KR100891353B1 - Silver mirror plating method for spray-type using plasma - Google Patents

Abstract

The present invention relates to a spray-type silver film coating method using a plasma, and to perform the surface modification by plasma to the undercoat formed by the UV cured paint to secure the adhesion of the silver film by chemically bonding the UV cured paint and the silver film. .

To this end, the present invention is a pre-treatment step (a) for removing foreign matters such as dust, oil, grooves and bends on the surface of the subject; (B) forming a UV undercoat by the first ultraviolet (UV) cured paint on the surface of the subject; (C) surface-modifying the surface of the UV undercoat to secure adhesion to the silver hard film; (D) forming a silver hard film by spraying a silver hard reaction solution on the surface of the surface-modified UV undercoat; Spraying and drying a second UV curable coating on the surface of the formed silver film to form a UV top coating film; providing a spray-type silver film coating method using plasma, including interior and exterior materials of automobiles, home appliances, communication devices, and kitchens. It can be applied eco-friendly to all fields of exterior plating replacement such as articles and toys.

Spray, Silver Film, Coating, Plasma, Surface Modification, UV Curing Paint

Description

Silver mirror plating method for spray-type using plasma}

The present invention relates to a spray-type silver film coating method using a plasma, and more particularly, the surface of the material requiring plating is subjected to surface treatment with an ultraviolet curable paint, and subsequently has a strong adhesion through surface modification by plasma. The present invention relates to a spray-type silver film coating method using plasma, which enables the formation of a film to economically form a silver film without causing environmental pollution.

In general, silver plating is a method of forming a silver film on a surface of a material requiring surface treatment by using a silver diameter reaction. Usually, silver and reducing liquids are mixed in respective amounts to form an electroless plating bath. According to the method, there is a problem such that the use time of the mixed liquid is limited, which is an obstacle to practical use.

As one of the conventional silver diameter plating methods, there is a method by electroplating to form a silver film by energizing a positive power source and a negative power source to a material to be treated and a metal material to be obtained in an electrolytic solution. Since the method emits heavy metals such as cyanide and hexavalent chromium, which are environmentally harmful substances, it requires a lot of cost and equipment for wastewater treatment and causes environmental pollution and is limited to materials because it is applied only to conductors. There was a problem.

In addition, the conventional method of forming a silver film by electroplating includes a method of vacuum deposition in which a silver film is deposited on a surface of a material by gasifying or ionizing a metal and an oxide with a certain sealed space in a vacuum state. The method has a problem of high facility investment cost and low productivity due to limited throughput.

On the other hand, the Republic of Korea Patent Publication No. 10-2002-80586 (name: spray coating method, published: October 26, 2002) is a silver ring reaction on the surface of all materials without being constrained to the environment at low cost without polluting the environment 1 is a process flow diagram illustrating the spray plating method, and FIG. 2 is a cross-sectional view of a silver film product which can be manufactured by FIG. It is designed to meet the trend of ban on the use of hazardous substances.

In the spray plating method disclosed in the above-described patent, a pretreatment step (S1) of removing foreign matter (dust, oil, etc.) on the surface of the material 1 to be applied as illustrated in FIGS. 1 and 2 using alkali or a solvent. And a coating process (S2) of forming a coating film (2) by epoxy paint or the like for improving smoothness and corrosion resistance on the surface of the pretreated material (1), and silver (Ag) on the surface of the coating film (2). Surface treatment and washing process to remove the residue by spraying tin chloride (SnCl ₂ ) liquid, a surface control agent to form a fine uneven surface (3) for the purpose of improving adhesion to S3) and the plating liquid A (silver liquid) and the reducing liquid B (ammonia water, etc.) using a two head spray gun using a compressed air to spray the plating liquid on the surface-treated and washed fine concavo-convex surface 3. Is sprayed at the same time and silver (Ag) precipitates by silver mirror reaction Spray plating process (S4) for forming the silver hard film (4) and the surface of the silver film (4) with pure water to remove the incomplete reactants and by-products generated during the reaction in the spray plating process and compressed Water washing and drying step of evaporating moisture by air and hot air (S5), and in order to protect the water washing and dried silver film (4) by applying a transparent paint such as polyurethane on the silver film (4) to be transparent It consists of a polyurethane resin coating process (S6) which forms the protective film 5.

In order to protect the silver film 4, a small amount of dye is added to the silver film 4 when the transparent paint is applied, so that colors inherent in various metals (eg, chromium, titanium, gold, etc.) may be expressed. To be able.

However, in the conventional spray plating method as described above, since the undercoat formed directly on the surface of the material is formed by the thermosetting paint to improve the smoothness and corrosion resistance, the drying (80 ° C. × 30 minutes) time is long, and the difficulty of automated production and It causes problems such as increase of defective products and decrease of productivity, and it is also difficult to produce a product having an appearance quality equivalent to that of chromium plating, and through etching to secure the adhesion of the silver film to be performed in the next process. Since the physical method is applied, there have been many difficulties in securing solid adhesion and reliability such as chrome plating.

Therefore, the present invention has been made to solve the above problems, the present invention is shortened the production process by treating the undercoating process by using a UV curing paint that is easy to handle and good smoothness after coating, while completely cured within a short period of time It is an object of the present invention to provide a spray-type silver film coating method using plasma that can minimize defect rate and maximize productivity through full automation.

In addition, the present invention by performing a surface modification by the plasma to the undercoat formed by the ultraviolet curable paint to combine the ultraviolet curing paint and the silver film chemically to ensure the adhesion of the silver film to achieve a unique and competitive price plasma An object of the present invention is to provide a sprayed silver film coating method.

In order to achieve the above object, one feature of the present invention is a pretreatment step of removing foreign matters such as dust, oil, grooves and bends through sealing and wet sanding on a surface of a subject requiring a silver film coating (a). and; A UV undercoat film forming step (b) of spraying and drying an ultraviolet (UV) cured paint to form a UV undercoat for surface adjustment and leveling of the pretreated material; (C) a UV undercoat surface modification process for surface modification to secure adhesion to the silver hard film on the surface of the UV undercoat; A silver film forming process (d) for forming a silver film by silver film coating by spraying a silver hard reaction solution on the surface of the surface-modified UV undercoat; It is a spray-type silver film coating method using a plasma consisting of; forming a UV top coating film (e) by spraying and drying an ultraviolet curable coating on the surface of the formed silver film.

In the spray-type silver film coating method using the plasma according to the present invention, a chemical surface modification method is applied in the surface modification process (c) of the UV undercoat, and the apparatus used for the chemical surface modification is an atmospheric pressure plasma. It may be any one selected from the surface modification method by the frame plasma, vacuum plasma.

In the spray-type silver film coating method using the plasma according to the present invention, the silver film forming step (d), the step of spraying the reaction promoter on the surface of the surface-modified UV coating film (d1) (d2) (d2) ); Spraying a silver cured reaction solution on the surface of the washed UV undercoat to form a silver film by silver coating, and then washing the surface of the silver film with pure water (d3) (d4); It may include a step (d5) (d6) of removing the pure water remaining on the surface of the silver film by spraying air on the surface of the silver film.

According to the spray-type silver film coating method using the plasma according to the present invention, since no harmful substances are contained in the silver film manufacturing process, automobile interior and exterior materials, home appliances, communication devices, kitchen appliances, toys, etc., which are currently being applied with chromium plating It can be applied environmentally over all the fields of the appearance plating replacement of the, and also easy to use and high productivity can be maintained.

In addition, according to the present invention, there is no restriction of the applied material in the case of the subject, and because it can solve the limitation of chromium plating in various colors, hexavalent chromium plating alternative method that is prohibited to use in accordance with the RoHS (Restriction of Use of Hazardous Substances) in the future. This can be usefully applied.

These objects, features and advantages of the present invention will be more readily understood by reference to the accompanying drawings and the following detailed description.

Hereinafter, with reference to the accompanying drawings will be described in detail the configuration and operation of the preferred embodiment of the present invention.

Figure 3 is a process flow diagram illustrating a spray-type silver film coating method using a plasma according to an embodiment of the present invention, Figure 4 is a process flow diagram illustrating the silver film forming process of Figure 3 in detail, Figure 5 is the Figure As a cross-sectional view of the silver film coating product that can be prepared by the embodiment of 3, the sprayed silver film coating method according to the present invention, the pre-treatment step (S100) to remove the foreign matter on the surface of the surface, the surface adjustment and leveling of the surface UV coating film forming process (S200), the surface of the UV coating film modification process (S300), the silver film forming process by the silver mirror coating (S400), UV top film forming process (S500) is made.

The pre-treatment step (S100), the surface of the subject 10 of Figure 5 requiring a silver film coating, the surface of the foreign material, such as dirt or oil, or grooves through surface cleaning, sealing and wet sanding with IPA (Isopropyl Alcohol) In addition, the process of removing the bending is carried out for 0.5 to 1 minutes at room temperature (20 ~ 25 ℃). The material applicable to the conductor 10 may be wood, plastic, ceramic, urethane, or the like.

The UV undercoat film forming process (S200), spraying a first ultraviolet (UV) cured paint for surface adjustment and leveling on the surface of the pre-treated substrate 10, IR (infrared drying furnace: 50 ± 5 [ ℃], UV: is a UV undercoat process to form a UV undercoat film 20 to a thickness of 10 ~ 20 [㎛] by drying for 3 to 5 minutes in the drying conditions of 1000 ~ 1500 [mJ / cm ² ]. The first ultraviolet curing paint used for the UV undercoat 20 is preferably 1 to 5% by weight of an ultraviolet curing initiator, 25 to 35% by weight of a specially modified acrylate oligomer, 15 to 25% by weight of an acrylate monomer, and 5-10% by weight of acetone alcohol, 5-15% by weight of xylene, 10-20% by weight of methyl isobutyl ketone, 5-15% by weight of normal butyl acetate, and 1-5% by weight of ethyl acetate.

The surface modification step (S300) is a plasma treatment step of modifying the surface of the UV undercoat 20 by plasma in order to secure the adhesion between the UV undercoat 20 and the silver hard membrane 30 in a later step, at room temperature It can be made by atmospheric pressure plasma (atmospheric pressure plasma apparatus) or frame plasma, or vacuum plasma for 0.5 to 1 minutes. In the case of surface modification by atmospheric pressure plasma, plasma is formed by electric discharge in the atmosphere or gas under normal temperature and atmospheric pressure, and the plasma reacts violently with the surface molecules of the UV undercoat 20 to change the surface molecular structure. In the case of surface modification by frame plasma, plasma and atmospheric oxygen or compressed oxygen are formed by flame treatment under normal temperature and atmospheric pressure to react with the surface of the UV undercoat 20 to change the surface molecular structure. In the case of surface modification by vacuum plasma, the plasma is formed by the discharge in the vacuum chamber, which can react with the surface molecules of the UV undercoat 20 to change the surface molecular structure.

For example, when the UV undercoat 20 having a low surface tension (about 20 DYNE) is put into a plasma apparatus in a steady state, a space is applied to both electrodes at a predetermined interval, and a high voltage is applied, thereby forming a discharge in the space between the electrodes. The ionization of the gas is carried out, and the numerous functional ions thus formed modify the surface of the material between the electrodes, that is, the surface of the UV undercoat 20 having a surface tension of 20 [DYNE] in a steady state. It is possible to improve the surface tension of the to 70 [DYNE] can be secured sufficient adhesion during silver coating in the post-process.

The silver film forming process (S400) is a process of forming a silver film by coating a silver hard solution on the surface of the surface-modified UV film 20, a surface-modified UV film 20 as shown in FIG. Step (d1) (d2) of spraying the reaction promoter on the surface of the) and then washing with pure water, and spraying the silver mirror reaction solution on the surface of the washed UV undercoat (20) by the silver mirror coating (30) (D3) (d4) of washing the surface of the silver film and then drying the pure water remaining on the surface of the silver film (d5) by spraying air on the surface of the silver film (30). d6).

As a reaction promoter initially sprayed on the surface of the UV undercoat 20 surface-modified in the step (d1) (d2), it is a mixture of tin chloride, hydrochloric acid and water, and preferably 5 to 50 wt% tin chloride hydrochloric acid. 10 wt% and 40-45 wt% of water are mixed solutions.

In the process (d3) and (d4), the silver light reaction solution sprayed to form a silver film is a solution in which a silver hard solution and a reducing solution are mixed. Preferably, the ratio of the silver hard solution and the reducing solution is 49:51. Or 50:50 mixed solution.

The silver solution is a silver silver nitrate, ammonia (ammonia) and a mixture of water and a first silver solution, caustic soda (caustic soda) and a second silver solution that is mixed with water must be used in a 1:18 ratio. The reducing solution may be a reducing agent including formaldehyde and water. Preferably, the first silver light solution is a solution in which 35% by weight of silver nitrate, 10 to 15% by weight of ammonia, and 50 to 55% by weight of water are mixed, and the second silver light solution is 0.5 to 1% by weight of caustic soda and 99 to 99.5% of water. The wt% is a mixed solution, the reducing solution is a solution of 0.5 to 2% by weight of formaldehyde and 98 to 99.5% by weight of water.

In addition, a device for injecting a silver hard reaction solution to form a silver film in the process (d3) may use a silver hard reaction liquid injection gun 50 in which the silver hard solution and the reducing solution are accurately mixed and injected 1: 1. In (a) and (b), the silver hard reaction liquid injection gun 50 is illustrated. The silver light reaction liquid spraying gun 50 (manufactured by Cosmichrome canada) is configured to turn on / off a metering valve in which the discharge amount is precisely adjusted by an electronic signal, so that the discharge amount is uniform and the discharge solution The special structure allows the inside to rotate inside, so that the silver light reaction solution is atomized by the centrifugal force of the rotating solution so that it can be perfectly mixed even after the discharge without interference of the two solutions.

The drying conditions for forming the silver film in the step (d5) and (d6) are preferably carried out at 50 [deg.] C. for 20 minutes, and the thickness of the silver film formed thereby is 1 to 2 [µm].

The UV top coating film forming step (S500), spraying a second ultraviolet curable paint for securing the reliability and appearance protection of the silver film on the surface of the silver film 30, IR (infrared drying furnace: 50 ± 5 [° C.]) UV: This is a UV top coat process to form a UV top coat 40 with a thickness of 10 ~ 20 [㎛] by drying for 3 ~ 5 minutes under the drying condition of 1000 ~ 1500 [mJ / cm ² ]. The second ultraviolet curable coating material used for the top coat 40 is preferably 1 to 5% by weight of an ultraviolet curing initiator, 20 to 30% by weight of a specially modified acrylate oligomer, 10 to 15% by weight of an acrylate monomer, and 10 toluene. 20% by weight, 5-15% by weight of xylene, 10-20% by weight ethyl acetate, 10-20% by weight methyl isobutyl ketone.

Hereinafter, the present invention will be described in detail for each process.

First, in the first step (S100), any one of wood or plastic or ceramic or urethane (hereinafter referred to as plastic, in particular polycarbonate / acrylonitrile-butadiene-styrene) In the case of using a conductor, the surface of the object 10 of the present invention is subjected to pre-treatment to remove foreign substances such as dust, oil, grooves or bends through surface cleaning, sealing and wet sanding (S100). .

In the second step (S200), the first ultraviolet curable paint (transparent color, gloss (60 °), 90 or more, specific gravity (25 [° C.]) is 0.96 ± 0.02, and the viscosity (25 [ ℃]) 36 ± 2 seconds) through air spray gun, coating film thickness 10 ~ 20 [㎛], dry condition IR: 50 ± 5 [℃], UV: 1000 ~ 1500 [mJ / ㎠], spray pressure 4 ~ It is sprayed at 5 [kgf / cm 2] to form the UV undercoat 20.

In the third step (S300), ionization of air molecules and UV undercoat by plasma treatment is performed by plasma treatment of the surface of the UV undercoat 20 through any one of an atmospheric pressure plasma, a frame plasma, or a vacuum plasma apparatus. (20) Due to the change in the molecular structure of the surface, the surface of the UV undercoat is subjected to a chemical reaction as shown in the following chemical formula to perform a surface modification treatment.

O ₂ , N ₂ , H ₂ O + e → O *, N *, H *

O *, N *, H *, OH * + O ₂ , N ₂ , H ₂ O + Light energy emission → O ₂ , N ₂ , H ₂ O

Cn-Hm + e → Cn-Hm-n + α

Therefore, the upper surface of the UV undercoat 20 is chemically surface-modified as shown in FIG. 7 so that the adhesion with the silver film to be coated in a later process may be changed to an increased state.

In the fourth step (S400), the reaction accelerator (A22) is mixed with 20 mg / pure water 1L one hour before the operation, and then sprayed through the air spray gun (d1) on the surface of the surface-modified UV undercoat (20) to pure water. Wash (d2). After mixing the silver light solution containing 18L of the first silver light solution (yellow) and 18L of the second silver light solution (colorless transparent) and 18L of the reducing solution stock solution was added to the silver light reaction solution spray gun and the silver light reaction solution spray gun On the surface of the UV undercoat 20 using a coating film thickness of 1 ~ 2 [㎛] by spraying the silver light reaction solution (d3) and washed with pure water (d4) to form a silver hard film (30). Again, compressed air and hot air are sprayed on the surface of the silver film 30 with an air spray gun (d5) and dried for 20 minutes at a drying condition of 50 [deg.] C (d6) to remove the pure water remaining on the surface of the silver film. do.

Finally, in the fifth step (S500), the second ultraviolet curing paint (transparent color, gloss (60 °) 90 or more, specific gravity (25 [° C.]) 0.96 ± 0.02, viscosity (25 [° C.)) 36 ± 2 seconds) Through the air spray gun on the surface of the silver film 30, coating film thickness 10 ~ 20 [㎛], dry conditions IR: 50 ± 5 [℃], UV: 1000 ~ 1500 [mJ / ㎠], injection pressure 4 ~ By spraying at 5 [kgf / cm 2], the UV top coat 40 can be formed.

Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples are merely illustrative of one embodiment of the present invention, and the scope of protection of the present invention is not limited by the Examples.

<Example 1>

The surface of the surface of the polycarbonate 5.5 [cm] × 13.5 [cm] surface was washed with isopropyl alcohol, 4% by weight of UV curing initiator, 30% by weight of specially modified acrylate oligomer, and acrylate. A first ultraviolet curable coating of 20% by weight of monomer, 8% by weight of diacetone alcohol, 10% by weight of xylene, 15% by weight of methyl isobutyl ketone, 10% by weight of normal butyl acetate, and 3% by weight of ethyl acetate was added to the air spray gun. sprayed with air pressure of 3.5 [kg / ㎠] through a nozzle of [mm] and dried at UV 1200) [mJ / ㎠] for 3 minutes in an infrared drying furnace (50 ± 5 [℃]) to a thickness of 15 [㎛]. A UV undercoat was formed.

After modifying the surface of the UV undercoat by atmospheric plasma method, 20 g of a reaction accelerator (A22; 47 wt% tin chloride, 8 wt% hydrochloric acid, and 45 wt% water) and 1000 g of distilled water were mixed to prepare the surface of the UV modified undercoat. Was sprayed and washed through the airspray gun.

On the surface of the UV undercoat, a first silver light solution (yellow) mixed with 35% by weight of silver nitrate, 15% by weight of ammonia and 50% by weight of water, 1% by weight of caustic soda and 99% by weight of a second silver light solution ( Colorless and transparent) 18g mixed solution (A solution) and 19g (reduced solution B) of reducing solution mixed with 1% by weight of formaldehyde and 99% by weight of water were sprayed at the same time through a silver hard reaction spray gun at 50: 50 to obtain a film thickness. A silver film of 1 [탆] was formed, washed with distilled water through a washing spray gun, and dried at 50 [캜] for 20 minutes.

4% by weight of UV curing initiator, 28% by weight of specially modified acrylate oligomer, 13% by weight of acrylate monomer, 17% by weight of toluene, 10% by weight of xylene, 12% by weight of ethyl acetate, 16% by weight of methyl isobutyl ketone 2 UV-cured paint is sprayed at a pressure of 3.5 [kg / ㎠] through a nozzle of 1.3 [mm] of the air spray gun and UV- 1200 [mJ / ㎠] for 3 minutes in an infrared drying furnace (50 ± 5 [℃]). It dried and the 15-micrometer-thick UV top coat was formed.

<Example 2>

The surface of the object of polycarbonate 5.5 [cm] x 13.5 [cm] was surface-washed with isopropyl alcohol, 2 weight% of UV curing initiators, 28 weight% of specially modified acrylate oligomers, and acrylates A first ultraviolet curable coating of 18% by weight of monomer, 6% by weight of diacetone alcohol, 13% by weight of xylene, 17% by weight of methyl isobutyl ketone, 12% by weight of normal butyl acetate, and 4% by weight of ethyl acetate, It is sprayed with air pressure of 3.5 [kg / ㎠] through a nozzle of [mm] and dried at UV 1200) [mJ / ㎠] for 3 minutes in an infrared dryer (50 ± 5 [℃]) to a thickness of 15 [㎛]. A UV undercoat was formed.

After modifying the surface of the UV undercoat by atmospheric plasma method, 20 g of a reaction accelerator (A22; 47 wt% tin chloride, 8 wt% hydrochloric acid, and 45 wt% water) and 1000 g of distilled water were mixed to prepare the surface of the UV modified undercoat. Was sprayed and washed through the airspray gun.

On the surface of the UV undercoat, a first silver light solution (yellow) mixed with 35% by weight of silver nitrate, 10% by weight of ammonia and 55% by weight of water, 0.5% by weight of caustic soda and 99.5% by weight of a second silver light solution ( Colorless transparent) 18 g of mixed solution (A solution) and 19 g (B solution) of reducing solution containing 0.5% by weight of formaldehyde and 99.5% by weight of water were simultaneously sprayed through a silver hard reaction spray gun at 49: 51 to coat thickness. A silver film of 1 [탆] was formed, washed with distilled water through a washing spray gun, and dried at 50 [캜] for 20 minutes.

2% by weight of UV curing initiator, 30% by weight of specially modified acrylate oligomer, 10% by weight of acrylate monomer, 15% by weight of toluene, 10% by weight of xylene, 15% by weight of ethyl acetate, 18% by weight of methyl isobutyl ketone 2 UV-cured paint is sprayed at a pressure of 3.5 [kg / ㎠] through a nozzle of 1.3 [mm] of the air spray gun and UV- 1200 [mJ / ㎠] for 3 minutes in an infrared drying furnace (50 ± 5 [℃]). It dried and the 15-micrometer-thick UV top coat was formed.

From the test specimens prepared in Examples 1 and 2 described above, performance tests on cutting properties, abrasion resistance, RCA wear, and fall were conducted, and all were determined to be normal.

In the case of cutting property, the test piece was drawn at intervals of 1 mm to make the goggles, and after the tape was attached, it was pulled five times in the vertical direction, and when the tape was attached or detached, the state without peeling of the processed surface (defect when peeling more than 2/3 of the go surface) was judged as normal. .

In the case of abrasion resistance, a 500 g load was applied to the eraser and placed on the surface of the coating film, and reciprocated 1,500 times (40 round trips / minute) to determine that the coating film (top and bottom) was not peeled off.

In the case of RCA wearability, a 275 g load was applied to the paper (speed: 33 times / minute) and the coating surface was reciprocated 30 times to determine that the base metal of the coating surface was not exposed.

In the case of a fall, 500g weight was dropped on the edge (6 places) of the test material at a height of 50cm, and it was judged that the fracture surface was not broken like a glass surface (tolerated tearing).

In the above, the present invention has been shown and described with respect to certain preferred embodiments. However, the present invention is not limited to the above-described embodiments, and those skilled in the art to which the present invention pertains can variously change variously without departing from the technical spirit of the present invention described in the following claims. You can do it.

1 is a process flow diagram illustrating a conventional spray plating method,

2 is a cross-sectional view of a silver film coating product by the conventional spray plating method,

3 is a process flow diagram illustrating a spray-type silver film coating method using plasma according to an embodiment of the present invention;

4 is a process flow diagram illustrating the silver film forming process of FIG. 3 in detail;

5 is a cross-sectional view of a silver film coating product that can be prepared by the embodiment of FIG.

Figure 6 (a) and (b) is an exemplary view of a silver hard reaction liquid injection gun,

FIG. 7 is a reference diagram for comparison of states before and after plasma treatment of a UV undercoat in the spray-type silver film plating process according to the present invention.

<Explanation of symbols for the main parts of the drawings>

10: subject 20: UV undercoat

20a: surface modified surface 30: silver film

40: UV top coat 50: spray gun for silver hard reaction solution

Claims (9)

A pretreatment step of cleaning the surface by removing foreign matters such as dust and oil, grooves and bends through surface washing, sealing and wet sanding on the surface of the object to be applied; A UV undercoat film forming process of spraying and drying a first ultraviolet (UV) cured paint on the pretreated target material (10) for surface adjustment leveling to form a UV undercoat (20); A UV undercoat surface modification process for modifying the surface of the UV undercoat 20 using a plasma apparatus to secure adhesion between the UV undercoat 20 and silver (Ag); A silver film forming process of forming a silver film (30) by silver film coating by spraying a silver diameter reaction solution on the surface of the surface-modified UV undercoat (20); UV coating film forming process of spraying and drying a second ultraviolet curable paint on the upper surface of the formed silver hard film 30 to form a UV top coating film 40; The 1st ultraviolet curing paint used at the said UV undercoat film forming process is 1-5 weight% of ultraviolet curing initiators, 25-35 weight% of specially modified acrylate oligomers, 15-25 weight% of acrylate monomers, and 5-diacetone alcohol 10% by weight, 5-15% by weight of xylene, 10-20% by weight of methyl isobutyl ketone, 5-15% by weight of normal butyl acetate, 1-5% by weight of ethyl acetate Way. delete The method of claim 1, wherein the second UV curable coating material used in the UV top coat film forming step, 1 to 5% by weight of UV curing initiator, 20 to 30% by weight of specially modified acrylate oligomer, 10 to 15% by weight of acrylate monomer, 10 to 20% by weight of toluene, 5 to 15% by weight of xylene, 10 to 20% by weight of ethyl acetate Spraying silver film coating method using a plasma, characterized in that 10 to 20% by weight methyl isobutyl ketone mixture. According to claim 1, The surface modification process of the UV undercoat, Spraying silver film coating method using a plasma, characterized in that formed by any one of atmospheric pressure plasma, frame plasma, vacuum plasma. The method of claim 1, wherein the silver film forming step, Spraying the reaction promoter on the surface of the UV undercoat film and then washing it with pure water; Spraying a silver hard reaction solution on the surface of the washed UV undercoat to form a silver hard film by silver hard coating; Spraying pure water on the surface of the silver film to wash the surface of the silver film; Spraying silver film coating method using a plasma comprising the step of removing air remaining on the surface of the silver film by spraying air on the surface of the silver film. The method of claim 5, wherein the reaction accelerator used in the silver film forming step, Spraying silver film coating method using a plasma, characterized in that the mixture of 45 to 50% by weight of tin chloride 5 to 10% by weight of hydrochloric acid and 40 to 45% by weight of water. The method of claim 5, wherein the silver hardening solution used in the silver film forming step, The nitric acid is composed of a first silver solution containing 35% by weight, 10-15% by weight of ammonia and 50-55% by weight of water, and a reducing solution containing 0.5-2% by weight of formaldehyde and 98-99.9% by weight of water. Spray type silver film coating method using a plasma. The method of claim 5, wherein the silver hardening solution used in the silver film forming step, A plasma comprising a second silver solution containing 0.5-1% by weight of caustic soda and 99-99.5% by weight of water, and a reducing solution containing 0.5-2% by weight of formaldehyde and 98-99.5% by weight of water. Sprayed silver film coating method using. The method of claim 5, wherein the silver hardening solution used in the silver film forming step, A first silver solution containing 35% by weight of nitric acid, 10-15% by weight of ammonia, and 50-55% by weight of water, a second silver solution containing 0.5-1% by weight of caustic soda and 99-99.5% by weight of water, Spraying silver film coating method using a plasma, characterized in that consisting of a reducing solution of 0.5 to 2% by weight of formaldehyde and 98 to 99.5% by weight of water.

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