KR101793252B1 - Metal-polymer complex and method for preparing the same - Google Patents

Abstract

The present invention relates to a metal-polymer composite and a method of manufacturing the same, and includes a metal layer and a polymer layer, wherein the metal layer and the polymer layer are bonded at a bonding force of 50 to 200 N, By simultaneously controlling the surface area, a remarkable effect is shown in improving the surface bonding strength with the polymer.

Description

METAL-POLYMER COMPLEX AND METHOD FOR MANUFACTURING THE SAME

The present invention relates to a metal-polymer composite having improved surface bonding strength at the interface between a metal and a polymer, and a method for producing the same.

In general, the technique of bonding a polymer to the surface of a metal has been used to insulate a metal surface or to form a protective film for preventing oxidation from the outside.

Particularly, in order to coat the metal surface with the polymer, the physical shape of the metal surface is changed. The physical methods include sand paper brushing, sand blasting, polishing, (Brushing), and the like. In addition, a pattern is formed by cutting the surface through various methods.

Among them, a physical surface change using a laser is proposed in US 5,916,461 in a manner simulating a sandblast method of roughening a metal surface. Probability information was introduced into the laser patterning to simulate the pattern of the sandblast so that the laser patterning method could follow the sandblasting pattern. An example of a commercial application through physical surface patterning can be found in US 7,192,174, in which a light guiding panel of LCD (liquid crystal display) panel is fabricated with particles of about 100-200 mesh and sandblasted To form a thin hexagonal pattern. Thus, the light was uniformly scattered through the light guide plate in the light source.

The technique of bonding the polymer to the metal surface fixes the polymer on the metal surface only by a physical surface or a chemical surface treatment method. In this way, the parameters that can control the surface bonding force between the metal and the polymer are not clear.

Accordingly, the present invention proposes a method of controlling surface roughness and surface area by controlling the surface bonding force between a metal and a polymer.

US Patent 5,916,461A U.S. Patent Publication No. 7,192,174A

The present invention provides a metal-polymer composite having improved surface bonding strength with a polymer by simultaneously controlling the roughness and surface area of a metal surface by applying a physical method and a chemical method in combination, and a method for producing the same.

According to an exemplary aspect of the present invention,

A metal layer; And

A polymer layer,

And the metal layer and the polymer layer are bonded to each other with a bonding force of 50 to 200 N.

According to another exemplary aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (A) etching a surface of a metal layer; And

(B) bonding the etched metal layer and the polymer layer,

The step (A) may include a first etching step (A-a) for etching by at least one method selected from sandblasting, sandpapering, laser patterning and pressing; And

And a second etching step (A-b) of supporting the metal layer in an etching solution and etching the metal layer.

According to another exemplary aspect of the present invention, there is provided a secondary battery including a metal-polymer composite manufactured according to various embodiments of the present invention.

The metal-polymer composite according to the present invention and the method for manufacturing the same exhibit a remarkable effect in improving the surface bonding strength with the polymer by simultaneously controlling the roughness and surface area of the metal surface by applying a physical method and a chemical method in combination.

1 is a cross-sectional view of an interface between a metal layer and a polymer layer according to an embodiment of the present invention.
FIG. 2 is a graph showing the results of measurement of the interfacial bonding force of the metal-polymer composite of Example 1-37 and Comparative Examples 1-16 and 19-32.
3 is a graph showing the results of measurement of surface roughness of the metal layer surfaces of Comparative Examples 15, 17, 18 and 21-33.
4 is a photograph showing the surface of the metal layer before the sandblasting process.
5 is a photograph showing the surface of the metal layer after the sandblast of Example 3 is treated.
6 is a photograph showing the surface of the metal layer after the sandblast of Example 7 is treated.
7 is a photograph showing the surface of the metal layer after the sandblast of Example 11 is treated.
8 is a photograph showing the result of observing the surface of the metal layer before the sandblasting with an optical microscope.
9 is a photograph showing the result of observing the surface of the metal layer with an optical microscope after the sandblast of Example 3 was treated.
10 is a photograph showing the result of observing the surface of the metal layer with an optical microscope after the sandblast of Example 7 was treated.
11 is a photograph showing the result of observing the surface of the metal layer with an optical microscope after the sandblast of Example 11 was treated.
12 is a photograph showing a state where a polymer is attached to a cylindrical battery cap down and a vent portion.
13 is a photograph showing a state after bonding strength is measured by a separation test after coupling the cap down and vent portions of FIG. 12 by hot lamination.
14 is a photograph showing the results of measurement of the surface of the metal layer by a three-dimensional confocal laser microscope after the sandblasting of Comparative Examples 15, 17, 18, and 33 was performed.
Fig. 15 is a photograph showing the results of measurement of the surface of the metal layer by a three-dimensional confocal laser microscope after the sandblast of Comparative Examples 25 to 28 was treated. Fig.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

According to an aspect of the present invention, there is provided a metal-polymer composite including a metal layer and a polymer layer, wherein the metal layer and the polymer layer are bonded at a bonding force of 50 to 200N.

The metal-polymer composite according to the present invention is characterized in that the surface bonding strength of the metal layer to the interface between the metal layer and the polymer layer is improved by using a physical etching method and a chemical etching method in combination.

As the physical etching method, at least one method selected from sand blasting, sand paper ring, laser patterning and pressing may be used. As the chemical etching method, an acidic, alkaline solution, The surface can be etched.

According to one embodiment, the metal layer is not limited to any particular kind but can be used in all, but is preferably at least one metal selected from aluminum, iron, copper, titanium, manganese, magnesium, zinc and silicon, It is an alloy of metals. More preferably, it is at least one selected from an aluminum-magnesium alloy, an aluminum-magnesium-manganese alloy, an aluminum-copper-manganese alloy, an aluminum-zinc-magnesium alloy and an aluminum-magnesium-silicon alloy.

The polymer layer is not limited as long as it can be used by being bonded to the metal layer and can be used. Preferably, the polymer layer is made of polypropylene, polypropylene, polybutylene terephthalate resin, polyphenylene sulfide resin, polyamide resin, A resin, a fluorine-ethylene-propylene resin, a poly (ethylene terephthalate) resin and a polyethylene.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (A) etching a surface of a metal layer; and (B) bonding the polymer layer with the etched metal layer, Comprising: a first etching step (Aa) for etching by at least one method selected from the group consisting of paper ring, laser patterning and pressing, and a second etching step (Ab) for carrying the metal layer in an etching solution for etching. - < / RTI >

According to one embodiment, the step (A) is a step of etching a surface of a metal layer, and the step (A) is a step of forming a metal layer by using at least one method selected from sandblasting, sandpapering, laser patterning and pressing. (Aa) for firstly etching the surface of the metal layer (Aa), and a second etching step (Ab) for secondarily etching the metal layer supported on the etching solution by the primary surface .

The etching step can simultaneously control the roughness and surface area of the metal surface through the step of etching the surface of the metal layer in a physical way (Aa) and the step of chemically etching (Ab) And the surface adhesion to the interface of the substrate.

That is, the present invention can control the physical shape of the metal surface, and at the same time, introduce a chemical functional group to exhibit the maximum bonding force between the metal and the polymer per unit surface area. Referring to Table 7 described below, It can be confirmed that the maximum bonding strength is 152.9 N.

The step (A-a) is a step of etching by a physical method, and it is preferable to use at least one method selected from among sandblasting, sandpapering, laser patterning and pressing, more preferably sandblasting or sandpapering.

In particular, the step (Aa) preferably cuts the surface of the metal for 5 to 60 seconds using the size of a single particle having a diameter of 20 to 130 占 퐉, more preferably i) the diameter of 10 to 100 占 퐉 Etching for 1 to 30 seconds at a particle size, and ii) etching for 1 to 30 seconds at a particle size of 100 to 150 탆 in diameter, wherein the particle size of each step is i) <ii) and , And the difference in size is preferably at least 30 탆.

The step (Aa) may further finely control the surface of the metal to be etched through the steps i) to ii), and in particular, increase the particle size to a size of i) at least 30 탆, (Ab), which is a chemical etching method. This effect increases the bonding durability of the metal layer and the polymer layer. That is, the initial bonding force is similar to that of the first etching with a single particle size, but the durability is increased, and the initial bonding force is maintained even after a long time. It has been confirmed that this can not be achieved by simply controlling the particle size but can be synergistic only if it is carried out in accordance with the chemical etching method according to the present invention.

The step of (Ab) is a step of secondly etching the surface of the metal, which is firstly etched through the step (Aa), by supporting the surface of the metal on the etching solution, and it is preferable to carry the etching solution for 5 seconds to 10 minutes Preferably 5 seconds to 3 minutes. If the thickness is out of the above range, the surface of the metal layer is excessively etched and the bonding force may be lowered, which is not preferable.

The etching solution may be any acidic or alkaline solution and may preferably be one selected from the group consisting of H ₂ CrO ₄ , HNO ₃ , HF, NaOH, HCl, FeCl ₃ , H ₃ PO ₄ , CuSO ₄ , NaCl and distilled water Or more.

More preferably, chromium oxide and sulfuric acid are carried in a chromic acid solution (H ₂ CrO ₄ ) dissolved in distilled water for 1 to 30 seconds and then carried on hydrochloric acid having a concentration of 5 to 20% for 30 seconds to 10 minutes As a result, when the chromic acid solution was used, the average bonding force was further improved, and it was confirmed that the oxide layer was effectively removed due to the surface treatment using hydrochloric acid, and the bonding force was further improved.

That is, it is possible to further improve the bonding force between the metal layer and the polymer layer by sequentially supporting the two solutions.

According to another embodiment, it is preferable that the surface of the metal layer etched through the step (A) is formed with a groove having a diameter of 100 탆 to 1 nm and a depth of 1 to 50 탆, If it is out of the above range, it is not preferable because the bonding force may be lowered.

According to another embodiment, the step (B) is a step of bonding the polymer layer with the metal layer whose surface has been etched through the step (A), and may be bonded with a bonding force of 50 to 200N. This bonding force can most effectively bond the metal layer and the polymer layer, and can be obtained by using a combination of a physical etching method and a chemical etching method as described above.

More specifically, the bonding step may be performed by coating the metal layer with the polymer, or may be bonded by various methods such as injection molding using a metal insert, extrusion molding, and molding through hot melting. More preferably, the metal layer is coated with a polymer by a method such as spin coating.

According to another embodiment, the metal layer is preferably at least one metal selected from aluminum, iron, copper, titanium, manganese, magnesium, zinc and silicon, or an alloy of the metals, At least one selected from the group consisting of magnesium alloy, aluminum-magnesium-manganese alloy, aluminum-copper-manganese alloy, aluminum-zinc-magnesium alloy and aluminum-magnesium-silicon alloy.

The polymer layer is preferably at least one selected from the group consisting of polypropylene, polybutylene terephthalate resin, polyphenylene sulfide resin, polyamide resin, polypropylene resin, fluorine ethylene propylene resin, polytetrafluoroethylene resin and polyethylene Do.

Particularly, when the metal layer is made of an aluminum-magnesium alloy and polypropylene is used as the polymer layer, the maximum bonding strength between the metal layer and the polymer layer is the most excellent. This is because the combination of any other metal and polymer It was confirmed that the bonding force between the metal and the polymer can be most effectively improved.

According to another aspect of the present invention, a secondary battery comprising a metal-polymer composite produced according to various embodiments of the present invention is disclosed.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. It is natural that it belongs to the claims.

In addition, the experimental results presented below only show representative experimental results of the embodiments and the comparative examples, and the respective effects of various embodiments of the present invention which are not explicitly described below will be specifically described in the corresponding part.

Example 1: Sand blast treatment of single particle size + chemical surface treatment (iron chloride solution)

As shown in FIG. 2, a 1050 specimen of metal aluminum fabricated in a circular shape having a diameter of 16.1 mm was etched by using a sand blast having a size of 25 탆 for 5 seconds for 5 seconds, and then the aluminum chloride solution was applied for 30 seconds to 2 minutes And dried and then coated with polypropylene to prepare a metal-polymer composite.

However, the iron chloride solution was prepared by mixing 100 mL of distilled water, 5 mg of iron chloride, and 50 mL of hydrochloric acid. The center portion except for the surface treatment region in the circumferential direction of the metal specimen was adhered with a protective film to prevent contact with the iron chloride solution.

Examples 2 to 12: Sand blast treatment of single particle size + chemical surface treatment (iron chloride solution)

The particle size of the sandblast and the time required for blasting were different from each other in the same manner as in Example 1, and the specific experimental conditions are shown in Table 1 below.

division Blast particle size (탆) Blast time (sec) Example 2 25 10 Example 3 25 20 Example 4 25 30 Example 5 50 5 Example 6 50 10 Example 7 50 20 Example 8 50 30 Example 9 90 5 Example 10 125 10 Example 11 125 20 Example 12 125 30

Example  13 to 20: Using a plurality of particle sizes (large particles to small particles) Sand  Blast treatment + Chemical surface treatment ( Chromium oxide  solution)

As shown in FIG. 2, a circular aluminum 1050 metal specimen having a diameter of 16.1 mm was sandblasted and etched, and then supported on a chromium oxide solution at 65 ° C for 10 seconds. Then, a 10% hydrochloric acid solution And the oxide layer was removed by drying for 1 minute to dry in an oven at 65 ° C and then coated with polypropylene to prepare a metal-polymer composite.

The chromium oxide solution was prepared by mixing 200 ml of distilled water, 12 g of chromium oxide and 2 g of sulfuric acid. The center portion except for the surface treatment region in the circumferential direction of the metal specimen was loaded with a protective film to prevent contact with the chromium oxide solution, The abrasive grain size and the time required for the sandblast treatment are shown in Table 2 below.

division Primary blast Secondary blast Third blast Particle size
(탆) Time
(sec) Particle size
(탆) Time
(sec) Particle size
(탆) Time
(sec) Example 13 50 15 25 15 - - Example 14 50 5 25 5 - - Example 15 125 15 25 15 - - Example 16 125 5 25 5 - - Example 17 125 15 50 15 - - Example 18 125 5 50 5 - - Example 19 125 10 50 10 25 10 Example 20 125 4 50 3 25 3

Example  21 to 28: Using a plurality of particle sizes Sand Blast  Treatment + chemical surface treatment (iron chloride solution)

The same procedure as in Examples 13 to 20 was carried out except that a ferric chloride solution was used in place of the chromium oxide solution and the hydrochloric acid solution.

(Except that the iron chloride solution used was the same as the iron chloride solution used in Example 1).

Examples 29 to 37: Sand blast treatment using a plurality of particle sizes (small particles? Large particles) + chemical surface treatment (chromium oxide solution)

2, aluminum-magnesium alloy metal specimens having a diameter of 16.1 mm were etched by sandblasting and then impregnated in a chromium oxide solution at 65 ° C for 10 seconds, Hydrochloric acid solution for one minute to remove the oxide layer, followed by drying in an oven at 65 DEG C, followed by coating with polypropylene to prepare a metal-polymer composite.

The chromium oxide solution was prepared by mixing 200 ml of distilled water, 12 g of chromium oxide and 2 g of sulfuric acid. The center portion except for the surface treatment region in the circumferential direction of the metal specimen was loaded with a protective film to prevent contact with the chromium oxide solution, The abrasive grain size and the time required for the sandblasting treatment are shown in Table 3 below.

division Primary blast 2 blast Particle size
(탆) Time
(sec) Particle size
(탆) Time
(sec) Example 29 25 5 125 3 Example 30 25 5 125 6 Example 31 25 5 125 9 Example 32 50 5 125 3 Example 33 50 5 125 6 Example 34 50 5 125 9 Example 35 90 5 125 3 Example 36 90 5 125 6 Example 37 90 5 125 9

Comparative Example  1 to 9: single particle size Sand Blast  Single etching

As shown in FIG. 2, the aluminum 1050 metal specimen made of a circle having a diameter of 16.1 mm was treated with a sandblast, etched, and then coated with polypropylene to prepare a metal-polymer composite.

However, the size of the abrasive grains and the time required for the sandblasting treatment are shown in Table 4 below.

division Blast particle size (탆) Blast time (sec) Comparative Example 1 25 10 Comparative Example 2 25 20 Comparative Example 3 25 30 Comparative Example 4 50 10 Comparative Example 5 50 20 Comparative Example 6 50 30 Comparative Example 7 125 10 Comparative Example 8 125 20 Comparative Example 9 125 30

Comparative Examples 10 to 20: Sandblast alone treatment using a plurality of particle sizes (large particles? Small particles)

As shown in FIG. 2, aluminum 1050 metal specimens having a diameter of 16.1 mm were treated by sandblasting and then subjected to primary and secondary steps, followed by coating with polypropylene to form a metal-polymer composite .

However, the size of the abrasive grains and the time required for the sandblasting treatment are shown in Table 5 below.

division Primary blast Secondary blast Third blast Particle size
(탆) Time
(sec) Particle size
(탆) Time
(sec) Particle size
(탆) Time
(sec) Comparative Example 10 50 15 25 15 - - Comparative Example 11 50 5 25 5 - - Comparative Example 12 125 15 25 15 - - Comparative Example 13 125 5 25 5 - - Comparative Example 14 125 15 50 15 - - Comparative Example 15 125 5 50 3 - - Comparative Example 16 125 5 50 5 - - Comparative Example 17 125 5 50 6 - - Comparative Example 18 125 5 50 9 - - Comparative Example 19 125 10 50 10 25 10 Comparative Example 20 125 4 50 3 25 3

Comparative Examples 21 to 33: Sandblast alone treatment using a single particle and a plurality of particle sizes (small particles? Large particles)

Comparative Example 10 was carried out in the same manner as in Comparative Example 10 except that the size and the time required for the abrasive grains were different in each sandblast treatment, and the experimental conditions are shown in Table 6 below.

division Primary blast 2 blast Particle size
(탆) Time
(sec) Particle size
(탆) Time
(sec) Comparative Example 21 25 5 - - Comparative Example 22 25 5 125 3 Comparative Example 23 25 5 125 6 Comparative Example 24 25 5 125 9 Comparative Example 25 50 5 - - Comparative Example 26 50 5 125 3 Comparative Example 27 50 5 125 6 Comparative Example 28 50 5 125 9 Comparative Example 29 90 5 - - Comparative Example 30 90 5 125 3 Comparative Example 31 90 5 125 6 Comparative Example 32 90 5 125 9 Comparative Example 33 125 5 - -

Test Example  1: Evaluation of bond strength between metal layer and polymer layer

The metal-polymer complexes of Examples 1-37 and Comparative Examples 1-14, 16, and 19-32 were separated by applying a constant force, and the binding force at the moment of separation was measured. The results are shown in FIG. 2 and Tables 7 and 8 Respectively.

division Minimum bond strength Maximum bond strength Average bond strength Example 1 83.2 150.4 107.6 Example 2 47.2 67.5 56.6 Example 3 71.8 122.4 100.2 Example 4 80.3 128.8 111.5 Example 5 85.6 121.4 97.8 Example 6 110.9 126.8 117.3 Example 7 104.8 152.9 125.5 Example 8 70.5 128.4 108.2 Example 9 99.2 140.5 120.9 Example 10 110.4 152.9 136.7 Example 11 16.7 51.3 32.7 Example 12 24.4 99.1 69.5 Example 13 19.9 106.1 76.1 Example 14 18.3 99.9 67.4 Example 15 51.1 109.7 84.3 Example 16 57.9 113.4 86.1 Example 17 33.1 118.4 84.6 Example 18 73.6 173.0 115.5 Example 19 21.4 119.1 86.1 Example 20 10.0 112.0 81.7 Example 21 45.8 73.1 58.1 Example 22 46.3 98.1 66.0 Example 23 43.8 72.9 58.8 Example 24 24.4 84.4 51.1 Example 25 40.4 114.4 69.3 Example 26 64.6 110.4 94.7 Example 27 25.8 93.0 60.7 Example 28 39.9 104.7 77.5 Example 29 113.8 137.0 125.9 Example 30 69.2 126.5 101.1 Example 31 93.1 149.3 113.5 Example 32 75.0 120.3 102.3 Example 33 65.9 119.9 98.2 Example 34 84.8 147.4 111.1 Example 35 97.5 148.4 122.4 Example 36 104.0 128.7 116.0 Example 37 93.2 117.3 104.1

division Minimum bond strength Maximum bond strength Average bond strength Comparative Example 1 30.7 59.2 45.1 Comparative Example 2 62.5 88.1 73.1 Comparative Example 3 6.3 88.0 44.6 Comparative Example 4 57.9 105.0 74.2 Comparative Example 5 59.8 104.3 84.9 Comparative Example 6 81.5 87.4 84.4 Comparative Example 7 35.0 112.9 68.0 Comparative Example 8 28.8 84.6 64.6 Comparative Example 9 75.2 113.4 88.7 Comparative Example 10 50.6 65.3 56.9 Comparative Example 11 13.8 82.2 61.1 Comparative Example 12 21.0 65.5 44.4 Comparative Example 13 41.5 73.9 56.0 Comparative Example 14 53.4 103.9 79.7 Comparative Example 16 31.3 82.9 61.8 Comparative Example 19 37.7 86.1 61.7 Comparative Example 20 59.3 76.8 67.1 Comparative Example 21 56.8 84.5 65.7 Comparative Example 22 61.9 83.8 74.3 Comparative Example 23 79.2 106.3 97.4 Comparative Example 24 80.5 130.0 107.2 Comparative Example 25 48.7 115.8 89.0 Comparative Example 26 47.9 100.9 81.0 Comparative Example 27 67.8 117.1 88.6 Comparative Example 28 89.4 130.2 101.8 Comparative Example 29 58.4 100.9 84.2 Comparative Example 30 70.3 90.2 83.3 Comparative Example 31 83.0 109.3 92.7 Comparative Example 32 94.8 127.9 108.3

As can be seen from Tables 7 and 8, as the treatment time of the sandblast increases, the bonding force increases, and the bonding force increases with the particle size, . Therefore, it can be seen that by simply increasing the particle size and the time required for the sandblast, the bonding force can be increased, but an optimal bonding force can be derived according to a specific combination.

Test Example 2: Analysis of roughness change of etched metal layer

The roughness of the metal-polymer composite of Comparative Examples 15, 17-18, and 21-33 on the surface of the etched metal layer was measured using a three-dimensional confocal optical microscope (Olympus LEXT 3D OLS4100 model) Are shown in Table 9 below.

division Surface roughness (micron) Comparative Example 15 3.952 Comparative Example 17 2.873 Comparative Example 18 2.739 Comparative Example 21 2.193 Comparative Example 22 1.363 Comparative Example 23 2.930 Comparative Example 24 3.323 Comparative Example 25 3.637 Comparative Example 26 2.243 Comparative Example 27 3.288 Comparative Example 28 3.462 Comparative Example 29 3.576 Comparative Example 30 2.170 Comparative Example 31 2.976 Comparative Example 32 3.815 Comparative Example 33 3.569

As shown in Table 9, in Comparative Examples 22-24, 26-28 and 30-32 in which large particles were used in small particles, the surface roughness was improved compared with Comparative Example 15-18 in which small particles were applied in large particles Can be confirmed.

Test Example 3: Surface analysis of the etched metal layer

The surfaces of the metal layers etched by the sandblasting treatment in Examples 3, 7, 11 and Comparative Examples 15, 17, 18, 25-28, and 33 were observed using a naked eye and an optical microscope, 7, 9 to 11 and 13 to 15, respectively.

Figs. 4 to 6 show the results of observing the surface of the metal with the naked eye, and Figs. 8 to 10 show the result of magnifying observation through an optical microscope. As can be seen from the figure, as the particle size of the sand blast increases, the roughness of the metal surface increases and the pores increase. Also, as the particle size of the sand blast increases, the roughness and pore height increase remarkably, and it can be confirmed that the surface area of the three-dimensional surface is increased.

Accordingly, the metal-polymer composite according to the present invention and the method for producing the same exhibit a remarkable effect in improving the surface bonding strength with the polymer by simultaneously controlling the roughness and the surface area of the metal surface by applying a physical method and a chemical method in combination .

10; Polymer layer
20; Metal layer
S; Surface area
f; asperity

Claims (15)

delete delete delete delete (A) etching a surface of a metal layer; And
(B) bonding the etched metal layer to the polymer layer, the method comprising:
The step (A) may include: a first etching step (Aa) of etching by at least one method selected from sandblasting, sandpapering, laser patterning and pressing; And
And a second etching step (Ab) for supporting and etching the metal layer in an etching solution,
The first etching step (Aa)
I) etching for 1 to 30 seconds at a particle size of 10 to 100 [mu] m in diameter; And
Ii) etching for 1 to 30 seconds at a particle size of 100 to 150 [mu] m in diameter,
Wherein the particle size of each step is i) < ii) and the difference in size is at least 30 mu m,
Wherein the second etching step (Ab) is carried out by firstly supporting H ₂ CrO ₄ for 1 to 30 seconds, and then secondarily supporting the HCl for 30 seconds to 10 minutes.
delete 6. The method of claim 5,
Wherein the surface of the metal layer etched through the step (A) is formed with a groove having a diameter of 100 to 1 nm and a depth of 1 to 50 占 퐉.
delete delete 6. The method of claim 5,
Wherein the metal layer is at least one metal selected from aluminum, iron, copper, titanium, manganese, magnesium, zinc, and silicon, or an alloy of the metals.
6. The method of claim 5,
Wherein the metal layer is at least one selected from an aluminum-magnesium alloy, an aluminum-magnesium-manganese alloy, an aluminum-copper-manganese alloy, an aluminum-zinc-magnesium alloy and an aluminum- magnesium- Gt;
6. The method of claim 5,
Wherein the polymer layer is at least one selected from the group consisting of polypropylene, polybutylene terephthalate resin, polyphenylene sulfide resin, polyamide resin, polypropylene resin, fluorine ethylene propylene resin, polytetrafluoroethylene resin and polyethylene By weight based on the total weight of the metal-polymer complex.
6. The method of claim 5,
Wherein the metal layer is an aluminum-magnesium alloy, and the polymer layer is polypropylene.
6. The method of claim 5,
Wherein the metal layer and the polymer layer are bonded to each other at a bonding force of 50 to 200N.
A secondary battery comprising a metal-polymer composite produced by the manufacturing method according to any one of claims 5, 7, 10 to 14.

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