KR102316251B1 - Metal paint composition and method for preparing polymer molding product with metal film using the same - Google Patents

Abstract

The present invention relates to a metal coating composition and a method for producing a polymer injection product having a metal film formed thereon using the same, and the metal coating composition comprising the metal ink composition including the metal complex compound and/or metal nanoparticles according to the present invention is used, Compared to the conventional technique for giving a metal texture to a polymer resin molded product, it is a very simplified process, and a polymer injection molded product having an excellent metal texture effect and applying various metal colors can be manufactured at a high production rate and in an eco-friendly way.

Description

Metal paint composition and manufacturing method of a polymer injection product having a metal film formed using the same

The present invention relates to a metal coating composition and a method for manufacturing a polymer injection product having a metal film formed thereon using the same. Specifically, the present invention is a metal ink composition comprising (a) at least one selected from the group consisting of a metal complex compound and metal nanoparticles; (b) a first binder resin; and (c) a metal coating composition for forming a metal film of an injection-molded polymer containing a first solvent, an injection-molded polymer having a metal film formed thereon by applying the metal coating composition, and (a) injection of a polymer resin to prepare an injection-molded polymer; (b) forming a surface treatment layer on the polymer injection product; (c) forming a metal film by applying the metal coating composition on the surface treatment layer; and (d) forming a transparent protective layer on the metal film.

According to the recent trends in the coating industry, the needs of consumers who demand a personalized, unique design and a variety of colors beyond the general design and color are increasing. In the automobile industry, for example, in the case of interior and exterior polymer injection moldings, most are coating a metallic paint with a metal pigment and wet chrome plating, and some deposition methods are used to obtain a metallic texture. Polymer injection molding is used in all fields closely related to color, so research to add aesthetics to the material has been steadily conducted.

Recently, the case of applying metallic paint is increasing, which has the advantage of low facility investment cost and high productivity because it uses the spray process. The problem is that it is difficult to obtain.

On the other hand, in the case of plating, although it has an excellent texture, the use of legally regulated substances such as hexavalent chromium and cyanide is unavoidable, and the productivity is very low as it involves a complex process ranging from 10 to 15 steps, and the defect rate caused by these processes This is a high situation. In addition, when a metal texture including various colors is required, a transparent protective layer with a specific color is additionally formed on the metal film formed by plating. However, it has a disadvantage in that it is difficult to secure the reliability characteristics required by the industry.

In the case of the dry method, the method of forming a reflective film using vapor deposition is the most common, and in this case, a complicated pre-treatment process is required, very expensive equipment is required, and there is a disadvantage of low productivity as the deposition process must be performed in a vacuum for a long time. In addition, due to the nature of the deposition process, it is difficult to form a metal layer with a uniform thickness on the top and side surfaces, so the design is limited and the metal film is formed in a closed chamber. There is a problem that the process is difficult.

Under this background, some industries have attempted to achieve a similar effect with the wet spray process using the silver film coating method, but dangerous raw materials containing strong acids and strong alkalis such as nitric acid and ammonia are required and there is a risk of explosion in the process of mixing them when used. However, there is a risk of burns to workers due to exposure to dangerous substances, and the reliability required by the industry cannot be secured, so it is currently applied only in very limited fields.

Therefore, in order to solve the above problems, while using the most common and productive method in the field of exterior coating such as spraying, it has a smooth surface treatment effect such as chrome plating, and is manufactured by an eco-friendly method for producing an injection product with a chrome plating feeling. There is a great need for technological development.

US 10-0727483 B1 US 10-0918231 B1

It is an object of the present invention to solve the problems of the conventional techniques for giving a metal texture to such a polymer resin injection molding, a high production speed and eco-friendly method while having an excellent metal texture effect. to provide technology.

Specifically, an object of the present invention is (a) a metal ink composition comprising at least one selected from the group consisting of a metal complex compound and metal nanoparticles; (b) a first binder resin; And (c) to provide a metal coating composition for forming a metal film of a polymer injection product comprising a first solvent.

Another object of the present invention is to provide an injection molded polymer in which a metal film is formed by applying the metal coating composition.

Another object of the present invention comprises the steps of (a) injecting a polymer resin to prepare a polymer injection product; (b) forming a surface treatment layer on the polymer injection product; (c) forming a metal film by applying the metal coating composition on the surface treatment layer; and (d) forming a transparent protective layer on the metal film.

In order to achieve the above object, the present invention is (a) a metal ink composition comprising at least one selected from the group consisting of a metal complex compound and metal nanoparticles; (b) a first binder resin; And (c) provides a metal coating composition for forming a metal film of a polymer injection product comprising a first solvent.

The present invention also provides a polymer injection product in which a metal film is formed by applying the metal coating composition.

The present invention also comprises the steps of (a) injecting a polymer resin to prepare a polymer injection product; (b) forming a surface treatment layer on the polymer injection product; (c) forming a metal film by applying the metal coating composition on the surface treatment layer; and (d) forming a transparent protective layer on the metal film.

Using a metal paint composition comprising a metal ink composition comprising a metal complex compound and/or metal nanoparticles according to the present invention, compared to the conventional technique for giving a metal texture to a polymer resin injection, it is a very simplified process, Polymer injection molding with excellent metal texture effect and various metal colors can be manufactured with high production rate and eco-friendly method.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

In one aspect, the present invention, (a) a metal ink composition comprising at least one selected from the group consisting of a metal complex compound and metal nanoparticles; (b) a first binder resin; And (c) relates to a metal coating composition for forming a metal film of a polymer injection product comprising a first solvent.

In another aspect, the present invention relates to a polymer injection molded product in which a metal film is formed by applying the metal coating composition.

In another aspect, the present invention comprises the steps of: (a) injecting a polymer resin to prepare a polymer injection product; (b) forming a surface treatment layer on the polymer injection product; (c) forming a metal film by applying the metal coating composition on the surface treatment layer; and (d) forming a transparent protective layer on the metal film.

In the metal coating composition for forming a metal film of a polymer injection product according to the present invention, (b) the first binder resin included in the metal coating composition is acrylic, cellulose, polyester, polyamide, polyether, vinyl, urethane, urea, Alkyd, silicone, fluorine, olefin, petroleum, rosin, epoxy, unsaturated polyester, diallyl phthalate resin, phenol, oxetane, oxazine, bismaleimide, modified silicone, melamine, acrylic resin, rubber, natural polymer, glass resin and at least one selected from the group consisting of glass frits.

In the present invention, (c) the first solvent is PGMEA (Propylene glycol methyl ether acetate), α-terpineol (α-terpineol, α-TPN), β-terpineol (β-terpineol), benzyl ethyl ether , tetrahydrofuran, dihexyl ether, dimethyl sulfoxide, ethylene glycol-n-butyl ether (butyl cellosolve), hexylene glycol, N-methylformamide, N,N-dimethylformamide , N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, caproic acid, caprylic acid, methyl ethyl ketone, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid Diethyl acid, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, butyl carbitol acetate (BCA), ethyl acetate (ethyl acetate), dibutyl phthalate (DBP), cyclohexanone , cyclopentanone, acetonylacetone, isophorone, methylmethoxypropionate, ethylethoxypropionate, γ-butyrolactone, γ-butyrolactam, 1-octanol, 1-nonanol , methoxy ethanol, methoxy propanol, ethoxy ethanol, ethoxy propanol, may be characterized in that at least one selected from the group consisting of ethoxy butanol and benzyl alcohol, but is not limited thereto.

In the metal coating composition for forming a metal film of a polymer injection product according to the present invention, (a) the metal of the metal ink composition is not limited thereto, but a metal having an achromatic color and an inherent color of the metal and high luminance (reflectance) is used Preferably, it may be characterized in that it is silver (Ag).

In the present invention, the metal complex compound described in Korean Patent Application No. 10-2006-0039107 may be used. In addition, as the metal nanoparticles, those described in Korean Patent Application No. 10-2007-0079072 may be used. When metal nanoparticles are used, as in the case of using a metal complex compound, a mirror-finished metal film can be formed, and at the same time, in the case of industries requiring high reliability, the use of binders and additives to supplement characteristics has the advantage of being relatively free. When using the metal complex compound and/or metal nanoparticles, it is possible to achieve excellent economic efficiency in terms of productivity, compared to the conventional process.

In the present invention, when metal nanoparticles are used, the size (particle size) of the metal nanoparticles may be preferably 20 to 150 nm, more preferably 20 to 50 nm. When the size of the metal nanoparticles is smaller than 20 nm, it is difficult to form the metal ink composition, and when the size of the metal nanoparticles is larger than 150 nm, there may be problems in that the reflectance of the coating composition is lowered and dispersion stability is unstable.

In the present invention, (a) the metal ink composition further comprises one or more additives selected from the group consisting of a second binder resin, a second solvent, a dispersant, a stabilizer, a wetting agent, a coupling agent, a thixotropic agent, and a leveling agent. can

In the present invention, the second binder resin is acrylic, cellulose, polyester, polyamide, polyether, vinyl, urethane, urea, alkyd, silicone, fluorine, olefin, petroleum, rosin, epoxy, unsaturated polyester, diallyl It may be characterized in that at least one selected from the group consisting of phthalate resin, phenol, oxetane, oxazine, bismaleimide, modified silicone, melamine, acrylic resin, rubber, natural polymer, glass resin and glass frit, but limited thereto it is not The binder resin may be included in an amount of 0.1 to 50.0 wt%, more preferably 0.5 to 30 wt%, based on the total weight of the metal ink composition. When the binder resin is used in an amount of less than 0.1% by weight, adhesion problems between the surface treatment layer and the metal film may occur.

In the present invention, the second solvent is water, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin, ethyl acetate, butyl acetate, carbitol acetate, butyl carbitol, diethyl ether, tetrahydrofuran, dioxane, It may be characterized in that at least one selected from the group consisting of methyl ethyl ketone, acetone, hexane, heptane, benzene, toluene, chloroform, methylene chloride and carbon tetrachloride, but is not limited thereto.

In the present invention, the dispersing agent is used to smoothly disperse the nanoparticles, for example, EFKA's 4000 series, BYK's Disperbyk series, Avecia's The solsperse series, Deguessa's TEGO Dispers series, etc. can be used. The dispersant may be used in an amount of 0.1 to 10 wt% based on the total weight of the metal ink composition. When the dispersant is used in an amount of less than 0.1% by weight, surface defects of the metal film due to particle aggregation are induced and the storage stability of the metal ink composition is deteriorated. fumes will occur.

In the present invention, a silane-based, titanium-based zirconium-based or aluminum-based coupling agent may be used to improve the coating film properties, and BYK’s 300 series, EFKA’s 3000 series, etc. can be used as a leveling agent. have.

In the present invention, the metal ink composition is preferably 1 to 60 parts by weight based on the total weight of the metal coating composition. When the amount of the metal ink composition used is less than 1 part by weight, the amount of metal formed is small, so that the injected product has a color see-through and the surface may not be uniform. there is a problem.

In the present invention, the metal coating composition may have a viscosity of 1 to 200 cPs. In addition, the metal coating composition may have a reflectance of 50 to 70%.

In the present invention, the polymer resin used for manufacturing the polymer injection molding is ABS (acrylonitrile-butadiene-styrene), PC (polycarbonate), PBT (polybutyrene terephthalate) and PET (polyethylene terephthalate). It may be characterized in that it is one or more resins selected from the group consisting of.

In the case of a polymer resin injection product that has been injected, it is difficult to have a surface made of a mirror surface like glass due to the limitations of injection mold technology. In addition, since the manufacturing process is complicated when additional mirror treatment is applied to the injection molded product, it is desirable to improve the surface roughness of the injection product surface through a separate surface treatment. It is effective to supplement For example, it is desirable to improve the roughness of the surface of the injection-molded product by a method that has productivity and low process cost, such as a spray process.

In the present invention, the surface treatment layer may be preferably formed by coating a surface treatment layer composition containing a thermosetting resin such as a urethane resin or a photocuring resin. The surface treatment layer composition includes an inorganic pigment and a dye as needed, and is a composition capable of a spray process. Since the metal film is printed as a relatively thin film unlike the existing metallic paint and is directly affected by the surface of the injection product, the thickness of the surface treatment layer is preferably 5 to 50 μm, more preferably 10 to 25 μm.

In the present invention, the metal film may be formed by a spray process. The metal ink composition used to form the metal film should be able to dry and form the metal film at a temperature at which the plastic injection product is not deformed. In the case of a metal ink composition using a metal complex compound, a dense metal film can be formed with a thermal reduction reaction film, and in the case of a metal ink composition using metal nanoparticles, a dense metal film can be formed using a low-temperature sintering reaction according to the particle size. .

The metal film formed by the metal coating composition is exposed to various external environments. For example, in the case of automobile parts, since they are continuously exposed to continuous friction or various organic/inorganic substances, transparent protection for protecting the metal film formed from these environments layer is needed

In the present invention, the transparent protective layer may be preferably formed by coating a transparent protective layer composition containing a thermosetting resin or a photocuring resin such as a urethane resin. In addition, the transparent protective layer composition may include various pigments to implement various colors on the metal film. In addition, in order to secure weather resistance, a mercaptan compound, a carboxylic acid compound, or a silane-based compound may be included, and a UV stabilizer may be included. As a UV stabilizer, a representative HALSHYBRID UV-G series can be used, but the present invention is not limited thereto.

Each composition required to form the above-mentioned surface treatment layer, metal film and transparent protective layer is most preferably applied by a spray process, and the viscosity required for each process is preferably 1 to 10,000 cps, more preferably 1 to 200 cps.

In the present invention, it may be characterized in that the polymer resin is injected at an injection speed of preferably 10 to 40 mm/sec in the step (a).

In the present invention, it may further include a drying step after performing step (c), preferably drying at 25 to 120 ℃, more preferably drying at 60 to 80 ℃ may be characterized .

In the present invention, the polymer injection molding may be a vehicle interior material or a component, a component of a home appliance or a portable electronic product, but is not limited thereto.

[Example]

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Example 1: Preparation of metallic ink composition

1-1: Preparation of metal complex compound type metal ink composition

Silver (Ag) 2-ethylhexyl carbamate 100g, solvent (butanol 100g), stabilizer (isobutylamine 50g), dispersant (BYK 111, 1g), binder resin (epoxy resin, 0.5g), wetting agent (anti-tera 204) , 0.2 g) and a leveling agent (EFKA 350, 0.05 g) were mixed to prepare a metal complex compound type metal ink composition having a viscosity of 5 cps and a surface tension of 23 dyne/cm.

1-2: Preparation of metal nanoparticulate metal ink composition

Silver (Ag) nanoparticles 40g (manufactured by Inktech), solvent (butylcarbitol 60g), dispersant (BYK 330, 4g), stabilizer (ethyl cellulose, 5g), binder resin (polyester resin, 1g) were placed in a 500ml reactor After mixing, using 0.3 mm beads, the mixture was uniformly mixed and reacted for 6 hours. After the reaction was completed, the beads were removed with a filter to obtain an ink in which silver nanoparticles were uniformly dispersed, and a metal nanoparticle-type metal ink composition having a viscosity of 50 cps and a surface tension of 26 dyne/cm was prepared.

Example 2: Preparation of metal coating composition

2-1: Preparation of metal coating composition 1 using metal complex compound type metal ink composition

To the metal complex compound type metal ink composition having a viscosity of 5 cps of Example 1-1, 10 parts by weight of a vehicle prepared by dissolving a polyester resin (Unichika, UE9800) in a solvent PGMEA was added, and 1 using a stirrer A metal coating composition 1 was prepared by stirring for a period of time. The viscosity of the prepared metal coating composition 1 was 50 cps.

2-2: Preparation of metal coating composition 2 using metal nanoparticulate metal ink composition

5 parts by weight of a vehicle prepared by dissolving an epoxy resin (Kukdo Chemical, YD017) in a solvent α-TPN was added to the metal nanoparticle-type metal ink composition having a viscosity of 50 cps in Example 1-2, and 1 using a stirrer A metal coating composition 2 was prepared by stirring for a period of time. The viscosity of the prepared metal coating composition 2 was 80 cps.

2-3: Preparation of metal coating composition 3 using a metal ink composition in which a metal complex compound and a metal nano-particle type are mixed

5 parts by weight of the metal complex compound type metal ink composition having a viscosity of 5 cps of Example 1-1 was added to the metal nanoparticle type metal ink composition having a viscosity of 50 cps of Example 1-2, and an epoxy resin (National Road Chemical company, YD017) was added to 6 parts by weight of a vehicle prepared by dissolving the mixture, followed by stirring for 1 hour using a stirrer to prepare a metal coating composition 3 . The viscosity of the prepared metal coating composition 3 was 70 cps.

Example 3: Preparation of surface treatment layer composition and transparent protective layer composition

3-1: Preparation of surface treatment layer composition

100 parts by weight of polypropylene glycol (Jiangsu Dynamic Chemical, PPG-400) was put into a reactor at room temperature, and then the temperature was gradually raised to 70° C. using a thermostat. After dropping 25 parts by weight of hexamethylene diisocyanate at 2.5 parts by weight per minute, the reaction was terminated by stirring at 200 rpm for 1 hour. After adding 200 parts by weight of an epoxy resin (Kukdo Chemical, YD017) to the resulting reactant, the temperature was raised to 180° C. to prepare a urethane epoxy resin. An antifoaming agent (BYK Corporation, BYK-052) and an amine curing agent (isophorone diamine) were added to the prepared urethane epoxy resin and mixed at 200 rpm to complete the preparation of the surface treatment layer composition.

3-2: Preparation of transparent protective layer composition

100 parts by weight of polypropylene glycol (Jiangsu Dynamic Chemical, PPG-200) was added to a reactor at room temperature, and then the temperature was gradually raised to 70° C. using a thermostat. After dropping 25 parts by weight of hexamethylene diisocyanate at 2.5 parts by weight per minute, the reaction was terminated by stirring at 200 rpm for 1 hour. After adding 150 parts by weight of an epoxy resin (Kukdo Chemical, YD014) to the resulting reactant, the temperature was raised to 180° C. to prepare a urethane epoxy resin. Antifoaming agent (BYK company, BYK-052), amine curing agent (Isophorone diamine), UV stabilizer (Nippon shokubai UV-G) and UV blocking agent (Chitec company, Chiguard 5571) were added to the prepared urethane epoxy resin and mixed at 200rpm Preparation of the transparent protective layer composition was completed.

Example 4: Manufacture of a polymer injection molded product having a metal film formed thereon

4-1: Preparation of polymer injection molding

After drying the ABS pellets in an oven at 100°C, using a Dongshin injection machine (PRO-WD), the injection process was performed under the conditions of a mold temperature of 80°C, a nozzle temperature of 300°C, and an injection speed of 25mm/sec to produce a polymer injection product. did.

4-2: Formation of surface treatment layer

The surface treatment layer composition prepared in Example 3 was applied to the polymer injection molded product prepared in Example 4-1 at a pressure of 5 bar using a spray device (Anest Iwata, W101) to form a surface treatment layer on the polymer injection molding product did.

4-3: metal film formation

4-3-1: Formation of a metal film using the metal coating composition 1

The metal coating composition 1 prepared in Example 2-1 was applied to the polymer injection molded product having the surface treatment layer in Example 4-2 using a spray device (Anest Iwata, W101) at a pressure of 5 bar. After spray-coating ink on the top and side surfaces, respectively, it was dried at 80° C. for 20 minutes to form a metal film.

4-3-2: Formation of a metal film using the metal coating composition 2

The metal coating composition 2 prepared in Example 2-2 was applied to the polymer injection molded product having the surface treatment layer formed in Example 4-2 using a spray device (Anest Iwata, W101) at a pressure of 5 bar. After spray-coating ink on the top and side surfaces, respectively, it was dried at 80° C. for 20 minutes to form a metal film.

4-3-3: Formation of a metal film using the metal coating composition 3

The metal paint composition 3 prepared in Example 2-3 was applied to the polymer injection molded product having the surface treatment layer formed in Example 4-2 using a spray device (Anest Iwata, W101) at a pressure of 5 bar. After spray-coating ink on the top and side surfaces, respectively, it was dried at 80° C. for 20 minutes to form a metal film.

4-3-4: Formation of a metal film using the metal coating composition 2

The metal coating composition 2 prepared in Example 2-2 was applied to the polymer injection molded product having the surface treatment layer formed in Example 4-2 using a spray device (Anest Iwata, W101) at a pressure of 5 bar. After spray-coating ink on the top and side surfaces, respectively, drying at 60° C. for 20 minutes to form a metal film.

4-4: Formation of a transparent protective layer

A transparent protective layer was formed by applying the transparent protective layer composition prepared in Example 3 to the polymer injection product on which the metal film was formed in Example 4-3 at a pressure of 5 bar using a spray device (Anest Iwata, W101).

Comparative Example 1: Formation of a metal film of a polymer injection product using a deposition process

A metal film was formed on the surface-treated polymer injection product prepared in Example 4-2 with an aluminum target using a sputtering device, DC magnetron sputtering device. At this time, the film formation conditions were room temperature, DC 500 W, oxygen concentration of 6%, and the annealing conditions were 300° C. × 1 hour in an atmospheric atmosphere. After forming the metal film, the transparent protective layer composition prepared in Example 3 was sprayed with a spray device (Anest Iwata, W101) was applied at a pressure of 5 bar to form a transparent protective layer.

Experimental Example 1: Comparison of properties of polymer injection molded products formed with metal films

Polymer injection moldings (Experimental Examples 1-1 to 1-5) having a metal film formed through the process of Example 4 or Comparative Example 1 are summarized in Table 1 below.

Experimental example Formation of surface treatment layer metal film formation Formation of transparent protective layer 1-1 Example 4-2 Example 4-3-1 Example 4-4 1-2 Example 4-2 Example 4-3-2 Example 4-4 1-3 Example 4-2 Example 4-3-3 Example 4-4 1-4 Example 4-2 Example 4-3-4 Example 4-4 1-5 Example 4-2 Comparative Example 1 Example 4-4

In order to compare the physical properties of the metal films of Experimental Examples 1-1 to 1-5, reflectance, luminance, and adhesion were measured and compared.

Specifically, the reflectance was measured with a Minolta CM-5 spectrophotometer, and the viscosity was measured with a Brookfield LVDV2+. The luminance was confirmed by visual inspection, and the results were displayed as follows.

◎: Excellent, ○: Average, △: Poor, X: Poor

According to ASTM D 3359 standard, cross cut / tape peel off evaluation was performed, and the adhesion was shown in the order of 5B to 1B (the closer to 5B, the better). The metal film formation time was expressed as a relative value based on the spray coating process 100.

Experimental example reflectivity(%) luminance
(Visually) initial adhesion
(Cross cut) Hot water adhesion
(100℃ water 2hr
immersion) Metal film formation time 1-1 62.1 ○ 5B 5B 100 1-2 66.8 ◎ 5B 5B 100 1-3 68.1 ◎ 5B 5B 100 1-4 58.4 △ 5B 3B 100 1-5 61.4 ○ 5B 4B 420

As a result, as shown in Table 2, the initial adhesion was the same for the metal films of Experimental Examples 1-1 to 1-5, but it was confirmed that the metal films of Experimental Example 1-4 showed insufficient luminance and relatively low adhesion to hot water. In addition, in the case of Experimental Examples 1-5, it was confirmed that the metal film formation time was relatively long.

Experimental Example 2: Comparison of properties according to the metal ratio in the composition

Next, it was attempted to compare the composition's viscosity, reflectance, spray painting workability, luminance, and whether or not the bottom color was reflected when the metal ratio in the coating composition was changed. The reflectance was evaluated in the same manner as in Experimental Example 1, and the luminance and whether the bottom color was reflected visually were evaluated.

Experimental example in the composition
metal ratio
(wt%) Viscosity (cPs) reflectivity(%) Spray painting workability luminance
(Visually) floor color bleed
(Visually) 2-1 70.0 1100 not measurable poor discharge not measurable not measurable 2-2 60.0 500 60.4. △ △ no see-through 2-3 40.0 80 66.8 ○ ◎ no see-through 2-4 26.0 75 65.9 ○ ◎ no see-through 2-5 20.0 70 65.5 ◎ ◎ no see-through 2-6 6.6 55 64.7 ◎ ◎ no see-through 2-7 3.6 40 63.4 ◎ ◎ no see-through 2-8 1.0 35 50.5 ◎ △ see through 2-9 0.7 40 32.4 ○ X see through 2-10 0.0 40 5.0 ○ X see through

As a result, as shown in Table 3, when the metal ratio in the composition was 60% by weight or more, the viscosity was high, the spray coating workability was low, and the luminance was poor (Experimental Examples 2-1 and 2-2), and the metal ratio was 1 When it was less than or equal to % by weight, it was confirmed that the luminance was poor and the functionality as a paint was deteriorated due to the reflection of the floor color (Experimental Examples 2-8 to 2-10).

On the other hand, it was confirmed that the compositions of Experimental Examples 2-3 to 2-7 exhibited excellent characteristics as metal coating compositions in viscosity, reflectance, paint workability, luminance, and bottom color reflectance.

Experimental Example 3: Confirmation of physical properties according to the size of metal nanoparticles

It was confirmed whether the physical properties of the coating composition were changed according to the size of the metal nanoparticles. Experimental examples 3-1 to 3-5 were prepared by varying the metal particle size as shown in Table 4, and luminance, reflectance, and dispersion stability were evaluated. Luminance and reflectance were evaluated in the same manner as in Experimental Example 1, and dispersion stability was evaluated as follows based on the time of occurrence of sedimentation of the metal particles.

◎ Excellent (more than 120 days) ○ Average (more than 30 days) △ Poor (more than 7 days) X Poor (within 1 day)

item 3-1 3-2 3-3 3-4 3-5 Metal particle size (nm) 20 50 150 200 1000 dispersant BYK-111 solvent PGMEA Evaluation items luminance ◎ ◎ ◎ ○ X reflectivity(%) 65.5 62.1 60.8 51.7 15.8 dispersion stability ◎ ◎ ◎ △ X

As a result, as shown in Table 4, it was confirmed that when the size of the metal particles was 200 nm or more, the reflectance was lowered and the dispersion stability was insufficient.

As described above in detail a specific part of the content of the present invention, for those of ordinary skill in the art, this specific description is only a preferred embodiment, and it is clear that the scope of the present invention is not limited thereby. something to do. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (19)

(a) injecting a polymer resin to prepare a polymer injection product;
(b) forming a surface treatment layer on the polymer injection product;
(c) forming a metal film by applying a metal coating composition on the surface treatment layer;
(d) drying at 60 to 80° C. after performing step (c); and
(e) forming a transparent protective layer on the metal film, characterized in that it comprises a method for producing a polymer injection molded product with a metal film,
The metal coating composition comprises:
A metal ink composition comprising a metal complex compound and metal nanoparticles, a first binder resin, and a first solvent,
The metal is silver (Ag),
The metal ink composition further comprises one or more additives selected from the group consisting of a second binder resin, a second solvent, a dispersant, a stabilizer, a wetting agent, a coupling agent, a thixotropic agent, and a leveling agent,
The metal coating composition exhibits a reflectance of 50 to 70%,
The metal nanoparticles have a size of 20 to 50 nm,
The first binder resin and the first solvent are included in an amount of 1 to 20% by weight,
The second binder resin is included in 0.5 to 30% by weight,
The coupling agent is a silane-based, titanium-based, zirconium-based or aluminum-based coupling agent. According to claim 1, wherein the first binder resin is acrylic, cellulose, polyester, polyamide, polyether, vinyl, urethane, urea, alkyd, silicone, fluorine, olefin, petroleum, rosin, epoxy, unsaturated polyester, di Polymer with a metal film, characterized in that at least one selected from the group consisting of allyl phthalate resin, phenol, oxetane, oxazine, bismaleimide, modified silicone, melamine, acrylic resin, rubber, natural polymer, glass resin and glass frit A method for manufacturing an extruded product. The method of claim 1, wherein the first solvent is propylene glycol methyl ether acetate (PGMEA), α-terpineol (α-terpineol, α-TPN), β-terpineol (β-terpineol), benzyl ethyl ether, Tetrahydrofuran, dihexyl ether, dimethyl sulfoxide, ethylene glycol-n-butyl ether (butyl cellosolve), hexylene glycol, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, caproic acid, caprylic acid, methyl ethyl ketone, benzyl acetate, ethyl benzoate, diethyl oxalate, dimaleic acid Ethyl, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, butyl carbitol acetate (BCA), ethyl acetate (ethyl acetate), dibutyl phthalate (DBP), cyclohexanone, Cyclopentanone, acetonylacetone, isophorone, methylmethoxypropionate, ethylethoxypropionate, γ-butyrolactone, γ-butyrolactam, 1-octanol, 1-nonanol, Methoxy ethanol, methoxy propanol, methoxy butanol, ethoxy ethanol, ethoxy propanol, ethoxy butanol and at least one selected from the group consisting of benzyl alcohol, a method for producing a polymer injection product having a metal film formed therein. According to claim 1, wherein the second binder resin is acrylic, cellulose, polyester, polyamide, polyether, vinyl, urethane, urea, alkyd, silicone, fluorine, olefin, petroleum, rosin, epoxy, unsaturated polyester, di Polymer with a metal film, characterized in that at least one selected from the group consisting of allyl phthalate resin, phenol, oxetane, oxazine, bismaleimide, modified silicone, melamine, acrylic resin, rubber, natural polymer, glass resin and glass frit A method for manufacturing an extruded product. According to claim 1, wherein the second solvent is water, methanol, ethanol, isopropanol, butanol, ethylene glycol, glycerin, ethyl acetate, butyl acetate, carbitol acetate, butyl carbitol, diethyl ether, tetrahydrofuran, dioxane , methyl ethyl ketone, acetone, hexane, heptane, benzene, toluene, chloroform, methylene chloride and carbon tetrachloride, characterized in that at least one selected from the group consisting of, a method for producing a polymer injection molded with a metal film. The method of claim 1 , wherein the metal ink composition is included in an amount of 1 to 60% by weight based on the total amount of the metal coating composition. The method of claim 1, wherein the metal coating composition has a viscosity of 1 to 200 cPs. According to claim 1, wherein the polymer resin is one selected from the group consisting of ABS (acrylonitrile-butadiene-styrene), PC (polycarbonate), PBT (polybutyrene terephthalate) and PET (polyethylene terephthalate) The method for manufacturing an injection-molded polymer with a metal film, characterized in that the above. The method of claim 1 , wherein the polymer injection molded product is a vehicle interior material or component, or a component of a home appliance or portable electronic product. delete delete delete delete delete delete delete delete delete delete