KR20220053736A - Thermoplastic resin composition of metal-like texture having very high brightness and molded article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition of metal-like texture having very high brightness and a molded article comprising the same, and more specifically, to a thermoplastic resin composition which comprises: an acrylonitrile-butadiene-styrene resin; an additional thermoplastic resin other than acrylonitrile-butadiene-styrene resin; a fluidizing agent; and metal particles in combination at a specific content ratio and exhibits an excellent appearance by reducing a flow mark and a weld line while having the ultra-high brightness metallic texture, and to a molded article comprising the same.

Description

Thermoplastic resin composition of metal-like texture having very high brightness and molded article comprising the same

The present invention relates to a thermoplastic resin composition having an ultra-high luminance metal texture and a molded article comprising the same, and more particularly, to an additional thermoplastic resin other than an acrylonitrile-butadiene-styrene resin, an acrylonitrile-butadiene-styrene resin, It relates to a thermoplastic resin composition comprising a combination of a fluidizing agent and metal particles in a specific content ratio, and having an ultra-high luminance metal texture and exhibiting excellent appearance by reducing flow marks and weld lines at the same time, and a molded article including the same.

Recently, the needs of consumers are changing rapidly, and the industry paradigm of the past technology push is changing into the emotional era of human-centered (Demand pull). From the industrial age to the information age, functionally meaningful products (Product that makes sense) were hit products. However, in the emotional age, it is no exaggeration to say that the product that makes me love is the most attractive product that consumers demand. In the past, consumers' purchases were made by 'persuasion', but now, purchases are made by capturing the attention of consumers by 'impression'. In other words, the paradigm that focused on “production” in the 1980s and “function” in the 1990s is now shifting to a paradigm that combines emotions beyond technology.

The importance of technology is fundamental, and moving the mind by stimulating human emotions is a decisive factor in recent consumption. putting a lot of effort into doing that.

It can be said that vision plays a very large role in emotional aspects. 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.

Therefore, recently, there is an increasing demand for an eco-friendly non-painting material, that is, a metallic material that can implement a metallic texture appearance similar to a metallic painting by itself without a painting process. Development of the material is in progress (eg, Korean Patent Application Laid-Open No. 10-2013-0078747).

However, these conventional unpainted metallic materials, after injection molding of the thermoplastic resin composition, have additional mold changes due to appearance problems (especially weld lines, flow marks, or aggregation of metal particles) generated by metal particles in the material. There is a problem that this is necessary or the application is limited. In addition, 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, but the concentration of metal particles during injection molding, There is a limit to improving the appearance problems caused by agglomeration, orientation, etc.

Therefore, due to the excellent luminance characteristics of the material itself, it is possible to implement an appearance close to that of a metal coated product without painting, and while maintaining the original physical properties of the thermoplastic resin, flow marks and / or The development of a thermoplastic resin composition capable of reducing a weld line and simultaneously improving gloss properties and appearance properties of a molded article has been requested.

The present invention can realize ultra-high brightness while maintaining the original physical properties of the thermoplastic resin, and realize reduction of flow marks and weld lines generated by metal particles during injection molding, so that excellent metal texture and appearance properties without an additional coating process It is a technical task to provide a thermoplastic resin composition and a molded article comprising the same.

The present invention to solve the above technical problem, (1) acrylonitrile-butadiene-styrene resin; (2) additional thermoplastic resins other than acrylonitrile-butadiene-styrene resins; (3) glidants; and (4) metal particles; wherein, in a total of 100 parts by weight of the acrylonitrile-butadiene-styrene resin and the additional thermoplastic resin, 55 to 95 parts by weight of the acrylonitrile-butadiene-styrene resin and the additional thermoplastic resin 5 to 45 parts by weight of the resin is included, the content of the fluidizing agent is 0.5 to 5.5 parts by weight based on 100 parts by weight of the total of the acrylonitrile-butadiene-styrene resin and the additional thermoplastic resin, and the content of the metal particles is 0.1 to 15 parts by weight, to provide a thermoplastic resin composition.

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 can realize the metallic texture of ultra-high brightness while maintaining the original physical properties of the thermoplastic resin and dramatically reducing the flow marks and weld lines, which were issues of existing metallic materials, so that excellent gloss without an additional coating process Molded articles exhibiting characteristics and appearance characteristics can be provided.

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 a photograph showing an exemplary appearance corresponding to each of scores 1 to 5 of the appearance evaluation (flow mark) performed in Examples and Comparative Examples of the present invention.
3 is a photograph showing exemplary appearances corresponding to “good” and “bad”, respectively, which are results of surface property evaluation performed in Examples and Comparative Examples of the present invention.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention comprises (1) an acrylonitrile-butadiene-styrene resin; (2) additional thermoplastic resins other than acrylonitrile-butadiene-styrene resins; (3) glidants; and (4) metal particles.

(1) acrylonitrile-butadiene-styrene resin

The acrylonitrile-butadiene-styrene resin included in the resin composition of the present invention may be used without limitation as long as it is applicable as an unpainted metallic material.

In one embodiment, the acrylonitrile-butadiene-styrene resin may be an acrylonitrile-butadiene-styrene (ABS) resin, a modified acrylonitrile-butadiene-styrene (mABS) resin, or a mixture thereof, but in particular However, the present invention is not limited thereto.

In the resin composition of the present invention, in a total of 100 parts by weight of the (1) acrylonitrile-butadiene-styrene resin and the (2) additional thermoplastic resin, the acrylonitrile-butadiene-styrene resin is 55 to 95 weight included in the amount of wealth. If the content of the acrylonitrile-butadiene-styrene resin in the total of 100 parts by weight of the resin components (1) and (2) is less than 55 parts by weight, the impact strength of the resin composition may deteriorate. Conversely, if the content exceeds 95 parts by weight, The tensile strength and glug strength of the resin composition may deteriorate.

In one embodiment, in a total of 100 parts by weight of the (1) acrylonitrile-butadiene-styrene resin and the (2) additional thermoplastic resin, the acrylonitrile-butadiene-styrene resin is, for example, 60 parts by weight or more , It may be included in an amount of 65 parts by weight or more or 70 parts by weight or more, and may be included in an amount of 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, or 75 parts by weight or less, but is not particularly limited thereto.

(2) Additional thermoplastic resins other than acrylonitrile-butadiene-styrene resins

In addition to the acrylonitrile-butadiene-styrene resin, the additional thermoplastic resin included in the resin composition of the present invention may be used without limitation as long as it is applicable as an unpainted metallic material.

In one embodiment, the additional thermoplastic resin other than the acrylonitrile-butadiene-styrene resin is a polyamide (PA) resin, a polycarbonate (PC) resin, a polyolefin resin (eg, polyethylene and polypropylene, etc.), polyether ether Ketone (PEEK) resin, polyphenylene sulfide (PPS) resin, modified polyphenylene ether (mPPE) resin, polymethyl methacrylate (PMMA) resin, polybutylene terephthalate (PBT) resin, styrene-acrylonitrile (SAN) resin, or a mixture of two or more thereof, more specifically, polycarbonate (PC) resin, polybutylene terephthalate (PBT) resin, polyamide (PA) resin, polymethyl methacrylate ( PMMA) resin, or a mixture of two or more thereof, but is not particularly limited thereto.

In the resin composition of the present invention, in a total of 100 parts by weight of the (1) acrylonitrile-butadiene-styrene resin and the (2) additional thermoplastic resin, the additional thermoplastic resin is contained in an amount of 5 to 45 parts by weight. . If the content of the additional thermoplastic resin in the total of 100 parts by weight of the resin components (1) and (2) is less than 5 parts by weight, the tensile strength and glug strength of the resin composition may deteriorate. Conversely, if the content exceeds 45 parts by weight, the resin composition impact strength may deteriorate.

In one embodiment, in a total of 100 parts by weight of the (1) acrylonitrile-butadiene-styrene resin and the (2) additional thermoplastic resin, the additional thermoplastic resin is, for example, 10 parts by weight or more, 15 parts by weight or more , may be included in an amount of 20 parts by weight or more or 25 parts by weight or more, and may be included in an amount of 40 parts by weight or less, 35 parts by weight or less, or 30 parts by weight or less, but is not particularly limited thereto.

(3) glidant

The fluidizing agent included in the resin composition of the present invention is for improving the metal texture and workability by increasing the fluidity of the composition, and can be used without limitation as long as it is applicable to the thermoplastic resin composition.

In one embodiment, the fluidizing agent may be a methyl methacrylate-based compound, a naphthalene-based compound, a ligrin-based compound, an ethylenevinyl acetate-based compound, a melamine-based compound, a polycarboxylic acid-based compound, or a mixture of two or more thereof. However, it is not particularly limited thereto.

In the resin composition of the present invention, the fluidizing agent is included in an amount of 0.5 to 5.5 parts by weight based on 100 parts by weight of the total of (1) acrylonitrile-butadiene-styrene resin and (2) additional thermoplastic resin. If the content of the fluidizing agent per 100 parts by weight of the resin components (1) and (2) in total is less than 0.5 parts by weight, the metal texture effect of the resin composition may be insignificant. Separation is possible and, at the same time, during the injection molding process, a large amount of gas is generated, which may deteriorate the appearance.

In one embodiment, in the resin composition of the present invention, the fluidizing agent is, for example, 1 part by weight or more, 1.5 parts by weight per 100 parts by weight in total of the (1) acrylonitrile-butadiene-styrene resin and the (2) additional thermoplastic resin It may be included in an amount of more than or equal to 2 parts by weight, and may be included in an amount of 5 parts by weight or less, 4.5 parts by weight or less, or 4 parts by weight or less, but is not particularly limited thereto.

(4) metal particles

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

The metal particle component may be any metal or an alloy of any two or more metals, and 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 40 μm, more specifically 10 to 35 μm, even more specifically 10 to 20 μm, and even more specifically may be 12 to 16 μm. If the average particle size of the metal particle component is excessively smaller than the above level, it is difficult to implement a desired level of metal feeling, and on the contrary, if it is excessively larger than the above level, an undesired sparkling effect may appear.

Further, in one embodiment, the thickness of the metal particle component may be 0.1 to 1 μm (more specifically 0.2 to 1 μm, even more specifically 0.4 to 1 μm), but is not particularly limited thereto. Also, in one embodiment, the aspect ratio of the metal particle component may be 8 to 120.

In the resin composition of the present invention, the metal particle component is included in an amount of 0.1 to 15 parts by weight based on 100 parts by weight in total of the (1) acrylonitrile-butadiene-styrene resin and the (2) additional thermoplastic resin. . If the content of metal particles per 100 parts by weight of the total of the resin components (1) and (2) is less than 0.1 parts by weight, a desired metallic feeling cannot be obtained, and if the content exceeds 15 parts by weight, there may be poor appearance and deterioration of physical properties. .

In one embodiment, in the resin composition of the present invention, the metal particle component per 100 parts by weight in total of the (1) acrylonitrile-butadiene-styrene resin and the (2) additional thermoplastic resin is, for example, 0.5 parts by weight or more , may be included in an amount of 1 part by weight or more, 1.5 parts by weight or more, or 2 parts by weight or more, and may be included in an amount of 12 parts by weight or less, 10 parts by weight or less, or 8 parts by weight or less, but is not particularly limited thereto.

In one embodiment, the resin composition of the present invention may further include a light diffusing agent.

The light diffusing agent that can be included in the resin composition of the present invention may be organic or inorganic particles, and more specifically, the organic particles are acrylic (eg, methyl methacrylate (MMA)) cross-linked particles, silicone-based cross-linked particles, and styrene-based particles. It may be crosslinked particles or a mixture of two or more thereof, and the inorganic particles include calcium carbonate particles, barium sulfate particles, titanium oxide particles, aluminum hydroxide particles, silica particles, glass particles, mica particles, magnesium oxide particles, zinc oxide particles, or It may be a mixture of two or more of them, but is not particularly limited thereto. The organic particles and inorganic particles may be used alone or in combination of two or more.

In one embodiment, the average particle size of the light diffusing agent component may be 3 to 60 μm, more specifically 3 to 20 μm, even more specifically 3 to 10 μm, even more specifically As a result, it may be 3 to 5 μm. If the average particle size of the light diffuser component is excessively smaller than the above level, the effect of reducing the weld line and flow line may be insignificant, and if it is excessively larger than the above level, the effect of improving the appearance of the metal texture may be insignificant.

The resin composition of the present invention, in addition to the above-mentioned component (d), may further include one or more other additives commonly added to the thermoplastic resin composition for injection molding or extrusion molding. The resin composition of the present invention, for example, an inorganic filler, antioxidant, lubricant, ultraviolet absorber, light stabilizer, impact modifier, matting agent, flame retardant or at least one additive selected from the group consisting of a mixture of two or more thereof is added can be included as

Specifically, the inorganic filler may be plate glass, mica, graphite, talc, pearl particles, wollastonite, TiO ₂ or a combination thereof, and more specifically, TiO ₂ . In addition, the inorganic filler may have an average particle diameter of 0.2 to 200 μm (more specifically, 1 to 200 μm, more specifically, 10 to 200 μm), and may have a thickness of 0.1 to 10 μm.

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

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

As the ultraviolet absorber, commercially available products may be used without any particular limitation.

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

Specifically, the matting agent may be inorganic or organic, and more specifically, the inorganic matting agent may be silica, magnesium oxide, zirconia, alumina, titania, or a mixture of two or more thereof, and the organic matting agent It may be a crosslinked vinyl copolymer, and the monomer of the vinyl copolymer may be at least one selected from styrene, acrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, or butyl (meth) acrylate. there is.

The content of the other additives is not particularly limited, and the thermoplastic resin composition of the present invention may be used in an amount that can be used to add additional functions within a range that does not impair the desired physical properties. For example, the content of each of the other additives may be 0.05 to 5 parts by weight, more specifically 0.5 to 2 parts by weight, based on 100 parts by weight of the total of the resin components (1) and (2) in the resin composition of the present invention. may be, but is not particularly limited thereto.

The thermoplastic resin composition of the present invention can realize ultra-high brightness while maintaining the original physical properties of the thermoplastic resin. In one embodiment, the thermoplastic resin composition of the present invention may have a flop index of 15 or more (eg, 15 to 20), and more specifically, 16 or more (eg, 16 to 19).

Therefore, using the thermoplastic resin composition of the present invention, it is possible to realize very excellent metallic luminance while remarkably reducing flow marks and/or weld lines without an additional coating process. can

Therefore, 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 an extrusion-molded article or an injection-molded article of the thermoplastic resin composition of the present invention, and more preferably an injection-molded article.

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]

Examples 1 to 9 and Comparative Examples 1 to 12

A thermoplastic resin composition was prepared by uniformly dispersing the composition components by mixing with a mixer with the components and contents shown in Table 1, and then, the prepared thermoplastic resin composition was heated at 220° C. in a twin-screw extruder with L/D=40 and Φ=25mm. to 250° C., manufactured in the form of pellets by extrusion under conditions of 200 rpm to 250 rpm, and an injection specimen was prepared using an injection machine having a clamping force of 100 tons to 200 tons under the same temperature conditions.

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

[Description of ingredients used]

ABS: acrylonitrile-butadiene-styrene resin

PMMA: polymethyl methacrylate resin

SAN: Styrene-Acrylonitrile Resin

PP: crystalline polypropylene resin

PBT: crystalline polybutylene terephthalate resin

PC: polycarbonate resin

Fluidizing Agent: Acrylic Fluidizing Agent

Light diffuser: methyl methacrylate (MMA) type) crosslinked particles (average particle size: 3 to 5 μm)

Metal particle 1: Aluminum metal particle (average particle size: 15 μm)

Metal particle 2: Aluminum metal particle (average particle size: 10 μm)

Metal particle 3: Aluminum metal particle (average particle size: 20 μm)

Metal particles 4: Aluminum metal particles (average particle size: 35 μm)

[Evaluation of physical properties]

(1) Metal texture (Normal_Flop index)

The flop index was measured using a BYK-Mac i Spectrophotometer manufactured by BYK. Specifically, the luminance of reflected light at angles of 15°, 45° and 110° with respect to the normal portion and the weld occurrence portion of the injection specimen prepared from the thermoplastic resin compositions of Examples and Comparative Examples. After the measurement, the flop index was calculated by substituting into Equation 1 below.

[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 or more, and the flop index of the surface coated with the coating composition used for automobile body painting is 12 to 14, and the metal texture with the naked eye The flop index of the surface where you can feel it is 6 or more.

1 is a photograph showing a flop index measured for a surface having a metal texture, and the metal texture according to the flop index value can be confirmed.

(2) Appearance evaluation (flow mark)

The appearance was evaluated by visually observing. Specifically, with respect to the injection specimens prepared from the thermoplastic resin compositions of Examples and Comparative Examples, 10 subjects were asked to observe the flow marks of the specimens with the naked eye, and the overall appearance was excellent in consideration of the phenomena such as flow marks. It was evaluated on a scale of 0 to 5, 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.

2 is a photograph showing exemplary appearances corresponding to points 1 to 5 of the appearance evaluation (flow mark), respectively.

(3) Evaluation of surface properties

If the surface is rough as judged by eye and touch, it is judged as poor in appearance.

3 is a photograph showing exemplary appearances corresponding to “good” and “poor” respectively, which are results of surface property evaluation.

(4) Tensile strength (kgf/cm ² )

Tensile strength (@break) was measured in accordance with ASTM D638 for 　 injection 　 specimens prepared from the thermoplastic resin compositions of Examples and Comparative Examples.

(5) Flexural strength (kgf/cm ² )

Flexural strength was measured according to ASTM D760 for the 　 injection 　 specimens prepared from the thermoplastic resin compositions of Examples and Comparative Examples.

(6) Impact strength (kgf*cm/cm)

Impact strength (Izod Notched type) was measured according to ASTM D256 for the 　 injection 　 specimens prepared from the thermoplastic resin compositions of Examples and Comparative Examples.

As can be seen from the results of Table 1, the compositions of Examples according to the present invention implement an excellent appearance with reduced flow marks while implementing an ultra-bright metal texture with a flop index of 16 or more, and at the same time maintaining excellent mechanical properties. On the other hand, the compositions of Comparative Examples have relatively low metal texture (Comparative Examples 1, 2, 6, 10 to 12), poor appearance or surface (Comparative Examples 2, 3, 6, 8, 9), or mechanical properties Falling, etc. (Comparative Examples 1, 4-8, 10, 11), at least one of the evaluated items was poor.

Claims (10)

(1) acrylonitrile-butadiene-styrene resin;
(2) additional thermoplastic resins other than acrylonitrile-butadiene-styrene resins;
(3) glidants; and
(4) metal particles;
55 to 95 parts by weight of the acrylonitrile-butadiene-styrene resin and 5 to 45 parts by weight of the additional thermoplastic resin are included in a total of 100 parts by weight of the acrylonitrile-butadiene-styrene resin and the additional thermoplastic resin,
The content of the fluidizing agent is 0.5 to 5.5 parts by weight based on a total of 100 parts by weight of the acrylonitrile-butadiene-styrene resin and the additional thermoplastic resin, and the content of the metal particles is 0.1 to 15 parts by weight,
Thermoplastic resin composition. The thermoplastic resin composition according to claim 1, wherein the acrylonitrile-butadiene-styrene resin is an acrylonitrile-butadiene-styrene resin, a modified acrylonitrile-butadiene-styrene resin, or a mixture thereof. According to claim 1, wherein the additional thermoplastic resin other than the acrylonitrile-butadiene-styrene resin is polyamide resin, polycarbonate resin, polyolefin resin, polyether ether ketone resin, polyphenylene sulfide resin, modified polyphenylene ether resin , polymethyl methacrylate resin, polybutylene terephthalate resin, styrene-acrylonitrile resin, or a mixture of two or more thereof, the thermoplastic resin composition. The method according to claim 1, wherein the fluidizing agent is a methyl methacrylate-based compound, a naphthalene-based compound, a ligrin-based compound, an ethylenevinyl acetate-based compound, a melamine-based compound, a polycarboxylic acid-based compound, or a mixture of two or more thereof. , a thermoplastic resin composition. The thermoplastic resin composition of claim 1, wherein the metal particles have an average particle size of 8 to 40 μm. The thermoplastic resin composition of claim 1, further comprising a light diffusing agent. 7. The method of claim 6, wherein the light diffusing agent is acryl-based cross-linked particles, silicone-based cross-linked particles, styrene-based cross-linked particles, calcium carbonate particles, barium sulfate particles, titanium oxide particles, aluminum hydroxide particles, silica particles, glass particles, mica particles, magnesium oxide Particles, zinc oxide particles, or a mixture of two or more thereof, the thermoplastic resin composition. The thermoplastic resin composition according to claim 7, wherein the light diffusing agent has an average particle size of 3 to 60 µm. According to claim 1, Flop index (Flop index) is 16 or more, the thermoplastic resin composition. A molded article comprising the thermoplastic resin composition of any one of claims 1 to 9.

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