented to the aluminum plating solution.
  • the component (C1) is changed to the next component (C2).
  • the aluminum plating solution according to the embodiment of the present invention is an aluminum plating solution further containing at least the following components (C2) and (D) in addition to the component (A) and the component (B).
  • C2 Component Any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound
  • D) Component Group consisting of alkyl halide, alkyne, alkene and alkane
  • the component (C2) has a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain.
  • the component (D) is a compound having 3 to 36 carbon atoms and having a linear or branched structure.
  • components (C2) those having a straight chain or branched alkyl group having 8 to 36 carbon atoms as a side chain contribute to the smoothness and elongation of the aluminum film. It also contributes to the solubility of the components.
  • components (C2) those having a linear or branched alkyl group having 1 to 7 carbon atoms as a side chain contribute to the solubility of the component (D). That is, when the component (C2) is contained in the aluminum plating solution, the component (D) can be easily dissolved.
  • the component (C2) is at least one selected from the group consisting of ammonium salts, phosphonium salts, sulfonium salts, amine compounds, phosphine compounds, and sulfide compounds.
  • the component (C2) only needs to have a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain, and the remaining side chains are particularly limited. It is not a thing. Examples of the remaining side chain include hydrogen, a group containing a benzene ring, and a linear or branched alkyl group having 1 to 36 carbon atoms.
  • the alkyl group that the (C2) component has as at least one side chain may be branched, but is preferably a straight chain.
  • the alkyl group having 1 or more carbon atoms can contribute to the solubility of the component (D), and if it is 36 or less, the viscosity of the aluminum plating solution should not be too high. Can do.
  • the number of carbon atoms of the alkyl group in the component (C2) is preferably 1 or more and 18 or less, and more preferably 3 or more and 12 or less.
  • the component (C2) is a salt, it is preferably a halogen salt. Among these, a salt of chlorine ion (Cl ⁇ ), bromine ion (Br ⁇ ), or iodine ion (I ⁇ ) is preferable.
  • component (C2) include trimethylamine, trimethylphosphine, ethylmethyl sulfide, stearylamine, dimethylstearylamine, N-docosyl-N-methyl1-docosamine, dimethyldistearylammonium chloride, dodecyltrimethylammonium chloride.
  • the concentration of the component (C2) in the aluminum plating solution is 1.0 g / L or more and 45 g / L or less. If the concentration of the component (C2) is less than 1.0 g / L, it will be difficult to dissolve the component (D) in the aluminum plating solution. On the other hand, if the concentration of the component (C2) exceeds 45 g / L, the viscosity of the plating solution becomes too high.
  • the concentration of the component (C2) is preferably 5.0 g / L or more and 30 g / L or less, and more preferably 10 g / L or more and 15 g / L or less.
  • the component (D) is one or more selected from the group consisting of alkyl halides, alkynes, alkenes and alkanes having 3 to 36 carbon atoms, and may be linear or branched You may have. Since the component (D) has a small polarity, it hardly dissolves in the aluminum plating solution composed of the component (A) and the component (B), but the component (C2) is contained in the aluminum plating solution. Since this plays a role of a surfactant, it is easily dissolved. The component (D) is cheaper than the component (C1) and is easily available. For this reason, it becomes possible to manufacture the aluminum plating solution which concerns on embodiment of this invention more cheaply by replenishing the said (D) component instead of the said (C1) component.
  • the component (D) contributes to the smoothness of the aluminum film by being taken into the aluminum film when aluminum is electrodeposited on the surface of the substrate.
  • the component (D) has a very low thermal decomposition temperature and boiling point, it is removed from the aluminum film at a temperature lower than the temperature at which aluminum carbide is formed when the resin as the base material is burned and removed. Therefore, unlike in 1,10-phenanthroline, it does not remain in the aluminum film to form aluminum carbide.
  • a small but small void is formed in the aluminum film. If the concentration of the component (D) in the aluminum plating solution is in the range of 0.5 g / L or more and 8.5 g / L or less, the smoothness and elongation of the aluminum film are not reduced by this void.
  • the component (D) can contribute to the smoothness of the aluminum film by having 3 or more carbon atoms. Moreover, when the carbon number of the component (D) is 36 or less, the viscosity of the aluminum plating solution can be prevented from becoming too high. From these viewpoints, the component (D) preferably has 5 or more and 24 or less carbon atoms, and more preferably 8 or more and 18 or less.
  • the component (D) is preferably liquid or solid at room temperature because it is easily dissolved in the aluminum plating solution.
  • the halogen atom contained in the said halogenated alkyl is not specifically limited, For example, it is preferable that they are chlorine (Cl), bromine (Br), or iodine (I).
  • the number of halogen atoms contained in the alkyl halide is not particularly limited, and is preferably about 1 or more and 2 or less. It is preferable that the number of triple bonds contained in the alkyne is one because the alkynes hardly react with each other. It is preferable that the number of double bonds contained in the alkene is one because the alkenes hardly react with each other.
  • component (D) examples include propane, butane, octane, pentane, tetradecane, octadecane, chloropropane, chlorobutane, lauryl chloride, stearyl chloride, pentene, hexene, decene, propyne, pentyne, butyne and the like. .
  • the concentration of the component (D) is 0.5 g / L or more and 8.5 g / L or less, so that an aluminum film that is smooth and excellent in elongation can be obtained. Can be formed. If the concentration of the component (D) is less than 0.5 g / L, the aluminum film may not be sufficiently smoothed. Further, when the concentration of the component (D) is more than 8.5 g / L, the amount of voids in the aluminum film formed when the substrate is burned and removed becomes too large.
  • the concentration of the component (D) is preferably 0.85 g / L or more and 4.5 g / L or less, and 1.0 g / L or more and 3.0 g / L or less. More preferred. Further, as described above, since the component (D) is taken into the aluminum film, when the aluminum plating is performed for a long time, the amount of the component (D) in the aluminum plating solution gradually decreases. When the amount of the component (D) in the aluminum plating solution decreases, the component (D) may be replenished appropriately so as to be in the concentration range.
  • an aluminum film having a smooth surface and excellent elongation can be formed.
  • the manufacturing method of the aluminum film which concerns on embodiment of this invention is a manufacturing method of the aluminum film which electrodeposits aluminum on the surface of a base material using the aluminum plating solution which concerns on the said embodiment of this invention.
  • an aluminum electrode (anode) is provided in the electrolytic solution, and a base in the electrolytic solution is provided. What is necessary is just to electrically connect and energize so that a material may become a cathode.
  • the current density is more preferably 1.5 A / dm 2 or more and 6.0 A / dm 2 or less, and further preferably 2.0 A / dm 2 or more and 4.0 A / dm 2 or less.
  • the temperature of the electrolyte When electrodepositing aluminum on the surface of the substrate, it is preferable to adjust the temperature of the electrolyte so as to be 15 ° C. or higher and 110 ° C. or lower.
  • the temperature of the electrolytic solution By setting the temperature of the electrolytic solution to 15 ° C. or higher, the viscosity of the electrolytic solution can be sufficiently lowered, and the electrodeposition efficiency of aluminum can be improved. Moreover, volatilization of the aluminum halide can be suppressed by setting the temperature of the electrolytic solution to 110 ° C. or lower.
  • the temperature of the electrolytic solution is more preferably 30 ° C. or higher and 80 ° C. or lower, and further preferably 40 ° C. or higher and 70 ° C. or lower.
  • the electrolytic solution when electrodepositing aluminum on the substrate surface, the electrolytic solution may be stirred or may not be stirred.
  • a smooth aluminum film having a surface arithmetic average roughness (Ra) of about 0.2 ⁇ m or less can be produced by the method for producing an aluminum film according to the embodiment of the present invention.
  • the substrate is not particularly limited as long as it has an application for forming an aluminum film on the surface.
  • a copper plate, a steel strip, a copper wire, a steel wire, a resin subjected to a conductive treatment, or the like can be used as the substrate.
  • a resin subjected to the conductive treatment for example, polyurethane, melamine resin, polypropylene, polyethylene or the like subjected to the conductive treatment can be used.
  • the resin as the substrate may have any shape, but by using a resin molded body having a three-dimensional network structure, finally, various filters, catalyst carriers, battery electrodes, etc.
  • An aluminum porous body having a three-dimensional network structure that exhibits excellent properties for use can be produced, which is preferable.
  • an aluminum porous body having a porous structure can be finally produced by using a resin having a nonwoven fabric shape, and the thus produced aluminum porous body having a nonwoven fabric shape is also used for various filters and catalysts. It can be preferably used for applications such as carriers and battery electrodes.
  • the resin molded body having the three-dimensional network structure for example, a foamed resin molded body produced using polyurethane, melamine resin or the like can be used.
  • a resin molded body having an arbitrary shape can be selected as long as it has continuous pores (continuous vent holes).
  • a porous body having a three-dimensional network structure is also simply referred to as a “porous body”.
  • the porosity of the porous body is preferably 80% or more and 98% or less, and the pore diameter is preferably 50 ⁇ m or more and 500 ⁇ m or less.
  • Foamed urethane and foamed melamine can be preferably used as a foamed resin molded article because they have high porosity, have pore connectivity and are excellent in thermal decomposability.
  • Foamed urethane is preferred in terms of pore uniformity and availability, and foamed melamine is preferred in that a product having a small pore diameter can be obtained.
  • foamed resin moldings such as foamed urethane and foamed melamine often have residues such as foaming agents and unreacted monomers in the foaming process, it is preferable to perform a washing treatment.
  • a resin molded body having the three-dimensional network structure As the resin molded body having the three-dimensional network structure, a resin molded body is used.
  • the conductive treatment of the resin surface can be selected including known methods.
  • a method of forming a metal layer such as nickel by electroless plating or a vapor phase method, or forming a metal or carbon layer by a conductive paint can be used.
  • the conductivity of the resin surface can be increased.
  • it is somewhat inferior from the viewpoint of electrical conductivity it is possible to make the resin surface conductive by carbon coating without introducing any metal other than aluminum into the aluminum structure after forming the aluminum film. It becomes possible to manufacture the structure which consists of. There is also an advantage that it can be made conductive at low cost.
  • a carbon paint as a conductive paint is prepared.
  • the suspension as the carbon paint preferably contains a binder, a dispersant and a dispersion medium in addition to the carbon particles.
  • the suspension needs to maintain a uniform suspended state.
  • the suspension is preferably maintained at 20 ° C. to 40 ° C. By maintaining the temperature of the suspension at 20 ° C. or higher, a uniform suspension can be maintained, and only the binder is concentrated on the surface of the skeleton forming the porous network structure to form a layer.
  • the carbon particles can be uniformly applied.
  • the particle size of the carbon particles is 0.01 to 5 ⁇ m, preferably 0.01 to 0.5 ⁇ m. If the particle size is large, the pores of the porous resin molded body may be clogged or smooth plating may be hindered. If it is too small, it is difficult to ensure sufficient conductivity.
  • the aluminum porous body according to the embodiment of the present invention is an aluminum porous body having an elongation of 1.5% or more.
  • the aluminum porous body obtained by the conventional manufacturing method using the aluminum plating solution has high strength and small elongation, whereas the aluminum porous body according to the embodiment of the present invention has a soft aluminum porous body with an elongation of 1.5% or more. Is the body.
  • the elongation of 1.5% or more is preferable because the porous aluminum body is strong against bending and vibration, and the range of usage of the porous aluminum body is widened. Accordingly, the larger the elongation of the aluminum porous body is, the more preferable, 1.8% or more is more preferable, and 2.5% or more is more preferable. According to the method for producing a porous aluminum body according to an embodiment of the present invention to be described later, an aluminum porous body having an elongation of about 1.5% or more and 5.0% or less can be produced.
  • the elongation of the aluminum porous body is when the weight of aluminum in the aluminum porous body is 100 g / m 2 or more and 180 g / m 2 or less and the thickness is 0.95 mm or more and 1.05 mm or less. And measured by a tensile test according to JIS Z 2241.
  • the crystal grain size in the cross section of the skeleton of the porous aluminum body is preferably 1 ⁇ m or more and 50 ⁇ m or less.
  • the crystal grain size of 1 ⁇ m or more is preferable because the aluminum film becomes soft and the elongation of the aluminum porous body becomes 1.5% or more.
  • the crystal grain size in the skeleton cross section of the porous aluminum body is more preferably 1.5 ⁇ m or more and 25 ⁇ m or less, and further preferably 2 ⁇ m or more and 15 ⁇ m or less.
  • a porous aluminum body having a relatively large crystal grain size can be obtained by using the aluminum plating solution.
  • Examples of a method for further increasing the crystal grain size include, for example, heat-treating the aluminum porous body, increasing the temperature of the aluminum plating solution when manufacturing the aluminum porous body, reducing the current density during plating, etc. The method is mentioned.
  • the aluminum porous body preferably has an aluminum carbide content of 0.8% by mass or less. It is preferable that the aluminum carbide content in the aluminum porous body is 0.8% by mass or less because the aluminum film becomes soft and the elongation of the aluminum porous body becomes 1.5% or more.
  • the aluminum carbide content in the aluminum porous body is more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less.
  • an aluminum porous body is produced using the aluminum plating solution according to the embodiment of the present invention, basically, when the base material is burned and removed, the component containing carbon is below the temperature at which aluminum carbide is formed. It is removed from the film. For this reason, the content of aluminum carbide in the aluminum porous body is 0% by mass.
  • a component containing carbon taken into the aluminum film reacts with aluminum when the base material is burned and removed, and aluminum carbide is formed in the aluminum film.
  • the component (B) may be taken into the aluminum film and cause aluminum carbide to be formed.
  • the aluminum porous body includes a step of forming a resin structure by forming an aluminum film on the surface of a conductive resin molded body having a three-dimensional network structure by molten salt electroplating, and the conductive resin from the resin structure. It can manufacture by passing through the process of removing a molded object. Each step will be described in detail below.
  • This step is a step of forming an aluminum film on the surface of the conductive resin molding having a three-dimensional network structure by performing electrolytic plating in a molten salt, that is, the aluminum plating solution. What is necessary is just to use what electrically conductively processed the surface of the resin molding which has the above-mentioned three-dimensional network structure as a conductive resin molding which has a three-dimensional network structure.
  • a uniformly thick aluminum film is formed on the surface of the skeleton of a molded body having a complicated skeleton structure such as a conductive resin molded body having a three-dimensional network structure. Can be formed.
  • a direct current may be applied in the aluminum plating solution using the conductive resin molded body as a cathode and aluminum as an anode.
  • the plating is preferably performed in an atmosphere of an inert gas such as nitrogen or argon and in a sealed environment.
  • the temperature of the aluminum plating solution can be 15 ° C to 110 ° C, and preferably 25 ° C to 45 ° C. The lower the temperature, the narrower the current density range that can be plated, and the more difficult it is to plate on the entire surface of the skeleton of the conductive resin molding. By plating in the range of 110 ° C. or lower, it is possible to prevent a problem that the shape of the conductive resin molded body serving as the base material is impaired. Through the above steps, a resin structure having a surface of an aluminum film and having the conductive resin molded body as the core of the skeleton can be obtained.
  • Example 1 (Aluminum plating solution)
  • Aluminum chloride (AlCl 3 ) is used as the component (A)
  • 1-ethyl-3-methylimidazolium chloride (EMIC) is used as the component (B)
  • the mixing ratio of the components (A) and (B) is molar ratio.
  • the molten salt was prepared by mixing at 2: 1. To this molten salt, dimethyl distearyl ammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) as a component (C1) was added to a concentration of 15 g / L to obtain an aluminum plating solution 1.
  • Formation of aluminum film Using a copper plate of 20 x 40 x 1.0 mm as the base material, in the aluminum plating solution 1 prepared above, connect the copper plate to the cathode side of the rectifier and the counter electrode aluminum plate (purity 99.99%) to the anode side. Then, aluminum was electrodeposited on the surface of the copper plate by applying a voltage. The temperature of the aluminum plating solution 1 was controlled to be 45 ° C., and the current density was controlled to be 3.0 A / dm 2 .
  • Example 2 ⁇ Preparation of porous aluminum> (Formation of aluminum film on substrate surface) Using the aluminum plating solution 1 prepared in Example 1, aluminum was electrodeposited on the surface of the base material to prepare a resin structure. A resin molded body having a three-dimensional network structure subjected to a conductive treatment was used as the base material. As the resin molding, foamed urethane (100 mm ⁇ 30 mm square) having a thickness of 1 mm, a porosity of 95%, and a pore number (number of cells) per inch of about 50 was used. The conductive treatment was performed by immersing the urethane foam in a carbon suspension and drying it.
  • the components of the carbon suspension include 25% graphite and carbon black, and include a resin binder, a penetrating agent, and an antifoaming agent.
  • the particle size of carbon black was 0.5 ⁇ m.
  • this base material was connected to the cathode side of a rectifier, and the aluminum plate (purity 99.99%) of the counter electrode was connected to the anode side.
  • the temperature of the aluminum plating solution 1 was controlled to 45 ° C., and the current density was controlled to 6.0 A / dm 2 .
  • the aluminum plating solution was stirred to 100 rpm.
  • the elongation (ratio of displacement to GL) of the porous aluminum body 1 was 1.8% at the smallest and 3.3% at the largest. And the average value of elongation was 2.6%.
  • the average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 1 was 3.5 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 1 was 0.35% by mass.
  • Example 3 The aluminum plating solution 2 was used in the same manner as in Example 1 except that the reagent dodecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C1) in the aluminum plating solution and the concentration thereof was 20 g / L. Got. Fifteen porous aluminum bodies 2 were produced in the same manner as in Example 2 except that the aluminum plating solution 2 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the porous aluminum body 2 was 1.9% at the smallest and 2.8% at the largest. And the average value of elongation was 2.3%. The average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 2 was 3 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 2 was 0.34% by mass.
  • the reagent dodecyltrimethylammonium chloride manufactured by Tokyo Chemical
  • Example 4 The aluminum plating solution 3 was used in the same manner as in Example 1 except that the reagent octyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C1) in the aluminum plating solution, and the concentration was 15 g / L. Got. Fifteen aluminum porous bodies 3 were produced in the same manner as in Example 2 except that the aluminum plating solution 3 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation of aluminum porous body 3 (ratio of displacement to GL) was 1.6% at the smallest and 3.0% at the largest. And the average value of elongation was 2.5%. The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 3 was 3.2 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 3 was 0.37% by mass.
  • the reagent octyltrimethylammonium chloride manufactured by
  • Example 5 Aluminum plating was carried out in the same manner as in Example 1 except that the reagent tributyltetradecylphosphonium chloride (manufactured by Kanto Chemical Co., Inc.) was used as the component (C1) in the aluminum plating solution, and the concentration was 5.0 g / L. Liquid 4 was obtained. Fifteen aluminum porous bodies 4 were produced in the same manner as in Example 2 except that the aluminum plating solution 4 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the aluminum porous body 4 was 1.8% at the smallest and 3.4% at the largest.
  • the reagent tributyltetradecylphosphonium chloride manufactured by Kanto Chemical Co., Inc.
  • the average value of elongation was 2.8%.
  • the average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 4 was 3.5 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 4 was 0.34% by mass.
  • Example 6 The aluminum plating solution 5 was prepared in the same manner as in Example 1 except that the reagent dimethylstearylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C1) for the aluminum plating solution, and the concentration was 15 g / L. Obtained. Fifteen aluminum porous bodies 5 were produced in the same manner as in Example 2 except that the aluminum plating solution 5 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the porous aluminum body 5 was 1.7% at the smallest and 2.8% at the largest. And the average value of elongation was 2.2%. The average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 5 was 4.0 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 5 was 0.28% by mass.
  • the reagent dimethylstearylamine manufactured by Tokyo Chemical Industry Co., Ltd.
  • Example 7 In Example 1, an aluminum plating solution 6 was obtained in the same manner as in Example 1, except that the concentration of the component (C1) was 1.0 g / L. Fifteen aluminum porous bodies 6 were produced in the same manner as in Example 2 except that the aluminum plating solution 6 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation of aluminum porous body 6 (ratio of displacement relative to GL) was 1.5% at the smallest and 2.7% at the largest. And the average value of elongation was 2.1%. The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 6 was 4.0 ⁇ m. Further, the amount of aluminum carbide contained in the aluminum porous body 6 was 0.24% by mass.
  • Example 8 In Example 1, an aluminum plating solution 7 was obtained in the same manner as in Example 1 except that the component (C1) was added so as to have a concentration of 45 g / L. Fifteen porous aluminum bodies 7 were produced in the same manner as in Example 2 except that the aluminum plating solution 7 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the porous aluminum body 7 was 1.9% at the smallest and 3.6% at the largest. And the average value of elongation was 2.7%. The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 7 was 3.2 ⁇ m. Further, the amount of aluminum carbide contained in the aluminum porous body 7 was 0.39% by mass.
  • Example 1 An aluminum plating solution A was obtained in the same manner as in Example 1 except that 1,10-phenanthroline monohydrate was used as the component (C1) in the aluminum plating solution and the concentration was 0.5 g / L. .
  • Fifteen aluminum porous bodies A were produced in the same manner as in Example 2 except that the aluminum plating solution A was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results)
  • the elongation (ratio of displacement to GL) of the aluminum porous body A was 0.6% at the smallest and 1.2% even at the largest. And the average value of elongation was 0.8%.
  • the average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body A was 1.0 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body A was 1.2% by mass.
  • Example 2 In Example 1, an aluminum plating solution B was obtained in the same manner as in Example 1 except that the component (C1) was added so as to have a concentration of 0.6 g / L. Fifteen porous aluminum objects B were produced in the same manner as in Example 2 except that the aluminum plating solution B was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation of aluminum porous body B (ratio of displacement to GL) was 0.5% at the smallest and 1.3% at the largest. And the average value of elongation was 0.7%. The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body B was 4.0 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body B was 0.24% by mass.
  • Example 3 In Example 1, an aluminum plating solution C was obtained in the same manner as in Example 1 except that the component (C1) was added so that the concentration thereof was 50 g / L. Fifteen porous aluminum objects C were produced in the same manner as in Example 2 except that the aluminum plating solution C was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the aluminum porous body C was 0.8% at the smallest and 1.2% even at the largest. And the average value of elongation was 1.0%. The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body C was 1.2 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body C was 0.84% by mass.
  • Example 9 1 L of the aluminum plating solution 1 prepared in Example 1 was prepared, and an aluminum porous body was produced in the same manner as in Example 2. And aluminum plating was performed for 42 hours, controlling so that the electric current of 3.6A might flow.
  • the basis weight of aluminum reached 140 g / m 2 , the substrate was replaced and aluminum plating was continued.
  • the elongation (ratio of displacement to GL) of the aluminum porous body 2 ′ obtained after 42 hours was measured. Twenty porous aluminum bodies 2 ′ were produced by the same method. The smallest growth was 1.2%, and the largest growth was reduced to 1.6%. The average value of elongation was 1.3%.
  • the aluminum plating solution at this time was designated as an aluminum plating solution 1 ′, and the components were analyzed by liquid chromatography mass spectrometry (LC / MS). As a result, it was confirmed that the alkyl group in the side chain in the (C1) component originally included was shortened and changed to the (C2) component having an alkyl group having 7 or less carbon atoms as the side chain. It was. The concentration of component (C2) was 15 g / L. (Aluminum plating solution) An aluminum plating solution 8 was prepared by adding stearyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) as a component (D) to the aluminum plating solution 1 ′ so as to have a concentration of 1 g / L.
  • stearyl chloride manufactured by Tokyo Chemical Industry Co., Ltd.
  • Example 10 Aluminum plating solution 9 was produced in the same manner as in Example 9 except that the concentration of stearyl chloride as component (D) was changed to 8.3 g / L. Fifteen aluminum porous bodies 9 were produced in the same manner as in Example 2 except that the aluminum plating solution 9 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the aluminum porous body 9 was 1.6% at the smallest and 2.5% at the largest. And the average value of elongation was 1.8%. The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 9 was 3.2 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 9 was 0.6% by mass.
  • Example 11 An aluminum plating solution 10 was obtained in the same manner as in Example 10 except that tetradecane (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the component (D) in the aluminum plating solution and the concentration thereof was 1 g / L.
  • Fifteen aluminum porous bodies 10 were produced in the same manner as in Example 2 except that the aluminum plating solution 10 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the porous aluminum body 10 was 2.5% at the smallest and 3.9% at the largest. And the average value of elongation was 2.8%.
  • the average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 10 was 4.0 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 10 was 0.3% by mass.
  • Example 12 An aluminum plating solution 11 was obtained in the same manner as in Example 10 except that decene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (D) in the aluminum plating solution, and the concentration was adjusted to 0.8 g / L.
  • Fifteen aluminum porous bodies 11 were produced in the same manner as in Example 2 except that the aluminum plating solution 11 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the aluminum porous body 11 was 1.8% at the smallest and 2.8% at the largest. And the average value of elongation was 2.2%.
  • the average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 11 was 3.6 ⁇ m. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 11 was 0.34% by mass.
  • Example 13 An aluminum plating solution 12 was obtained in the same manner as in Example 10 except that dichlorooctane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (D) in the aluminum plating solution and the concentration thereof was 3.0 g / L. .
  • Fifteen aluminum porous bodies 12 were produced in the same manner as in Example 2 except that the aluminum plating solution 12 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the aluminum porous body 12 was 2.1% at the smallest and 2.8% at the largest. And the average value of elongation was 2.4%.
  • the average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 12 was 6.0 ⁇ m. Further, the amount of aluminum carbide contained in the aluminum porous body 12 was 0.52% by mass.
  • Example 14 An aluminum plating solution 13 was obtained in the same manner as in Example 10 except that chloropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (D) in the aluminum plating solution and the concentration thereof was 3 g / L.
  • Fifteen aluminum porous bodies 13 were produced in the same manner as in Example 2 except that the aluminum plating solution 13 was used, and the elongation, crystal grain size, and aluminum carbide content were measured. (Evaluation results) The elongation (ratio of displacement to GL) of the aluminum porous body 13 was 1.7% at the smallest and 2.9% at the largest. And the average value of elongation was 2.3%.
  • the average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 13 was 12 ⁇ m. Further, the amount of aluminum carbide contained in the aluminum porous body 13 was 0.46% by mass.
  • Example 9 an aluminum plating solution D was obtained in the same manner as in Example 9 except that the concentration of the component (D) was 0.3 g / L.
  • Fifteen porous aluminum bodies D were produced in the same manner as in Example 2 except that the aluminum plating solution D was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
  • the elongation (ratio of displacement to GL) of the aluminum porous body D was 0.8% at the smallest and 1.6% even at the largest. And the average value of elongation was 1.1%.
  • the average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body D was 4.8 ⁇ m. Further, the amount of aluminum carbide contained in the aluminum porous body D was 0.12% by mass.
  • Example 9 an aluminum plating solution E was obtained in the same manner as in Example 9 except that the concentration of the component (D) was added so as to be 9 g / L.
  • Fifteen aluminum porous bodies E were produced in the same manner as in Example 2 except that the aluminum plating solution E was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
  • the elongation (ratio of displacement to GL) of the aluminum porous body E was 1.2% at the smallest and 1.8% even at the largest. And the average value of elongation was 1.4%.
  • the average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body E was 0.6 ⁇ m.
  • the amount of aluminum carbide contained in the aluminum porous body E was 2.6% by mass.

Abstract

Provided is an aluminum plating solution capable of continuously manufacturing an aluminum film, the surface of which is smooth and which has excellent elongation. The aluminum plating solution, which is capable of electrodepositing aluminum on a substrate surface: comprises, as components, (A) an aluminum halide, (B) at least one compound selected from a group consisting of alkylimidazolium halides, alkylpyridinium halides and urea compounds, and (C1) at least one species selected from a group consisting of ammonium salts, phosphonium salts, sulfonium salts, amine compounds, phospine compounds and sulfide compounds; the component (C1) has a C8-36 straight or branched alkyl group for at least one side chain; the mixing ratio of the component (A) with the component (B) is in the range of 1:1 - 3:1 in mole ratio; and the concentration of the component (C1) is 1.0 g/L to 45 g/L.

Description

アルミニウムめっき液、アルミニウム膜の製造方法、及びアルミニウム多孔体Aluminum plating solution, method for producing aluminum film, and porous aluminum body
　本発明は、表面平滑性に優れ、かつ柔軟性に優れるアルミニウム膜を製造することが可能なアルミニウムめっき液に関する。更には、前記アルミニウムめっき液を用いたアルミニウム膜の製造方法及びアルミニウム多孔体に関する。 The present invention relates to an aluminum plating solution capable of producing an aluminum film having excellent surface smoothness and excellent flexibility. Furthermore, the present invention relates to an aluminum film manufacturing method using the aluminum plating solution and an aluminum porous body.
　アルミニウムは導電性、耐腐食性、軽量、無毒性など多くの優れた特徴を有しており、金属製品等へのめっきに広く利用されている。しかしながらアルミニウムは酸素に対する親和力が大きく、酸化還元電位が水素より低いため、水溶液系のめっき浴では電気めっきを行うことが困難である。 Aluminum has many excellent features such as conductivity, corrosion resistance, light weight, and non-toxicity, and is widely used for plating metal products. 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 plating bath.
　このため、アルミニウムを電気めっきする方法としては溶融塩浴を用いる方法が行われている。しかし、従来の溶融塩によるめっき浴は高温にする必要があるため、樹脂製品に対してアルミニウムを電気めっきしようとすると樹脂が溶けてしまい、電気めっきをすることができないという問題があった。 Therefore, as a method for electroplating aluminum, a method using a molten salt bath is performed. However, since the plating bath with a conventional molten salt needs to be at a high temperature, there is a problem that when the aluminum is electroplated on the resin product, the resin is melted and the electroplating cannot be performed.
　この問題に対して特開２０１２－１４４７６３号公報（特許文献１）では、１－エチル－３－メチルイミダゾリウムクロリド（ＥＭＩＣ）や、１－ブチルピリジニウムクロリド（ＢＰＣ）などの有機塩化物塩と塩化アルミニウム（ＡlＣl3）とを混合して室温で液体のアルミニウムめっき浴を形成し、このめっき浴を用いて樹脂成形体の表面にアルミニウムを電気めっきすればよいことが記載されている。 In order to solve this problem, Japanese Patent Application Laid-Open No. 2012-144663 (Patent Document 1) discloses an organic chloride salt such as 1-ethyl-3-methylimidazolium chloride (EMIC) or 1-butylpyridinium chloride (BPC) and a chloride. It is described that aluminum (AlCl 3 ) is mixed to form a liquid aluminum plating bath at room temperature, and aluminum is electroplated on the surface of the resin molded body using this plating bath.
　特に、特許文献１に記載のＥＭＩＣ－ＡlＣl3系のめっき液は液の特性が良好であり、アルミニウムめっき液として非常に有用である。また、特許文献１には前記アルミニウムめっき液に１，１０－フェナントロリンを濃度が０．２５ｇ／Ｌ～７．０ｇ／Ｌとなるように添加することで、平滑なアルミニウム膜が形成されることが記載されている。 In particular, the EMIC-AlCl 3 -based plating solution described in Patent Document 1 has good liquid properties and is very useful as an aluminum plating solution. Patent Document 1 discloses that a smooth aluminum film can be formed by adding 1,10-phenanthroline to the aluminum plating solution so as to have a concentration of 0.25 g / L to 7.0 g / L. Are listed.
　三次元網目構造を有する金属多孔体として、上記特許文献１に記載の方法により製造したアルミニウム多孔体は、例えば、リチウムイオン電池の正極の容量を向上させるものとして非常に有望である。アルミニウムは導電性、耐腐食性、軽量などの優れた特徴があるため、現在では、アルミニウム箔の表面にコバルト酸リチウム等の活物質を塗布したものがリチウムイオン電池の正極として使用されている。この正極をアルミニウムからなる多孔体により形成することで、表面積を大きくし、アルミニウムの内部にも活物質を充填することが可能となる。これにより、電極を厚くしても活物質の利用率が減少することがなくなり、単位面積当たりの活物質の利用率が向上し、正極の容量を向上させることが可能となる。 As a porous metal body having a three-dimensional network structure, an aluminum porous body manufactured by the method described in Patent Document 1 is very promising, for example, for improving the capacity of a positive electrode of a lithium ion battery. Since aluminum has excellent characteristics such as conductivity, corrosion resistance, and light weight, currently, an aluminum foil whose surface is coated with an active material such as lithium cobaltate is used as a positive electrode of a lithium ion battery. By forming the positive electrode with a porous body made of aluminum, the surface area can be increased and the active material can be filled inside the aluminum. Thereby, even if the electrode is thickened, the utilization factor of the active material is not reduced, the utilization factor of the active material per unit area is improved, and the capacity of the positive electrode can be improved.
　上記のように三次元網目状構造を有するアルミニウム多孔体は非常に有用なものであるが、前記特許文献１に記載の方法によって連続的に大量に生産するとアルミニウム膜の平滑性が徐々に低下してしまうため、めっき液を適宜新しいものに交換する必要があった。
このような問題に対して特開２０１４－０５８７１５号公報（特許文献２）では、アルミニウムめっき液中の１，１０－フェナントロリン一水和物の濃度が０．０５ｇ／Ｌ以上、７．５ｇ／Ｌ以下となるように制御することが有効であることが記載されている。 As described above, the aluminum porous body having a three-dimensional network structure is very useful, but when it is continuously produced in large quantities by the method described in Patent Document 1, the smoothness of the aluminum film gradually decreases. Therefore, it was necessary to replace the plating solution with a new one as appropriate.
In order to solve this problem, Japanese Patent Application Laid-Open No. 2014-058715 (Patent Document 2) discloses that the concentration of 1,10-phenanthroline monohydrate in the aluminum plating solution is 0.05 g / L or more and 7.5 g / L. It is described that it is effective to control the following.
特開２０１２－１４４７６３号公報JP 2012-144663 A 特開２０１４－０５８７１５号公報JP 2014-058715 A
　特許文献１に記載のように、アルミニウムめっき液中に１，１０－フェナントロリン一水和物を添加してその濃度が０．０５ｇ／Ｌ以上、７．５ｇ／Ｌ以下となるように制御しながらアルミニウムめっきを行うことで、平滑なアルミニウム膜の形成を連続的に大量に行うことができる。このようにして得られるアルミニウム膜は表面が鏡面となるほどに平滑性に優れているが、アルミニウム膜が硬く高い強度を有しており、伸び難いという性質を有していた。 As described in Patent Document 1, 1,10-phenanthroline monohydrate is added to the aluminum plating solution while controlling the concentration to be 0.05 g / L or more and 7.5 g / L or less. By performing aluminum plating, a smooth aluminum film can be continuously formed in a large amount. The aluminum film thus obtained is excellent in smoothness so that the surface becomes a mirror surface, but the aluminum film is hard and has high strength and has a property that it is difficult to stretch.
　三次元網目状構造を有するアルミニウム多孔体の用途によってはアルミニウム膜に柔軟性と伸びを求められる場合があるため、本発明者らはアルミニウム多孔体に熱を加えてアルミニウムに柔軟性を持たせることを検討した。一般に金属は熱処理をすると柔らかくなるという性質を有しているが、特許文献１に記載の方法によって得たアルミニウム多孔体の場合には熱処理をしても柔軟性を有するようにはならなかった。 Depending on the application of the porous aluminum body having a three-dimensional network structure, the aluminum film may be required to have flexibility and elongation. Therefore, the present inventors apply heat to the aluminum porous body to make the aluminum flexible. It was investigated. In general, metals have the property of becoming soft when heat-treated, but in the case of an aluminum porous body obtained by the method described in Patent Document 1, it did not become flexible even when heat-treated.
　そこで本発明は、表面が平滑であり、かつ伸びにも優れるアルミニウム膜を連続的に製造することが可能なアルミニウムめっき液を提供することを目的とする。 Therefore, an object of the present invention is to provide an aluminum plating solution capable of continuously producing an aluminum film having a smooth surface and excellent elongation.
　本発明の一態様に係るアルミニウムめっき液は、
（１）基材表面にアルミニウムを電着させることが可能なアルミニウムめっき液であって、
　前記アルミニウムめっき液は、
（Ａ）アルミニウムハロゲン化物と、
（Ｂ）アルキルイミダゾリウムハロゲン化物、アルキルピリジニウムハロゲン化物及び尿素化合物からなる群より選択されるいずれか一種以上の化合物と、
（Ｃ１）アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上と、
を成分として含み、
　前記（Ｃ１）成分は、炭素数が８以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有し、
　前記（Ａ）成分と前記（Ｂ）成分の混合比はモル比で１：１～３：１の範囲にあり、
　前記（Ｃ１）成分の濃度が１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下である
アルミニウムめっき液、である。
　なお、上記（１）に記載のアルミニウムめっき液において、前記（Ｃ１）成分が有する「側鎖」とは、各塩又は各化合物のＮ原子、Ｐ原子又はＳ原子に結合している基のことをいうものとする。 The aluminum plating solution according to one aspect of the present invention is:
(1) An aluminum plating solution capable of electrodepositing aluminum on a substrate surface,
The aluminum plating solution is
(A) an aluminum halide;
(B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds;
(C1) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound;
As an ingredient,
The component (C1) has a linear or branched alkyl group having 8 to 36 carbon atoms as at least one side chain,
The mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio,
An aluminum plating solution having a concentration of the component (C1) of 1.0 g / L or more and 45 g / L or less.
In the aluminum plating solution described in (1) above, the “side chain” of the component (C1) is a group bonded to the N atom, P atom or S atom of each salt or compound. It shall be said.
　また、本発明の一態様に係るアルミニウムめっき液は、
（２）基材表面にアルミニウムを電着させることが可能なアルミニウムめっき液であって、
　前記アルミニウムめっき液は、
（Ａ）アルミニウムハロゲン化物と、
（Ｂ）アルキルイミダゾリウムハロゲン化物、アルキルピリジニウムハロゲン化物及び尿素化合物からなる群より選択されるいずれか一種以上の化合物と、
（Ｃ２）アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上と、
（Ｄ）ハロゲン化アルキル、アルキン、アルケン及びアルカンからなる群より選択されるいずれか一種以上と、
を成分として含み、
　前記（Ｃ２）成分は、炭素数が１以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有し、
　前記（Ｄ）成分は、炭素数が３以上、３６以下であって、直鎖状もしくは分岐を有する化合物であり、
　前記（Ａ）成分と前記（Ｂ）成分の混合比はモル比で１：１～３：１の範囲にあり、
　前記（Ｃ２）成分の濃度は１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下であり、
　前記（Ｄ）成分の濃度は０．５ｇ／Ｌ以上、８．５ｇ／Ｌ以下である
アルミニウムめっき液、である。
　なお、上記（２）に記載のアルミニウムめっき液において、前記（Ｃ２）成分が有する「側鎖」とは、各塩又は各化合物のＮ原子、Ｐ原子又はＳ原子に結合している基のことをいうものとする。 In addition, the aluminum plating solution according to one aspect of the present invention,
(2) An aluminum plating solution capable of electrodepositing aluminum on the substrate surface,
The aluminum plating solution is
(A) an aluminum halide;
(B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds;
(C2) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound;
(D) any one or more selected from the group consisting of alkyl halides, alkynes, alkenes and alkanes;
As an ingredient,
The component (C2) has a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain,
The component (D) is a compound having 3 to 36 carbon atoms and having a linear or branched structure,
The mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio,
The concentration of the component (C2) is 1.0 g / L or more and 45 g / L or less,
The concentration of the component (D) is an aluminum plating solution having a concentration of 0.5 g / L or more and 8.5 g / L or less.
In the aluminum plating solution described in (2) above, the “side chain” of the component (C2) is a group bonded to the N atom, P atom or S atom of each salt or compound. It shall be said.
　上記発明によれば、表面が平滑であり、かつ伸びにも優れるアルミニウム膜を連続的に製造することが可能なアルミニウムめっき液を提供することができる。 According to the above invention, an aluminum plating solution capable of continuously producing an aluminum film having a smooth surface and excellent elongation can be provided.
［本発明の実施形態の説明］
　最初に本発明の実施態様を列記して説明する。
（１）本発明の一態様に係るアルミニウムめっき液は、
　基材表面にアルミニウムを電着させることが可能なアルミニウムめっき液であって、
　前記アルミニウムめっき液は、
（Ａ）アルミニウムハロゲン化物と、
（Ｂ）アルキルイミダゾリウムハロゲン化物、アルキルピリジニウムハロゲン化物及び尿素化合物からなる群より選択されるいずれか一種以上の化合物と、
（Ｃ１）アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上と、
を成分として含み、
　前記（Ｃ１）成分は、炭素数が８以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有し、
　前記（Ａ）成分と前記（Ｂ）成分の混合比はモル比で１：１～３：１の範囲にあり、
　前記（Ｃ１）成分の濃度が１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下である
アルミニウムめっき液、である。
　上記（１）に記載の発明の態様によれば、表面が平滑であり、かつ伸びにも優れるアルミニウム膜を連続的に製造することが可能なアルミニウムめっき液を提供することができる。 [Description of Embodiment of the Present Invention]
First, embodiments of the present invention will be listed and described.
(1) The aluminum plating solution according to one aspect of the present invention is:
An aluminum plating solution capable of electrodepositing aluminum on the substrate surface,
The aluminum plating solution is
(A) an aluminum halide;
(B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds;
(C1) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound;
As an ingredient,
The component (C1) has a linear or branched alkyl group having 8 to 36 carbon atoms as at least one side chain,
The mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio,
An aluminum plating solution having a concentration of the component (C1) of 1.0 g / L or more and 45 g / L or less.
According to the aspect of the invention described in (1), an aluminum plating solution capable of continuously producing an aluminum film having a smooth surface and excellent elongation can be provided.
（２）本発明の一態様に係るアルミニウムめっき液は、基材表面にアルミニウムを電着させることが可能なアルミニウムめっき液であって、
　前記アルミニウムめっき液は、
（Ａ）アルミニウムハロゲン化物と、
（Ｂ）アルキルイミダゾリウムハロゲン化物、アルキルピリジニウムハロゲン化物及び尿素化合物からなる群より選択されるいずれか一種以上の化合物と、
（Ｃ２）アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上と、
（Ｄ）ハロゲン化アルキル、アルキン、アルケン及びアルカンからなる群より選択されるいずれか一種以上と、
を成分として含み、
　前記（Ｃ２）成分は、炭素数が１以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有し、
　前記（Ｄ）成分は、炭素数が３以上、３６以下であって、直鎖状もしくは分岐を有する化合物であり、
　前記（Ａ）成分と前記（Ｂ）成分の混合比はモル比で１：１～３：１の範囲にあり、
　前記（Ｃ２）成分の濃度は１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下であり、
　前記（Ｄ）成分の濃度は０．５ｇ／Ｌ以上、８．５ｇ／Ｌ以下である
アルミニウムめっき液、である。
　上記（２）に記載の発明の態様によれば、表面が平滑であり、かつ伸びにも優れるアルミニウム膜を連続的に製造することが可能なアルミニウムめっき液を、より安価に提供することができる。 (2) The aluminum plating solution according to one aspect of the present invention is an aluminum plating solution capable of electrodepositing aluminum on the surface of a substrate,
The aluminum plating solution is
(A) an aluminum halide;
(B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds;
(C2) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound;
(D) any one or more selected from the group consisting of alkyl halides, alkynes, alkenes and alkanes;
As an ingredient,
The component (C2) has a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain,
The component (D) is a compound having 3 to 36 carbon atoms and having a linear or branched structure,
The mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio,
The concentration of the component (C2) is 1.0 g / L or more and 45 g / L or less,
The concentration of the component (D) is an aluminum plating solution having a concentration of 0.5 g / L or more and 8.5 g / L or less.
According to the aspect of the invention described in (2) above, an aluminum plating solution capable of continuously producing an aluminum film having a smooth surface and excellent elongation can be provided at a lower cost. .
（３）上記（１）又は上記（２）に記載のアルミニウムめっき液は、前記（Ａ）成分が塩化アルミニウムであり、かつ前記（Ｂ）成分が１－エチル－３－メチルイミダゾリウムクロリドであることが好ましい。
　上記（３）に記載の発明の態様によれば、表面平滑性により優れたアルミニウム膜を連続的に安定して得ることが可能なアルミニウムめっき液を提供することができる。 (3) In the aluminum plating solution according to (1) or (2), the component (A) is aluminum chloride, and the component (B) is 1-ethyl-3-methylimidazolium chloride. It is preferable.
According to the aspect of the invention described in the above (3), an aluminum plating solution capable of continuously and stably obtaining an aluminum film excellent in surface smoothness can be provided.
（４）本発明の一態様に係るアルミニウム膜の製造方法は、上記（１）から上記（３）のいずれか一項に記載のアルミニウムめっき液を用いて基材の表面にアルミニウムを電着させるアルミニウム膜の製造方法、である。
　上記（４）に記載の発明の態様によれば、表面平滑性に優れ、かつ伸びにも優れるアルミニウム膜の製造方法を提供することができる。 (4) In the method for producing an aluminum film according to one aspect of the present invention, aluminum is electrodeposited on the surface of a substrate using the aluminum plating solution according to any one of (1) to (3) above. It is a manufacturing method of an aluminum film.
According to the aspect of the invention as described in said (4), the manufacturing method of the aluminum film which is excellent in surface smoothness and excellent in elongation can be provided.
（５）本発明の一態様に係るアルミニウム多孔体は、上記（１）上記（３）のいずれか一項に記載のアルミニウムめっき液を用いて得られたアルミニウム多孔体であって、三次元網目状構造を有し、伸びが１．５％以上であるアルミニウム多孔体、である。
　上記（５）に記載のアルミニウム多孔体は柔らかく伸びに優れているため、曲げや振動が加えられるような用途にも利用可能なアルミニウム多孔体である。
　なお、本発明の一態様に係るアルミニウム多孔体の伸びは、アルミニウムの目付け量による影響を受けるため、前記伸びは、アルミニウム多孔体のアルミニウムの目付け量が１００ｇ/ｍ2以上、１８０ｇ/ｍ2以下で、厚さが０．９５ｍｍ以上、１．０５ｍｍ以下の場合における伸びであるものとする。
　また、前記伸びは、ＪＩＳ　Ｚ　２２４１の規定により引張試験を行った場合に計測される伸びをいうものであり、評点間距離（Ｇａｇｅ　Ｌｅｎｇｔｈ：ＧＬ）に対する変位量の割合をいうものとする。 (5) An aluminum porous body according to an aspect of the present invention is an aluminum porous body obtained using the aluminum plating solution according to any one of (1) and (3) above, and has a three-dimensional network. A porous aluminum body having an elongated structure and an elongation of 1.5% or more.
Since the aluminum porous body described in the above (5) is soft and excellent in elongation, it is an aluminum porous body that can be used for applications where bending and vibration are applied.
In addition, since the elongation of the aluminum porous body according to one embodiment of the present invention is affected by the weight of aluminum, the elongation is 100 g / m 2 or more and 180 g / m 2 or less of the aluminum weight of the aluminum porous body. Thus, the elongation is in the case where the thickness is 0.95 mm or more and 1.05 mm or less.
The elongation refers to the elongation measured when a tensile test is performed according to JIS Z 2241, and refers to the ratio of the displacement amount to the distance between ratings (Gage Length: GL).
（６）上記（５）に記載のアルミニウム多孔体は、骨格の断面における結晶粒径が１μｍ以上、５０μｍ以下であることが好ましい。
　上記（６）に記載のアルミニウム多孔体は結晶粒径が大きいため、柔らかく伸びに優れたアルミニウム多孔体である。 (6) The porous aluminum body described in (5) above preferably has a crystal grain size of 1 μm or more and 50 μm or less in the cross section of the skeleton.
Since the aluminum porous body described in (6) has a large crystal grain size, the aluminum porous body is soft and excellent in elongation.
（７）上記（５）又は上記（６）に記載のアルミニウム多孔体は、炭化アルミニウムの含有量が０．８質量％以下であることが好ましい。
　上記（７）に記載のアルミニウム多孔体は、アルミニウム膜中に含まれる炭化アルミニウムが少ないため、熱処理をすることでアルミニウムの再結晶化が進行し、より柔らかいアルミニウム膜からなるアルミニウム多孔体とすることができる。 (7) In the aluminum porous body described in (5) or (6) above, the aluminum carbide content is preferably 0.8% by mass or less.
Since the aluminum porous body described in the above (7) has a small amount of aluminum carbide contained in the aluminum film, recrystallization of aluminum proceeds by heat treatment, and the aluminum porous body is made of a softer aluminum film. Can do.
［本発明の実施形態の詳細］
　本発明の実施形態に係るアルミニウムめっき液、アルミニウム膜の製造方法及びアルミニウム多孔体の具体例を、以下に、より詳細に説明する。なお、本発明はこれらの例示に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。 [Details of the embodiment of the present invention]
Specific examples of the aluminum plating solution, the aluminum film manufacturing method, and the aluminum porous body according to the embodiment of the present invention will be described in more detail below. In addition, this invention is not limited to these illustrations, is shown by the claim, and intends that all the changes within the meaning and range equivalent to a claim are included.
　本発明者等は従来のアルミニウムめっき液を用いて得たアルミニウム多孔体に柔軟性を持たせるべくアルミニウム多孔体を熱処理してみたが、熱処理後にも高強度で伸びが少ないという特性が維持されることが見出された。この理由について詳細に検討したところ、熱処理によってアルミニウムの結晶の粒界に炭化アルミニウムが形成されてしまうために再結晶化が進行しないことが見出された。そして、この炭化アルミニウムは、アルミニウム膜の形成時に膜中に取り込まれた１，１０－フェナントロリンが原因であった。 The present inventors tried heat-treating the aluminum porous body to give flexibility to the aluminum porous body obtained by using a conventional aluminum plating solution, but the characteristics of high strength and low elongation are maintained even after the heat treatment. It was found. When this reason was examined in detail, it was found that recrystallization did not proceed because aluminum carbide was formed at the grain boundaries of the aluminum crystals by the heat treatment. This aluminum carbide was caused by 1,10-phenanthroline incorporated into the aluminum film when it was formed.
＜アルミニウムめっき液＞
　そこで、本発明者等は更なる検討を重ねた結果、アルミニウム膜の平滑性に寄与する添加剤として前記（Ｃ１）成分が有効であることを見出した。
　すなわち、本発明の実施形態に係るアルミニウムめっき液は、前記した通り少なくとも以下の（Ａ）～（Ｃ１）成分を混合して得られるアルミニウムめっき液である。
（Ａ）成分：アルミニウムハロゲン化物
（Ｂ）成分：アルキルイミダゾリウムハロゲン化物、アルキルピリジニウムハロゲン化物及び尿素化合物からなる群より選択されるいずれか一種以上の化合物
（Ｃ１）成分：アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上
　但し、前記（Ｃ１）成分は、炭素数が８以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有する。 <Aluminum plating solution>
As a result of further studies, the present inventors have found that the component (C1) is effective as an additive that contributes to the smoothness of the aluminum film.
That is, the aluminum plating solution according to the embodiment of the present invention is an aluminum plating solution obtained by mixing at least the following components (A) to (C1) as described above.
Component (A): Aluminum halide (B) Component: One or more compounds selected from the group consisting of alkyl imidazolium halides, alkyl pyridinium halides, and urea compounds (C1) Component: ammonium salts, phosphonium salts, Any one or more selected from the group consisting of a sulfonium salt, an amine compound, a phosphine compound and a sulfide compound. However, the component (C1) is a linear or branched alkyl group having 8 to 36 carbon atoms. As at least one side chain.
　なお、本発明の実施形態に係るアルミニウムめっき液は、不可避的不純物として他の成分を含んでいても構わない。また、平滑性と伸びに優れたアルミニウム膜を形成できるという本発明の実施形態に係るアルミニウム膜の効果を損なわない範囲において意図的に他の成分を含有していても構わない。 Note that the aluminum plating solution according to the embodiment of the present invention may contain other components as inevitable impurities. Moreover, you may contain other components intentionally in the range which does not impair the effect of the aluminum film which concerns on embodiment of this invention that can form the aluminum film excellent in smoothness and elongation.
　前記（Ａ）成分であるアルミニウムハロゲン化物は、前記（Ｂ）成分と混合した場合に１１０℃程度以下で溶融塩を形成するものであれば良好に用いることができる。例えば、塩化アルミニウム（ＡlＣl3）、臭化アルミニウム（ＡlＢr3）、ヨウ化アルミニウム（ＡlＩ3）等が挙げられるが、これらの中でも塩化アルミニウムが最も好ましい。 The aluminum halide as the component (A) can be favorably used as long as it forms a molten salt at about 110 ° C. or less when mixed with the component (B). For example, aluminum chloride (AlCl 3 ), aluminum bromide (AlBr 3 ), aluminum iodide (AlI 3 ) and the like can be mentioned. Among these, aluminum chloride is most preferable.
　前記（Ｂ）成分のアルキルイミダゾリウムハロゲン化物も、前記（Ａ）成分と混合した場合に１１０℃程度以下で溶融塩を形成するものを良好に用いることができる。
　例えば、１，３位にアルキル基（炭素原子数１～５）を持つイミダゾリウムクロリド、１，２，３位にアルキル基（炭素原子数１～５）を持つイミダゾリウムクロリド、１，３位にアルキル基（炭素原子数１～５）を持つイミダゾリウムヨーシド等が挙げられる。
　より具体的には、１－エチル－３－メチルイミダゾリウムクロリド（ＥＭＩＣ）、１－ブチル－３－メチルイミダゾリウムクロリド（ＢＭＩＣ）、１－メチル－３－プロピルイミダゾリウムクロリド（ＭＰＩＣ）等が挙げられるが、これらの中でも１－エチル－３－メチルイミダゾリウムクロリド（ＥＭＩＣ）を最も好ましく用いることができる。 As the alkylimidazolium halide of the component (B), those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
For example, imidazolium chloride having an alkyl group (1 to 5 carbon atoms) at positions 1, 3; imidazolium chloride having an alkyl group (1 to 5 carbon atoms) at positions 1, 2, 3; And imidazolium ioside having an alkyl group (having 1 to 5 carbon atoms).
More specifically, 1-ethyl-3-methylimidazolium chloride (EMIC), 1-butyl-3-methylimidazolium chloride (BMIC), 1-methyl-3-propylimidazolium chloride (MPIC) and the like can be mentioned. Of these, 1-ethyl-3-methylimidazolium chloride (EMIC) can be most preferably used.
　前記（Ｂ）成分のアルキルピリジニウムハロゲン化物は、前記（Ａ）成分と混合した場合に１１０℃程度以下で溶融塩を形成するものを良好に用いることができる。
　例えば、１－ブチルピリジニウムクロリド（ＢＰＣ）、１－エチルピリジニウムクロリド（ＥＰＣ）、１－ブチル－３－メチルピリジニウムクロリド（ＢＭＰＣ）等が挙げられるが、これらの中でも１－ブチルピリジニウムクロリドが最も好ましい。 As the alkylpyridinium halide of the component (B), those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
Examples thereof include 1-butylpyridinium chloride (BPC), 1-ethylpyridinium chloride (EPC), 1-butyl-3-methylpyridinium chloride (BMPC), etc. Among them, 1-butylpyridinium chloride is most preferable.
　前記（Ｂ）成分の尿素化合物は、尿素及びその誘導体を意味するものであり、前記（Ａ）成分と混合した場合に１１０℃程度以下で溶融塩を形成するものを良好に用いることができる。
　例えば、下記式（１）で表される化合物を好ましく用いることができる。 The urea compound of the component (B) means urea and derivatives thereof, and those that form a molten salt at about 110 ° C. or less when mixed with the component (A) can be used favorably.
For example, a compound represented by the following formula (1) can be preferably used.
Figure JPOXMLDOC01-appb-C000001
　但し、式（１）においてＲは、水素原子、炭素原子数が１個～６個のアルキル基、又はフェニル基であり、互いに同一であっても、異なっていてもよい。
　前記尿素化合物は上記の中でも、尿素、ジメチル尿素を特に好ましく用いることができる。
Figure JPOXMLDOC01-appb-C000001
However, in the formula (1), R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, which may be the same or different.
Among the above urea compounds, urea and dimethylurea can be particularly preferably used.
　前記アルミニウムめっき液は、前記（Ａ）成分と前記（Ｂ）成分との混合比が、モル比で１：１～３：１の範囲にあるようにすることで、前記基材表面にアルミニウム膜を電着させるのに適したアルミニウムめっき液が得られる。
　前記（Ｂ）成分を１とした場合の前記（Ａ）成分のモル比が１未満の場合にはアルミニウムの電析反応が生じない。また、前記（Ｂ）成分を１とした場合の前記（Ａ）成分のモル比が３を超える場合には、アルミニウムめっき液中に塩化アルミニウムが析出し、アルミニウム膜に取り込まれ、膜の品質が低下する。 In the aluminum plating solution, the mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio, so that the aluminum film is formed on the substrate surface. An aluminum plating solution suitable for electrodeposition is obtained.
When the molar ratio of the component (A) is less than 1 when the component (B) is 1, no aluminum electrodeposition reaction occurs. Further, when the molar ratio of the component (A) is more than 3 when the component (B) is 1, aluminum chloride is precipitated in the aluminum plating solution and taken into the aluminum film, and the quality of the film is improved. descend.
　前記（Ｃ１）成分は、アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上である。また、前記（Ｃ１）成分は、炭素数が８以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有していればよく、残りの側鎖は特に限定されるものではない。残りの側鎖としては、例えば、水素、ベンゼン環を含む基、及び炭素数が１以上、３６以下の直鎖状もしくは分岐を有するアルキル基等が挙げられる。 The component (C1) is at least one selected from the group consisting of ammonium salts, phosphonium salts, sulfonium salts, amine compounds, phosphine compounds, and sulfide compounds. The component (C1) only needs to have a linear or branched alkyl group having 8 to 36 carbon atoms as at least one side chain, and the remaining side chains are particularly limited. It is not a thing. Examples of the remaining side chain include hydrogen, a group containing a benzene ring, and a linear or branched alkyl group having 1 to 36 carbon atoms.
　前記（Ｃ１）成分が少なくとも１つの側鎖として有するアルキル基は、分岐があっても構わないが直鎖状のものであることが好ましい。また、前記アルキル基の炭素数が８以上であることによりアルミニウム膜の平滑性に寄与することができ、３６以下であることによりアルミニウムめっき液の粘度が高くなり過ぎないようにすることができる。これらの観点から、前記（Ｃ１）成分が側鎖として有するアルキル基の炭素数は、８以上、２２以下であることが好ましく、１２以上、１８以下であることがより好ましい。
　また、前記（Ｃ１）成分が塩の場合にはハロゲン塩であることが好ましい。なかでも、塩素イオン（Ｃｌ－）、臭素イオン（Ｂｒ－）、又はヨウ素イオン（Ｉ－）の塩であることが好ましい。 The alkyl group that the (C1) component has as at least one side chain may be branched, but is preferably a straight chain. Further, when the alkyl group has 8 or more carbon atoms, it can contribute to the smoothness of the aluminum film, and when it is 36 or less, the viscosity of the aluminum plating solution can be prevented from becoming too high. From these viewpoints, the number of carbon atoms of the alkyl group which the component (C1) has as a side chain is preferably 8 or more and 22 or less, and more preferably 12 or more and 18 or less.
When the component (C1) is a salt, it is preferably a halogen salt. Among these, a salt of chlorine ion (Cl − ), bromine ion (Br − ), or iodine ion (I − ) is preferable.
　前記（Ｃ１）成分としては、具体的には、ステアリルアミン、ジメチルステアリルアミン、Ｎ‐ドコシル‐Ｎ‐メチル１－ドコサンアミン、ジメチルジステアリルアンモニウムクロリド、ドデシルトリメチルアンモニウムクロリド、オクチルトリメチルアンモニウムクロリド、及びトリブチルテトラデシルホスホニウムクロリドなどが挙げられる。 Specific examples of the component (C1) include stearylamine, dimethylstearylamine, N-docosyl-N-methyl1-docosamine, dimethyldistearylammonium chloride, dodecyltrimethylammonium chloride, octyltrimethylammonium chloride, and tributyltetra Examples include decylphosphonium chloride.
　前記アルミニウムめっき液における前記（Ｃ１）成分の濃度が１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下であることにより、平滑で、かつ伸びに優れたアルミニウム膜を形成することができる。前記（Ｃ１）成分の濃度が１．０ｇ／Ｌ未満であるとアルミニウム膜を十分に平滑にすることができず、また、４５ｇ／Ｌ超であるとアルミニウム膜中に前記（Ｃ１）成分が取り込まれるようになってしまい硬くなるものの脆く、伸びが少ないアルミニウム膜となってしまう。前記（Ｃ１）成分の濃度は、５ｇ／Ｌ以上、２５ｇ／Ｌ以下であることが好ましく、７．５ｇ／Ｌ以上、２０ｇ／Ｌ以下であることが更に好ましい。 When the concentration of the component (C1) in the aluminum plating solution is 1.0 g / L or more and 45 g / L or less, a smooth aluminum film excellent in elongation can be formed. If the concentration of the component (C1) is less than 1.0 g / L, the aluminum film cannot be sufficiently smoothed, and if it exceeds 45 g / L, the component (C1) is taken into the aluminum film. However, the aluminum film becomes brittle and has little elongation. The concentration of the component (C1) is preferably 5 g / L or more and 25 g / L or less, and more preferably 7.5 g / L or more and 20 g / L or less.
　なお、前記（Ｃ１）成分を含むアルミニウムめっき液を用いて長時間めっきを行うと前記（Ｃ１）成分が減少してしまうため、アルミニウムめっき液中に前記（Ｃ１）成分を適宜補充する必要がある。前記（Ｃ１）成分をアルミニウムめっき液に補充する場合には、上記のように、アルミニウムめっき液における前記（Ｃ１）成分の濃度が１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下となるようにすればよい。 In addition, since it will reduce the said (C1) component when plating using the aluminum plating solution containing the said (C1) component for a long time, it is necessary to replenish the said (C1) component suitably in an aluminum plating solution. . When the component (C1) is supplemented to the aluminum plating solution, the concentration of the component (C1) in the aluminum plating solution is 1.0 g / L or more and 45 g / L or less as described above. Good.
　本発明者等はアルミニウムめっき液中から前記（Ｃ１）成分が減少する理由を検討したところ、前記（Ｃ１）成分が有する側鎖、すなわち炭素数が８以上、３６以下の直鎖状もしくは分岐を有するアルキル基が徐々にではあるが分解してしまうためであることを見出した。更に、その切断されたアルキル基がアルミニウム膜中に取り込まれることでアルミニウム膜の平滑性に寄与していることが分かった。 The present inventors examined the reason why the component (C1) decreases from the aluminum plating solution. As a result, the side chain of the component (C1), that is, linear or branched having 8 to 36 carbon atoms. It has been found that the alkyl group is gradually decomposed. Furthermore, it was found that the cut alkyl group contributes to the smoothness of the aluminum film by being taken into the aluminum film.
　上記のように前記（Ｃ１）成分を含むアルミニウムめっき液を用いて長時間めっきを行うとアルキル基の鎖長が徐々に短くなっていき、炭素数が７以下のアルキル基を側鎖に有する成分が蓄積してしまう。この場合に、前記（Ｃ１）成分の替わりに次の（Ｄ）成分をアルミニウムめっき液に補充してもよい。なお、このときのアルミニウムめっき液は前記（Ｃ１）成分が次の（Ｃ２）成分に変化している。 As described above, when plating is performed for a long time using the aluminum plating solution containing the component (C1), the chain length of the alkyl group gradually decreases, and the component having an alkyl group having 7 or less carbon atoms in the side chain Will accumulate. In this case, instead of the component (C1), the following component (D) may be supplemented to the aluminum plating solution. In this case, in the aluminum plating solution at this time, the component (C1) is changed to the next component (C2).
　すなわち、本発明の実施形態に係るアルミニウムめっき液は、前記（Ａ）成分及び前記（Ｂ）成分に、更に、少なくとも以下の（Ｃ２）成分及び（Ｄ）成分を含むアルミニウムめっき液である。
（Ｃ２）成分：アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上
（Ｄ）成分：ハロゲン化アルキル、アルキン、アルケン及びアルカンからなる群より選択されるいずれか一種以上
　但し、前記（Ｃ２）成分は、炭素数が１以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有するものである。また、前記（Ｄ）成分は炭素数が３以上、３６以下であって、直鎖状もしくは分岐を有する化合物である。 That is, the aluminum plating solution according to the embodiment of the present invention is an aluminum plating solution further containing at least the following components (C2) and (D) in addition to the component (A) and the component (B).
(C2) Component: Any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound (D) Component: Group consisting of alkyl halide, alkyne, alkene and alkane However, the component (C2) has a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain. In addition, the component (D) is a compound having 3 to 36 carbon atoms and having a linear or branched structure.
　前記（Ｃ２）成分のうち、炭素数が８以上、３６以下の直鎖状もしくは分岐を有するアルキル基を側鎖として有するものはアルミニウム膜の平滑性と伸びに寄与し、更に、前記（Ｄ）成分の溶解性にも寄与する。また、前記（Ｃ２）成分のうち、炭素数が１以上、７以下の直鎖状もしくは分岐を有するアルキル基を側鎖として有するものは、前記（Ｄ）成分の溶解性に寄与する。すなわち、前記（Ｃ２）成分がアルミニウムめっき液中に含まれていることによって、前記（Ｄ）成分を容易に溶解させることができるようになる。 Among the components (C2), those having a straight chain or branched alkyl group having 8 to 36 carbon atoms as a side chain contribute to the smoothness and elongation of the aluminum film. It also contributes to the solubility of the components. Among the components (C2), those having a linear or branched alkyl group having 1 to 7 carbon atoms as a side chain contribute to the solubility of the component (D). That is, when the component (C2) is contained in the aluminum plating solution, the component (D) can be easily dissolved.
　前記（Ｃ２）成分は、アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上である。また、前記（Ｃ２）成分は、炭素数が１以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有していればよく、残りの側鎖は特に限定されるものではない。残りの側鎖としては、例えば、水素、ベンゼン環を含む基、及び炭素数が１以上、３６以下の直鎖状もしくは分岐を有するアルキル基等が挙げられる。 The component (C2) is at least one selected from the group consisting of ammonium salts, phosphonium salts, sulfonium salts, amine compounds, phosphine compounds, and sulfide compounds. The component (C2) only needs to have a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain, and the remaining side chains are particularly limited. It is not a thing. Examples of the remaining side chain include hydrogen, a group containing a benzene ring, and a linear or branched alkyl group having 1 to 36 carbon atoms.
　前記（Ｃ２）成分が少なくとも１つの側鎖として有するアルキル基は、分岐があっても構わないが直鎖状のものであることが好ましい。また、前記アルキル基の炭素数が１以上であることにより前記（Ｄ）成分の溶解性に寄与することができ、３６以下であることによりアルミニウムめっき液の粘度が高くなり過ぎないようにすることができる。これらの観点から、前記（Ｃ２）成分におけるアルキル基の炭素数は、１以上、１８以下であることが好ましく、３以上、１２以下であることがより好ましい。
　また、前記（Ｃ２）成分が塩の場合にはハロゲン塩であることが好ましい。なかでも、塩素イオン（Ｃｌ－）、臭素イオン（Ｂｒ－）、又はヨウ素イオン（Ｉ－）の塩であることが好ましい。 The alkyl group that the (C2) component has as at least one side chain may be branched, but is preferably a straight chain. In addition, the alkyl group having 1 or more carbon atoms can contribute to the solubility of the component (D), and if it is 36 or less, the viscosity of the aluminum plating solution should not be too high. Can do. From these viewpoints, the number of carbon atoms of the alkyl group in the component (C2) is preferably 1 or more and 18 or less, and more preferably 3 or more and 12 or less.
Further, when the component (C2) is a salt, it is preferably a halogen salt. Among these, a salt of chlorine ion (Cl − ), bromine ion (Br − ), or iodine ion (I − ) is preferable.
　前記（Ｃ２）成分としては、具体的には、トリメチルアミン、トリメチルホスフィン、エチルメチルスルフィド、ステアリルアミン、ジメチルステアリルアミン、Ｎ‐ドコシル‐Ｎ‐メチル１－ドコサンアミン、ジメチルジステアリルアンモニウムクロリド、ドデシルトリメチルアンモニウムクロリド、オクチルトリメチルアンモニウムクロリド、テトラブチルアンモニウムクロリド、テトラブチルホスホニウムクロリド、トリブチルテトラデシルホスホニウムクロリド、及びトリエチルフェニルアンモニウムクロリドなどが挙げられる。 Specific examples of the component (C2) include trimethylamine, trimethylphosphine, ethylmethyl sulfide, stearylamine, dimethylstearylamine, N-docosyl-N-methyl1-docosamine, dimethyldistearylammonium chloride, dodecyltrimethylammonium chloride. Octyltrimethylammonium chloride, tetrabutylammonium chloride, tetrabutylphosphonium chloride, tributyltetradecylphosphonium chloride, triethylphenylammonium chloride, and the like.
　前記アルミニウムめっき液における前記（Ｃ２）成分の濃度は１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下である。前記（Ｃ２）成分の濃度が１．０ｇ／Ｌ未満であると前記（Ｄ）成分をアルミニウムめっき液に溶解させることが困難になってしまう。また、前記（Ｃ２）成分の濃度が４５ｇ／Ｌ超であるとめっき液の粘度が高くなり過ぎる。
　前記（Ｃ２）成分の濃度は、５．０ｇ／Ｌ以上、３０ｇ／Ｌ以下であることが好ましく、１０ｇ／Ｌ以上、１５ｇ／Ｌ以下であることが更に好ましい。 The concentration of the component (C2) in the aluminum plating solution is 1.0 g / L or more and 45 g / L or less. If the concentration of the component (C2) is less than 1.0 g / L, it will be difficult to dissolve the component (D) in the aluminum plating solution. On the other hand, if the concentration of the component (C2) exceeds 45 g / L, the viscosity of the plating solution becomes too high.
The concentration of the component (C2) is preferably 5.0 g / L or more and 30 g / L or less, and more preferably 10 g / L or more and 15 g / L or less.
　前記（Ｄ）成分は、炭素数は３以上、３６以下の、ハロゲン化アルキル、アルキン、アルケン及びアルカンからなる群より選択されるいずれか一種以上であり、直鎖状であってもよいし分岐を有していてもよい。前記（Ｄ）成分は極性が小さいため、前記（Ａ）成分及び前記（Ｂ）成分からなるアルミニウムめっき液には殆ど溶解しないが、アルミニウムめっき液中に前記（Ｃ２）成分が含まれているとこれが界面活性剤の役割を担うため、容易に溶解するようになる。また、前記（Ｄ）成分は前記（Ｃ１）成分よりも安価であり、入手が容易である。このため前記（Ｃ１）成分の替わりに前記（Ｄ）成分を補充することで、本発明の実施形態に係るアルミニウムめっき液を、より安価に製造することが可能となる。 The component (D) is one or more selected from the group consisting of alkyl halides, alkynes, alkenes and alkanes having 3 to 36 carbon atoms, and may be linear or branched You may have. Since the component (D) has a small polarity, it hardly dissolves in the aluminum plating solution composed of the component (A) and the component (B), but the component (C2) is contained in the aluminum plating solution. Since this plays a role of a surfactant, it is easily dissolved. The component (D) is cheaper than the component (C1) and is easily available. For this reason, it becomes possible to manufacture the aluminum plating solution which concerns on embodiment of this invention more cheaply by replenishing the said (D) component instead of the said (C1) component.
　また、前記（Ｄ）成分は、基材の表面にアルミニウムが電着する際にアルミニウム膜中に取り込まれることでアルミニウム膜の平滑性に寄与する。しかしながら、前記（Ｄ）成分は熱分解温度や沸点が非常に低いため、基材である樹脂を燃焼除去する際に、炭化アルミニウムを形成する温度未満でアルミニウム膜中から除去される。このため、１，１０－フェナントロリンのようにアルミニウム膜中に残存して炭化アルミニウムを形成することがない。
　なお、アルミニウム膜中から前記（Ｄ）成分が除去されるとアルミニウム膜中に、多少ではあるが微小なボイドが形成される。アルミニウムめっき液における前記（Ｄ）成分の濃度が０．５ｇ／Ｌ以上、８．５ｇ／Ｌ以下の範囲にあれば、このボイドによってアルミニウム膜の平滑性や伸びが低下することはない。 The component (D) contributes to the smoothness of the aluminum film by being taken into the aluminum film when aluminum is electrodeposited on the surface of the substrate. However, since the component (D) has a very low thermal decomposition temperature and boiling point, it is removed from the aluminum film at a temperature lower than the temperature at which aluminum carbide is formed when the resin as the base material is burned and removed. Therefore, unlike in 1,10-phenanthroline, it does not remain in the aluminum film to form aluminum carbide.
Note that, when the component (D) is removed from the aluminum film, a small but small void is formed in the aluminum film. If the concentration of the component (D) in the aluminum plating solution is in the range of 0.5 g / L or more and 8.5 g / L or less, the smoothness and elongation of the aluminum film are not reduced by this void.
　前記（Ｄ）成分は、炭素数が３以上であることによりアルミニウム膜の平滑性に寄与することができる。また、前記（Ｄ）成分の炭素数が３６以下であることにより、アルミニウムめっき液の粘度が高くなり過ぎないようにすることができる。これらの観点から、前記（Ｄ）成分の炭素数は５以上、２４以下であることが好ましく、８以上、１８以下であることがより好ましい。 The component (D) can contribute to the smoothness of the aluminum film by having 3 or more carbon atoms. Moreover, when the carbon number of the component (D) is 36 or less, the viscosity of the aluminum plating solution can be prevented from becoming too high. From these viewpoints, the component (D) preferably has 5 or more and 24 or less carbon atoms, and more preferably 8 or more and 18 or less.
　前記（Ｄ）成分は室温で液体あるいは固体であるものの方が、アルミニウムめっき液中に溶解させやすいため好ましい。
　前記ハロゲン化アルキルに含まれるハロゲン原子は特に限定されるものではないが、例えば、塩素（Ｃｌ）、臭素（Ｂｒ）又はヨウ素（Ｉ）であることが好ましい。また、前記ハロゲン化アルキルに含まれるハロゲン原子の数は特に限定されるものではなく、１以上、２以下程度であることが好ましい。
　前記アルキンに含まれる三重結合の数は１つであると、アルキン同士が反応しにくくなるため好ましい。
　前記アルケンに含まれる二重結合の数は１つであると、アルケン同士が反応しにくくなるため好ましい。 The component (D) is preferably liquid or solid at room temperature because it is easily dissolved in the aluminum plating solution.
Although the halogen atom contained in the said halogenated alkyl is not specifically limited, For example, it is preferable that they are chlorine (Cl), bromine (Br), or iodine (I). The number of halogen atoms contained in the alkyl halide is not particularly limited, and is preferably about 1 or more and 2 or less.
It is preferable that the number of triple bonds contained in the alkyne is one because the alkynes hardly react with each other.
It is preferable that the number of double bonds contained in the alkene is one because the alkenes hardly react with each other.
　前記（Ｄ）成分としては、具体的には、プロパン、ブタン、オクタン、ペンタン、テトラデカン、オクタデカン、クロロプロパン、クロロブタン、ラウリルクロリド、ステアリルクロリド、ペンテン、ヘキセン、デセン、プロピン、ペンチン、ブチンなどが挙げられる。 Specific examples of the component (D) include propane, butane, octane, pentane, tetradecane, octadecane, chloropropane, chlorobutane, lauryl chloride, stearyl chloride, pentene, hexene, decene, propyne, pentyne, butyne and the like. .
　前記（Ｃ２）成分を含むアルミニウムめっき液においては、前記（Ｄ）成分の濃度が０．５ｇ／Ｌ以上、８．５ｇ／Ｌ以下であることにより、平滑で、かつ伸びに優れたアルミニウム膜を形成することができる。前記（Ｄ）成分の濃度が０．５ｇ／Ｌ未満であるとアルミニウム膜を十分に平滑にすることができない場合がある。また、前記（Ｄ）成分の濃度が８．５ｇ／Ｌ超であると、基材を燃焼除去する際に形成されるアルミニウム膜中のボイドの量が多くなり過ぎてしまう。これらの観点から、前記（Ｄ）成分の濃度は、０．８５ｇ／Ｌ以上、４．５ｇ／Ｌ以下であることが好ましく、１．０ｇ／Ｌ以上、３．０ｇ／Ｌ以下であることがより好ましい。
　また、前述のように前記（Ｄ）成分はアルミニウム膜中に取り込まれるため、長時間アルミニウムめっきを行うと徐々にアルミニウムめっき液中の（Ｄ）成分の量が減少してしまう。アルミニウムめっき液中の（Ｄ）成分の量が減少した場合には、前記（Ｄ）成分を前記濃度範囲となるように適宜補充すればよい。 In the aluminum plating solution containing the component (C2), the concentration of the component (D) is 0.5 g / L or more and 8.5 g / L or less, so that an aluminum film that is smooth and excellent in elongation can be obtained. Can be formed. If the concentration of the component (D) is less than 0.5 g / L, the aluminum film may not be sufficiently smoothed. Further, when the concentration of the component (D) is more than 8.5 g / L, the amount of voids in the aluminum film formed when the substrate is burned and removed becomes too large. From these viewpoints, the concentration of the component (D) is preferably 0.85 g / L or more and 4.5 g / L or less, and 1.0 g / L or more and 3.0 g / L or less. More preferred.
Further, as described above, since the component (D) is taken into the aluminum film, when the aluminum plating is performed for a long time, the amount of the component (D) in the aluminum plating solution gradually decreases. When the amount of the component (D) in the aluminum plating solution decreases, the component (D) may be replenished appropriately so as to be in the concentration range.
　以上の本発明の一態様に係るアルミニウムめっき液を用いることで、表面が平滑でかつ伸びに優れるアルミニウム膜を形成することができる。 By using the aluminum plating solution according to one embodiment of the present invention, an aluminum film having a smooth surface and excellent elongation can be formed.
＜アルミニウム膜の製造方法＞
　本発明の実施形態に係るアルミニウム膜の製造方法は、前記本発明の実施形態に係るアルミニウムめっき液を用いて基材の表面にアルミニウムを電着させるアルミニウム膜の製造方法、である。 <Method for producing aluminum film>
The manufacturing method of the aluminum film which concerns on embodiment of this invention is a manufacturing method of the aluminum film which electrodeposits aluminum on the surface of a base material using the aluminum plating solution which concerns on the said embodiment of this invention.
　本発明の実施形態に係るアルミニウム膜の製造方法において、前記電解液中の基材表面にアルミニウムを電着させるには、前記電解液中にアルミニウム電極（陽極）を設けて前記電解液中の基材が陰極となるように電気的に接続し、通電すればよい。
　このとき、電流密度が０．５Ａ／ｄｍ2以上、１０．０Ａ／ｄｍ2以下となるようにして基材表面にアルミニウムを電着させることが好ましい。電流密度が前記範囲内にあることにより、より平滑性に優れたアルミニウム膜を得ることができる。前記電流密度は、１．５Ａ／ｄｍ2以上、６．０Ａ／ｄｍ2以下であることがより好ましく、２．０Ａ／ｄｍ2以上、４．０Ａ／ｄｍ2以下であることが更に好ましい。 In the method for producing an aluminum film according to an embodiment of the present invention, in order to electrodeposit aluminum on the surface of a substrate in the electrolytic solution, an aluminum electrode (anode) is provided in the electrolytic solution, and a base in the electrolytic solution is provided. What is necessary is just to electrically connect and energize so that a material may become a cathode.
At this time, it is preferable that aluminum be electrodeposited on the surface of the substrate so that the current density is 0.5 A / dm 2 or more and 10.0 A / dm 2 or less. When the current density is within the above range, an aluminum film having better smoothness can be obtained. The current density is more preferably 1.5 A / dm 2 or more and 6.0 A / dm 2 or less, and further preferably 2.0 A / dm 2 or more and 4.0 A / dm 2 or less.
　基材表面にアルミニウムを電着させる際には、前記電解液の温度は１５℃以上、１１０℃以下となるように調整しながら行うことが好ましい。電解液の温度を１５℃以上にすることにより、電解液の粘度を充分に低くすることができ、アルミニウムの電着効率を向上させることができる。また、電解液の温度を１１０℃以下にすることで、アルミニウムハロゲン化物の揮発を抑制することができる。前記電解液の温度は３０℃以上、８０℃以下であることがより好ましく、４０℃以上、７０℃以下であることが更に好ましい。
　なお、基材表面にアルミニウムを電着させる際において、前記電解液は攪拌しても良いし、攪拌しなくても構わない。
　前記本発明の実施形態に係るアルミニウム膜の製造方法により、表面の算術平均粗さ（Ｒａ）が０．２μｍ以下程度の平滑なアルミニウム膜を製造することができる。 When electrodepositing aluminum on the surface of the substrate, it is preferable to adjust the temperature of the electrolyte so as to be 15 ° C. or higher and 110 ° C. or lower. By setting the temperature of the electrolytic solution to 15 ° C. or higher, the viscosity of the electrolytic solution can be sufficiently lowered, and the electrodeposition efficiency of aluminum can be improved. Moreover, volatilization of the aluminum halide can be suppressed by setting the temperature of the electrolytic solution to 110 ° C. or lower. The temperature of the electrolytic solution is more preferably 30 ° C. or higher and 80 ° C. or lower, and further preferably 40 ° C. or higher and 70 ° C. or lower.
In addition, when electrodepositing aluminum on the substrate surface, the electrolytic solution may be stirred or may not be stirred.
A smooth aluminum film having a surface arithmetic average roughness (Ra) of about 0.2 μm or less can be produced by the method for producing an aluminum film according to the embodiment of the present invention.
　前記基材は表面にアルミニウム膜を形成する用途があるものであれば特に限定されるものではない。基材としては、例えば、銅板、鋼帯、銅線、鋼線、導電化処理を施した樹脂等を利用することができる。前記導電化処理を施した樹脂としては、例えば、ポリウレタン、メラミン樹脂、ポリプロピレン、ポリエチレン等に導電化処理を施したものを利用することができる。 The substrate is not particularly limited as long as it has an application for forming an aluminum film on the surface. As the substrate, for example, a copper plate, a steel strip, a copper wire, a steel wire, a resin subjected to a conductive treatment, or the like can be used. As the resin subjected to the conductive treatment, for example, polyurethane, melamine resin, polypropylene, polyethylene or the like subjected to the conductive treatment can be used.
　また、前記基材としての樹脂の形状はどのようなものでも構わないが、三次元網目状構造を有する樹脂成形体を用いることにより、最終的に、各種フィルタ、触媒担体、電池用電極などの用途に優れた特性を発揮する三次元網目状構造を有するアルミニウム多孔体を作製することができ、好ましい。また、不織布形状を有する樹脂を用いることによっても最終的に多孔質構造を有するアルミニウム多孔体を作製することができ、このようにして作製された不織布形状を有するアルミニウム多孔体も、各種フィルタ、触媒担体、電池用電極などの用途に好ましく用いることができる。 The resin as the substrate may have any shape, but by using a resin molded body having a three-dimensional network structure, finally, various filters, catalyst carriers, battery electrodes, etc. An aluminum porous body having a three-dimensional network structure that exhibits excellent properties for use can be produced, which is preferable. In addition, an aluminum porous body having a porous structure can be finally produced by using a resin having a nonwoven fabric shape, and the thus produced aluminum porous body having a nonwoven fabric shape is also used for various filters and catalysts. It can be preferably used for applications such as carriers and battery electrodes.
　前記三次元網目状構造を有する樹脂成形体としては、例えば、ポリウレタン、メラミン樹脂等を用いて作製された発泡樹脂成形体を利用することができる。なお、発泡樹脂成形体と表記したが、連続した気孔（連通気孔）を有するものであれば任意の形状の樹脂成形体を選択できる。例えば、ポリプロピレン、ポリエチレン等の繊維状の樹脂を絡めて不織布のような形状を有するものも発泡樹脂成形体に代えて使用可能である。
　なお、以下では三次元網目状構造の多孔体を単に「多孔体」とも記載する。 As the resin molded body having the three-dimensional network structure, for example, a foamed resin molded body produced using polyurethane, melamine resin or the like can be used. In addition, although described as a foamed resin molded body, a resin molded body having an arbitrary shape can be selected as long as it has continuous pores (continuous vent holes). For example, what has a shape like a nonwoven fabric entangled with a fibrous resin such as polypropylene and polyethylene can be used in place of the foamed resin molding.
Hereinafter, a porous body having a three-dimensional network structure is also simply referred to as a “porous body”.
　前記多孔体の気孔率は８０％以上、９８％以下、気孔径は５０μｍ以上、５００μｍ以下とするのが好ましい。発泡ウレタン及び発泡メラミンは気孔率が高く、また気孔の連通性があるとともに熱分解性にも優れているため発泡樹脂成形体として好ましく使用できる。発泡ウレタンは気孔の均一性や入手の容易さ等の点で好ましく、発泡メラミンは気孔径の小さなものが得られる点で好ましい。なお、発泡ウレタンや発泡メラミン等の発泡樹脂成形体には発泡過程での製泡剤や未反応モノマーなどの残留物があることが多いため、洗浄処理を行っておくことが好ましい。 The porosity of the porous body is preferably 80% or more and 98% or less, and the pore diameter is preferably 50 μm or more and 500 μm or less. Foamed urethane and foamed melamine can be preferably used as a foamed resin molded article because they have high porosity, have pore connectivity and are excellent in thermal decomposability. Foamed urethane is preferred in terms of pore uniformity and availability, and foamed melamine is preferred in that a product having a small pore diameter can be obtained. In addition, since foamed resin moldings such as foamed urethane and foamed melamine often have residues such as foaming agents and unreacted monomers in the foaming process, it is preferable to perform a washing treatment.
　前記多孔体の気孔率は、次式で定義される。
　気孔率＝（１－（多孔体の重量［ｇ］／（多孔体の体積［ｃｍ3］×素材密度）））×１００［％］
　また、気孔径は、多孔体表面を顕微鏡写真等で拡大し、１インチ（２５．４ｍｍ）あたりの気孔数をセル数として計数して、平均孔径＝２５．４ｍｍ／セル数として平均的な値を求める。 The porosity of the porous body is defined by the following equation.
Porosity = (1− (weight of porous body [g] / (volume of porous body [cm 3 ] × material density))) × 100 [%]
The pore diameter is an average value obtained by enlarging the surface of the porous body with a micrograph, etc., and counting the number of pores per inch (25.4 mm) as the number of cells, and the average pore diameter = 25.4 mm / cell number. Ask for.
　前記三次元網目状構造を有する樹脂成形体としては導電化処理を施したものを用いる。
樹脂表面の導電化処理は既知の方法を含めて選択可能である。無電解めっきや気相法によるニッケル等の金属層の形成や、導電性塗料による金属やカーボン層の形成による方法が利用可能である。
　無電解めっきや気相法により樹脂表面に金属層を形成することにより、樹脂表面の導電率を高くすることができる。一方、導電率の観点からは多少劣るが、カーボン塗布による樹脂表面の導電化は、アルミニウム膜形成後のアルミニウム構造体にアルミニウム以外の金属を混入することなくできることから、金属として実質的にアルミニウムのみからなる構造体を製造することが可能となる。また安価に導電化できる利点もある。 As the resin molded body having the three-dimensional network structure, a resin molded body is used.
The conductive treatment of the resin surface can be selected including known methods. A method of forming a metal layer such as nickel by electroless plating or a vapor phase method, or forming a metal or carbon layer by a conductive paint can be used.
By forming a metal layer on the resin surface by electroless plating or a vapor phase method, the conductivity of the resin surface can be increased. On the other hand, although it is somewhat inferior from the viewpoint of electrical conductivity, it is possible to make the resin surface conductive by carbon coating without introducing any metal other than aluminum into the aluminum structure after forming the aluminum film. It becomes possible to manufacture the structure which consists of. There is also an advantage that it can be made conductive at low cost.
　導電化処理をカーボン塗布により行う場合には、まず導電性塗料としてのカーボン塗料を準備する。カーボン塗料としての懸濁液は、カーボン粒子の他に、粘結剤、分散剤および分散媒を含むことが好ましい。
　前記三次元網目状構造を有する樹脂成形体を使用する場合に、多孔体中にカーボン粒子の塗布を均一に行うには、懸濁液が均一な懸濁状態を維持している必要がある。そのためには、懸濁液は２０℃～４０℃に維持されていることが好ましい。懸濁液の温度を２０℃以上に維持することにより、均一な懸濁状態を保つことができ、多孔体の網目構造をなす骨格の表面に粘結剤のみが集中して層をなすということがなくなり、均一にカーボン粒子の塗布を行うことができる。このようにして均一に塗布されたカーボン粒子の層は剥離し難いため、強固に密着した金属めっきの形成が可能となる。一方、懸濁液の温度が４０℃以下であることにより、分散剤の蒸発を抑制することができるため、塗布処理時間の経過とともに懸濁液が濃縮され難くなる。
　また、カーボン粒子の粒径は、０．０１～５μｍで、好ましくは０．０１～０．５μｍである。粒径が大きいと多孔質樹脂成形体の空孔を詰まらせたり、平滑なめっきを阻害したりする要因となり、小さすぎると十分な導電性を確保することが難しくなる。 When conducting the conductive treatment by applying carbon, first, a carbon paint as a conductive paint is prepared. The suspension as the carbon paint preferably contains a binder, a dispersant and a dispersion medium in addition to the carbon particles.
When the resin molded body having the three-dimensional network structure is used, in order to uniformly apply the carbon particles in the porous body, the suspension needs to maintain a uniform suspended state. For this purpose, the suspension is preferably maintained at 20 ° C. to 40 ° C. By maintaining the temperature of the suspension at 20 ° C. or higher, a uniform suspension can be maintained, and only the binder is concentrated on the surface of the skeleton forming the porous network structure to form a layer. The carbon particles can be uniformly applied. Since the layer of carbon particles uniformly applied in this manner is difficult to peel off, it is possible to form a metal plating that is firmly adhered. On the other hand, when the temperature of the suspension is 40 ° C. or less, evaporation of the dispersant can be suppressed, and therefore, the suspension becomes difficult to concentrate as the coating processing time elapses.
The particle size of the carbon particles is 0.01 to 5 μm, preferably 0.01 to 0.5 μm. If the particle size is large, the pores of the porous resin molded body may be clogged or smooth plating may be hindered. If it is too small, it is difficult to ensure sufficient conductivity.
＜アルミニウム多孔体＞
　本発明の実施形態に係るアルミニウム多孔体は、伸びが１．５％以上であるアルミニウム多孔体である。従来のアルミニウムめっき液を用いた製造方法によって得られるアルミニウム多孔体は強度が高く伸びが小さかったのに対し、本発明の実施形態に係るアルミニウム多孔体は伸びが１．５％以上と柔らかいアルミニウム多孔体である。 <Porous aluminum body>
The aluminum porous body according to the embodiment of the present invention is an aluminum porous body having an elongation of 1.5% or more. The aluminum porous body obtained by the conventional manufacturing method using the aluminum plating solution has high strength and small elongation, whereas the aluminum porous body according to the embodiment of the present invention has a soft aluminum porous body with an elongation of 1.5% or more. Is the body.
　前記伸びが１．５％以上であることにより、アルミニウム多孔体が曲げや振動に対して強くなり、アルミニウム多孔体の使用用途の範囲が広くなり好ましい。従って、アルミニウム多孔体の伸びは大きければ大きい程好ましく、１．８％以上であることがより好ましく、２．５％以上であることが更に好ましい。後述する本発明の実施形態に係るアルミニウム多孔体の製造方法によれば、前記伸びが１．５％以上、５．０％以下程度のアルミニウム多孔体を製造することができる。
　なお、前述のように、アルミニウム多孔体の前記伸びはアルミニウム多孔体のアルミニウムの目付け量が１００ｇ/ｍ2以上、１８０ｇ/ｍ2以下で、厚さが０．９５ｍｍ以上、１．０５ｍｍ以下の場合における伸びであり、また、ＪＩＳ　Ｚ　２２４１の規定による引張試験によって測定されるものである。 The elongation of 1.5% or more is preferable because the porous aluminum body is strong against bending and vibration, and the range of usage of the porous aluminum body is widened. Accordingly, the larger the elongation of the aluminum porous body is, the more preferable, 1.8% or more is more preferable, and 2.5% or more is more preferable. According to the method for producing a porous aluminum body according to an embodiment of the present invention to be described later, an aluminum porous body having an elongation of about 1.5% or more and 5.0% or less can be produced.
As described above, the elongation of the aluminum porous body is when the weight of aluminum in the aluminum porous body is 100 g / m 2 or more and 180 g / m 2 or less and the thickness is 0.95 mm or more and 1.05 mm or less. And measured by a tensile test according to JIS Z 2241.
　前記アルミニウム多孔体の骨格の断面における結晶粒径は１μｍ以上、５０μｍ以下であることが好ましい。前記結晶粒径が１μｍ以上であることにより、アルミニウム膜が柔らかくなり、前記アルミニウム多孔体の伸びが１．５％以上となるため好ましい。一方、前記結晶粒径が５０μｍ以下であることにより、アルミニウム多孔体が柔らかくなり過ぎて強度が低下することを抑制でき好ましい。これらの観点から前記アルミニウム多孔体の骨格断面における結晶粒径は、１．５μｍ以上、２５μｍ以下であることがより好ましく、２μｍ以上、１５μｍ以下であることが更に好ましい。 The crystal grain size in the cross section of the skeleton of the porous aluminum body is preferably 1 μm or more and 50 μm or less. The crystal grain size of 1 μm or more is preferable because the aluminum film becomes soft and the elongation of the aluminum porous body becomes 1.5% or more. On the other hand, when the crystal grain size is 50 μm or less, it is possible to suppress the strength of the aluminum porous body from being too soft and the strength is reduced, which is preferable. From these viewpoints, the crystal grain size in the skeleton cross section of the porous aluminum body is more preferably 1.5 μm or more and 25 μm or less, and further preferably 2 μm or more and 15 μm or less.
　前記アルミニウムめっき液を用いることで比較的結晶粒径が大きいアルミニウム多孔体をえることができる。また、結晶粒径を更に大きくする方法としては、例えば、アルミニウム多孔体を熱処理する、アルミニウム多孔体を製造する際にアルミニウムめっき液の液温を高くする、めっき時の電流密度を低くする、等の方法が挙げられる。 A porous aluminum body having a relatively large crystal grain size can be obtained by using the aluminum plating solution. Examples of a method for further increasing the crystal grain size include, for example, heat-treating the aluminum porous body, increasing the temperature of the aluminum plating solution when manufacturing the aluminum porous body, reducing the current density during plating, etc. The method is mentioned.
　前記アルミニウム多孔体は、炭化アルミニウムの含有量が０．８質量％以下であることが好ましい。アルミニウム多孔体における炭化アルミニウムの含有量が０．８質量％以下であることによりアルミニウム膜が柔らかくなり、前記アルミニウム多孔体の伸びが１．５％以上となるため好ましい。前記アルミニウム多孔体における炭化アルミニウムの含有量は、０．５質量％以下であることがより好ましく、０．３質量％以下であることが更に好ましい。 The aluminum porous body preferably has an aluminum carbide content of 0.8% by mass or less. It is preferable that the aluminum carbide content in the aluminum porous body is 0.8% by mass or less because the aluminum film becomes soft and the elongation of the aluminum porous body becomes 1.5% or more. The aluminum carbide content in the aluminum porous body is more preferably 0.5% by mass or less, and further preferably 0.3% by mass or less.
　前記本発明の実施形態に係るアルミニウムめっき液を用いてアルミニウム多孔体を製造した場合には、基本的には基材を燃焼除去する際に炭素を含む成分が炭化アルミニウムを形成する温度未満でアルミニウム膜中から除去される。このため、アルミニウム多孔体における炭化アルミニウムの含有量は０質量％となる。しかしながら、ごくわずかではあるがアルミニウム膜中に取り込まれた炭素を含む成分が、前記基材を燃焼除去する際にアルミニウムと反応し、アルミニウム膜中に炭化アルミニウムが形成されてしまう場合がある。また、前記（Ｂ）成分がアルミニウム膜中に取り込まれて炭化アルミニウムが形成される原因となる場合も有り得る。 When an aluminum porous body is produced using the aluminum plating solution according to the embodiment of the present invention, basically, when the base material is burned and removed, the component containing carbon is below the temperature at which aluminum carbide is formed. It is removed from the film. For this reason, the content of aluminum carbide in the aluminum porous body is 0% by mass. However, there is a case where a component containing carbon taken into the aluminum film reacts with aluminum when the base material is burned and removed, and aluminum carbide is formed in the aluminum film. The component (B) may be taken into the aluminum film and cause aluminum carbide to be formed.
（アルミニウム多孔体の製造方法）
　前記アルミニウム多孔体は、三次元網目状構造を有する導電化樹脂成形体の表面に溶融塩電解めっきによってアルミニウム膜を形成して樹脂構造体を製造する工程と、前記樹脂構造体から前記導電化樹脂成形体を除去する工程と、を経ることにより製造することができる。
　以下に各工程を詳述する。 (Method for producing porous aluminum body)
The aluminum porous body includes a step of forming a resin structure by forming an aluminum film on the surface of a conductive resin molded body having a three-dimensional network structure by molten salt electroplating, and the conductive resin from the resin structure. It can manufacture by passing through the process of removing a molded object.
Each step will be described in detail below.
－アルミニウム膜の形成工程－
　この工程は、溶融塩すなわち前記アルミニウムめっき液中で電解めっきを行うことで、三次元網目状構造を有する導電化樹脂成形体の表面にアルミニウム膜を形成する工程である。三次元網目状構造を有する導電化樹脂成形体としては、前述の三次元網目状構造を有する樹脂成形体の表面を導電化処理したものを用いればよい。
　前記アルミニウムめっき液中でアルミニウム膜の形成を行うことで、三次元網目状構造を有する導電化樹脂成形体のように複雑な骨格構造を有する成形体の骨格の表面にも均一に厚いアルミニウム膜を形成することができる。溶融塩電解めっきを行うには、前記導電化樹脂成形体を陰極とし、アルミニウムを陽極として前記アルミニウムめっき液中で直流電流を印加すればよい。 -Aluminum film formation process-
This step is a step of forming an aluminum film on the surface of the conductive resin molding having a three-dimensional network structure by performing electrolytic plating in a molten salt, that is, the aluminum plating solution. What is necessary is just to use what electrically conductively processed the surface of the resin molding which has the above-mentioned three-dimensional network structure as a conductive resin molding which has a three-dimensional network structure.
By forming an aluminum film in the aluminum plating solution, a uniformly thick aluminum film is formed on the surface of the skeleton of a molded body having a complicated skeleton structure such as a conductive resin molded body having a three-dimensional network structure. Can be formed. In order to perform the molten salt electroplating, a direct current may be applied in the aluminum plating solution using the conductive resin molded body as a cathode and aluminum as an anode.
　アルミニウムめっき液中に水分や酸素が混入するとめっき液が劣化するため、めっきは窒素、アルゴン等の不活性ガス雰囲気下で、かつ密閉した環境下で行うことが好ましい。
　また、アルミニウムめっき液の温度は１５℃から１１０℃とすることができ、２５℃から４５℃とすることが好ましい。低温になる程めっき可能な電流密度範囲が狭くなり、導電化樹脂成形体の骨格の表面全体へのめっきが難しくなる。１１０℃以下の範囲でめっきをすることで基材となる導電化樹脂成形体の形状が損なわれる不具合が生じないようにすることができる。
　以上の工程により、表面がアルミニウム膜で、その骨格の芯として前記導電化樹脂成形体を有する樹脂構造体を得ることができる。 When water or oxygen is mixed in the aluminum plating solution, the plating solution deteriorates. Therefore, the plating is preferably performed in an atmosphere of an inert gas such as nitrogen or argon and in a sealed environment.
The temperature of the aluminum plating solution can be 15 ° C to 110 ° C, and preferably 25 ° C to 45 ° C. The lower the temperature, the narrower the current density range that can be plated, and the more difficult it is to plate on the entire surface of the skeleton of the conductive resin molding. By plating in the range of 110 ° C. or lower, it is possible to prevent a problem that the shape of the conductive resin molded body serving as the base material is impaired.
Through the above steps, a resin structure having a surface of an aluminum film and having the conductive resin molded body as the core of the skeleton can be obtained.
－導電化樹脂成形体を除去する工程－
　上記のようにして得られた樹脂構造体を、窒素雰囲気下あるいは大気下等で樹脂が分解される３７０℃以上、好ましくは５００℃以上に加熱する熱処理を行うことで樹脂及び導電層を焼失させ、アルミニウム多孔体を得ることができる。また、この際に、アルミニウム膜中に取り込まれた炭素を含む成分も除去することができる。 -Process for removing conductive resin molding-
The resin structure obtained as described above is subjected to heat treatment at 370 ° C. or higher, preferably 500 ° C. or higher where the resin is decomposed in a nitrogen atmosphere or in the air, and the resin and the conductive layer are burned out. An aluminum porous body can be obtained. At this time, a component containing carbon taken into the aluminum film can also be removed.
　以下、実施例に基づいて本発明をより詳細に説明するが、これらの実施例は例示であって、本発明のアルミニウムめっき液等はこれらに限定されるものではない。本発明の範囲は特許請求の範囲の範囲によって示され、特許請求の範囲の範囲と均等の意味及び範囲内でのすべての変更が含まれる。 Hereinafter, the present invention will be described in more detail based on examples. However, these examples are merely examples, and the aluminum plating solution of the present invention is not limited thereto. The scope of the present invention is defined by the scope of the claims, and includes meanings equivalent to the scope of the claims and all modifications within the scope.
［実施例１］
（アルミニウムめっき液）
　（Ａ）成分として塩化アルミニウム（ＡlＣl3）を、（Ｂ）成分として１－エチル－３－メチルイミダゾリウムクロリド（ＥＭＩＣ）を用い、（Ａ）成分と（Ｂ）成分との混合比がモル比で２：１となるように混合して溶融塩を準備した。この溶融塩に（Ｃ１）成分として試薬のジメチルジステアリルアンモニウムクロリド（東京化成工業株式会社製）を１５ｇ/Ｌの濃度となるように添加してアルミニウムめっき液１を得た。 [Example 1]
(Aluminum plating solution)
Aluminum chloride (AlCl 3 ) is used as the component (A), 1-ethyl-3-methylimidazolium chloride (EMIC) is used as the component (B), and the mixing ratio of the components (A) and (B) is molar ratio. The molten salt was prepared by mixing at 2: 1. To this molten salt, dimethyl distearyl ammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) as a component (C1) was added to a concentration of 15 g / L to obtain an aluminum plating solution 1.
（アルミニウム膜の形成）
　基材として２０×４０×１．０ｍｍの銅板を用い、上記で用意したアルミニウムめっき液１中で、銅板を整流器の陰極側に、対極のアルミニウム板（純度９９．９９％）を陽極側に接続して電圧を印加することで銅板の表面にアルミニウムを電着させた。アルミニウムめっき液１の温度は４５℃となるようにし、また、電流密度は３．０Ａ/ｄｍ2となるように制御した。 (Formation of aluminum film)
Using a copper plate of 20 x 40 x 1.0 mm as the base material, in the aluminum plating solution 1 prepared above, connect the copper plate to the cathode side of the rectifier and the counter electrode aluminum plate (purity 99.99%) to the anode side. Then, aluminum was electrodeposited on the surface of the copper plate by applying a voltage. The temperature of the aluminum plating solution 1 was controlled to be 45 ° C., and the current density was controlled to be 3.0 A / dm 2 .
＜アルミニウム膜の評価＞
（評価方法）
　上記と同様にして５０枚の銅板の表面にアルミニウム膜を形成し、それぞれのアルミニウム膜の表面粗さ（算術平均粗さＲａ）を測定した。
　平面粗さ（算術平均粗さＲａ）は株式会社キーエンス社製のレーザー顕微鏡により測定した。
（評価結果）
　アルミニウム膜の表面の算術平均粗さＲａの平均は０．１１μｍであった。 <Evaluation of aluminum film>
(Evaluation methods)
In the same manner as described above, an aluminum film was formed on the surface of 50 copper plates, and the surface roughness (arithmetic average roughness Ra) of each aluminum film was measured.
The planar roughness (arithmetic average roughness Ra) was measured with a laser microscope manufactured by Keyence Corporation.
(Evaluation results)
The average arithmetic average roughness Ra of the surface of the aluminum film was 0.11 μm.
［実施例２］
＜アルミニウム多孔体の作製＞
（基材表面へのアルミニウム膜の形成）
　上記実施例１で用意したアルミニウムめっき液１を用いて、基材の表面にアルミニウムを電着させて樹脂構造体を作製した。基材には導電化処理をした三次元網目構造を有する樹脂成形体を用いた。樹脂成形体には、厚み１ｍｍ、気孔率９５％、１インチ当たりの気孔数（セル数）約５０個の発泡ウレタン（１００ｍｍ×３０ｍｍ角）を用いた。導電化処理は前記発泡ウレタンをカーボン懸濁液に浸漬して乾燥させることにより行った。カーボン懸濁液の成分は、黒鉛とカーボンブラックを２５％含み、樹脂バインダー、浸透剤、消泡剤を含むものとした。カーボンブラックの粒径は０．５μｍとした。
　そして、この基材を整流器の陰極側に接続し、対極のアルミニウム板（純度９９．９９％）を陽極側に接続した。アルミニウムめっき液１の温度が４５℃となるようにし、また、電流密度が６．０Ａ/ｄｍ2となるように制御した。アルミニウムめっき液は１００ｒｐｍとなるように攪拌した。 [Example 2]
<Preparation of porous aluminum>
(Formation of aluminum film on substrate surface)
Using the aluminum plating solution 1 prepared in Example 1, aluminum was electrodeposited on the surface of the base material to prepare a resin structure. A resin molded body having a three-dimensional network structure subjected to a conductive treatment was used as the base material. As the resin molding, foamed urethane (100 mm × 30 mm square) having a thickness of 1 mm, a porosity of 95%, and a pore number (number of cells) per inch of about 50 was used. The conductive treatment was performed by immersing the urethane foam in a carbon suspension and drying it. The components of the carbon suspension include 25% graphite and carbon black, and include a resin binder, a penetrating agent, and an antifoaming agent. The particle size of carbon black was 0.5 μm.
And this base material was connected to the cathode side of a rectifier, and the aluminum plate (purity 99.99%) of the counter electrode was connected to the anode side. The temperature of the aluminum plating solution 1 was controlled to 45 ° C., and the current density was controlled to 6.0 A / dm 2 . The aluminum plating solution was stirred to 100 rpm.
（基材の除去）
　アルミニウムの目付け量が１４０ｇ／ｍ2となったところで、前記樹脂構造体をアルミニウムめっき液１から取り出し、水洗処理した後に、大気下にて、６１０℃で２０分の熱処理を行った。これにより前記基材が焼失してアルミニウム多孔体１が得られた。 (Removal of substrate)
When the basis weight of aluminum reached 140 g / m 2 , the resin structure was taken out from the aluminum plating solution 1, washed with water, and then heat-treated at 610 ° C. for 20 minutes in the atmosphere. Thereby, the said base material was burned down and the aluminum porous body 1 was obtained.
＜アルミニウム多孔体の評価＞
（評価方法）
　上記と同様の方法によりアルミニウム多孔体１を１５個作製し、それぞれのアルミニウム多孔体の、伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
　各アルミニウム多孔体１の伸びは、ＪＩＳ　Ｚ　２２４１に基づいて引張試験を行うことにより測定した。装置としては、株式会社島津製作所社製のオートグラフを用いた。
　骨格断面のアルミニウム結晶粒径は、前記アルミニウム多孔体１を切断後、その断面を株式会社日立ハイテクノロジーズ社製の走査電子顕微鏡を用いて観察することにより測定した。
　アルミニウム多孔体１に含まれる炭化アルミニウムの量は株式会社島津製作所社製のＸ線回折装置を用いて測定した。 <Evaluation of aluminum porous body>
(Evaluation methods)
Fifteen aluminum porous bodies 1 were produced by the same method as described above, and the elongation, crystal grain size, and aluminum carbide content of each aluminum porous body were measured.
The elongation of each aluminum porous body 1 was measured by conducting a tensile test based on JIS Z 2241. As an apparatus, an autograph manufactured by Shimadzu Corporation was used.
The aluminum crystal grain size of the skeletal cross section was measured by cutting the aluminum porous body 1 and observing the cross section using a scanning electron microscope manufactured by Hitachi High-Technologies Corporation.
The amount of aluminum carbide contained in the porous aluminum body 1 was measured using an X-ray diffractometer manufactured by Shimadzu Corporation.
（評価結果）
　アルミニウム多孔体１の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．８％であり、最も大きいものは３．３％であった。そして、伸びの平均値は２．６％であった。
　また、アルミニウム多孔体１の骨格断面のアルミニウムの平均結晶粒径は３．５μｍであった。更に、アルミニウム多孔体１に含まれる炭化アルミニウムの量は０．３５質量％であった。 (Evaluation results)
The elongation (ratio of displacement to GL) of the porous aluminum body 1 was 1.8% at the smallest and 3.3% at the largest. And the average value of elongation was 2.6%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 1 was 3.5 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 1 was 0.35% by mass.
［実施例３］
　アルミニウムめっき液における（Ｃ１）成分として試薬のドデシルトリメチルアンモニウムクロリド（東京化成工業株式会社製）を用い、その濃度が２０ｇ／Ｌとなるようにした以外は実施例１と同様にしてアルミニウムめっき液２を得た。
　上記アルミニウムめっき液２を用いた以外は実施例２と同様にしてアルミニウム多孔体２を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体２の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．９％であり、最も大きいものは２．８％であった。そして、伸びの平均値は２．３％であった。
　また、アルミニウム多孔体２の骨格断面のアルミニウムの平均結晶粒径は３μｍであった。更に、アルミニウム多孔体２に含まれる炭化アルミニウムの量は０．３４質量％であった。 [Example 3]
The aluminum plating solution 2 was used in the same manner as in Example 1 except that the reagent dodecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C1) in the aluminum plating solution and the concentration thereof was 20 g / L. Got.
Fifteen porous aluminum bodies 2 were produced in the same manner as in Example 2 except that the aluminum plating solution 2 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the porous aluminum body 2 was 1.9% at the smallest and 2.8% at the largest. And the average value of elongation was 2.3%.
The average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 2 was 3 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 2 was 0.34% by mass.
［実施例４］
　アルミニウムめっき液における（Ｃ１）成分として試薬のオクチルトリメチルアンモニウムクロリド（東京化成工業株式会社製）を用い、その濃度が１５ｇ／Ｌとなるようにした以外は実施例１と同様にしてアルミニウムめっき液３を得た。
　上記アルミニウムめっき液３を用いた以外は実施例２と同様にしてアルミニウム多孔体３を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体３の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．６％であり、最も大きいものは３．０％であった。そして、伸びの平均値は２．５％であった。
　また、アルミニウム多孔体３の骨格断面のアルミニウムの平均結晶粒径は３．２μｍであった。更に、アルミニウム多孔体３に含まれる炭化アルミニウムの量は０．３７質量％であった。 [Example 4]
The aluminum plating solution 3 was used in the same manner as in Example 1 except that the reagent octyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C1) in the aluminum plating solution, and the concentration was 15 g / L. Got.
Fifteen aluminum porous bodies 3 were produced in the same manner as in Example 2 except that the aluminum plating solution 3 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation of aluminum porous body 3 (ratio of displacement to GL) was 1.6% at the smallest and 3.0% at the largest. And the average value of elongation was 2.5%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 3 was 3.2 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 3 was 0.37% by mass.
［実施例５］
　アルミニウムめっき液における（Ｃ１）成分として試薬のトリブチルテトラデシルホスホニウムクロリド（関東化学株式会社製）を用い、その濃度が５．０ｇ／Ｌとなるようにした以外は実施例１と同様にしてアルミニウムめっき液４を得た。
　上記アルミニウムめっき液４を用いた以外は実施例２と同様にしてアルミニウム多孔体４を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体４の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．８％であり、最も大きいものは３．４％であった。そして、伸びの平均値は２．８％であった。
　また、アルミニウム多孔体４の骨格断面のアルミニウムの平均結晶粒径は３．５μｍであった。更に、アルミニウム多孔体４に含まれる炭化アルミニウムの量は０．３４質量％であった。 [Example 5]
Aluminum plating was carried out in the same manner as in Example 1 except that the reagent tributyltetradecylphosphonium chloride (manufactured by Kanto Chemical Co., Inc.) was used as the component (C1) in the aluminum plating solution, and the concentration was 5.0 g / L. Liquid 4 was obtained.
Fifteen aluminum porous bodies 4 were produced in the same manner as in Example 2 except that the aluminum plating solution 4 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body 4 was 1.8% at the smallest and 3.4% at the largest. And the average value of elongation was 2.8%.
The average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 4 was 3.5 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 4 was 0.34% by mass.
［実施例６］
　アルミニウムめっき液に（Ｃ１）成分として試薬のジメチルステアリルアミン（東京化成工業株式会社製）を用い、その濃度が１５ｇ／Ｌとなるようにした以外は実施例１と同様にしてアルミニウムめっき液５を得た。
　上記アルミニウムめっき液５を用いた以外は実施例２と同様にしてアルミニウム多孔体５を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体５の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．７％であり、最も大きいものは２．８％であった。そして、伸びの平均値は２．２％であった。
　また、アルミニウム多孔体５の骨格断面のアルミニウムの平均結晶粒径は４．０μｍであった。更に、アルミニウム多孔体５に含まれる炭化アルミニウムの量は０．２８質量％であった。 [Example 6]
The aluminum plating solution 5 was prepared in the same manner as in Example 1 except that the reagent dimethylstearylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (C1) for the aluminum plating solution, and the concentration was 15 g / L. Obtained.
Fifteen aluminum porous bodies 5 were produced in the same manner as in Example 2 except that the aluminum plating solution 5 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the porous aluminum body 5 was 1.7% at the smallest and 2.8% at the largest. And the average value of elongation was 2.2%.
The average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 5 was 4.0 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 5 was 0.28% by mass.
［実施例７］
　実施例１において、（Ｃ１）成分の濃度が１．０ｇ／Ｌとなるように添加した以外は実施例１と同様にしてアルミニウムめっき液６を得た。
　上記アルミニウムめっき液６を用いた以外は実施例２と同様にしてアルミニウム多孔体６を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体６の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．５％であり、最も大きいものでも２．７％であった。そして、伸びの平均値は２．１％であった。
　また、アルミニウム多孔体６の骨格断面のアルミニウムの平均結晶粒径は４．０μｍであった。更に、アルミニウム多孔体６に含まれる炭化アルミニウムの量は０．２４質量％であった。 [Example 7]
In Example 1, an aluminum plating solution 6 was obtained in the same manner as in Example 1, except that the concentration of the component (C1) was 1.0 g / L.
Fifteen aluminum porous bodies 6 were produced in the same manner as in Example 2 except that the aluminum plating solution 6 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation of aluminum porous body 6 (ratio of displacement relative to GL) was 1.5% at the smallest and 2.7% at the largest. And the average value of elongation was 2.1%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 6 was 4.0 μm. Further, the amount of aluminum carbide contained in the aluminum porous body 6 was 0.24% by mass.
［実施例８］
　実施例１において、（Ｃ１）成分の濃度が４５ｇ／Ｌとなるように添加した以外は実施例１と同様にしてアルミニウムめっき液７を得た。
　上記アルミニウムめっき液７を用いた以外は実施例２と同様にしてアルミニウム多孔体７を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体７の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．９％であり、最も大きいものでも３．６％であった。そして、伸びの平均値は２．７％であった。
　また、アルミニウム多孔体７の骨格断面のアルミニウムの平均結晶粒径は３．２μｍであった。更に、アルミニウム多孔体７に含まれる炭化アルミニウムの量は０．３９質量％であった。 [Example 8]
In Example 1, an aluminum plating solution 7 was obtained in the same manner as in Example 1 except that the component (C1) was added so as to have a concentration of 45 g / L.
Fifteen porous aluminum bodies 7 were produced in the same manner as in Example 2 except that the aluminum plating solution 7 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the porous aluminum body 7 was 1.9% at the smallest and 3.6% at the largest. And the average value of elongation was 2.7%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 7 was 3.2 μm. Further, the amount of aluminum carbide contained in the aluminum porous body 7 was 0.39% by mass.
［比較例１］
　アルミニウムめっき液における（Ｃ１）成分として１，１０－フェナントロリン一水和物を用い、その濃度が０．５ｇ／Ｌとなるようにした以外は実施例１と同様にしてアルミニウムめっき液Ａを得た。
　上記アルミニウムめっき液Ａを用いた以外は実施例２と同様にしてアルミニウム多孔体Ａを１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体Ａの伸び（ＧＬに対する変位量の割合）は、最も小さいもので０．６％であり、最も大きいものでも１．２％であった。そして、伸びの平均値は０．８％であった。
　また、アルミニウム多孔体Ａの骨格断面のアルミニウムの平均結晶粒径は１．０μｍであった。更に、アルミニウム多孔体Ａに含まれる炭化アルミニウムの量は１．２質量％であった。 [Comparative Example 1]
An aluminum plating solution A was obtained in the same manner as in Example 1 except that 1,10-phenanthroline monohydrate was used as the component (C1) in the aluminum plating solution and the concentration was 0.5 g / L. .
Fifteen aluminum porous bodies A were produced in the same manner as in Example 2 except that the aluminum plating solution A was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body A was 0.6% at the smallest and 1.2% even at the largest. And the average value of elongation was 0.8%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body A was 1.0 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body A was 1.2% by mass.
［比較例２］
　実施例１において、（Ｃ１）成分の濃度が０．６ｇ／Ｌとなるように添加した以外は実施例１と同様にしてアルミニウムめっき液Ｂを得た。
　上記アルミニウムめっき液Ｂを用いた以外は実施例２と同様にしてアルミニウム多孔体Ｂを１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体Ｂの伸び（ＧＬに対する変位量の割合）は、最も小さいもので０．５％であり、最も大きいものでも１．３％であった。そして、伸びの平均値は０．７％であった。
　また、アルミニウム多孔体Ｂの骨格断面のアルミニウムの平均結晶粒径は４．０μｍであった。更に、アルミニウム多孔体Ｂに含まれる炭化アルミニウムの量は０．２４質量％であった。 [Comparative Example 2]
In Example 1, an aluminum plating solution B was obtained in the same manner as in Example 1 except that the component (C1) was added so as to have a concentration of 0.6 g / L.
Fifteen porous aluminum objects B were produced in the same manner as in Example 2 except that the aluminum plating solution B was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation of aluminum porous body B (ratio of displacement to GL) was 0.5% at the smallest and 1.3% at the largest. And the average value of elongation was 0.7%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body B was 4.0 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body B was 0.24% by mass.
［比較例３］
　実施例１において、（Ｃ１）成分の濃度が５０ｇ／Ｌとなるように添加した以外は実施例１と同様にしてアルミニウムめっき液Ｃを得た。
　上記アルミニウムめっき液Ｃを用いた以外は実施例２と同様にしてアルミニウム多孔体Ｃを１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体Ｃの伸び（ＧＬに対する変位量の割合）は、最も小さいもので０．８％であり、最も大きいものでも１．２％であった。そして、伸びの平均値は１．０％であった。
　また、アルミニウム多孔体Ｃの骨格断面のアルミニウムの平均結晶粒径は１．２μｍであった。更に、アルミニウム多孔体Ｃに含まれる炭化アルミニウムの量は０．８４質量％であった。 [Comparative Example 3]
In Example 1, an aluminum plating solution C was obtained in the same manner as in Example 1 except that the component (C1) was added so that the concentration thereof was 50 g / L.
Fifteen porous aluminum objects C were produced in the same manner as in Example 2 except that the aluminum plating solution C was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body C was 0.8% at the smallest and 1.2% even at the largest. And the average value of elongation was 1.0%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body C was 1.2 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body C was 0.84% by mass.
［実施例９］
　上記実施例１で用意したアルミニウムめっき液１を１Ｌ用意し、実施例２と同様にしてアルミニウム多孔体を作製した。そして、３．６Ａの電流が流れるように制御しつつ、４２時間、アルミニウムめっきを行った。なお、アルミニウムの目付量が１４０ｇ／ｍ2となったところで基材を交換してアルミニウムめっきを続けた。
　４２時間後に得られたアルミニウム多孔体２’の伸び（ＧＬに対する変位量の割合）を測定した。同様の方法によりアルミニウム多孔体２’を２０個作製した。伸びは、最も小さいものは１．２％であり、最も大きいものでも１．６％に低下していた。伸びの平均値は１．３％になっていた。
　このときのアルミニウムめっき液をアルミニウムめっき液１’とし、液体クロマトグラフィー質量分析法（ＬＣ／ＭＳ）によって成分を分析した。その結果、当初含まれていた（Ｃ１）成分における側鎖のアルキル基が短くなっており、炭素数が７以下のアルキル基を側鎖として有する（Ｃ２）成分に変化していることが確認された。（Ｃ２）成分の濃度は１５ｇ／Ｌであった。
（アルミニウムめっき液）
　上記のアルミニウムめっき液１’に（Ｄ）成分としてステアリルクロリド（東京化成工業社製）を１ｇ／Ｌの濃度となるように添加してアルミニウムめっき液８を作製した。
＜アルミニウム多孔体の作製＞
　上記アルミニウムめっき液８を用いた以外は実施例２と同様にしてアルミニウム多孔体８を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体８の伸び（ＧＬに対する変位量の割合）は、最も小さいもので２．０％であり、最も大きいものは３．５％であった。そして、伸びの平均値は２．３％であった。
　また、アルミニウム多孔体８の骨格断面のアルミニウムの平均結晶粒径は４.２μｍであった。更に、アルミニウム多孔体８に含まれる炭化アルミニウムの量は０．３質量％であった。 [Example 9]
1 L of the aluminum plating solution 1 prepared in Example 1 was prepared, and an aluminum porous body was produced in the same manner as in Example 2. And aluminum plating was performed for 42 hours, controlling so that the electric current of 3.6A might flow. When the basis weight of aluminum reached 140 g / m 2 , the substrate was replaced and aluminum plating was continued.
The elongation (ratio of displacement to GL) of the aluminum porous body 2 ′ obtained after 42 hours was measured. Twenty porous aluminum bodies 2 ′ were produced by the same method. The smallest growth was 1.2%, and the largest growth was reduced to 1.6%. The average value of elongation was 1.3%.
The aluminum plating solution at this time was designated as an aluminum plating solution 1 ′, and the components were analyzed by liquid chromatography mass spectrometry (LC / MS). As a result, it was confirmed that the alkyl group in the side chain in the (C1) component originally included was shortened and changed to the (C2) component having an alkyl group having 7 or less carbon atoms as the side chain. It was. The concentration of component (C2) was 15 g / L.
(Aluminum plating solution)
An aluminum plating solution 8 was prepared by adding stearyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) as a component (D) to the aluminum plating solution 1 ′ so as to have a concentration of 1 g / L.
<Preparation of porous aluminum>
Fifteen aluminum porous bodies 8 were produced in the same manner as in Example 2 except that the aluminum plating solution 8 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (percentage of displacement with respect to GL) of the aluminum porous body 8 was 2.0% at the smallest and 3.5% at the largest. And the average value of elongation was 2.3%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 8 was 4.2 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 8 was 0.3% by mass.
［実施例１０］
　（Ｄ）成分であるステアリルクロリドの濃度を８．３ｇ／Ｌとした以外は実施例９と同様にしてアルミニウムめっき液９を作製した。
　上記アルミニウムめっき液９を用いた以外は実施例２と同様にしてアルミニウム多孔体９を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体９の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．６％であり、最も大きいものは２．５％であった。そして、伸びの平均値は１．８％であった。
　また、アルミニウム多孔体９の骨格断面のアルミニウムの平均結晶粒径は３.２μｍであった。更に、アルミニウム多孔体９に含まれる炭化アルミニウムの量は０．６質量％であった。 [Example 10]
Aluminum plating solution 9 was produced in the same manner as in Example 9 except that the concentration of stearyl chloride as component (D) was changed to 8.3 g / L.
Fifteen aluminum porous bodies 9 were produced in the same manner as in Example 2 except that the aluminum plating solution 9 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body 9 was 1.6% at the smallest and 2.5% at the largest. And the average value of elongation was 1.8%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 9 was 3.2 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 9 was 0.6% by mass.
［実施例１１］
　アルミニウムめっき液における（Ｄ）成分としてテトラデカン（和光純薬工業社製）を用い、その濃度が１ｇ／Ｌとなるようにした以外は実施例１０と同様にしてアルミニウムめっき液１０を得た。
　上記アルミニウムめっき液１０を用いた以外は実施例２と同様にしてアルミニウム多孔体１０を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体１０の伸び（ＧＬに対する変位量の割合）は、最も小さいもので２．５％であり、最も大きいものは３．９％であった。そして、伸びの平均値は２．８％であった。
　また、アルミニウム多孔体１０の骨格断面のアルミニウムの平均結晶粒径は４．０μｍであった。更に、アルミニウム多孔体１０に含まれる炭化アルミニウムの量は０．３質量％であった。 [Example 11]
An aluminum plating solution 10 was obtained in the same manner as in Example 10 except that tetradecane (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the component (D) in the aluminum plating solution and the concentration thereof was 1 g / L.
Fifteen aluminum porous bodies 10 were produced in the same manner as in Example 2 except that the aluminum plating solution 10 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the porous aluminum body 10 was 2.5% at the smallest and 3.9% at the largest. And the average value of elongation was 2.8%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 10 was 4.0 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 10 was 0.3% by mass.
［実施例１２］
　アルミニウムめっき液における（Ｄ）成分としてデセン（東京化成工業社製）を用い、その濃度が０．８ｇ／Ｌとなるようにした以外は実施例１０と同様にしてアルミニウムめっき液１１を得た。
　上記アルミニウムめっき液１１を用いた以外は実施例２と同様にしてアルミニウム多孔体１１を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体１１の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．８％であり、最も大きいものは２．８％であった。そして、伸びの平均値は２．２％であった。
　また、アルミニウム多孔体１１の骨格断面のアルミニウムの平均結晶粒径は３.６μｍであった。更に、アルミニウム多孔体１１に含まれる炭化アルミニウムの量は０．３４質量％であった。 [Example 12]
An aluminum plating solution 11 was obtained in the same manner as in Example 10 except that decene (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (D) in the aluminum plating solution, and the concentration was adjusted to 0.8 g / L.
Fifteen aluminum porous bodies 11 were produced in the same manner as in Example 2 except that the aluminum plating solution 11 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body 11 was 1.8% at the smallest and 2.8% at the largest. And the average value of elongation was 2.2%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 11 was 3.6 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 11 was 0.34% by mass.
［実施例１３］
　アルミニウムめっき液における（Ｄ）成分としてジクロロオクタン（東京化成工業社製）を用い、その濃度が３．０ｇ／Ｌとなるようにした以外は実施例１０と同様にしてアルミニウムめっき液１２を得た。
　上記アルミニウムめっき液１２を用いた以外は実施例２と同様にしてアルミニウム多孔体１２を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体１２の伸び（ＧＬに対する変位量の割合）は、最も小さいもので２．１％であり、最も大きいものは２．８％であった。そして、伸びの平均値は２．４％であった。
　また、アルミニウム多孔体１２の骨格断面のアルミニウムの平均結晶粒径は６．０μｍであった。更に、アルミニウム多孔体１２に含まれる炭化アルミニウムの量は０．５２質量％であった。 [Example 13]
An aluminum plating solution 12 was obtained in the same manner as in Example 10 except that dichlorooctane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (D) in the aluminum plating solution and the concentration thereof was 3.0 g / L. .
Fifteen aluminum porous bodies 12 were produced in the same manner as in Example 2 except that the aluminum plating solution 12 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body 12 was 2.1% at the smallest and 2.8% at the largest. And the average value of elongation was 2.4%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 12 was 6.0 μm. Further, the amount of aluminum carbide contained in the aluminum porous body 12 was 0.52% by mass.
［実施例１４］
　アルミニウムめっき液における（Ｄ）成分としてクロロプロパン（東京化成工業社製）を用い、その濃度が３ｇ／Ｌとなるようにした以外は実施例１０と同様にしてアルミニウムめっき液１３を得た。
　上記アルミニウムめっき液１３を用いた以外は実施例２と同様にしてアルミニウム多孔体１３を１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体１３の伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．７％であり、最も大きいものは２．９％であった。そして、伸びの平均値は２．３％であった。
　また、アルミニウム多孔体１３の骨格断面のアルミニウムの平均結晶粒径は１２μｍであった。更に、アルミニウム多孔体１３に含まれる炭化アルミニウムの量は０．４６質量％であった。 [Example 14]
An aluminum plating solution 13 was obtained in the same manner as in Example 10 except that chloropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the component (D) in the aluminum plating solution and the concentration thereof was 3 g / L.
Fifteen aluminum porous bodies 13 were produced in the same manner as in Example 2 except that the aluminum plating solution 13 was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body 13 was 1.7% at the smallest and 2.9% at the largest. And the average value of elongation was 2.3%.
The average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 13 was 12 μm. Further, the amount of aluminum carbide contained in the aluminum porous body 13 was 0.46% by mass.
［比較例４］
　実施例９において、（Ｄ）成分の濃度が０．３ｇ／Ｌとなるように添加した以外は実施例９と同様にしてアルミニウムめっき液Ｄを得た。
　上記アルミニウムめっき液Ｄを用いた以外は実施例２と同様にしてアルミニウム多孔体Ｄを１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体Ｄの伸び（ＧＬに対する変位量の割合）は、最も小さいもので０．８％であり、最も大きいものでも１．６％であった。そして、伸びの平均値は１．１％であった。
　また、アルミニウム多孔体Ｄの骨格断面のアルミニウムの平均結晶粒径は４．８μｍであった。更に、アルミニウム多孔体Ｄに含まれる炭化アルミニウムの量は０．１２質量％であった。 [Comparative Example 4]
In Example 9, an aluminum plating solution D was obtained in the same manner as in Example 9 except that the concentration of the component (D) was 0.3 g / L.
Fifteen porous aluminum bodies D were produced in the same manner as in Example 2 except that the aluminum plating solution D was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body D was 0.8% at the smallest and 1.6% even at the largest. And the average value of elongation was 1.1%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body D was 4.8 μm. Further, the amount of aluminum carbide contained in the aluminum porous body D was 0.12% by mass.
［比較例５］
　実施例９において、（Ｄ）成分の濃度が９ｇ／Ｌとなるように添加した以外は実施例９と同様にしてアルミニウムめっき液Ｅを得た。
　上記アルミニウムめっき液Ｅを用いた以外は実施例２と同様にしてアルミニウム多孔体Ｅを１５個作製し、それぞれの伸び、結晶粒径、炭化アルミニウムの含有量を測定した。
（評価結果）
　アルミニウム多孔体Ｅの伸び（ＧＬに対する変位量の割合）は、最も小さいもので１．２％であり、最も大きいものでも１．８％であった。そして、伸びの平均値は１．４％であった。
　また、アルミニウム多孔体Ｅの骨格断面のアルミニウムの平均結晶粒径は０．６μｍであった。更に、アルミニウム多孔体Ｅに含まれる炭化アルミニウムの量は２．６質量％であった。 [Comparative Example 5]
In Example 9, an aluminum plating solution E was obtained in the same manner as in Example 9 except that the concentration of the component (D) was added so as to be 9 g / L.
Fifteen aluminum porous bodies E were produced in the same manner as in Example 2 except that the aluminum plating solution E was used, and the elongation, crystal grain size, and aluminum carbide content were measured.
(Evaluation results)
The elongation (ratio of displacement to GL) of the aluminum porous body E was 1.2% at the smallest and 1.8% even at the largest. And the average value of elongation was 1.4%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body E was 0.6 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body E was 2.6% by mass.

Claims (7)

  1. 　基材表面にアルミニウムを電着させることが可能なアルミニウムめっき液であって、
    　前記アルミニウムめっき液は、
    （Ａ）アルミニウムハロゲン化物と、
    （Ｂ）アルキルイミダゾリウムハロゲン化物、アルキルピリジニウムハロゲン化物及び尿素化合物からなる群より選択されるいずれか一種以上の化合物と、
    （Ｃ１）アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上と、
    を成分として含み、
    　前記（Ｃ１）成分は、炭素数が８以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有し、
    　前記（Ａ）成分と前記（Ｂ）成分の混合比はモル比で１：１～３：１の範囲にあり、
    　前記（Ｃ１）成分の濃度が１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下である
    アルミニウムめっき液。     An aluminum plating solution capable of electrodepositing aluminum on the substrate surface,
    The aluminum plating solution is
    (A) an aluminum halide;
    (B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds;
    (C1) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound;
    As an ingredient,
    The component (C1) has a linear or branched alkyl group having 8 to 36 carbon atoms as at least one side chain,
    The mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio,
    An aluminum plating solution in which the concentration of the component (C1) is 1.0 g / L or more and 45 g / L or less.
  2. 　基材表面にアルミニウムを電着させることが可能なアルミニウムめっき液であって、
    　前記アルミニウムめっき液は、
    （Ａ）アルミニウムハロゲン化物と、
    （Ｂ）アルキルイミダゾリウムハロゲン化物、アルキルピリジニウムハロゲン化物及び尿素化合物からなる群より選択されるいずれか一種以上の化合物と、
    （Ｃ２）アンモニウム塩、ホスホニウム塩、スルホニウム塩、アミン化合物、ホスフィン化合物及びスルフィド化合物からなる群より選択されるいずれか一種以上と、
    （Ｄ）ハロゲン化アルキル、アルキン、アルケン及びアルカンからなる群より選択されるいずれか一種以上と、
    を成分として含み、
    　前記（Ｃ２）成分は、炭素数が１以上、３６以下の直鎖状もしくは分岐を有するアルキル基を少なくとも１つの側鎖として有し、
    　前記（Ｄ）成分は、炭素数が３以上、３６以下であって、直鎖状もしくは分岐を有する化合物であり、
    　前記（Ａ）成分と前記（Ｂ）成分の混合比はモル比で１：１～３：１の範囲にあり、
    　前記（Ｃ２）成分の濃度は１．０ｇ／Ｌ以上、４５ｇ／Ｌ以下であり、
    　前記（Ｄ）成分の濃度は０．５ｇ／Ｌ以上、８．５ｇ／Ｌ以下である
    アルミニウムめっき液。     An aluminum plating solution capable of electrodepositing aluminum on the substrate surface,
    The aluminum plating solution is
    (A) an aluminum halide;
    (B) any one or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds;
    (C2) any one or more selected from the group consisting of ammonium salt, phosphonium salt, sulfonium salt, amine compound, phosphine compound and sulfide compound;
    (D) any one or more selected from the group consisting of alkyl halides, alkynes, alkenes and alkanes;
    As an ingredient,
    The component (C2) has a linear or branched alkyl group having 1 to 36 carbon atoms as at least one side chain,
    The component (D) is a compound having 3 to 36 carbon atoms and having a linear or branched structure,
    The mixing ratio of the component (A) and the component (B) is in the range of 1: 1 to 3: 1 by molar ratio,
    The concentration of the component (C2) is 1.0 g / L or more and 45 g / L or less,
    The concentration of the component (D) is an aluminum plating solution that is 0.5 g / L or more and 8.5 g / L or less.
  3. 　前記（Ａ）成分が塩化アルミニウムであり、かつ前記（Ｂ）成分が１－エチル－３－メチルイミダゾリウムクロリドである請求項１又は請求項２に記載のアルミニウムめっき液。 3. The aluminum plating solution according to claim 1, wherein the component (A) is aluminum chloride and the component (B) is 1-ethyl-3-methylimidazolium chloride.
  4. 　請求項１から請求項３のいずれか一項に記載のアルミニウムめっき液を用いて基材の表面にアルミニウムを電着させるアルミニウム膜の製造方法。 A method for producing an aluminum film, in which aluminum is electrodeposited on the surface of a substrate using the aluminum plating solution according to any one of claims 1 to 3.
  5. 　請求項１から請求項３のいずれか一項に記載のアルミニウムめっき液を用いて得られたアルミニウム多孔体であって、三次元網目状構造を有し、伸びが１．５％以上であるアルミニウム多孔体。 An aluminum porous body obtained using the aluminum plating solution according to any one of claims 1 to 3, wherein the aluminum porous body has a three-dimensional network structure and has an elongation of 1.5% or more. Porous body.
  6. 　骨格の断面における結晶粒径が１μｍ以上、５０μｍ以下である請求項５に記載のアルミニウム多孔体。 The porous aluminum body according to claim 5, wherein the crystal grain size in the cross section of the skeleton is 1 μm or more and 50 μm or less.
  7. 　炭化アルミニウムの含有量が０．８質量％以下である請求項５又は請求項６に記載のアルミニウム多孔体。 The aluminum porous body according to claim 5 or 6, wherein the content of aluminum carbide is 0.8 mass% or less.
PCT/JP2015/066132 2014-06-24 2015-06-04 Alluminum plating solution, aluminum film manufacturing method, and porous aluminum object WO2015198819A1 (en)

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