KR102305164B1 - Thermoplastic resin composition of metal texture having antistatic properties and molded article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition having a metallic texture having antistatic properties and a molded article comprising the same, and more particularly, by applying a specific content of metal particles and a specific type and a specific content of an antistatic agent to the thermoplastic resin, It is possible to realize metallic luminance while maintaining the original physical properties of the resin while remarkably reducing the flow marks and/or weld lines generated by metal particles during injection molding. It relates to a thermoplastic resin composition that can be provided and a molded article comprising the same.

Description

Thermoplastic resin composition of metal texture having antistatic properties and molded article comprising the same

The present invention relates to a thermoplastic resin composition having a metallic texture having antistatic properties and a molded article comprising the same, and more particularly, by applying a specific content of metal particles and a specific type and a specific content of an antistatic agent to the thermoplastic resin, It is possible to realize metallic luminance while maintaining the original physical properties of the resin while remarkably reducing the flow marks and/or weld lines generated by metal particles during injection molding. It relates to a thermoplastic resin composition that can be provided and a molded article comprising the same.

In recent years, in the age of human-centered technology, satisfaction with sensibility causes changes in consumer needs and demands a paradigm shift in the industry. The industrial paradigm of the past technology push is changing to a demand pull. In other words, the paradigm that focused on “production” in the 1980s and “function” in the 1990s is now being transformed into a paradigm that combines technology and emotion. Recently, while the importance of technology has been maintained, human emotions are acting as important determinants of purchase, and companies have begun to build “emotional power” that affects the emotions of buyers such as design, touch, and UI (User Interface). .

It can be said that vision plays a very large role in the emotional aspect. The important thing in terms of vision is related to the natural color and luminance of the material. And it can be said that the metallic material technology that can realize natural color and luminance without an additional painting process is very rare, and it is currently being applied in various fields.

One of the application fields for metallic materials is injection molding using thermoplastic resins. After injection molding, thermoplastic resins are delivered to consumers in many products, including electrical and electronic products and automobile parts. After injection molding, the product exterior is designed by painting and spraying, which is environmentally harmful and uneconomical due to additional painting processing costs.

Recently, as the demand for eco-friendly unpainted materials increases, there is an increasing demand for metallic materials that can implement a metal texture appearance similar to metal painting with the material itself without a painting process. For the application of unpainted material excluding such a painting process, development of a metallic material in which metal particles are applied to the thermoplastic resin itself is continuously being developed, but after injection molding of the thermoplastic resin composition, There is a problem in that an additional mold change is required or application is limited due to an appearance problem (especially, a weld line, flow mark, or aggregation of metal particles, etc.).

In order to solve this problem, studies such as adjusting the size, thickness, distribution, or aspect ratio of metal particles or improving the surface coating material of metal particles are continuously being studied. There is a limit in improving the appearance problem caused by orientation and the like.

Therefore, in order to solve this problem, it is possible to reduce flow marks and/or weld lines that may be caused by metal particles during injection molding while maintaining the original properties of the thermoplastic resin, and at the same time improve the gloss and appearance characteristics of the molded product. There is an urgent need to develop a thermoplastic resin composition for interior and exterior materials that can be used. In addition, there is a need for research on metal particles that can realize an appearance close to a metal coating product without painting.

In addition, the treatment of static electricity is a big issue in the overall industry including the electronics industry, the semiconductor industry, and the automobile industry, and stable quality is required even under various changing environments such as the influence of season/humidity/temperature, etc. are doing Therefore, in order to solve such a problem, the development of a thermoplastic resin composition having improved antistatic properties compared to conventional ones is required.

An object of the present invention is to provide a thermoplastic resin composition containing metal particles in order to exhibit a metal texture, have stable antistatic properties, maintain the original physical properties of the thermoplastic resin, and at the same time as flow marks generated by metal particles during injection molding and It is to provide a thermoplastic resin composition and a molded article including the same, which can provide a molded article having excellent gloss properties and appearance properties without an additional coating process by implementing metallic luminance while remarkably reducing the weld line and/or reducing the weld line.

In order to solve the above technical problem, the present invention includes a thermoplastic resin, metal particles, and an antistatic agent, wherein the antistatic agent is a polymer-type antistatic agent having a nylon-polyether skeleton, and based on 100 parts by weight of the total composition, the Provided is a thermoplastic resin composition wherein the content of the metal particles is greater than 0.6 parts by weight and less than 3 parts by weight, and the content of the antistatic agent is greater than 9 parts by weight and less than 16 parts by weight.

According to another aspect of the present invention, there is provided a molded article including the thermoplastic resin composition of the present invention.

The thermoplastic resin composition of the present invention has stable antistatic properties, maintains the original physical properties of the thermoplastic resin, and can realize metallic luminance while dramatically reducing flow marks and/or weld lines, which were issues of existing metallic materials, It is possible to provide a molded article exhibiting excellent gloss properties and appearance properties without an additional coating process.

1 is a photograph showing the flop index measured for each surface having various metal textures so as to check the metal texture difference according to the flop index value.
2 is an exemplary image showing a flow line according to the content of metal particles.
3 is an exemplary image showing a flow line according to the inorganic particle (TiO ₂ ) content (metal particle content: fixed at 2 wt%).

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention includes a thermoplastic resin, metal particles, and an antistatic agent.

As the thermoplastic resin component included in the thermoplastic resin composition of the present invention, it can be used without limitation as long as it is applicable as an unpainted metallic material.

The thermoplastic resin component is, for example, polycarbonate (PC) resin, acrylonitrile-butadiene-styrene (ABS) resin, polyamide (PA) resin, modified acrylonitrile-butadiene-styrene (mABS) resin, polyethylene and polyolefin resins such as polypropylene, polyether ether ketone (PEEK) resin, polyphenylene sulfide (PPS) resin, modified polyphenylene ether (mPPE) resin, polymethyl methacrylate (PMMA) resin, polybutylene tere. It may be selected from a phthalate (PBT) resin, and a mixture of two or more thereof, but is not particularly limited thereto.

According to one embodiment of the present invention, as the thermoplastic resin component, a PC resin, an ABS resin, a PA resin, a PMMA resin, a PBT resin, and a mixture of two or more thereof may be used.

In one embodiment, the thermoplastic resin composition of the present invention may include the thermoplastic resin component in an amount of 50 parts by weight to 90 parts by weight based on 100 parts by weight of the total composition. If the content of the thermoplastic resin component in the thermoplastic resin composition is too less than the above level, it is difficult to maintain the original physical properties of the thermoplastic resin. may be lowered.

More specifically, the content of the thermoplastic resin component in 100 parts by weight of the thermoplastic resin composition of the present invention may be 55 parts by weight or more, 60 parts by weight or more, or 65 parts by weight or more, and also 85 parts by weight or less, 80 parts by weight or less, or 75 parts by weight or more. It may be less than or equal to parts by weight.

The material of the metal particle component included in the thermoplastic resin composition of the present invention is not particularly limited, and the material of the metal particle may be selected according to a metallic appearance required for a molded article to which the thermoplastic resin composition of the present invention is applied.

In one embodiment, the metal particle component may be any metal or an alloy of any two or more metals, and more specifically, may be aluminum or an aluminum-based alloy, but is not limited thereto. In addition, the surface of the metal particles may be coated or surface-treated.

In one embodiment, the average particle size of the metal particle component may be 8 to 24 μm, and more specifically, 8 to 15 μm. If the average particle size of the metal particle component is less than the above level, it may be difficult to implement a desired level of metallic feeling, and on the contrary, if it exceeds the above level, an undesired sparkling effect may appear.

In one embodiment, the thickness of the metal particle component may be 0.2 to 1.0 μm, more specifically 0.2 to 0.4 μm. Also, in one embodiment, the aspect ratio of the metal particle component may be 8 to 120.

The thermoplastic resin composition of the present invention includes the metal particle component in an amount greater than 0.6 parts by weight and less than 3 parts by weight, based on 100 parts by weight of the total composition. If the content of the metal particle component in 100 parts by weight of the thermoplastic resin composition is 0.6 parts by weight or less, the metal feeling of the molded article is lowered and the flow marks are severe and the appearance deteriorates. Defect gets worse

More specifically, the content of the metal particle component in 100 parts by weight of the thermoplastic resin composition of the present invention may be 0.7 parts by weight or more, 1 part by weight or more, or 1.5 parts by weight or more, and also 2.9 parts by weight or less, 2.7 parts by weight or less, or 2.5 parts by weight or less. It may be less than or equal to parts by weight.

The antistatic agent included in the thermoplastic resin composition of the present invention is a polymer-type antistatic agent having a nylon-polyether skeleton. Here, the nylon skeleton is responsible for the rigidity, and the polyether skeleton is responsible for the ductility. In one embodiment, the antistatic agent may be a silane (silane) coating. Also, in one embodiment, the antistatic agent may be an ionic polymer.

The thermoplastic resin composition of the present invention includes the antistatic agent component in an amount greater than 9 parts by weight and less than 16 parts by weight, based on 100 parts by weight of the total composition. If the content of the antistatic agent in 100 parts by weight of the thermoplastic resin composition is 9 parts by weight or less, desired antistatic properties cannot be obtained, and on the contrary, if it is 16 parts by weight or more, the appearance of the molded article is poor and physical properties are deteriorated.

More specifically, the content of the antistatic agent component in 100 parts by weight of the thermoplastic resin composition of the present invention may be 9.1 parts by weight or more, 9.3 parts by weight or more, or 9.5 parts by weight or more, and also 15.9 parts by weight or less, 15.7 parts by weight or less, or 15.5 parts by weight or more. It may be less than or equal to parts by weight.

In addition, the thermoplastic resin composition of the present invention may further include an impact modifier.

As the impact modifier, at least one core-shell structure copolymer selected from an acrylate-based copolymer, an ethylene-acrylate-based copolymer, a silicone-containing copolymer, or a polyalkyl methacrylate-based copolymer may be used. It is not limited. The impact modifier may perform a function of stabilizing excellent and uniform physical properties by improving compatibility between resins or components in the composition as well as the function of impact reinforcement.

When the thermoplastic resin composition of the present invention further comprises an impact modifier, its content may be 1 part by weight or more, 3 parts by weight or more, or 5 parts by weight or more, and 15 parts by weight or less, based on 100 parts by weight of the composition; It may be 12 parts by weight or less or 10 parts by weight or less, but is not limited thereto.

In addition, the thermoplastic resin composition of the present invention may further include a flame retardant.

The flame retardant may include, but is not limited to, at least one of a phosphate compound, a phosphonate compound, a polysiloxane, a phosphazene compound, a phosphinate compound, or a melamine-based compound, which is a material that reduces combustibility.

When the thermoplastic resin composition of the present invention further comprises a flame retardant, the content thereof may be 1 part by weight or more, 3 parts by weight or more, or 5 parts by weight or more, and 15 parts by weight or less, 12 based on 100 parts by weight of the composition. It may be less than or equal to 10 parts by weight, but is not limited thereto.

In addition, the thermoplastic resin composition of the present invention may further include inorganic particles.

As the inorganic particles, glass particles, mica, graphite, talc, pearl particles, wollastonite, TiO _{2 ,} and combinations thereof may be used, and among them, TiO ₂ is effective for reducing flow marks.

As the glass particles, those having a plate-like structure may be used, which is different from glass fibers having a cylindrical shape. The cylindrical glass fiber does not reflect light, so it is difficult to show a metallic appearance.

The inorganic particles may have an average particle diameter of 10 to 200 μm, and a thickness of 0.1 to 10 μm. If the inorganic particles are properly mixed together with the metal particles and used, it is possible to implement a product that maintains an excellent metal appearance and has almost no flow marks.

When the thermoplastic resin composition of the present invention further comprises inorganic particles, the content thereof may be 0.05 parts by weight or more, 0.1 parts by weight or more, or 0.5 parts by weight or more, and 5 parts by weight or less, based on 100 parts by weight of the composition; It may be 4 parts by weight or less or 3 parts by weight or less, but is not limited thereto.

In addition, the thermoplastic resin composition of the present invention may further include one or more other additives commonly added to the thermoplastic resin composition for injection molding or extrusion molding in addition to the above-mentioned components. Such other additives include, for example, light diffusing agents, antioxidants, lubricants, ultraviolet absorbers, light stabilizers, matting agents, or mixtures of two or more thereof.

Specifically, the light diffusing agent may serve to assist the effect of improving the flow mark, for example, a silicone-based light diffusing agent, an acrylic light diffusing agent, a polystyrene-based light diffusing agent, or a mixture of two or more thereof. and the like can be used as the light diffusing agent.

Specifically, as the antioxidant, phenol-based, phosphite-based, thioester-based, or a mixture of two or more thereof may be used.

Specifically, as the lubricant, polyethylene, ethylene-ester, ethylene glycol-glycerin ester, montan, ethylene glycol-glycerin-montanic acid ester, or a mixture of two or more thereof may be used.

The ultraviolet absorber is not particularly limited, and commercially available products may be used.

Specifically, as the light stabilizer, a benzotriazole-based compound, a hydroxyphenyltriazine-based compound, a pyrimidine-based compound, a cyanoacrylate-based compound, or a mixture of two or more thereof may be used.

Specifically, an inorganic compound or an organic compound may be used as the matting agent. Silica, magnesium oxide, zirconia, alumina, titania, or a mixture of two or more thereof may be used as the inorganic compound, and a crosslinked vinyl copolymer may be used as the organic compound, and The monomer may be one or more monomers selected from styrene, acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, or butyl (meth) acrylate.

The content of the other additives is not particularly limited, and is an amount that can be used to add additional functions within a range that does not impair the desired physical properties of the thermoplastic resin composition of the present invention.

According to one embodiment of the present invention, the content of other additives may be 0.1 to 5 parts by weight, more specifically 0.5 to 2 parts by weight, based on 100 parts by weight of the resin composition. When the content of other additives is less than 0.1 parts by weight, the effect of improving various functions according to the use of other additives may be insignificant, and when the content of other additives is more than 5 parts by weight, mechanical properties may deteriorate.

When the thermoplastic resin composition of the present invention is used, it is possible to realize metallic luminance while remarkably reducing flow marks and/or weld lines, thereby obtaining a molded article of a metallic material exhibiting excellent gloss characteristics and appearance characteristics.

In one embodiment, the thermoplastic resin composition of the present invention may have a surface resistance of 10 ⁹ to 10 ¹² (Ω/sq.) and a Normal_Flop index of 9.60 to 15.

Accordingly, according to another aspect of the present invention, there is provided a molded article including the thermoplastic resin composition of the present invention.

The molded article may be manufactured by extruding or injection molding the thermoplastic resin composition of the present invention.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Example One

Polycarbonate (PC) as a thermoplastic resin, impact modifier (silicone-based impact modifier), flame retardant (phosphorus-based flame retardant), aluminum metal particles (average particle size: 10 μm), antistatic agent A, TiO ₂ and other additives (antioxidant, lubricant) was added to a mixer at the composition ratio shown in Table 1 below, mixed well and uniformly dispersed to prepare a thermoplastic resin composition. After that, extrusion was performed on the prepared thermoplastic resin composition using a 32-pi twin-screw extruder (L/D=40, 25mm) at 220°C to 250°C and 200 rpm to 250 rpm conditions, and 100 tons under the same temperature condition. Injection specimens were prepared using an injection machine having a clamping force of to 200 tons.

In case of injection specimen for evaluation of metal texture and appearance (flow mark), it was prepared as a rectangular multi-stage specimen with a size of 900 mm × 650 mm. , an injection specimen meeting each ASTM standard was prepared.

Example 2 to 7

An injection specimen was prepared in the same manner as in Example 1, except that the type and content of the thermoplastic resin, and the content of antistatic agent A, inorganic particles and other additives were changed as described in Table 1.

comparative example 1 to 12

The injection specimen was performed in the same manner as in Example 1, except that the type and content of the thermoplastic resin, the type and content of the antistatic agent, the aluminum metal particle content, and the content of other components were changed as described in Table 2 was prepared.

[Type of antistatic agent used]

Antistatic agent A: Polar ionic polymer (U1, CRODA) having a nylon-polyether backbone and coated with silane

Antistatic Agent B: Polar Nylon Salt Polymer (P-22, BASF)

Antistatic agent C: polar isocyanate Li/F ion polymer (AP-18, (Hexagen Co., Ltd.)

For the thermoplastic resin compositions prepared in Examples and Comparative Examples, physical properties were measured and evaluated in the following manner, and the results are shown in Tables 1 (Examples 1 to 7) and Table 2 (Comparative Examples 1 to 12) below. indicated.

[Measurement and evaluation of physical properties]

Appearance evaluation ( flow Mark)

The appearance was evaluated by visually observing. Specifically, for the injection specimen prepared from the thermoplastic resin composition, 10 test subjects were asked to observe the flow mark of the specimen with the naked eye, and the overall appearance was evaluated on a scale of 0 to 10 in consideration of the phenomenon of the flow mark, etc. and the average value of 10 subjects was described. A score of 0 indicates no flow mark, indicating an excellent appearance, and a higher score indicates that the flow mark is severe and poor in appearance.

metal texture

The flop index was measured using a BYK-Mac i Spectrophotometer manufactured by BYK. Specifically, after measuring the luminance of the reflected light at angles of 15 °, 45 ° and 110 ° with respect to the normal (Normal) portion and the weld (Weld) portion of the injection specimen prepared from the thermoplastic resin composition, the following mathematical By substituting in Equation 1, the flop index was calculated.

[Equation 1]

Luminance of reflected light measured at an angle of L* _{15° = 15°}

L* _45° = luminance of reflected light measured at an angle of 45°

L* _110° = luminance of reflected light measured at an angle of 110°

The flop index of the surface of an object without a metallic texture is 0, the flop index of the actual metal surface is 15 to 17, the flop index of the surface coated with the coating composition used for car body painting is 12 to 14, The flop index of the textured surface is 6 or higher.

1 is a photograph exemplarily showing a flop index measured with respect to a surface having a metal texture, and a difference in the metal texture according to the flop index value can be confirmed.

tensile strength

Tensile strength was measured according to ASTM D638 for the 　 injection 　 specimen prepared from the thermoplastic resin composition.

flexural strength

Flexural strength was measured according to ASTM D760 for the 　 injection 　 specimen prepared from the thermoplastic resin composition.

impact strength

Impact strength (Izod Notched type) was measured according to ASTM D256 for the 　 injection 　 specimen prepared from the thermoplastic resin composition.

importance

The specific gravity was measured according to ASTM D792 for the 　 injection specimen prepared from the thermoplastic resin composition.

surface resistance

Surface resistance (Ω/sq.) was measured using MCP-HT800 manufactured by MITSUBISHI CHEMICAL ANALYTECH.

[Table 1]

As can be seen from the results of Table 1, the compositions of Examples 1 to 7 according to the present invention all have antistatic properties, reduce flow marks and implement an appearance showing excellent metal texture, and at the same time, excellent balance of mechanical properties was kept

[Table 2]

As can be seen from the results of Table 2, the composition of Comparative Example 1 had a poor metal texture and showed severe flow marks and had a poor appearance, and the composition of Comparative Example 2 had a poor appearance due to severe flow marks. The composition of Comparative Example 3 had poor metal texture and low impact strength, the compositions of Comparative Examples 4 and 5 had significantly lower tensile strength, flexural strength, and impact strength, and the composition of Comparative Example 6 lacked antistatic properties and had a surface resistance The value was over (not measured as a specific numerical value), the composition of Comparative Example 7 had poor impact strength, and the composition of Comparative Example 8 showed severe flow marks and had a poor appearance, and the tensile strength, flexural strength, and impact strength were also significantly lowered. The composition of Comparative Examples 9 and 10 had a poor metal texture, showed severe flow marks and had a poor appearance, and the composition of Comparative Example 11 including ABS lacked antistatic properties, so the surface resistance value compared to the composition of Example 7 including ABS appeared high. The composition of Comparative Example 12 including ABS had poor metal texture compared to the composition of Example 7.

Claims (9)

a thermoplastic resin, metal particles, and an antistatic agent;
The thermoplastic resin is a polycarbonate resin, an acrylonitrile-butadiene-styrene resin, or a combination thereof,
The antistatic agent is a polymer-type antistatic agent having a nylon-polyether skeleton,
Based on 100 parts by weight of the total composition, the content of the metal particles is 1 to 2.5 parts by weight, the content of the antistatic agent is 12 to 15 parts by weight,
The surface resistance is 5.91 * 10 ⁹ to 10 ¹² (Ω / sq.), the normal area flop index (Normal_Flop index) is 10.85 to 15,
Thermoplastic resin composition. The thermoplastic resin composition according to claim 1, wherein the metal particles are aluminum or an aluminum-based alloy. The thermoplastic resin composition according to claim 1, wherein the metal particles have an average particle size of 8 to 24 µm. The thermoplastic resin composition of claim 1, wherein the antistatic agent is silane-coated. The thermoplastic resin composition of claim 1, further comprising an impact modifier or a flame retardant, or both. The thermoplastic resin composition of claim 1, further comprising inorganic particles selected from glass particles, mica, graphite, talc, pearl particles, wollastonite, TiO _{2 and combinations thereof.} delete A molded article comprising the thermoplastic resin composition of any one of claims 1 to 6. delete

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