JP2017137517A - Aluminum plating solution, production method of aluminum plating film, and aluminum porous body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aluminum plating solution enabling an aluminum film having a smooth surface and excellent elongation to be continuously produced.SOLUTION: The aluminum plating solution is provided that enables aluminum to be electro-deposited on a surface of a substrate. The aluminum plating solution includes, as components, an aluminum halogenide (A), any one or more type of compounds (B) selected from a group consisting of an alkyl imidazolium halogenide, an alkyl pyridinium halogenide, and a urea compound, and an organic compound (C) that is an organic compound containing a benzene ring, is a solid at a room temperature, and has constituent elements which are any one or more type selected from the group consisting of hydrogen, carbon and halogen atoms, a blend ratio of the component (A) and the component (B) being in the range of 1:1-3:1 by a molar ratio, and the concentration of the component (C) being 0.10 g/L or more and 20 g/L or less.SELECTED DRAWING: None

Description

  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 nontoxicity, and is widely used for plating on metal products and the like. However, since aluminum has a high affinity for oxygen and a lower oxidation-reduction potential than hydrogen, it is difficult to perform electroplating in an aqueous plating bath.

  For this reason, as a method of 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.

In order to solve this problem, JP 2012-144663 A (Patent Document 1) discloses organic chloride salts such as 1-ethyl-3-methylimidazolium chloride (EMIC) and 1-butylpyridinium chloride (BPC) and 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.

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 that the concentration is 0.25 g / L to 7.0 g / L. Have been described.

  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.

  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. With respect to such a problem, in Japanese Patent Application Laid-Open No. 2014-058715 (Patent Document 2), 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.

JP 2012-144663 A JP 2014-058715 A

  As described in Patent Document 1, while adding 1,10-phenanthroline monohydrate to the aluminum plating solution and 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.

  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.

  Accordingly, 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 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;
(C) an organic compound containing a benzene ring, which is a solid at room temperature and whose constituent elements are any one or more selected from the group consisting of hydrogen, carbon, oxygen and halogen atoms;
As an ingredient,
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 (C) is 0.10 g / L or more and 20 g / L or less.

  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.

[Description of Embodiment of the Present Invention]
First, embodiments of the present invention will be listed and described.
(1) An aluminum plating solution according to an aspect of the present invention is an aluminum plating solution capable of electrodepositing aluminum on a substrate surface, and the aluminum plating solution includes (A) an aluminum halide and ( B) Any one or more compounds selected from the group consisting of alkyl imidazolium halides, alkyl pyridinium halides and urea compounds, and (C) an organic compound containing a benzene ring, which is solid at room temperature An organic compound that is one or more selected from the group consisting of hydrogen, carbon, oxygen, and halogen atoms as a component, and the mixing ratio of the component (A) and the component (B) is a molar ratio. An aluminum plating solution in the range of 1: 1 to 3: 1 and having a concentration of the component (C) of 0.10 g / L or more and 20 g / L or less. It is.
According to the aspect of the invention described in (1) above, an aluminum plating solution capable of continuously producing an aluminum film having a smooth surface and excellent elongation can be provided.
The room temperature means an atmosphere of 0 ° C. or higher and 25 ° C. or lower.

(2) In the aluminum plating solution described in (1) above, the component (A) is preferably aluminum chloride, and the component (B) is preferably 1-ethyl-3-methylimidazolium chloride.
According to the aspect of the invention described in (2) above, it is possible to provide an aluminum plating solution capable of continuously and stably obtaining an aluminum film excellent in surface smoothness.

(3) A method for producing an aluminum film according to an aspect of the present invention is 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 (1) or (2) above. It is.
According to the aspect of the invention as described in said (3), the aluminum film which is excellent in surface smoothness and excellent in elongation can be provided.

(4) An aluminum porous body according to one aspect of the present invention is an aluminum porous body obtained using the aluminum plating solution according to (1) or (2) above, and has a three-dimensional network structure. , A porous aluminum body having an elongation of 1.5% or more.
Since the porous aluminum body described in the above (4) 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).

(5) The porous aluminum body described in (4) above preferably has a crystal grain size in the cross section of the skeleton of 1 μm or more and 20 μm or less.
Since the aluminum porous body described in the above (5) has a large crystal grain size, it is an aluminum porous body that is soft and excellent in elongation.

(6) The aluminum porous body according to (4) or (5) preferably has an aluminum carbide content of 0.8 mass% or less.
Since the aluminum porous body described in the above (6) 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.

[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.

<Aluminum plating solution>
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 film during the formation of the aluminum film.

As a result of further studies, the present inventors have found that the component (C) is effective as an additive that contributes to the smoothness of the aluminum film and is not taken into the aluminum film.
That is, the aluminum plating solution according to the embodiment of the present invention can be aluminum plated obtained by mixing at least the following components (A) to (C) as described above.
Component (A): Aluminum halide (B) Component: One or more compounds selected from the group consisting of alkylimidazolium halides, alkylpyridinium halides, and urea compounds (C) Component: Organic compounds containing a benzene ring An organic compound that is solid at room temperature and whose constituent elements are one or more selected from the group consisting of hydrogen, carbon, oxygen, and halogen atoms

  The aluminum plating solution according to the embodiment of the present invention may contain other components as unavoidable 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). 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.

  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.

  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.

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.

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。

However, in Formula (1), R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and may be the same or different.
Among the above urea compounds, urea and dimethylurea can be particularly preferably used.

The aluminum plating solution has an aluminum film on the surface of the base material by making the mixing ratio of the component (A) and the component (B) in a molar ratio of 1: 1 to 3: 1. 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.

The component (C) is an organic compound containing a benzene ring, which is a solid at room temperature, and whose constituent element is at least one selected from the group consisting of hydrogen, carbon, oxygen and halogen atoms. .
Since the organic compound of component (C) is a solid at room temperature, it has a high flash point and can improve safety during handling.

Moreover, as an element which comprises the organic compound of the said (C) component, although a halogen atom and an oxygen atom (O) may be contained, a nitrogen atom (N), a sulfur atom (S), a phosphorus atom (P ) Is not effective. Further, the organic compound as the component (C) needs to contain a benzene ring.
Specific examples of the component (C) include diphenylmethane, benzophenone, benzoic acid, triphenylmethane, trityl chloride, and quinizarin.

When the concentration of the component (C) in the aluminum plating solution is 0.10 g / L or more and 20 g / L or less, a smooth and excellent aluminum film can be formed. If the concentration of the component (C) is less than 0.10 g / L, the aluminum film cannot be sufficiently smoothed, and if it exceeds 20 g / L, the component (C) is taken into the aluminum film. However, the aluminum film becomes brittle and has little elongation. The concentration of the component (C) is preferably 0.5 g / L or more and 15 g / L or less, and more preferably 1.0 g / L or more and 10 g / L or less.
In addition, since the said (C) component is not taken in in an aluminum film, the density | concentration of (C) component is 0.00 at the time of manufacture of an aluminum plating solution, ie, the said (A)-(C) component being mixed. If it is in the range of 10 g / L or more and 20 g / L, it is not necessary to newly add the component (C) during the subsequent plating operation.

  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.

<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.

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.

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.
By the method for producing an aluminum film according to the embodiment of the present invention, a smooth aluminum film having a surface arithmetic average roughness (Ra) of about 0.25 μm or less can be produced.

  The base material 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.

  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.

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”.

  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. Urethane foam is preferable in terms of pore uniformity and availability, and urethane foam is preferable in that a material 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.

The porosity of the porous body is defined by the following equation.
Porosity = (1− (weight of porous material [g] / (volume of porous material [cm ³ ] × material density))) × 100 [%]
The pore diameter is an average of the average pore diameter = 25.4 mm / cell count by enlarging the surface of the resin molded body with a micrograph and counting the number of pores per inch (25.4 mm) as the number of cells. Find the value.

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.

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.

<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.

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.

  The crystal grain size in the cross section of the skeleton of the aluminum porous body is preferably 1 μm or more and 20 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 20 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 aluminum porous body is more preferably 1.5 μm or more and 15 μm or less, and further preferably 2 μm or more and 10 μm or less.

  By using the aluminum plating solution, an aluminum porous body having a relatively large crystal grain size can be obtained. 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 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.

  When the porous aluminum body is manufactured using the aluminum plating solution according to the embodiment of the present invention, basically, the component (C) is not taken into the aluminum film. The aluminum content is 0% by mass. However, the component (C) may be entangled in the aluminum film, or the component (B) may be entangled in the aluminum film, although it is very slight. In this case, when the base material is burned and removed, the component (B) or (C) taken into the aluminum film reacts with aluminum to become aluminum carbide, so that the aluminum carbide is contained in the aluminum film. Will be formed.

(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.

-Aluminum plating 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 the aluminum plating film in the aluminum plating solution, the aluminum film is uniformly thick even on the surface of the skeleton of the 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.

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.

-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.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, these Examples are illustrations, Comprising: The aluminum plating solution of this invention etc. are not limited to these. 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.

[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, the reagent diphenylmethane (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a component (C) to a concentration of 1.0 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 .

<Evaluation of aluminum film>
(Evaluation method)
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 0.14 μm.

[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.

(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.

<Evaluation of aluminum porous body>
(Evaluation method)
Ten 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 the aluminum porous body was measured by performing 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.

(Evaluation results)
The elongation of aluminum porous body 1 (ratio of displacement to GL) was 1.8% at the smallest and 3.4% 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 1 was 3.5 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 1 was 0.42% by mass.

[Example 3]
The aluminum plating solution 2 was used in the same manner as in Example 1 except that the reagent benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the component (C) in the aluminum plating solution, and the concentration was 5.0 g / L. Got.
Ten aluminum porous 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 of aluminum porous body 2 (ratio of displacement to GL) was 1.5% at the smallest and 2.2% 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 2 was 2.3 μm. Further, the amount of aluminum carbide contained in the aluminum porous body 2 was 0.40% by mass.

[Example 4]
The aluminum plating solution 3 was used in the same manner as in Example 1 except that the reagent quinizarin (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the component (C) in the aluminum plating solution, and the concentration was 0.50 g / L. Got.
Ten 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 (ratio of displacement with respect to GL) of the aluminum porous body 3 was 1.7% at the smallest and 2.4% at the largest. And the average value of elongation was 1.9%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 3 was 3.1 μm. Further, the amount of aluminum carbide contained in the aluminum porous body 3 was 0.45% by mass.

[Example 5]
In Example 1, an aluminum plating solution 4 was obtained in the same manner as in Example 1, except that the concentration of the component (C) was added to be 0.10 g / L.
Ten 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 1.5% at the smallest and 2.3% at the largest. And the average value of elongation was 2.0%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body 4 was 4.1 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body 4 was 0.28% by mass.

[Example 6]
In Example 1, an aluminum plating solution 5 was obtained in the same manner as in Example 1, except that the concentration of the component (C) was 20 g / L.
Ten 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 of aluminum porous body 5 (ratio of displacement to GL) was 1.9% at the smallest and 3.4% at the largest. And the average value of elongation was 2.7%.
Moreover, the average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body 5 was 3.0 μm. Further, the amount of aluminum carbide contained in the aluminum porous body 5 was 0.49% by mass.

[Comparative Example 1]
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 (C) in the aluminum plating solution and the concentration was 0.50 g / L. .
Ten 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.

[Comparative Example 2]
In Example 1, an aluminum plating solution B was obtained in the same manner as in Example 1, except that the concentration of the component (C) was 0.05 g / L.
Ten aluminum porous bodies 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 (ratio of displacement to GL) of the aluminum porous body B was 0.5% at the smallest and 1.1% even at the largest. And the average value of elongation was 0.7%.
Moreover, the average crystal grain size of aluminum in the skeleton cross section of the aluminum porous body B was 4.8 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body B was 0.12% by mass.

[Comparative Example 3]
In Example 1, an aluminum plating solution C was obtained in the same manner as in Example 1, except that the concentration of the component (C) was 23 g / L.
Ten aluminum porous bodies 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 of aluminum porous body C (ratio of displacement to GL) was 0.6% at the smallest and 1.2% at the largest. And the average value of elongation was 0.9%.
The average crystal grain size of aluminum in the skeleton cross section of the porous aluminum body C was 1.1 μm. Furthermore, the amount of aluminum carbide contained in the aluminum porous body C was 1.2% by mass.

Claims (6)

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;
(C) an organic compound containing a benzene ring, which is a solid at room temperature and whose constituent elements are any one or more selected from the group consisting of hydrogen, carbon, oxygen and halogen atoms;
As an ingredient,
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 (C) is 0.10 g / L or more and 20 g / L or less.   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.   The manufacturing method of the aluminum film which electrodeposits aluminum on the surface of a base material using the aluminum plating solution of Claim 1.   A porous aluminum body obtained by using the aluminum plating solution according to claim 1, wherein the porous aluminum body has a three-dimensional network structure and has an elongation of 1.5% or more.   The porous aluminum body according to claim 4, wherein the crystal grain size in the cross section of the skeleton is 1 μm or more and 20 μm or less.   The aluminum porous body according to claim 4 or 5, wherein the content of aluminum carbide is 0.8 mass% or less.