JPH07246679A - Resin coated aluminum-containing metal composite material excellent in conductivity and production thereof - Google Patents

Abstract

PURPOSE:To produce a resin coated aluminum-containing metal composite material excellent in both capacities of high-order conductivity and corrosion resistance by forming an intermediate layer having fine metal particles present therein on the surface of a substrate composed of an aluminum-containing metal material and coating the same with a resin surface layer. CONSTITUTION:An intermediate layer containing fine metal particles with a particle size of 0.1-10mum in particle distribution density of 10<3>-10<7>/mm<2> is formed on the surface of an aluminum-containing metal material and coated with a resin surface layer with a thickness of 0.2-10mm. As the state of fine metal particles in the intermediate layer at the time of the coating with the resin surface layer with a thickness of 0.2-10mum, it is necessary that the particle size of the fine metal particles is 0.1-10mum and the particle distribution density thereof is 10<3>-10<7>/mm<2>. By this intermediate layer, the obtained resin coated composite material shows excellent conductivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated aluminum-containing metal composite material having excellent conductivity and a method for producing the same. More specifically, the present invention provides the conductivity, antistatic property, weldability, electromagnetic wave shielding property,
The present invention relates to a resin-coated aluminum-containing metal composite material having excellent adhesion and corrosion resistance, and a method for producing the same. In the present invention, the aluminum-containing metal includes aluminum and aluminum-containing alloy.

[0002]

2. Description of the Related Art Conventionally, resin-coated aluminum-containing metal composite materials have been used in many fields because of their excellent corrosion resistance and light weight. However, this resin-coated aluminum-containing metal composite material is inferior in conductivity as compared with a metal material not resin-coated, and because the weldability is significantly inferior to a galvanized steel sheet, for example, home appliances, automobiles, It is rarely used in the processing and assembly industries such as building materials. So to improve conductivity,
JP-A-3-270932, JP-A-1-130762
Several technologies are disclosed in the gazette and the like.

Japanese Unexamined Patent Publication (Kokai) No. 3-270932 discloses a means for improving the conductivity of a resin film. By this means, metal powder such as zinc and nickel or a conductive material such as carbon black is dispersed and contained in the resin film. However, in this means, in order to obtain a sufficient conductive effect, it is necessary to contain the conductive material in the resin film at a considerably large content rate of about 20 to 50%. Further, when such a large amount of conductive material is contained, there is a problem that the appearance of the obtained resin film is colored in a specific color. Further, the compounding of the conductive material corresponding to the pigment component deteriorates the resin characteristics, and therefore the corrosion resistance and the like of the resin film also deteriorates. Further, there is a problem that the required amount of the conductive material is large and many of the conductive materials are high in unit price, so that the cost of the product becomes high. Therefore, the conventional conductive resin-coated aluminum-containing metal composite material cannot be said to be versatile. As another method, it has been proposed to improve conductivity by using a conductive resin such as polyacetylene resin or polypyrrole resin doped with a specific compound as a component for forming a resin film. However, it is not practical to apply such a conductive resin to general-purpose industrial products because the reliability of the conductive resin over time is low and the cost increases.

In Japanese Patent Laid-Open No. 1-130762, an emulsion particle formed by electrostatic atomization of an organic resin emulsion is dispersed and applied to a galvanized steel material.
A technique for improving the conductivity of the resin film is disclosed.
In this technique, a resin film having a high resistance value can be thinned or made nonexistent by forming a resin film discontinuously on a substrate, so that the entire resin film can be easily energized and the conductivity can be reduced. It improves the sex. However, even if this technique is used, it is not possible to obtain conductivity equal to or higher than that of the aluminum-containing metal material without resin coating. Further, in the resin coating material obtained by this technique, the coverage of the substrate surface with the resin coating layer is reduced, so that the corrosion resistance is reduced. If the amount of the resin film is increased to improve the corrosion resistance, the surface coverage is improved, but the conductivity is decreased. as mentioned above,
Conventionally, it has not been possible to obtain a resin-coated aluminum-containing metal composite material excellent in both high conductivity and corrosion resistance by the conventional means.

Usually, the resin film has a composition in which an additive such as a pigment is added to a base resin such as an acrylic resin, an epoxy resin, a polyester resin or a polyurethane resin according to a desired function. In the film obtained by film-forming these base resins, the base resin is polymerized. This polymerized resin is often
It belongs to an insulator having a volume resistivity of about 10 ¹² to 10 ¹⁵ Ω · cm. As a means for imparting conductivity to this, there are roughly two methods. One of them is Ag powder, N
A conductive filler such as i powder or carbon powder is dispersed in the resin film to form a composite. The other one is
In this method, a surfactant is added to the resin film or a hydrophilic group is introduced into the polymer chain. In addition, conductive polymer materials such as polyacetylene and TCNQ-TTF complex are not at the stage of being evaluated in industrial applications at present. However, the volume resistivity of 10 ^-2 ~
A paint having conductivity of 10 ⁵ Ω · cm is commercially available under the name of conductive paint.

The conductive paint is a composition in which the original resin film is modified as described above. However, instead of improving the conductivity, various functions are deteriorated. When a filler component is added, the original mechanical film properties are significantly reduced, and therefore, when a metal surface is coated with this conductive paint, its corrosion resistance, adhesion performance and processing performance become insufficient. . Further, in many cases, since the resin film is colored in a specific color, the appearance color tone is limited from the viewpoint of designability, which is a disadvantage. With conductive paints that add a surfactant or introduce hydrophilic groups into the polymer chain, the hydrophilicity of the resulting resin film becomes stronger, and this reduces the corrosion resistance and adhesion performance when coating a metal surface. To do. Further, the conductivity also has a volume resistivity of about 10 ⁸ to 10 ¹² Ω · cm, so it cannot be said that the conductivity is significantly improved.

When the aluminum-containing metal material is directly coated with the highly insulating resin film without any surface treatment, the conductivity of the obtained composite material is significantly lowered. In general, some kind of surface treatment is performed on a metal material for the purpose of improving corrosion resistance and adhesion. Examples of such a surface treatment include a reaction type treatment such as a chromate phosphate or a chromic chromate or a coating type treatment for forming an amorphous chromate film on the surface of a metal material, a crystal such as zinc phosphate. Examples of the treatment include a treatment for forming a conductive coating and a treatment for forming an alumite oxide coating on the surface of a metal material by an anodic electrolysis method. When a high-insulating resin film is coated after coating such a film, the conductivity is greatly reduced as in the case where no surface treatment is performed, although the degree varies depending on the type of surface treatment. As is clear from the above, it can be said that no technique has been found that can significantly improve the conductivity of the resin-coated aluminum-containing metal material by surface treatment.

[0008]

The present invention improves the electrical conductivity of resin-coated aluminum-containing metal composites,
An object of the present invention is to provide a resin-coated aluminum-containing metal composite material excellent in both high conductivity and corrosion resistance, and a method for producing the same.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on the means for solving the above problems, and as a result, without adding a conductive substance to a resin film coating an aluminum-containing metal material. , The characteristics of the original highly insulating resin film, such as excellent corrosion resistance and adhesion (adhesion)
The present invention has been accomplished by newly finding a means for improving conductivity while effectively retaining the above.

The resin-coated aluminum-containing metal composite material having excellent conductivity according to the present invention coats the base made of an aluminum-containing metal and the surface of the base with 0.1.
Conductive metal fine particles having a particle size of 10 μm are 10 ³ to 10 ⁷
An intermediate layer dispersedly contained at a distribution density of pcs / mm ² , and a resin surface layer which covers the intermediate layer and has a thickness of 0.2 to 10 μm. .

In the composite material of the present invention, the conductive metal fine particles are composed of one member selected from chromium, iron, copper, cobalt, nickel, zinc, tin, gold, silver and alloys of two or more of these. It is preferably one.

In the composite material of the present invention, the content of the conductive metal fine particles in the intermediate layer is preferably 5 to 500 mg / m ² .

In the composite material of the present invention, the resin surface layer preferably contains a lubricating resin.

The method for producing a resin-coated aluminum-containing metal composite material having excellent conductivity according to the present invention has a particle size of 0.1 to 10 μm on the surface of an aluminum-containing metal material by a cathodic electrolysis method or an electroless method. Conductive metal fine particles having a density of 10 ³ to 10 ⁷ / mm ² are deposited and coated to form an intermediate layer, and the intermediate layer is coated with a resin to have a thickness of 0.2 to 10 μm. A resin surface layer having a thickness is formed.

[0015]

The structure of the present invention will be described in detail below. In the surface treatment means found by the present inventors, an intermediate layer containing metal fine particles having a diameter of 0.1 to 10 μm and a particle distribution density of 10 ³ to 10 ⁷ particles / mm ² is formed on the surface of an aluminum-containing metal material. To be done. The method for forming the intermediate layer is not particularly limited. However, when the method of electrodepositing metal fine particles on the surface by the cathodic electrolysis method is adopted, when the highly insulating resin film is coated on the obtained intermediate layer, the electrical conductivity of the obtained composite material is particularly improved. You can The reason why the type of substrate material to be coated is limited to aluminum materials or aluminum alloy materials is that the metal is electrodeposited, that is, when plating is performed, the electrodeposited metal is distributed in the form of fine particles. This is because The presence of the metal fine particles makes a great contribution to improving the conductivity of the obtained resin-coated composite material.

Coating a resin film with a thickness of 0.2 to 10 μm
The state of the fine metal particles in the intermediate layer when
The diameter is 0.1 to 10 μm, and the particle distribution density is 10³ ~
10 ⁷ Pieces / mm² Need to be like this
Due to the intermediate layer, the resulting resin-coated composite material has excellent electrical conductivity.
It shows sex. Resin film thickness less than 0.2 μm
In the case of a thin film, the effect of coating a resin film is small and practical
Poor. The diameter of the metal fine particles in the intermediate layer is 10 μm
If the size is more than
Therefore, the resin coating is included.
The adhesion when coated is reduced. In addition, fine metal particles
If the diameter of the child exceeds 10 μm, the appearance will be colored.
Therefore, a clear or white resin film is applied for the purpose of design.
Not suitable for coating. In addition, the metal fine particles are 10
When the grain size exceeds μm, the result is as described above.
Agglomerated particles are formed in the
Then, a continuous film is formed. In this way, serialization
A resin is further applied to the surface covered with the metal film
When coated, the resulting composite material has satisfactory and excellent conductivity.
It does not show sex. That is, in the present invention,
The fine metal particles in the layer are distributed substantially apart from each other.
It is necessary to have

The lower limit of the metal fine particle diameter is 0.1 μm, but even if particles having a particle diameter of less than 0.1 μm coexist, a problem occurs unless the metal fine particles having a particle diameter of 0.1 to 10 μm form a continuous film. There is no. The reason why the particle dispersion density of the metal fine particles having such a particle diameter is required to be 10 ³ to 10 ⁷ particles / mm ² is as follows. That is, when the particle distribution density is less than 10 ³ particles / mm ^{2, the} effect of improving the conductivity of the obtained composite material is small and not suitable. Further, when it exceeds 10 ⁷ pieces / mm ² , the obtained intermediate layer is in a covering state close to a continuous film, and thus the effect of improving the conductivity of the obtained composite material is insufficient.
When the cathodic electrolysis method is used, the distribution density of the coated metal fine particles can be controlled by controlling the current density. That is, the control of the number of initial precipitation nuclei of the metal particles has a very high correlation with the distribution density of the coated metal particles. The current density that determines the prescribed number of initial precipitation nuclei should be set appropriately according to the processing conditions such as the type of electrolyte, solution temperature and flow rate, and the surface condition of the basic material to be coated (existence of oxide film, etc.). You can

The metal species of the intermediate layer fine particles for coating the aluminum-containing metal material substrate of the present invention include chromium, iron, copper,
It can be selected from metals such as cobalt, nickel, zinc, tin, gold and silver, and alloys of two or more of these,
The type is not particularly limited. Further, when the resin is coated on the intermediate layer, the conductivity of the obtained composite material is greatly improved as compared with the case where the metal is not coated, although there is a slight difference in the kind of the metal of the intermediate layer. . The degree of conductivity of the composite material obtained by the present invention shows a resistance value which is rather smaller than the numerical value when the surface of aluminum or aluminum alloy is not completely covered, which is extremely low with the conductive paint of the prior art. It is possible to obtain excellent conductivity that was not achieved. The reason why the composite material of the present invention exhibits better conductivity than the aluminum-containing metal material surface which is not coated at all is that the coated metal fine particles are not present on the highly insulating stubborn oxide film, It is considered that it is due to the fact that it is in direct contact with the metal substrate having excellent conductivity.
Chromium is particularly preferable as the metal species to be coated. That is, when the chromium fine particles are coated, the corrosion resistance and adhesion of the composite material obtained by coating the intermediate layer with the resin are significantly improved.

As a method for coating the surface of the aluminum-containing metal material with metal fine particles, the case where the metal species is chromium will be exemplified. The source of chromium is not particularly limited,
For example, when hexavalent chromium ions are used, an acidic aqueous solution containing chromic anhydride of 4 to 300 g / L and sulfuric acid of 0.04 to 3 g / L and having a pH of 2.0 or less, or a metal complex fluoride is further added thereto. It is preferable to use the added acidic aqueous solution. The electrolysis conditions are also not particularly limited,
The bath temperature is controlled at 40-60 ° C and the current density is 0.5-60A.
It is preferable to perform the deposition treatment under the condition of / dm ² . The treatment time can be appropriately set depending on the target coating state of the metal fine particles. From the performance, the preferred total chromium coating weight is 5 to 500 mg / m ^2, in the case of using a hexavalent chromium bath is a current density of about 1-2A / dm ^2, a cathode in about 10 to 120 seconds electrolysis time By electrolysis, it is possible to obtain a predetermined amount of chromium with a predetermined coating state.

As a method for forming an intermediate layer using metal fine particles, the cathodic electrolysis method is preferable because it is the easiest and surest control, as described above. However, the method is not limited to this method. For example, it is possible to deposit / deposit metal fine particles by substitution deposition of aluminum and a target metal by using an electroless plating solution containing a metal ion that is more noble than the base metal. The particle size of the metal fine particles deposited by substitution by this method is preferably 0.5 μm or less. In this case, when the particle size of the metal fine particles is larger than 0.5 μm, the increase in the number of nuclei by the microcell is prioritized, and finally, the metal fine particles to be formed have a small particle size and 10 ⁷ particles / mm ²
The distribution density may exceed. But,
When the substitution deposition solution for obtaining the initial deposition nuclei is deposited with a solution in which a reducing agent is used in combination, such as a so-called chemical plating solution, an intermediate layer composed of desired metal fine particles is formed as in the case of electrolytic deposition. Can be formed. Of course, similar effects can be obtained by substituting and depositing fine particles of a reducing catalyst such as palladium prior to chemical plating.

The reason why the metal material substrate coated with the metal in the form of fine particles is an aluminum material or an aluminum alloy material is as follows. That is, in a stubborn oxide film on the surface of an aluminum-containing metal material, or in an aluminum alloy, the presence of surface segregated substances such as silicon or magnesium, which is an additive metal, or compatibility of the boundary bonding between aluminum and plated metal Is a bad thing. The presence of the former oxide film or surface segregation makes the surface of the aluminum-containing metal material electrochemically non-uniform. In fact, the self-potential distribution of the surface of the aluminum alloy which has not been subjected to any surface treatment and the surface of the cold rolled steel sheet and the electrogalvanized steel sheet is 10
^{-3 When} measured using the scanning oscillating electrode method in NaCl,
On the surface of the aluminum alloy material, it is recognized that the electric potential distribution is extremely uneven depending on the place.

That is, it is considered that when cathodic electrolytic plating is applied to the surface of an aluminum-containing metal, the initial precipitation of the metal occurs selectively depending on the nonuniformity of the surface potential, and this precipitate serves as a nucleus to grow into fine particles. To be Since the oxide film on the surface of aluminum-containing metal has a particularly high electrical resistance, the number of precipitation nuclei does not increase beyond the number that was initially generated, and the normal current selectively grows the initial precipitation nuclei with a very low electrical resistance. Thought to be spent only on. In the case of cold-rolled steel sheets and electrogalvanized steel sheets, the growth of initial precipitation nuclei causes an increase in new precipitation nuclei, the coating area increases, and finally a continuous film is formed. This difference in the substrate metal surface characteristics is the reason why aluminum and aluminum alloy materials are suitable as the substrates for coating the metal fine particles according to the present invention.

On the surface of the metal to be coated, in addition to the fine metal particles, depending on the coating conditions, they may be present in the form of metal oxides and hydroxides. When metal ions in the surface treatment solution are deposited by cathodic electrolysis and are not sufficiently reduced to a metal state in terms of potential, a layer of metal oxide and hydroxide is formed without growing as metal fine particles. This layer improves its corrosion resistance and adhesion when a resin film is coated on it. However, since this layer generally has high insulating properties, it becomes a factor that reduces the conductivity of the obtained composite material. Further, since the coloring occurs when the coating amount is large, it is preferable to reduce the formation of metal oxide and hydroxide layers as much as possible in applications where the conductivity is high and the appearance color is limited.

When the metal fine particles are a metal species that is easily oxidized, a metal oxide and hydroxide layer may be formed on the outermost surface of the deposited metal fine particles. When the bath for depositing the metal fine particles undergoes a chemical conversion reaction with the surface of the substrate, a metal oxide and hydroxide layer may be formed on the surface of the substrate to be coated. Further, when the metal species is chromium, metal oxides and hydroxides may be formed not only on the substrate to be coated but also on the outermost surface of the deposited metal fine particles. In the case of the present invention, it is difficult to define the amount of metal in the metal fine particles and the amount of metal contained in the oxide and hydroxide layers in terms of the analytical method. In the present invention, the overall performance can be controlled by limiting the existence state of the metal fine particles observed in appearance and further limiting the total metal adhesion layer.
The coating amount of the coating layer having metal particles is 5 to 50 in terms of total metal.
When the amount is controlled to 0 mg / m ² , when the resin is coated thereon, the resulting composite material has an excellent balance of properties such as electrical conductivity, corrosion resistance, and adhesion. That is 5 mg / m ²
If it is less than the above range, the resulting composite material may have insufficient conductivity, corrosion resistance, and adhesion. In addition, it is 500mg /
If more than m ^2, the the conductive composite material obtained, and the adhesion becomes insufficient.

There is no particular limitation on the kind of the resin film to be further coated on the metal fine particle-containing intermediate layer obtained in the present invention. For the purpose of improving conductivity only, a commercially available conductive coating material may be used for coating to obtain a composite material having particularly excellent conductivity. However, in most cases, since various functions and performances such as appearance color tone are required, a resin film that cannot impart conductivity is often coated. Even if the non-conductive resin surface layer is formed as described above, the composite material of the present invention has desired conductivity.

Among the resins for forming the resin surface layer, the use of a highly insulating and hydrophobic lubricating resin is particularly effective for the present invention. The lubricating resin film is generally composed of a base resin and a hydrophobic lubricating additive. The lubricant additives are typified by PTFE (polytetrafluoroethylene), polyethylene wax and the like, which are organic substances having a small polarity and a high insulating property.
The lubricating resin film containing this highly insulating substance has particularly low conductivity among the resin films. In addition, if a known conductive additive is added to the lubricating resin film, the lubricity is reduced, so it is not preferable to add these. Therefore, in the prior art, it has been required to improve the conductivity of the composite material obtained by coating the lubricating resin film with some method. By forming the metal fine particle-containing intermediate layer of the present invention, sufficient conductivity can be obtained without lowering the lubricity of the resin surface layer. When the metal fine particle-containing intermediate layer having an appropriate particle size and distribution density is coated, the lubricity of the resin surface layer thereon may be improved. The reason why the lubricity of the resin surface layer is not deteriorated or improved by forming the metal fine particle intermediate layer is that the metal fine particles have a function of preventing adhesion and rolling friction. it is conceivable that. The resin used for forming the resin surface layer of the present invention is, in addition to the above-mentioned lubricating resin, a finger drawing resistant resin, an antifouling resin, a highly rustproof resin, a primer resin, a retort resistant resin, and a conductive resin. It can be appropriately selected from corrosion-resistant resins such as.

The resin-coated aluminum-containing metal composite material obtained according to the present invention has, due to its excellent conductivity, practically greatly improved performances relating to electric characteristics such as charging characteristics, weldability and electromagnetic wave shielding. Is. The substrate to which the present invention is applied is typified by an aluminum material or an aluminum alloy material, but also for a plated material having an aluminum-based surface such as a hot-dip aluminum plated steel sheet,
The present invention can be applied as described above.

[0028]

EXAMPLES The present invention will be specifically described with reference to Examples of the present invention together with Comparative Examples. Below, the manufacturing method of a test piece, the evaluation method, and the test result are demonstrated. In addition, Table 1 shows the compositions and treatment conditions of the cathodic electrolysis bath Nos. 1 to 4, Table 2 shows the composition and treatment conditions of the electroless plating bath No. 5, and Table 3 shows the above Tables 1 and 2. The levels of metallization treatment Nos. 1 to 14 using the treated treatment baths are shown.

Examples 1 to 11 and Comparative Examples 1 to 13 1. Method for producing test piece The test piece used in each of Examples 1 to 11 and Comparative Examples 1 to 13 was produced by the following steps (1) to (7). (1) Test aluminum material-A5052 plate material (plate thickness 1.0 mm) (2) Alkaline degreasing 2% aqueous solution of non-etching type alkaline degreasing agent (manufactured by Nippon Parkerizing, Fine Cleaner 4327), temperature 60 ° C, 1 Spray degreasing was performed for a minute. (3) Cleaning Spray cleaning was performed for 20 seconds using deionized water.

(4-1) Cathodic electrolysis treatment or electroless treatment Under the conditions shown in Tables 1, 2 and 3, the test material cathodic electrolysis treatment or electroless treatment was performed to obtain a coating state of chromium, nickel or tin. It was adjusted. (4-2) Anodizing treatment Anodizing film is formed to a thickness of 5 μm on the test material under the conditions of bath temperature of 30 ° C., current density of 3 A / dm ² and electrolysis time of 20 minutes in a treatment bath of 15% sulfuric acid. Let (4-3) Reactive Chromate Treatment A test material was sprayed with a 1% aqueous solution of Alchrome 3703 manufactured by Nippon Parkerizing at a temperature of 40 ° C. for 30 seconds to form a reactive chromate film. The amount of chromium (Cr) deposited at this time was 50 mg / m ² . (5) Cleaning Spray cleaning was performed for 20 seconds using deionized water. (6) Drying Draining was performed for 2 minutes in an oven set to 100 ° C.

(7) Resin film coating The following three kinds of coating materials were applied to the test materials by a bar coater so as to have a predetermined dry film thickness. The baking was performed under the optimum conditions for each paint. The film thickness of the resin film is as shown in Table 4. A. Anti-corrosion paint An aqueous clear anti-corrosion paint (nonvolatile content 25%) containing ethylene-acrylic copolymer resin as a main component was applied. The baking was performed so that the reached plate temperature was 120 ° C. in 30 seconds. B. Conductive paint A commercially available solvent-based conductive paint (trade name: Wannier 200, manufactured by Yuko Co., Ltd., solid content: 64%) in which metallic Ni was mixed with an acrylic base resin was applied. The baking was performed so that the ultimate plate temperature reached 150 ° C. in 30 seconds. C. Lubricating paint A water-based clear lubricating resin paint (nonvolatile content 25%) containing a polyester urethane resin emulsion as a main component and a water-dispersible polyethylene wax was applied to the test material. The baking was performed so that the reached plate temperature reached 140 ° C. in 30 seconds. Table 4 shows the intermediate layer forming conditions and the resin surface layer forming conditions of Examples 1 to 11 and Comparative Examples 1 to 13.

2. Performance Evaluation Method (1) Observation of Film Morphology The surface of the produced test piece was observed with a scanning electron microscope to measure the particle size of the deposited metal fine particles. In addition, the number of metal particles per unit area was measured to obtain the particle distribution density (particles / mm ² ). (2) Conductivity Based on JIS-C2550 (regulation of 1986),
The interlayer resistance was measured. The test conditions were as specified. The measured value was evaluated by dividing it into the following ranks using the average value of n = 5.・ Interlayer resistance tester: Toei Kogyo Co., Ltd., LRT-1A ・ Measurement conditions: 20 ° C, applied pressure 2N / mm ² , voltage 0.5V ・ Standard sample: Interlayer resistance value when using a clean electrolytic copper plate Was measured to be 0.2 Ω · cm ² / sheet or less. <Evaluation Criteria> ◎: interlayer resistance value less than 0.5 (unit: Ω · cm ² / sheet) ○: interlayer resistance value 0.5 or more and less than 2.0 Δ: interlayer resistance value 2.0 or more and less than 10 ×: interlayer Resistance value 10 or more (3) Weldability Using an R type (16 mmφ, 20 mmR) Cu-Cr electrode, energization cycle: 45 cycles, pressure: 350 kg,
Current value: 27 KA, single-phase alternating current continuous dot printing, 4 ×
The number of hit points until a nugget diameter of t ^-2 (t: plate thickness) or more was secured was measured and evaluated according to the following ranks. <Evaluation criteria> ◎: 500 RBI or more ◯: 300 RBI or more and less than 500 RBI △: 150 RBI or more and less than 300 RBI ×: Less than 150 RBI

(4) Corrosion resistance Based on JIS-Z2371, a salt spray test was performed 100 times.
The area of occurrence of white rust after 0 hours was measured, and evaluated according to the following ranks. <Evaluation Criteria> ◎: White rust 0% ◯: White rust 0 or more and less than 10% △: White rust 10% or more and less than 30% ×: White rust 30% or more (5) Adhesion test Painted surface coated with resin film Then, draw 100 squares of 1 mm square to reach the base with an NT cutter, and further extrude 5 mm with an Erichsen extrusion tester, and peel off the surface with cellophane tape. The evaluation was performed according to the following ranks according to the number of squares remaining after tape peeling. ◎: No abnormality ○: 95/100 or more of the remaining grids △: 80/100 or more of the remaining grids ×: Less than 80/100 of the remaining grids

(6) Observation of film appearance Using an untreated sample as a reference, JIS-Z
The color difference specified in 8730 was measured and evaluated according to the following ranks. <Evaluation Criteria> A: Color difference 0 or more and less than 3.2 (no discoloration by visual observation) O: Color difference 3.2 or more and less than 6.5 (slightly discoloration) Δ: Color difference 6.5 or more and less than 13 (clear discoloration) X: Color difference of 13 or more (strong discoloration)

(7) Lubricity test A blank plate having a diameter of 90 mmφ was used, and the punch diameter was 50.
mmφ, wrinkle pressing pressure = 1.0 Ton, deep drawing speed = 30 m
A high speed cylindrical deep drawing test was carried out under the condition of / min. At this time, the drawing ratio (blank diameter / punch diameter) is 1.80.
In addition, in the case of the omission of the aperture, the test was performed with a blank having a larger diameter by 5 mmφ. <Evaluation Criteria> ∘: Aperture draw, aperture ratio of 2.0 aperture o: Aperture draw, aperture ratio of 1.9 aperture Δ: Aperture draw, film damage on cylindrical part ×: No aperture draw

3. Test Results Table 5 shows a list of evaluation test results.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

As shown in Examples 1 to 11, in the range of the present invention, excellent performance was exhibited in all items of conductivity, weldability, corrosion resistance and adhesion. Regarding conductivity and weldability, it is slightly inferior when the resin film has a thick level,
However, it showed better performance than the untreated material. Regarding the corrosion resistance, Examples 3, 4, in which the metal species of the metal coating is other than chromium
In the case of No. 5, in the case of Example 9 in which the amount of deposited metal is small, and in the cases of Examples 8 and 10 in which the resin film is a conductive paint,
Although a little inferior to the other examples, it showed excellent performance that was practically sufficient. Regarding the film appearance, Example 6,
The levels of 8 and 10 are colored because the amount of metal adhered is considerably large and the resin film is a conductive paint.
In other examples, it showed an excellent appearance. Examples 5, 6, and 9 in which the resin surface layer was formed from a lubricating coating.
Then, the lubricity was particularly excellent.

In Comparative Examples 1, 2, 3 and 4, the metal coating conditions were out of the range of the present invention, but the conductivity was largely inferior. Comparative Examples 6, 7 and 8 are the conventional surface treatments, but the conductivity was largely inferior as in the above case. In Comparative Examples 9, 10, and 11, the metal coating conditions were within the scope of the present invention, but the resin coating conditions were out of the range, so that both conductivity and corrosion resistance were not excellent. Comparative Examples 12 and 13 are cases where the resin film is not coated,
The corrosion resistance was greatly inferior.

[0044]

INDUSTRIAL APPLICABILITY An intermediate layer having metal fine particles having a diameter of 0.1 to 10 μm and a particle distribution density of 10 ³ to 10 ⁷ particles / mm ² is formed on the surface of a substrate made of an aluminum-containing metal material. By further coating a resin surface layer having a thickness of 0.2 to 10 μm, a resin-coated aluminum-containing metal composite material having excellent conductivity, corrosion resistance and adhesion can be obtained.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C23C 18/52 A C25D 5/30 15/02 EN H01B 5/02 A

Claims (5)

[Claims] 1. A substrate made of an aluminum-containing metal,
An intermediate layer covering the surface of the substrate and containing conductive metal fine particles having a particle size of 0.1 to 10 μm dispersed at a distribution density of 10 ³ to 10 ⁷ particles / mm ² ; A resin-coated aluminum-containing metal composite material having excellent conductivity, which is covered with a resin surface layer having a thickness of 0.2 to 10 μm. 2. The conductive metal fine particles are chromium, iron,
The composite material according to claim 1, comprising one member selected from copper, cobalt, nickel, zinc, tin, gold, silver, and alloys of two or more of these. 3. The composite material according to claim 1, wherein the content of the conductive metal fine particles in the intermediate layer is 5 to 500 mg / m ² . 4. The composite material according to claim 1, wherein the resin surface layer contains a lubricating resin. 5. On the surface of the aluminum-containing metallic material,
By the cathodic electrolysis method or the electroless method, 10 ³ to 10 ⁷ conductive metal fine particles having a particle diameter of 0.1 to 10 μm /
An intermediate layer is formed by deposition coating with a distribution density of mm ² , and the intermediate layer is coated with a resin to form a resin surface layer having a thickness of 0.2 to 10 μm. , A method for producing a resin-coated aluminum-containing metal composite material having excellent conductivity.