KR102044239B1

KR102044239B1 - A nucleating agent for laser direct structuring, preparation thereof, and a method for preparing conductive copper thin-film pattern using the same

Info

Publication number: KR102044239B1
Application number: KR1020160020654A
Authority: KR
Inventors: 정진미; 신부건; 정유진
Original assignee: 주식회사 엘지화학
Priority date: 2016-02-22
Filing date: 2016-02-22
Publication date: 2019-11-13
Also published as: KR20170098567A

Abstract

Provided are a nucleating agent for laser direct structuring using an additive including a plate-shaped copper oxide nanomaterial instead of a conventional additive, a method for manufacturing the same, and a method for manufacturing a conductive copper thin film pattern using the same. Uniform conductive thin film patterns can be effectively produced without affecting the mechanical properties of the product.

Description

Nucleating agent for laser direct structuring, preparation method thereof, and method for manufacturing a conductive copper thin film pattern using the same {A nucleating agent for laser direct structuring, preparation invention, and a method for preparing conductive copper thin-film pattern using the same}

Provided are a nucleating agent for laser direct structuring, a method of manufacturing the same, and a method of manufacturing a conductive copper thin film pattern using the same. More specifically, the present invention relates to a nucleating agent for laser direct structuring using an additive including a plate-shaped copper oxide nanomaterial instead of a conventional additive, a method for manufacturing the same, and a method for manufacturing a conductive copper thin film pattern using the same.

Laser direct structuring (LDS) is a method of directly forming a conductive thin film pattern using a laser. The circuit directly forms a conductive thin film pattern on a three-dimensional structure by shortening the pattern formation time and facilitating the formation of a three-dimensional pattern. And the antenna manufacturing process.

In the LDS process, the thermoplastic resin composition may be doped with an additive for the metal-containing LSD to be activated by a laser.

Laser direct structuring uses a laser to irradiate the surface of the resin molding containing the additive before the plating process to pattern the surface of the resin molding to have a certain roughness, and at the same time act as a nucleating agent with energy absorbed by the laser irradiated surface. It is based on allowing the material of the additive to be substituted to form a metal seed.

Due to the roughness of the surface of the metal seed and the resin molded body, the surface on which the metal seed is formed becomes the plating selectivity, and as a result, a metal layer that is densely and tightly bonded only to the region to which the laser is irradiated is formed and plated.

Meanwhile, the thermoplastic resin composition used in the LSD process may further include a supporting material. The support may be iron oxide or aluminum oxide in the form of natural and / or synthetic mica, talc, kaolin, flakes, glass flakes, SiO ₂ flakes, TiO ₂ flakes, mixed oxides in flake form, for example FeTiO ₃ , Fe ₂ TiO ₅ , graphite flakes and the like. In general, the support serves as an inorganic filler added to the thermoplastic resin composition to be laser direct structuring to improve mechanical strength.

The most important part of the formation mechanism of the conductive metal pattern is the formation of the metal seed by the interaction of the additives added to the thermoplastic resin composition and the laser energy to be irradiated.

As additives for LDS, spinel-based metal oxides (e.g., copper chromium oxides), organometallic complexes (e.g. palladium complexes, copper complexes) are used, but in the case of organometallic complexes when activated by laser irradiation A relatively high amount must be introduced into the resin for dense nucleation, which can change or negatively affect the basic properties of the final product. In addition, commercially available laser-absorbing additive species are added granulated mostly in the order of tens to tens of micrometers for dispersion. No examples of nanomaterials being used as LDS additives have been reported so far, because it is difficult to disperse in solution without special surface treatment and it is difficult to maintain a particularly uniform dispersion in a compounding process that is not a complete fluidized bed.

The technical problem to be achieved by the present invention is to provide a nucleating agent for laser direct structuring, including a nanostructured additive in place of the conventional additives, a method for manufacturing the same and a method for producing a conductive copper thin film pattern using the same.

According to an aspect of the present invention to achieve the above technical problem,

Support;

A plate-type copper oxide nanomaterial layer coated on the support; And

Provided is a nucleating agent for laser direct structuring comprising a reducing agent layer coated on the plate-shaped copper oxide nanomaterial layer.

According to another aspect of the invention,

Adding copper acetate solution and sodium hydroxide solution to the support and then stirring to grow copper oxide nano flakes on the support;

Filtering and drying the resultant to obtain a support coated with a plate-shaped copper oxide nanomaterial layer; And

Adding the support coated with the plate-shaped copper oxide nanomaterial layer to an aqueous solution containing a reducing agent, followed by stirring to coat the reducing agent layer.

A method for producing a nucleating agent for laser direct structuring is provided.

According to another aspect of the invention,

Support; A plate-type copper oxide nanomaterial layer coated on the support; And producing a nucleating agent for laser direct structuring comprising a reducing agent layer coated on the plate-shaped copper oxide nanomaterial layer.

Coating a solution comprising the nucleating agent for laser direct structuring on a substrate;

Irradiating a laser onto the substrate coated with the laser direct structuring nucleating agent to form a copper seed; And

Plating the substrate on which the copper seed is formed;

A method of forming a conductive copper thin film pattern is provided.

According to another aspect of the invention,

Combining the substrate with the nucleating agent for direct laser structuring;

Irradiating a laser onto the blended substrate to form a metal seed; And

Plating the substrate on which the copper seed is formed;

A method of forming a conductive copper thin film pattern is provided.

According to an aspect of the present invention, it is possible to obtain a desired conductive copper thin film pattern while not damaging the mechanical properties of the final product. In addition, the spinel-based nucleating agent is used at least 2wt% to 10wt% with respect to the total resin mass as the additives for the reinforcement of physical properties are basically included in the production of engineering plastic injection products. By coating nanomaterials on the surface of inorganic additives, it is possible to simplify the process and efficiently disperse the resin by acting as a nucleating agent at the same time as reinforcing properties.

1 is a view showing step by step a method for producing a laser direct structuring nucleating agent according to an embodiment of the present invention.
2 is a step-by-step view showing a method for manufacturing a laser direct structuring nucleating agent according to another embodiment of the present invention.
3 is a view schematically illustrating a step of forming a copper seed by irradiating a laser to a laser direct structuring nucleating agent prepared according to an embodiment of the present invention.
Figure 4 is a SEM photograph showing the copper oxide nanoflakes formed on the support according to Preparation Example 2 of the present invention, compared to the independently formed copper oxide nanoflakes.
5 is a photograph showing a conductive copper thin film in the form of a spot formed in accordance with Example 1 of the present invention.
Figure 6a is a view showing the laser processing conditions performed in Example 2 of the present invention, Figure 6b is a photograph showing a conductive copper thin film plated according to Example 2 with a control.

Hereinafter, the present invention will be described in more detail.

Nucleating agent for laser direct structuring according to an aspect of the present invention support; A plate-type copper oxide nanomaterial layer coated on the support; And a reducing agent layer coated on the plate-shaped copper oxide nanomaterial layer.

As used herein, the term "nucleating agent" is a component that is reduced during laser irradiation to form a metal seed that acts as a nucleus for forming a metal thin film in a subsequent plating process, and may be used in the same sense as a conventional laser direct structuring additive. In addition, other components other than the laser direct structuring additive, for example, may be used in the sense including a support and a reducing agent.

In the present invention, instead of adding the plate-shaped copper oxide nanomaterial serving as a conventional additive to the thermoplastic resin composition separately from the support, the composition is grown and coated on the support to simplify the composition of the thermoplastic resin composition and to simultaneously disperse the plate-shaped metal oxide nanomaterial. By evening the metal seed formation can be effectively achieved. In addition, in the present invention, unlike the metal oxide particles used as a conventional additive, by using a plate-shaped copper oxide nanomaterial, the copper plating proceeding afterwards through a more effective seed formation can be made dense and effective.

In the present invention, the base material of the nucleating agent is a nanometer sized copper oxide material, characterized in that the support of the micrometer scale for uniform dispersion thereof.

The support may be used without limitation, inorganic materials generally used in the thermoplastic resin composition used for laser direct structuring, for example, mica flakes, SiO ₂ flakes, Al ₂ O ₃ flakes, Fe ₂ O ₃ It may be at least one selected from flakes, glass flakes, kaolin and talc.

The support may generally be used without limitation the size of the thermoplastic resin composition to be subjected to laser direct structuring, for example, the length of one side may be 1㎛ to 100㎛.

The plate-shaped copper oxide nanomaterial may be a material grown in a plate shape having a side length of 50 to 500 nm and a thickness of 5 to 50 nm.

In addition, the support may be coated with TiO ₂ or ZnO. TiO ₂ generally has an effect of improving plating performance in a thermoplastic resin composition for laser direct structuring. However, TiO ₂ is known to reduce mechanical properties of a product. In the present invention, TiO ₂ is added to a support instead of being included in a thermoplastic resin composition. The TiO ₂ was fixed by coating and again coating the plate-shaped copper oxide nanomaterial thereon.

The reducing agent layer includes a reducing agent that serves to reduce the plate-shaped copper oxide nanomaterials upon laser irradiation to form a copper seed, and may be, for example, polyvinylpyrrolidone or polyethylene glycol.

The reducing agent layer may further include an absorption additive, for example, carbon black, and the carbon black may form a black color and efficiently increase the laser absorption rate.

According to another aspect of the present invention, a method for preparing a laser direct structuring nucleating agent includes adding copper acetate solution and sodium hydroxide solution to a support, followed by stirring to grow copper oxide nanoflakes on the support; Filtering and drying the resultant to obtain a support coated with a plate-shaped copper oxide nanomaterial layer; And adding the support coated with the plate-shaped copper oxide nanomaterial layer to an aqueous solution including a reducing agent, followed by stirring to coat the reducing agent layer.

1 is a view showing step by step a method for producing a laser direct structuring nucleating agent according to an embodiment of the present invention.

According to FIG. 1, a support is first prepared (S100), and copper oxide nanoflakes are grown on the support and then coated with a plate-shaped copper oxide nanomaterial layer (S110). Then, it is coated with a reducing agent layer (S120).

The support may be at least one selected from mica flakes, SiO ₂ flakes, Al ₂ O ₃ flakes, Fe ₂ O ₃ flakes, glass flakes, kaolin and talc, for example 1 μm. To 100 μm.

For example, copper acetate aqueous solution, sodium hydroxide aqueous solution and additionally a particle growth stabilizer are mixed with the support, and the obtained precipitate is filtered and dried, and copper oxide nano flakes are grown on the support and plate-like through filtration and drying. A support coated with a copper oxide nanomaterial can be obtained.

At this time, the copper oxide nano flakes may be prepared by reacting the copper acetate and sodium hydroxide in a molar ratio of 1: 2 to 1:10.

Thioglycerol, 1,6-hexadiamine, hexamethylenetetraamine, etc. can be used as said particle growth stabilizer.

The particle growth stabilizer may be 0.005 to 1% by weight based on the combined amount of copper acetate and sodium hydroxide.

The plate-shaped copper oxide nanomaterial is a material grown in a plate shape having a side length of 1 μm or less, and the ratio of the length (thickness) in the vertical direction to the length of one side of the plate surface is 0.5 or less, and the shape of the surface is approximately square. The shape is not limited thereto. For example, when the plate-shaped copper oxide nanomaterial has a rectangular plate surface, the length of one side is 500 nm or less, for example, the length of one side is 50 to 200 nm, and the thickness is 5 to 50 nm. Can be.

The support coated with the plate-shaped copper oxide nanomaterial obtained as described above was added to an aqueous solution containing a reducing agent and then stirred, and the resulting product was filtered and coated with a reducing agent layer on the plate-shaped copper oxide nanomaterial layer coated on the support. You get a nucleating agent.

The aqueous solution containing the reducing agent may further include an absorption additive, for example, carbon black.

Before the support is coated with the plate-shaped copper oxide nanomaterial layer, the support may be coated with TiO ₂ , for example, by a sol-gel method. Through this, it is possible to minimize the deterioration of mechanical properties by the additional introduction of TiO ₂ and to increase the plating performance.

2 is a step-by-step view showing a method for manufacturing a laser direct structuring nucleating agent according to another embodiment of the present invention.

As shown in FIG. 2, first, a support is prepared (S200), and copper oxide nanoflakes are grown on the support and then coated with a plate-shaped copper oxide nanomaterial layer (S210). Then, it is coated with a reducing agent layer (S220). At this time, the step of preparing a support (S200) further comprises the step of coating the support with TiO ₂ .

According to another aspect of the present invention, a method of manufacturing a conductive copper thin film pattern includes a support; A plate-type copper oxide nanomaterial layer coated on the support; And producing a nucleating agent for laser direct structuring comprising a reducing agent layer coated on the plate-shaped copper oxide nanomaterial layer. Coating a solution comprising the nucleating agent for laser direct structuring on a substrate; Irradiating a laser onto the substrate coated with the laser direct structuring nucleating agent to form a copper seed; And plating the substrate on which the copper seed is formed.

The support may be at least one selected from mica flakes, SiO ₂ flakes, Al ₂ O ₃ flakes, Fe ₂ O ₃ flakes, glass flakes, kaolin and talc, and have a size of 1 μm to 100 μm.

The plate-shaped copper oxide nanomaterial may have a length of 100 to 200 nm and a thickness of 5 to 50 nm.

The support may be, for example, coated with TiO ₂ by a sol-gel method.

The plate-shaped copper oxide nanomaterial may be prepared by reacting copper acetate and sodium hydroxide in a molar ratio of 1: 2 to 1:10.

The laser may be performed under conditions of an output of 3 to 25 W, a repetition rate of 20 to 200 kHz, and a speed of 800 mm / s to 2500 mm / s based on a 1064 nm pulse laser.

3 is a view schematically illustrating a step of forming a copper seed by irradiating a laser to a laser direct structuring nucleating agent prepared according to an embodiment of the present invention.

As shown in FIG. 3, when a laser is irradiated to a nucleating agent coated with a reducing agent layer on a layer of a copper oxide nanomaterial coated on a support, for example, mica, the copper oxide nanomaterial coated on the mica is reduced by a reducing agent to form a metal. Seeds are formed.

Plating copper on the copper seed layer is not particularly limited, and may be performed through a general plating process. For example, it can be performed by electroless plating.

According to another aspect of the present invention, a method of manufacturing a conductive copper thin film pattern includes a support; A plate-type copper oxide nanomaterial layer coated on the support; And producing a nucleating agent for laser direct structuring comprising a reducing agent layer coated on the plate-shaped copper oxide nanomaterial layer. Combining the substrate with the nucleating agent for direct laser structuring; Irradiating a laser onto the blended substrate to form a metal seed; And plating the substrate on which the copper seed is formed.

When blending the substrate and the nucleating agent for laser direct structuring according to the present invention, the compound can be irradiated with laser after injection molding, for example.

In the present invention, the laser direct structuring nucleating agent is directly coated on the surface of the molded thermoplastic resin, or blended into the thermoplastic resin composition, and then, after molding the compound and irradiating a laser, the laser direct structuring nucleating agent is substituted for plating. Serving as a metal seed, a desired conductive metal thin film pattern can be obtained.

The plate-shaped copper oxide nanomaterial may be prepared by, for example, mixing a copper acetate aqueous solution, an aqueous sodium hydroxide solution, and additionally, a particle growth stabilizer, and then drying the obtained precipitate. At this time, the copper acetate may be prepared by reacting sodium hydroxide in a molar ratio of 1: 2 to 1:10.

The plate-shaped copper oxide nanomaterial may have a particle size of 1 μm or less. For example, the plate-shaped copper oxide nanomaterial may have a particle size of 500 nm or less, specifically, the plate-shaped copper oxide nanomaterial may have a length of 100 to 200 nm and a thickness of 5 to 50 nm.

The laser may have a wavelength of 1064 nm, 1090 nm, 9.3 μm, or 10.6 μm, and is most suitable for the current process while the laser of 1064 nm wavelength is widely used.

When irradiating a laser to the laser direct structuring nucleating agent, a laser irradiation method using a laser or a high output flash lamp may be used.

In the present invention, a pulsed laser or continuous wave (CW) laser may be used as the laser light. When the laser is irradiated to the support coated with the reducing agent layer and the plate-shaped copper oxide nanomaterial layer in turn, the copper oxide is reduced to copper and simultaneously sintered to form a metal seed layer.

According to one embodiment of the present invention, a copper conductive thin film pattern can be effectively obtained compared to the conventional laser direct structuring (LDS) method without being adversely affecting the mechanical properties of the substrate.

The present invention will be described in more detail with reference to the following examples. These examples are merely exemplary and do not limit the technical scope of the present invention.

Preparation of nucleating agent for laser direct structuring

Preparation Example 1

250 g of 0.5 M CuCH ₃ (COO) ₂ H ₂ O solution was added to 50 g of mica (Ecotec, 15 to 20 μm), followed by stirring at 1500 rpm for several minutes. Then, 100 μl of thioglycerol was added thereto, followed by stirring for several minutes. Was added. Then, the resulting product was filtered, washed several times with distilled water and dried. The powder thus obtained was added to an aqueous solution in which 0.5 g of polyvinylpyrrolidone and 3 g of polyethylene glycol were dissolved in 100 ml of ethanol, stirred for 1 day, and filtered to coat a reducing agent.

Preparation Example 2

TiO ₂ was coated on the mica by the sol-gel method. Then, 250 ml of 0.5 M CuCH ₃ (COO) ₂ H ₂ O solution was added to the resulting solution, followed by stirring at 1500 rpm for several minutes. Then, 100 μl of thioglycerol was added thereto, followed by stirring for several minutes, and then 250 ml of 5 M NaOH solution was added thereto.

Then, the resulting product was filtered, washed several times with distilled water and dried.

The powder thus obtained was added to an aqueous solution in which 0.5 g of polyvinylpyrrolidone and 3 g of polyethylene glycol were dissolved in 100 ml of ethanol, stirred for 1 day, and filtered to coat a reducing agent.

4 is a SEM photograph showing the copper oxide nanoflakes formed on the TiO ₂ -coated support body according to Preparation Example 2 of the present invention compared to the independently formed copper oxide nanoflakes.

As shown in FIG. 4, when the plate-shaped copper oxide nanomaterial layer was formed on TiO ₂ coated mica, it was confirmed that the TiO ₂ was formed in the same shape and scale as those synthesized independently.

In addition, the composition was confirmed through EDS, and the results are shown in Tables 1 and 2 below.

element weight% atom% C K 5.18 9.08 O K 45.87 60.46 Al K 13.54 10.58 Si K 17.58 13.20 Ti K 14.30 6.30 Pt K 3.52 0.38 Sum 100.00

element weight% atom% C K 17.04 27.22 O K 44.76 53.67 Al K 8.93 6.35 Si K 10.75 7.34 Ti K 3.44 1.38 Cu L 12.54 3.79 Pt K 2.53 0.25 Sum 100.00

Table 1 shows the results for which the TiO ₂ coating on the mica sample, the Table 2 and the TiO ₂ coating on mica, the results for the coated sample copper oxide nano-material layer on the TiO _2. As shown in Table 1 and Table 2, it can be confirmed that the copper oxide nanomaterial layer was formed.

Example 1

A solution obtained by dispersing the laser direct structuring agent prepared in Preparation Example 1 in 5 wt% in ethanol was coated on the surface of the polycarbonate substrate, and then irradiated with a 1062 nm CW laser in the form of a spot (1 W, 5 seconds).

The surface including the unreacted portion was washed, the substrate was immersed in a copper plating solution, and reacted.

Plating solution was prepared using MSMID-70 provided by MS Co., Ltd. The manufacturing process is as follows. 40 ml of Cu solution (MSMID-70A), 120 ml of complexing agent (MSMID-70B), 3.5 ml of auxiliary complexing agent (MSMID-70C), and 2 ml of stabilizer (MSMID-70D) were dissolved in 700 ml of deionized water to prepare a Cu plating solution. .

45 ml of 25% NaOH and 12 ml of 37% formaldehyde were added to 1 L of the prepared plating solution. The resin structure whose surface was activated with a laser was immersed in the plating solution at 58 ° C. for 3 to 5 hours, and then washed with distilled water.

5 is a photograph showing a conductive copper thin film in the form of a spot formed in accordance with Example 1 of the present invention.

As shown in FIG. 5, it was confirmed that the copper seed was formed in the laser irradiated region and the copper thin film grew well after plating.

Example 2

3 wt% of the nucleating agent obtained in Preparation Example 2 was added to the polycarbonate resin (LUPOY, LGChem) to obtain a circular disk substrate by an injection molding process, and as a control, a substrate having the same basic additive but no nucleating agent was obtained.

After the laser patterning was performed under the process conditions shown in FIG. 6A, the same plating process as in Example 1 was performed.

Figure 6b is a photograph showing the result of the plating in Example 2 and the plating result of the control.

As shown in FIG. 6B, in the control group, a metal film was not formed on the surface of the substrate even after plating after laser patterning, whereas a resin containing a nucleating agent obtained a plated surface when plating after laser patterning.

Claims

Support;
A plate-type copper oxide nanomaterial layer coated on the support; And
It comprises a reducing agent layer coated on the plate-shaped copper oxide nanomaterial layer,
The plate-shaped copper oxide nanomaterial has a length of 50-200 nm on one side and a nanoflake having a thickness of 5-50 nm.

The method of claim 1,
The support is at least one selected from mica flakes, SiO ₂ flakes, Al ₂ O ₃ flakes, Fe ₂ O ₃ flakes, glass flakes, kaolin and Talc nucleating agent for laser direct structuring.

The method of claim 1,
The support is a laser direct structuring nucleator having a size of 1㎛ to 100㎛.

delete

The method of claim 1,
The support is coated with TiO ₂ nucleating agent for laser direct structuring.

The method of claim 1,
The reducing agent layer is a laser direct structuring nucleating agent comprising polyvinylpyrrolidone or polyethylene glycol as a reducing agent.

The method of claim 1,
The reducing agent layer is a laser direct structuring nucleating agent further comprises carbon black.

Adding copper acetate solution and sodium hydroxide solution to the support, followed by stirring to grow copper oxide nanoflakes having a length of 50 to 200 nm, a thickness of 5 to 50 nm, and a plate shape on the support;
Filtering the resultant of the above step and drying to obtain a support coated with a plate-shaped copper oxide nanomaterial layer;
Method for producing a nucleating agent for laser direct structuring comprising the step of adding a support coated with a plate-shaped copper oxide nanomaterial layer to an aqueous solution containing a reducing agent and then stirred to coat the reducing agent layer.

The method of claim 8,
The support is a method for producing a nucleating agent for laser direct structuring is coated TiO ₂ by the sol-gel method.

The method of claim 8,
The aqueous solution containing the reducing agent is a method for producing a laser direct structuring nucleating agent further comprises carbon black.

Support; A plate-type copper oxide nanomaterial layer coated on the support; And a reducing agent layer coated on the plate-shaped copper oxide nanomaterial layer, wherein the plate-shaped copper oxide nanomaterial has a length of 50 to 200 nm on one side and a nanoflake having a thickness of 5 to 50 nm. Making;
Coating a solution comprising the nucleating agent for laser direct structuring on a substrate;
Irradiating a laser onto the substrate coated with the laser direct structuring nucleating agent to form a copper seed; And
Plating the substrate on which the copper seed is formed;
Method for forming a conductive copper thin film pattern.

The method of claim 11,
The support is a method of forming a conductive copper thin film pattern of at least one selected from mica flakes, SiO ₂ flakes, Al ₂ O ₃ flakes, Fe ₂ O ₃ flakes, glass flakes, kaolin and talc.

The method of claim 11,
The support is a method for forming a conductive copper thin film pattern having a size of 1㎛ to 100㎛.

delete

The method of claim 11,
The support is a method of forming a conductive copper thin film pattern is coated with TiO ₂ .

The method of claim 11,
The plate-shaped copper oxide nanomaterial is a method of forming a conductive copper thin film pattern is prepared by reacting copper acetate and sodium hydroxide in a molar ratio of 1: 2 to 1:10.

The method of claim 11,
The laser is a conductive copper thin film pattern forming method is performed under the conditions of output 3 ~ 25W, repetition rate 20 ~ 200kHz, speed 800mm / s ~ 2500mm / s based on 1064nm pulse laser.

Support; A plate-type copper oxide nanomaterial layer coated on the support; And a reducing agent layer coated on the plate-shaped copper oxide nanomaterial layer, wherein the plate-shaped copper oxide nanomaterial has a length of 50 to 200 nm on one side and a nanoflake having a thickness of 5 to 50 nm. Making;
Combining the substrate with the nucleating agent for direct laser structuring;
Irradiating a laser onto the blended substrate to form a copper seed; And
Plating the substrate on which the copper seed is formed;
Method for forming a conductive copper thin film pattern.

The method of claim 18,
The support is a method of forming a conductive copper thin film pattern of at least one selected from mica flakes, SiO ₂ flakes, Al ₂ O ₃ flakes, Fe ₂ O ₃ flakes, glass flakes, kaolin and talc.

The method of claim 18,
The support is a method for forming a conductive copper thin film pattern having a size of 1㎛ to 100㎛.

delete

The method of claim 18,
The support is a method of forming a conductive copper thin film pattern is coated with TiO ₂ .

The method of claim 18,
The plate-shaped copper oxide nanomaterial is a method of forming a conductive copper thin film pattern is prepared by reacting copper acetate and sodium hydroxide in a molar ratio of 1: 2 to 1:10.

The method of claim 18,
The laser is a conductive copper thin film pattern forming method is performed under the conditions of output 3 ~ 25W, repetition rate 20 ~ 200kHz, speed 800mm / s ~ 2500mm / s based on 1064nm pulse laser.