KR20190002220A - Process for preparing metal-polymer composite material - Google Patents

Abstract

A method of manufacturing a metal-polymer composite material is disclosed. The method includes a step of firstly spraying a first composition comprising a monomer, a diazonium salt and a first solvent on the surface of a metal substrate; a step of secondarily spraying a second composition comprising a reducing agent and a second solvent onto the surface of the first sprayed metal substrate to form an organic thin film layer where a polymer is grafted with the monomer; and a step of attaching the polymer substrate on the organic thin film layer. It is possible to perform bulk processing.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a process for preparing a metal-polymer composite material,

The present invention relates to a method for producing a metal-polymer composite material, and more particularly, to a method for producing a metal-polymer composite material having an excellent durability by preventing the separation of the interface of the composite material by improving the adhesive strength.

The organic thin film coated material can be utilized in various industrial fields because it can utilize the characteristics of the coating film and the material itself.

It is possible to apply the functional group to the structural material and the functional material by forming necessary functional groups on the surface according to the application and imparting the paintability, corrosion resistance and biocompatibility of the material. In order for this utilization to be effective, the organic thin film should be stably bonded to the substrate without deformation or loss of the organic thin film in an extreme environment. To form such a stable thin film, a coating method having a chemical covalent bond instead of a physical bond between the metal surface and the organic thin film layer desirable.

A coating method having a chemical bond between such a substrate and a thin film is referred to as grafting. Although the number of grafting methods is extremely limited, grafting by oxidation-reduction of diazonium is one of the effective grafting methods. One application of this type of surface modification technique is metal-CFRP hybrid composites. Metal-CFRP composites are composite materials with excellent mechanical properties because they have both the advantages of metal with high fracture toughness and fiber reinforced composites with high specific strength. In order to make the metal-plastic composite material bonded by the film-thermo-compression process act as a structural material, a strong adhesion force between the two materials is required. In this case, formation of an organic thin film having a covalent bond on the metal surface is advantageous for improving interfacial adhesion It makes it.

In general, there are physical and chemical treatment methods for enhancing the bonding force between metal and polymer. There are methods such as sandblasting, laser etching and the like. These methods treat impurities that may exist at the interface and cause roughness on the surface to cause mechanical interlocking ). The chemical treatment is to treat the acid / base or plasma on the surface and induces a strong secondary bonding of the interface by using an activating functional group.

This strengthened adhesion is helpful in the short and long term, but when exposed to moisture or other chemical environments, the stability tends to be poor and it is difficult to apply it to the structural materials field which must withstand repeated and repeated loads. In the field of using a metal-polymer composite material as a structural material at present, the physical bonding through riveting is mainly used to secure the stability, but this causes an increase in weight and requires an additional process, which is undesirable.

The problem to be solved by the present invention is to improve the interfacial bonding force, thereby preventing interfacial separation of the composite material, thereby enhancing durability. The present invention provides a method for producing a metal-polymer composite material capable of mass-processing by grafting a spraying process to the grafting process.

To solve these problems, according to one aspect of the present invention,

First spraying a first composition comprising a monomer, a diazonium salt and a first solvent on the surface of a metal substrate;

A second composition comprising a reducing agent and a second solvent is sprayed secondarily onto the surface of the first sprayed metal substrate to form an organic thin film layer; And

And a step of attaching the polymer substrate on the organic thin film layer.

The monomer may include at least one member selected from the group consisting of acrylonitrile, methyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, acrylic acid, lactic acid, glycolic acid, and epsilon -caprolactone.

Wherein the diazonium salt is at least one selected from the group consisting of p-chlorobenzene diazonium, 2,4-dichlorobenzene diazonium, 2,5-dichlorobenzene diazonium, 2,4,6-trichlorobenzene diazonium, Nitrobenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, Benzene diazonium, 3-methylbenzene diazonium, 2,4-dimethoxybenzene diazonium, 2,4-dimethyl-6-nitrobenzene diazonium, and 2-chloro-4-dimethyl- And at least one selected from the group consisting of

Wherein the diazonium salt is selected from the group consisting of 4-nitrobenzene diazonium tetrafluoroborate, 4-methoxybenzene diazonium tetrafluoroborate, 4-nitrobenzene diazonium perchlorate, and 4-trifluoromethyl Benzene tetrafluoroborate, and the like.

The reducing agent may include at least one selected from the group consisting of ascorbic acid, iron powder, trisodium citrate, NaBH ₄ , phenylhydrazine HCl, phenylhydrazine, and hydrazine.

The first composition may include 100 parts by weight of the monomer, 10 to 30 parts by weight of the diazonium salt, and 60 to 100 parts by weight of the first solvent.

The second composition may include 100 parts by weight of a reducing agent and 4,000 to 6,000 parts by weight of a second solvent.

The first composition may be applied onto the metal substrate in particles of 0.5 탆 to 50 탆 in size when the first spray is applied.

The second composition may be applied onto the primary sprayed metal substrate with particles of size 0.5 탆 to 50 탆 when the second composition is sprayed.

The primary spray and the secondary spray may be independently performed at a pressure of 1 to 10 kg / cm < ² > at room temperature.

The step of forming the organic thin film layer may include a step of secondly spraying the second composition onto the surface of the first sprayed metal substrate and drying and washing the second sprayed metal substrate.

Wherein the metal substrate comprises at least one member selected from the group consisting of steel, electrogalvanized steel (EG), galvannealed steel (GA), and galvanized steel (GI) .

The polymer base material may include at least one selected from polyolefins, polyamides, polyesters, polyacrylates, and polymethacrylates.

The step of attaching the polymer substrate on the organic thin film layer may be performed by a melt adhesion method.

The melt adhesion method may be carried out under a pressure of 1 to 20 MPa for 5 to 20 minutes at a temperature 20 to 40 DEG C higher than the melting point of the polymer base.

According to the method for producing a metal-polymer composite material of the present invention, a primary bond between a metal and a polymer is formed by grafting a polymer onto the surface of a metal substrate, It has a strong bonding force as compared with the secondary bonding using a functional group, and is resistant to moisture and other chemical environments, so that the long and short term stability of the composite material can be secured.

In the present invention, by applying the spray process differently from the conventional dipping process, the time required per surface area can be remarkably shortened and the amount of treatment can be greatly increased.

In addition, the metal-polymer composite material according to the present invention is expected to contribute greatly in the fields of automobiles and aerospace, which require high strength and light weight.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate preferred embodiments of the invention and, together with the description of the invention given below, serve to further augment the technical spirit of the invention. And should not be construed as limiting.
Figure 1 is a schematic diagram of a redox active grafting reaction.
FIG. 2 is a schematic view showing a stepwise process using the grafting reaction mechanism according to FIG. 1; FIG.
3 is a schematic view of a process of grafting a metal substrate using a continuous spray process according to an embodiment of the present invention.
4 is a schematic view of a specimen for measuring the shear strength of a metal-polymer composite according to an embodiment of the present invention.
5 is a photograph of a UTM instrument for measuring the shear strength of a metal-polymer composite according to an embodiment of the present invention.
6 is a graph showing the shear strength measurement results of the metal-polymer composite material according to Example 1 and Comparative Example 1. Fig.

Hereinafter, the present invention will be described in detail. Prior to this, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms, and the inventor should appropriately interpret the concepts of the terms appropriately It should be interpreted in accordance with the meaning and concept consistent with the technical idea of the present invention based on the principle that it can be defined.

Therefore, the configurations shown in the embodiments described herein are merely the most preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents And variations are possible.

Conventionally, a grafting process such as electrographing has been applied in order to impart functionality to the surface of a metal substrate or the like. Specifically, the prevention of oxidation of the metal surface and the insulating effect can be seen as typical functions. However, there is no application of the grafting process to improve the adhesion between metal and CFRP.

In the present invention, the polymer grafting process is applied to ensure the stability and reliability of a metal-polymer composite material. In addition, by applying the grafting process to a continuous spray process, a new grafting technique that can be mass-produced at low cost can be suggested.

According to an aspect of the present invention, there is provided a method of manufacturing a metal-

First spraying a first composition comprising a monomer, a diazonium salt and a first solvent on the surface of a metal substrate;

A second composition comprising a reducing agent and a second solvent is secondarily sprayed onto the surface of the first sprayed metal substrate to form an organic thin film layer comprising a monomer grafted with the monomer; And

And attaching the polymer substrate on the organic thin film layer.

The monomer may be any monomer as long as it is capable of graft polymerization, and vinyl monomer or cyclic monomer may be used. Specific examples of such vinyl-based monomers include at least one member selected from the group consisting of acrylonitrile, methyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, and acrylic acid. As the cyclic monomer, lactic acid, glycolic acid And? -Caprolactone may be applied.

The diazonium salt can be applied without limitation as long as it is a substance that generates a benzene diazonium cation. For example, the diazonium salt may be used in the form of tetrafluoroborates, halides, sulphates, phosphates, carboxylates, perchlorates or hexafluoro phosphates, Or a mixture of these salts. Specific examples of the diazonium salt include p-chlorobenzene diazonium, 2,4-dichlorobenzene diazonium, 2,5-dichlorobenzene diazonium, 2,4,6-trichlorobenzene diazonium, 2,4- 2-nitrobenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, , 4-methylbenzene diazonium, 3-methylbenzene diazonium, 2,4-dimethoxybenzene diazonium, 2,4-dimethyl-6-nitrobenzene diazonium, 2-chloro-4-dimethyl- Diazonium, and the like.

More specifically, the diazonium salt is selected from the group consisting of 4-nitrobenzene diazonium tetrafluoroborate, 4-methoxybenzene diazonium tetrafluoroborate, 4-nitrobenzene diazonium perchlorate, and 4- Trifluoromethylbenzene tetrafluoroborate, and the like.

In addition, the first solvent may be any solvent that can dissolve the diazonium salt and the monomer to form a homogeneous solution, and the non-limiting example thereof may include water.

The first composition may include 100 parts by weight of the monomer, 10 to 50 parts by weight of the diazonium salt, and 5,000 to 7,000 parts by weight of the first solvent.

Specifically, the content of the diazonium salt may be 10 to 50 parts by weight, specifically 20 to 40 parts by weight, more specifically 28 to 32 parts by weight based on 100 parts by weight of the monomer.

When the content of the diazonium satisfies the above range, the grafting efficiency with respect to the process cost can be maximized. In order for the grafting to occur densely on the metal surface, a large amount of diazonium is preferred, but in general, the diazonium salt minimizes the amount of extra diazonium salt that is not involved in the reaction, There is a need. The amount of the diazonium is an amount capable of optimizing the amount.

The content of the first solvent may be 5,000 to 7,000 parts by weight, specifically 5,500 to 6,500 parts by weight, more specifically 6,200 to 6,300 parts by weight based on 100 parts by weight of the monomer.

When the first solvent satisfies this content range, it is possible to optimize the length of the polymer chain produced through the grafting. As the length of the polymer chain increases, the adhesive strength generally increases. However, when the polymer chain is too large, the movement of the chain is limited. As a result, entanglement with the bulk polymer is not smoothly performed, . The content is an amount capable of optimizing the length of the polymer chain.

The reducing agent serves to reduce the diazonium salt in the solution. Specifically, the diazonium salt is formed into an aryl radical to cause a redox-active grafting reaction.

As the reducing agent, ascorbic acid (or vitamin C), iron powder, trisodium citrate, NaBH ₄ , phenylhydrazine HCl, phenylhydrazine, and hydrazine may be applied. In this case, for example, a product having a diameter of 1 to 30 탆 may be used as the iron powder. When the diameter of the iron powder satisfies the above range, the iron powder has a large specific surface area. As a result, a small amount of iron powder It maximizes the reducing power even when it is in use and can induce quick reaction.

The second composition may include 100 parts by weight of a reducing agent and 200,000 to 300,000 parts by weight of a second solvent. Specifically, the content of the second solvent based on 100 parts by weight of the reducing agent may be 200,000 to 300,000 parts by weight, specifically 250,000 to 300,000, more specifically 280,000 to 290,000 parts by weight.

When the second solvent satisfies this content range, the amount of unnecessary reducing agent can be minimized. In the case of the reducing agent, it does not require a large amount because it only serves to assist the reaction, and if it is too much, it may act as an impurity in the solution, which is not preferable. The content is an amount capable of maximizing the reaction rate.

1 shows a schematic diagram of a redox active grafting reaction, in which 4-nitrobenzene diazonium is used as a diazonium salt and vitamin C (VC) is used as a reducing agent, a diazonium salt is formed as an aryl radical by a reducing agent , The resulting aryl radical is grafted onto the metal substrate, and then the chain is extended by the reaction of the aryl radicals continuously.

That is, 4-nitrobenzene diazonium (NBD, diazonium salt) which is stably dissolved in distilled water or an aqueous acid solution has a positive reduction potential relative to a standard hydrogen electrode, so that it can easily receive electrons and be reduced. On the other hand, the open circuit potential of a metal substrate such as steel used in the present invention has a negative value relative to a standard hydrogen electrode, so that the NBD salt can be reduced by a potential difference without supplying a special external power source.

In addition, the reduced diazonium salt forms an aryl radical with nitrogen (N ₂ ), and the generated aryl radical is bonded to the surface of the metal substrate in the solution to form a poly (nitrophenylene) (PNP) organic layer. In the present invention, the PNP organic layer is processed by the redox active reaction. By carrying out the redox active reaction by grafting with the addition of a reducing agent, the reaction time can be shortened and the grafting efficiency can be improved.

FIG. 2 is a schematic view showing a stepwise process using the grafting reaction mechanism according to FIG. 1; FIG.

First, a diazonium salt solution (20) is prepared by preparing a first solvent (10), and then a diazonium salt solution (20) is applied to the substrate (30). Subsequently, when a reducing agent is added to the diazonium salt solution (20), a reducing agent generates a diazonium salt as an aryl radical, and then a grafting reaction proceeds on the substrate with the aryl radical.

The metal substrate may be made of steel, gold (Au), copper (Cu) or the like. The steel may be pure steel (steel plate), galvanized steel, electrogalvanized steel Galvanized steel (GA), galvanized steel (GI), and the like can be applied.

According to the present invention, a grafting process for polymer grafting on a metal substrate surface introduces a spray process rather than a conventional immersion process.

The spray process comprises the steps of first spraying a first composition comprising a monomer, a diazonium salt and a first solvent onto the surface of a metal substrate, and a second composition comprising a reducing agent and a second solvent, And secondarily spraying the surface of the metal substrate to form a layer of an organic thin film on the metal substrate, the polymer including the polymer grafted with the monomer.

That is, continuous grafting is possible by first spraying the diazonium salt and the monomer dissolved in the first solvent, and then spraying the second composition containing the reducing agent secondarily. The spray pressure and temperature can be kept constant during the process to produce uniform grafting on the metal substrate and can be subjected to a cleaning step after the grafting through the spray process is complete.

3 is a schematic view of a process of grafting a metal substrate using a continuous spray process according to an embodiment of the present invention.

The metal substrate 110 is continuously supplied to the constant temperature zone 120 where the diazonium salt and monomers are dissolved in a first solvent to provide a first composition for storing and supplying the first composition A feed tank 130 and a second composition feed tank 140 for storing and supplying a second composition prepared by dissolving a reducing agent in a second solvent are connected through a feed line. When the metal substrate 110 is supplied to the constant temperature zone 120, the first composition containing the diazonium salt and the monomer is supplied to the surface of the metal substrate through the spraying (120) facility in the first composition supply tank 130, And then a second composition comprising a reducing agent is secondarily sprayed onto the first sprayed metal substrate surface from the second composition feed tank.

Since the spraying process is carried out twice in the same manner as in the present invention, the spray time of the diazonium salt and the reducing agent are distinguished, and these solutions can be stably stored until they are used.

In addition, as the particles of the composition to be sprayed are smaller, the laplace pressure is increased and the wettability is improved, so that the composition can be completely penetrated to the surface of the metal base material and the metal base material having a high roughness Can be easily applied to the surface of the substrate.

The first composition may be applied onto the metal substrate with the particles being 0.5 to 50 microns, particularly 1 to 20 microns, and more particularly 5 to 15 microns in size when sprayed first.

The second composition may be applied on the primary sprayed metal substrate with the particles being 0.5 to 50 microns, particularly 1 to 20 microns, and more particularly 5 to 15 microns in size when sprayed second .

When the particle size of the first composition and the second composition during spraying satisfies this range, it is possible to optimize the amount of grafting to obtain a resultant maximized adhesive force, and the wettability of the sprayed particles to the metal surface increases , Enabling more uniform grafting of the metal surface.

The primary spray and the secondary spray can be independently performed at a pressure of 1 to 10 kg / cm < ² > at room temperature.

The step of forming the organic thin film layer may include the steps of: secondarily spraying a second composition containing the reducing agent and a second solvent on the surface of the first sprayed metal substrate; and drying and cleaning the second sprayed metal substrate .

The washing may be performed by drying the metal substrate at 25 to 80 ° C for 1 to 2 hours after completion of the secondary spray, confirming that the solution is dried, and using an organic solvent such as acetone. By removing the organic materials (monomers, diazonium salts, etc.) which can not properly form the organic thin film layer on the surface of the metal substrate through the cleaning step, these unreacted organic materials act as foreign substances when forming the interface with the polymer substrate Can be prevented.

The polymer substrate is attached to and bonded to the organic thin film layer of the polymer-grafted metal substrate to form a metal-polymer composite material.

As the polymer substrate, any thermoplastic polymer capable of melt bonding with the organic thin film layer can be used without limitation. Specific examples thereof include polyolefin (polyethylene, polypropylene, etc.), polyamide (nylon, etc.), polyester (polyethylene terephthalate ), Polyacrylate, polymethacrylate (polymethylmethacrylate (PMMA), etc.) can be applied.

The step of attaching the polymer substrate on the organic thin film layer may be performed by a melt adhesion method. The melt adhesion method may be carried out under a pressure of 1 to 20 MPa for 5 to 20 minutes at a temperature 20 to 40 DEG C higher than the melting point of the polymer base.

According to one embodiment of the present invention, the polymer grafted to the surface of the metal substrate may have physical properties similar to those of the polymer itself by forming an entanglement structure with a bulk polymer such as a polymer substrate.

That is, when the polymer and the metal have weak secondary bonding, weak interface property occurs due to the adhesive failure at the interface. However, when the polymer and the metal have strong primary bonding, A cohesive failure may occur, and the interfacial properties can be improved to be close to the physical properties of the polymer. Then, by maximizing the entanglement between the grafted polymer density of the organic thin film layer on the surface of the metal substrate and the polymer substrate, an interface having the maximum adhesive force can be obtained.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to the following examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the following embodiments. Embodiments of the invention are provided to more fully describe the present invention to those skilled in the art.

Example 1

(1) Preparation of Grafting Composition

0.02 M of 4-nitrobenzene diazonium tetrafluoroborate solution in deionized water as a diazonium salt and 0.3 M of acrylonitrile solution in deionized water as a monomer were mixed to prepare a first composition.

Further, a second composition was prepared by adding 0.002 M ascorbic acid solution in deionized water as a reducing agent.

(2) Preparation of metal substrate

Steel (manufactured by Hyundai Steel Co., Ltd., electroplated steel sheet) having a length of 101 mm and a width of 25.4 mm was prepared as a metal base material.

(3) Spray process

With the aid of a manual spray device (atomizer), the first composition was first sprayed on a steel surface with 1 ml at 25 占 폚. The first sprayed first composition was then allowed to stand for one minute to allow complete penetration of the steel surface. The second composition was then secondarily sprayed onto the surface of the primary sprayed metal substrate at 25 占 폚 in 1 ml.

After 20 minutes, the second composition was dried. After immersing in the acetone solution, it was washed with acetone for 1 minute using sonication to form an organic thin film layer.

The average particle size of the first composition at the time of primary spraying was 10 mu m and the average particle size of the second composition at the secondary spraying was 10 mu m on average.

(4) Attachment of polymer substrate

A polypropylene film (Goodfellow Co.) having a thickness of 0.125 mm was laminated on the organic thin film layer of the metal substrate prepared above, and then heated to 40 ° C higher than the melting point (about 170 ° C) of the polymer by using a hot press equipment The resultant was treated at a temperature of 210 캜 at a pressure of 5 MPa for 10 minutes and then cooled at room temperature to form an adhesion between the polymer and the metal to prepare a metal-polymer composite material.

Comparative Example 1

A metal substrate similar to that of Example 1 was prepared and a polypropylene substrate having a thickness of 0.1 mm was attached to the surface of the metal substrate using a melt adhesion method to prepare a metal-polymer composite material.

Adhesion evaluation

The shear strength of the composite material prepared in Example 1 and Comparative Example 1 was measured using an ASTM D1002 (single lap joint test) evaluation method to evaluate the adhesive strength.

At this time, a specimen (single lap shear specimen) for measurement was prepared as shown in FIG. 4, the metal-polymer composite material prepared in Example 1 and the metal having only the organic thin film layer formed thereon before attaching the polymer substrate to the metal substrate 200 / organic thin film layer 220 / 210 / organic thin film layer 220 / metal substrate 200, and the overlapped section was 25.4 x 12.7 mm ² .

Length of specimen (following ASTM D1002)

a: width of specimen (25.4 mm)

b is the length of the tab attached to the specimen, used to generate pure shear deformation only at the interface between superposed shear tests. (25.4 mm)

c: length of metal substrate (101.6 mm)

d: overlap length for overlapping shear test (12.7 mm)

The shear strength was measured using the UTM equipment shown in Fig.

The results are shown in Table 1 and FIG.

Shear strength (MPa) Example 1 1.63 Comparative Example 1 0.12

Referring to Table 1 and FIG. 6, it was confirmed that the single lap shear test showed that the polypropylene base material having almost no adhesive force in the pure steel had a significantly improved adhesion on the steel surface subjected to the spraying process.

This is because the organic thin film layer 220, that is, the polymer layer grafted on the surface of the metal substrate, becomes an intermediate material connecting the metal substrate and the polymer substrate, and thus forms a primary bond with the metal substrate, and entanglement with the polymer substrate, The results of this study are as follows.

Claims (15)

First spraying a first composition comprising a monomer, a diazonium salt and a first solvent on the surface of a metal substrate;
A second composition comprising a reducing agent and a second solvent is secondarily sprayed onto the surface of the first sprayed metal substrate to form an organic thin film layer comprising a monomer grafted with the monomer; And
And attaching the polymer substrate on the organic thin film layer. The method according to claim 1,
Wherein the monomer is at least one selected from the group consisting of acrylonitrile, methyl acrylate, butyl methacrylate, hydroxyethyl methacrylate, acrylic acid, lactic acid, glycolic acid, and epsilon -caprolactone. ≪ / RTI > The method according to claim 1,
Wherein the diazonium salt is at least one selected from the group consisting of p-chlorobenzene diazonium, 2,4-dichlorobenzene diazonium, 2,5-dichlorobenzene diazonium, 2,4,6-trichlorobenzene diazonium, Nitrobenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, 4-methylbenzene diazonium, Benzene diazonium, 3-methylbenzene diazonium, 2,4-dimethoxybenzene diazonium, 2,4-dimethyl-6-nitrobenzene diazonium, and 2-chloro-4-dimethyl- Based on the total weight of the metal-polymer composite material. The method according to claim 1,
Wherein the diazonium salt is selected from the group consisting of 4-nitrobenzene diazonium tetrafluoroborate, 4-methoxybenzene diazonium tetrafluoroborate, 4-nitrobenzene diazonium perchlorate, and 4-trifluoromethyl Benzene tetrafluoroborate, wherein the metal-polymer composite material comprises at least one selected from the group consisting of benzene tetrafluoroborate. The method according to claim 1,
Wherein the reducing agent comprises at least one selected from the group consisting of ascorbic acid, iron powder, trisodium citrate, NaBH ₄ , phenylhydrazine HCl, phenylhydrazine, and hydrazine. The method according to claim 1,
Wherein the first composition comprises 100 parts by weight of a monomer, 10 to 30 parts by weight of a diazonium salt, and 60 to 100 parts by weight of a first solvent. The method according to claim 1,
Wherein the second composition comprises 100 parts by weight of a reducing agent and 4,000 to 6,000 parts by weight of a second solvent. The method according to claim 1,
Wherein the first composition is applied on the metal substrate with the particles having a size of 0.5 탆 to 50 탆 when the first composition is sprayed. The method according to claim 1,
Wherein the second composition is applied on the first sprayed metal substrate with particles of a size between 0.5 and 50 micrometers when the second composition is sprayed second. The method according to claim 1,
Wherein the primary spray and the secondary spray are independently performed at room temperature at a pressure of 1 to 10 kg / cm < ² >. The method according to claim 1,
Wherein the step of forming the organic thin film layer comprises the steps of: secondarily spraying the second composition onto the surface of the first sprayed metal substrate; and drying and washing the second sprayed metal substrate. A method for manufacturing a composite material. The method according to claim 1,
Wherein the metal substrate is a metal-polymer composite material comprising at least one selected from the group consisting of steel, electrogalvanized steel, galvannealed steel, and galvanized steel Gt; The method according to claim 1,
Wherein the polymer substrate comprises at least one selected from the group consisting of polyolefins, polyamides, polyesters, polyacrylates, and polymethacrylates. The method according to claim 1,
Wherein the step of attaching the polymer substrate on the organic thin film layer is performed by a melt adhesion method. 15. The method of claim 14,
Wherein the melt adhesion method is carried out under a pressure of 1 to 20 MPa for 5 to 20 minutes at a temperature 20 to 40 DEG C higher than the melting point of the polymer base material.

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