KR20010058443A - Polyamide resin composition for plating - Google Patents

Abstract

PURPOSE: A polyamide resin composition for plating is provided which improves compatibility between the polyamide resin and a carboxylic acid reformed copolymer and has improved shock-resistance, heat-proof property, plating property and rigidity. CONSTITUTION: The polyamide resin composition for plating comprises: (i) 40-75 wt.% of polyamide 6 or polyamide 66 resin; (ii) 10-20 wt.% of a carboxylic acid reformed copolymer prepared by copolymerizing 40-80 wt.% of an aromatic vinyl compound, 15-35 wt.% of a vinyl cyan compound and 5-15 wt.% of α,β-unsaturated mono carboxylic acid; (iii) 5-10 wt.% of a butadiene containing styrenic rubber copolymer wherein 0.5-10 wt.% of an anhydrous maleic acid is grafted; and (iv) 10-30 wt.% of talc.

Description

Polyamide resin composition for plating

The present invention relates to a polyamide resin composition for plating, and more particularly, butadiene-containing styrenic rubbers based on polyamide resins, alloyed with carboxylic acid-modified copolymers, and grafted with maleic anhydride; The present invention relates to a polyamide resin composition for plating improved by making it suitable for plating automotive parts and electrical and electronic parts by adding talc and providing excellent adhesion strength and surface appearance as well as excellent impact resistance, heat resistance, and moldability. .

Resin products having a plated metal layer formed on the surface by the plating method have already been commercialized as a material for replacing metals, such as automobile grills, door handles, wheel caps, and the like. By utilizing the advantages of corrosion resistance and high rigidity, it is attempting to apply it to applications such as wheel covers, which are exterior materials.

Commonly used resin compositions for plating include acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resins, alloys of polycarbonate resins with ABS resins, polyphenylene ether resins, polysulfone resins, and polyether sulfones. And polyetherimide resins.

In connection with these resins, Japanese Patent Laid-Open No. 61-239694 and Japanese Patent Publication No. 54-36290 disclose resin compositions for plating polysulfone, resin compositions for plating polyether sulfone, and resin compositions for plating polyetherimide. Has been disclosed.

However, these resin compositions are disadvantageous because of their high cost and are difficult to plasticize.

On the other hand, it was intended to be used as a plating resin using various advantages of the polyamide resin, that is, moldability, toughness, stiffness, weather resistance, and the like. As a plating composition related to polyamide resin, Japanese Patent Application Laid-Open No. 61-268754 In this case, inorganic material was used, and in this case, there was a limitation in use due to a decrease in impact strength. In Japanese Patent Laid-Open No. 60-96648, a polyolefin having urastonite and an epoxy group as an inorganic material was also used for plating adhesion, heat resistance, and rigidity. However, there was a limit to the improvement of impact strength.

In addition, in the case of Japanese Patent Application Laid-Open No. 60-99163, although urastonite and silicone oil were used as inorganic fillers, it was also uneconomical because the impact strength had to be thickened over a certain thickness when applied to the product.

In Japanese Patent Laid-Open No. 61-253373, a plating method for ABS resin is disclosed. However, if the pretreatment process using organic solvent is applied to ABS resin in the same way as described here, it affects the additional materials in the main components of ABS resin, which hinders the surface roughness and the adhesion strength of plating film. There is a problem of poor heat resistance.

As another resin composition for plating, US Pat. Nos. 3,663,654 and 3,383,435 disclose compositions of ABS resins and polyphenylene ether resins, in which case both of them are composed of amorphous polymers, so the plating properties are excellent. Also, there is a limit to overcome the limitation of heat resistance, there is a limitation in use.

As described above, in the case of the plating resin of the conventional polyamide resin, there is a limit in application of the application due to the limit of impact strength, and the heat resistance of the ABS or polycarbonate resin or its alloy resin is inferior.

In other words, in the case of polyamide resin alone, the plating adhesion strength is insufficient when plating, and inorganic materials are used to overcome this problem. In this case, the impact strength is lowered and the surface roughness is reduced.

The present invention is to solve the problem of the polyamide resin composition for plating formed by adding an inorganic substance to the polyamide resin as described above, to improve the impact strength of the copolymer resin modified with carboxylic acid to improve compatibility The purpose of the present invention is to provide a polyamide resin composition comprising butadiene-containing styrene rubber grafted with maleic anhydride in order to improve heat resistance and plating properties and to add fine talc for surface roughness after plating.

Plating polyamide resin composition of the present invention for achieving the above object is 40 to 75% by weight of polyamide 6 or polyamide 66 resin; 10 to 20% by weight of a carboxylic acid-modified copolymer resin copolymerized with 40 to 80% by weight of an aromatic vinyl compound, 15 to 35% by weight of a vinyl cyan compound and 5 to 15% by weight of an α, β-unsaturated monocarboxylic acid; 5-10% by weight of butadiene-containing styrenic rubber resin grafted 0.5-10% by weight of maleic anhydride; And talc of 10 to 30% by weight.

The present invention is to improve the compatibility of the polyamide resin with the carboxylic acid modified copolymer and at the same time to induce chemical bonding of the plating performance, to further enhance the compatibility between the two resins and to improve impact resistance By using a butadiene-containing styrenic rubber resin grafted with maleic anhydride and adding a fine inorganic filler to the polyamide resin composition for plating which improves heat resistance and rigidity by inducing physical adsorption force during plating by inorganic addition effect. It is about.

Referring to the composition of the present invention in more detail as follows.

(1) polyamide resin

In the present invention, the base resin uses a polyamide resin, and specific examples thereof include polyamide homopolymers, copolymerized polyamides, and polyamide blends.

Wherein the polyamide homopolymer is a polymerization product of aminocarboxylic acids such as 6-aminohexanoic acid, 7-aminoheptanoic acid, 12-aminodecanoic acid, p-aminocyclohexylcarboxylic acid and the like; Dodecamethylenediamine, methaxylenediami, paraxylenediamine, hexamethylenediamine, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, 1,3-bisaminomethylcyclohexane, bis-p-amino Diamines such as cyclohexyl methane and the like; Polymerization products of dicarboxylic acids such as adipic acid, sebacic acid, schweric acid, pimelic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and the like; Polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polymethaxylene / paraxyleneadipamide, polymethaxylene / paraxen sebacamide, polymetha Xylene / paraxen schweramide, polymethaxylene / paraxen azelamide, etc.

Examples of the copolymer polyamide include copolymers obtained by amide exchange reaction of at least 22 hd selected from the above polyamide homopolymers, including lactams such as caprolactane and lauryl lactam; Aminocarboxylic acids such as 6-aminohexanoic acid, 7-aminoheptanoic acid, 12-aminododecanoic acid and p-aminocyclohexylcarboxylic acid; Such as methaxylenediamine, paraxylenediamine, hexamethylenediami, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, 1,3-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane and the like Diamine; And at least two copolymerized products selected from dicarboxylic acids such as adipic acid, sebacic acid, schweric acid, pimelic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and the like.

In the present invention, it is preferable to use polyamide 6 or polyamide 66, which is the polyamide homopolymer, among the polyamide resins used as the basic polymer. These resins exhibit excellent mechanical properties, plating properties and good appearance.

Meanwhile, in the present invention, these two kinds of resins may be blended in a certain weight ratio, and in this case, the content of any one polyamide resin of polyamide 6 and polyamide 66 may be less than 20% by weight relative to the other polyamide resin. It is preferable to use. At this time, when the amount of the blend exceeds 20% by weight, the amide exchange reaction is insufficient at the time of blending, resulting in a phase separation of the two resins, resulting in inferior mechanical properties.

Relative viscosity 2.4-3.5 for polyamide 6 resin (1 g of polymer in 100 ml of 20% 96% sulfuric acid), polyamide 66 resin for relative viscosity 2.5-3.2 (1 g solution of polyamide 66 in 100 ml of 20 ° C 96% sulfuric acid) It is preferable to use one.

If the viscosity of the polyamide resin is less than the above range, the stiffness is lowered. On the other hand, if the viscosity of the polyamide resin is more than the above range, surface manifestation of the inorganic material may occur due to poor fluidity, or the molding is not preferable.

Such polyamide 6 or polyamide 66 resin is used in 40 to 75% by weight of the total resin composition. If the content is less than 40% by weight, the heat resistance is lowered and the surface of the product becomes poor during molding and exceeds 75% by weight. In case of surface plating, adhesion strength is poor, which is not desirable.

(2) carboxylic acid modified copolymer resin

On the other hand, in the present invention, for kneading with carboxylic acid-modified copolymer resin having excellent plating performance in order to have excellent mechanical properties, plating properties and good appearance after plating, specifically, aromatic vinyl compound, vinyl cyan compound and α, β- Copolymers containing monomeric units derived from unsaturated monocarboxylic acids.

Here, looking at the monomer constituting the carboxylic acid modified copolymer in detail;

First of all, the aromatic vinyl compound is styrene, α-methylstyrene, o-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, pt-butylstyrene, ethylstyrene vinylnaphthalene, o- It is single or 2 or more types selected from the group which consists of methylstyrene.

The vinyl cyan compound is selected from acrylonitrile, methacrylonitrile and fumaronitrile, preferably acrylonitrile.

Such aromatic vinyl compounds and vinyl cyan compounds may be used in the range of 40 to 80% by weight and 15 to 35% by weight, respectively, of the total carboxylic acid modified copolymer resin. If the content is less than the above range, the adhesion strength is reduced after plating. If it exceeds the above range, the stiffness, corrosion resistance and impact strength are lowered.

In addition, α, β-unsaturated monocarboxylic acid is acrylic acid, methacrylic acid and mixtures thereof, and is contained in 5 to 15% by weight for use with polyamide resin, if the content is less than 5% by weight polyamide Its compatibility with the resin is inferior, and if it is more than 15% by weight, the reactivity is good, but the surface condition of the molded article is not good, so the surface roughness after plating is lowered.

Preparation of such modified carboxylic acid modified copolymer can be prepared by conventional suspension, emulsion polymerization method.

When the carboxylic acid-modified copolymer is added to 10 to 20% by weight in the final polyamide resin composition, if the content is less than 10% by weight, the adhesion strength during plating becomes poor, while if it is added in excess of 20% by weight. Heat resistance and rigidity become poor.

(3) Styrene rubbers containing butadiene grafted with maleic anhydride

Meanwhile, in the present invention, butadiene-containing styrenic rubber grafted with maleic anhydride is used in order to promote better compatibility between the polyamide resin and the carboxylic acid modified copolymer and to maximize the impact strength in the mechanical properties of the final composition.

It is also referred to as a thermoplastic rubber elastomer, which is widely known as the impact resistance or water resistant modifier of a conventional polyamide resin, and has a functional group which is excellent in reactivity with a matrix functional group of polyamide, that is, an amide group. It is a main acid or (alpha), (beta)-unsaturated anhydride, or its derivative (s).

In the present invention, styrene-ethylene-butadiene-styrene is used as a copolymer containing 0.5 to 10% by weight of maleic anhydride and containing butadiene latex and ethylene and containing aromatic vinyl.

If the graft ratio of maleic anhydride is less than 0.5% by weight, the compatibility with polyamides is insufficient, and the impact strength improvement effect is insignificant. If the content is more than 10% by weight, the surface quality is poor due to the decrease in fluidity.

The amount of such rubber elastomer is 5 to 15% by weight in the final composition. If the content is less than 5% by weight, the impact strength and elongation improvement effect is insignificant. There is a disadvantage in inferior plating adhesion.

(4) inorganic filler

On the other hand, in the present invention, to overcome the limitations of heat resistance and rigidity and to place fine unevenness on the surface during plating etching to improve the adhesion strength of the plating, by adding an inorganic filler of fine particles to further improve the plating adhesion strength and heat resistance and rigidity more excellent I want to.

Inorganic fillers that can be used in the present invention are in the form of fibrous, granular, acicular, lobed, panic acid, and the like, carbonates and oxides, alkali silicates, metal fibers, ceramic fibers, aluminum oxide, mica, talc, sulfuric acid Barium, gypsum, zirconium oxide, antimony oxide, clay, silica, aluminum silica, diatomaceous earth, magnesium carbonate, glass beads and the like can be used.

In the present invention, talc, which is a general-purpose inorganic filler, is used because the chemical component of the filler exhibits excellent properties in adhesion strength during plating and product surface roughness after plating.

Talc and the like are as 3MgO · 4SiO ₂ · H ₂ O, and used to have a SiO ₂ and MgO are contained in more than 85% by weight, the particle size is preferably not more than 4㎛.

If the two compounds of SiO ₂ and MgO are less than 85% by weight, the adhesion strength during plating decreases, which is not preferable. If the particle size is larger than 4 μm, the surface roughness after plating becomes poor and the appearance is not beautiful.

In the present invention, such talc is added at 10 to 30% by weight of the total polyamide resin composition. If the content is less than 10% by weight, the surface has little fine unevenness during plating etching, so it is difficult to expect physical adsorption force, and thus adhesion is performed during plating. There is a problem in lowering the strength and lowering the stiffness and heat resistance in the final composition, whereas the surface roughness after the 30% by weight is severe and the surface roughness of the product is poor, so the appearance is not beautiful, which is undesirable.

(5) other

Meanwhile, additives such as heat stabilizers, lubricants, flame retardants, antistatic agents, plasticizers, light stabilizers, etc. may be appropriately added as necessary within the scope of not impairing the object of the present invention, and an amide group may be used to prevent decomposition by heat. IRGANOX B1171, a 1: 1 mixture of tris- (2,4-dibutylbutylphenyl) -phosphate having and N, N'-hexamethylenebis (3,5-dibutylbutyl-4-hydroxy-hydrocinamide) You can also use

In order to apply the polyamide resin composition prepared in the above composition, the plating is completed through three processes of etching, plating, and electric processes.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Examples 1-10 and Comparative Examples 1-9

The composition and content of the following Table 1, but melted kneaded in a twin screw extruder heated to 245 ℃ when using polyamide 6, to 275 ℃ when using polyamide 66, and then chipped at 90 ℃ 5 Each specimen was fabricated using a screw injection machine heated to the same temperature after drying using a dehumidifying dryer for a period of time. Since the adhesion strength and surface roughness of the plating may vary depending on the mold temperature when the specimen is manufactured, the specimen was manufactured by adjusting the mold temperature to 90 ° C. using a mold with a mold temperature controller.

In order to plate the surface of the specimen, the specimen was first dried at 100 ° C. for 4 hours, and then fine particles such as dust were removed from the surface.

First, the etching step was immersed in a 200 mL / L hydrochloric acid liquid composition for 15 minutes at 45 ℃. Subsequently, in the post-etching, the liquid composition of hydrochloric acid was carried out at a temperature of 23 ° C. for 2 minutes at 60 ml / l, and in the first active step, PdCl ₂ (0.3 g / l) and SnCl ₂ · 2H ₂ O (25 g / l ), Using a metal complex salt of hydrochloric acid (280 mL / ℓ) as an aqueous solution for 5 minutes at a temperature of 30 ℃, in the second active step to enable the deposition of chemical plating on the catalyst layer given in the first active step and At the same time, the Sn component was removed and Pd was activated to accelerate and wash for 3 minutes at a temperature of 45 ° C. in a 30 ml / l liquid composition of 98% sulfuric acid. Thereafter, in the third activation step, sodium hydroxide was used to remove Sn, which was not removed in the second activation step, to promote activation of Pd, and sodium hydroxide was 15 g / l at 23 ° C. for 1 minute.

Next, Pd attached to the surface was used as a catalyst nucleus to precipitate metal nickel to impart conductivity. 3 g / l of nickel ions were carried out at 35 ° C. for 4 minutes, and dried at room temperature for 2 minutes. It was immersed in% sulfuric acid solution for 30 minutes. After the copper lactate plating process to enhance the adhesion, copper sulfate 220g / ℓ, sulfuric acid 55g / ℓ and some polish was carried out for 45 minutes at 25 ℃.

Next, the semi-bright nickel plating process step for imparting corrosion resistance and to make the off-white nickel plating in semi-gloss with _{NiSO 4 280g / ℓ, NiCl 2} 40g / ℓ, H 3 BO 3 40g / ℓ and a few polisher 54 ℃ For 14 minutes. The same process as the semi-gloss nickel plating process, but only 7 minutes time was repeated once more to give a better gloss and then again subjected to a gloss process for 2 minutes. This was followed by chromium plating in the final process to prepare a desired chromium plated specimen by performing CrO ₃ 280g / l and sulfuric acid 0.5g / l solution at a temperature of 40 ° C. for 2 minutes.

The chromium plated specimens thus prepared were allowed to stand for one week at 23 ° C. and 50% absolute humidity to evaluate surface roughness and adhesion.

In addition, each resin composition was evaluated for physical properties based on the following evaluation method, and the results are shown in Table 2 below. On the other hand, since the adhesion strength or surface roughness of the plating is different depending on the surface of the resin, the mold temperature was performed at 90 ° C. among the injection molding conditions which have a great influence on the surface during the manufacture of the injection-molded specimen.

<Test method>

1) Heat Deflection Temperature: A 6.4 mm thick specimen was prepared according to ASTM D648 and measured at 66 psi (4.6 kg / cm 2).

2) Impact Strength: A 3.2 mm thick specimen was prepared according to ASTM D256 and measured at room temperature.

3) Evaluation of adhesion strength (plating strength) of plating: Using a 100mm disc specimen, draw parallel lines at intervals of 10mm on the surface of the plate and pull them at a speed of 20mm / min in a direction perpendicular to the direction in which the lines were engraved. The minimum force required was measured.

4) Evaluation of swelling of plating: 1 hour at 80 ° C, 30 minutes at room temperature, 1 hour at -30 ° C, and 1 hour at room temperature again to evaluate the swelling visually after a total of 3 cycles.

5) Exterior surface roughness: The smoothness of 100 mm disc specimens was visually evaluated at a distance of 60 cm under a light source of 150 lux or more.

Comparative Examples 10-11

The same procedure as in Example 1, except that kaolin and ulastonite were used instead of talc as the inorganic filler.

The evaluation results are shown in Table 2.

(Unit: weight%) Polyamide resin Carboxylic Acid Modified Copolymers ⁽¹⁾ Styrene Rubber ⁽²⁾ Talc ⁽³⁾ Kinds content Example One PA 6 70 CSAN-1 (15) RUB-2 (5) T-1 (10) 2 PA 66 58 CSAN-2 (15) RUB-1 (7) T-2 (20) 3 PA 6 50 CSAN-2 (10) RUB-1 (10) T-2 (30) 4 PA 66 53 CSAN-1 (20) RUB-2 (7) T-2 (20) 5 PA 6 57 CSAN-3 (15) RUB-2 (8) T-1 (20) 6 PA 66 67 CSAN-2 (15) RUB-3 (8) T-2 (10) 7 PA 6 55 CSAN-3 (20) RUB-3 (5) T-2 (20) 8 PA 66 52 CSAN-1 (10) RUB-1 (8) T-1 (30) 9 PA 6 55 CSAN-1 (15) RUB-1 (10) T-1 (20) 10 PA 66 58 CSAN-2 (15) RUB-2 (7) T-2 (20) Comparative example One PA 6 65 CSAN-2 (15) - T-2 (20) 2 PA 66 72 - RUB-1 (8) T-1 (20) 3 PA 6 67 CSAN-3 (5) RUB-2 (8) T-2 (20) 4 PA 66 47 CSAN-2 (25) RUB-1 (8) T-2 (20) 5 PA 6 62 CSAN-2 (15) RUB-3 (3) T-2 (20) 6 PA 66 53 CSAN-1 (15) RUB-1 (12) T-1 (20) 7 PA 6 80 - - T-2 (20) 8 PA 6 73 CSAN-1 (15) RUB-2 (7) T-3 (5) 9 PA 66 42 CSAN-2 (15) RUB-3 (8) T-3 (35) 10 PA 6 57 CSAN-2 (15) RUB-3 (8) 20 ⁽⁴⁾ 11 PA 66 57 CSAN-3 (15) RUB-2 (8) 20 ⁽⁵⁾ PA6: polyamide 6 resin, PA66: polyamide 66 resin (1) carboxylic acid modified copolymer CSAN-1: 10% by weight of methacrylic acid, 60% by weight of styrene, 30% by weight of acrylonitrile copolymer resin CSAN-2: 12% by weight acrylic acid, 70% by weight styrene, 18% by weight acrylonitrile copolymer resin CSAN-3: 15% by weight methacrylic acid, 65% by weight styrene, 20% by weight acrylonitrile copolymer resin (2) styrenic rubber -1: maleic anhydride 1.5 wt% grafted styrene-ethylene-butadiene-styrene thermoplastic rubber elastomer RUB-2: maleic anhydride 5 wt% grafting styrene-ethylene-butadiene-styrene thermoplastic rubber elastomer RUB-3: maleic anhydride 7.5% by weight of grafted styrene-butadiene-styrene thermoplastic rubber elastomer (3) Talc T-1: average particle diameter of 2.5 mu m, T-2: average particle diameter of 4 mu m, T-3: average particle diameter of 7 mu m (4) kaolin (5) Woollastonite

Impact strength (kgcm / cm) Heat deflection temperature (℃) Peel Strength (kgf / cm) Swelling Surface roughness Example One 18.5 158 1.4 ○ ○ 2 23 198 1.6 ○ ○ 3 27.5 169 1.4 ○ ○ 4 22 190 1.8 ○ ○ 5 25 150 1.7 ○ ○ 6 27.5 191 1.4 ○ ○ 7 18 159 1.9 ○ ○ 8 21.5 200 1.4 ○ ○ 9 25 160 1.9 ○ ○ 10 20 198 1.6 ○ ○ Comparative example One 7 119 1.2 ○ ○ 2 17.5 201 0.5 × × 3 20.5 175 0.8 × ○ 4 25 140 0.5 ○ × 5 11.5 123 1.4 ○ ○ 6 30.5 151 1.2 ○ × 7 6.5 155 1.4 × × 8 17 111 0.6 ○ × 9 20 197 1.4 ○ × 10 24.5 154 0.8 × ○ 11 15 165 1.1 × × ○: good x: bad

As described in detail above, the polyamide resin is alloyed with a carboxylic acid-modified copolymer, and at the same time, a chemical is used for plating by using butadiene-containing styrenic rubber grafted with maleic anhydride, which is a thermoplastic elastomer, and an inorganic filler. It can induce bonding strength and physical adsorption to maximize adhesion strength and surface roughness after plating, and has excellent impact resistance, heat resistance and moldability, so it can exhibit even better physical properties than conventional polyamide plating resin compositions. It can be used for plating of electric and electronic parts, and it can be applied to automobile wheel caps and door handle products, grill products and other decorative parts as main uses, and especially for complex structures, conventionally used plating resins such as Acrylonitrile-butadiene-styrene resins, polycarbonate / Acrylonitrile-butadiene-styrene alloy resin, polyphenylene oxide resin, etc. have difficulty in application due to surface defects during molding, poor strength of product, poor heat resistance, etc. It can be excellent in the effect and the impact resistance is significantly improved compared to the conventional polyamide resin plating composition.

Claims (6)

40 to 75% by weight of polyamide 6 or polyamide 66 resin; 10 to 20% by weight of a carboxylic acid-modified copolymer copolymerized with 40 to 80% by weight of an aromatic vinyl compound, 15 to 35% by weight of a vinyl cyan compound and 5 to 15% by weight of a compound selected from α, β-unsaturated monocarboxylic acid; 5-10% by weight of butadiene-containing styrenic rubber copolymer grafted 0.5-10% by weight of maleic anhydride; And Plating polyamide resin composition consisting of 10 to 30% by weight of talc. The polyamide resin composition for plating according to claim 1, wherein the alpha, beta -unsaturated monocarboxylic acid in the carboxylic acid modifying copolymer component is acrylic acid or methacrylic acid. The polyamide resin composition for plating according to claim 1, wherein the butadiene-containing styrene rubber copolymer is styrene-ethylene-butadiene-styrene or styrene-butadiene-styrene copolymer. The polyamide resin composition for plating according to claim 1, wherein talc has a particle size of 4 µm or less. An automotive product made of the polyamide resin composition according to claim 1, having an impact strength of 18 kg · cm / cm or higher based on ASTM D256, and a heat deformation temperature of 155 ° C. or higher according to ASTM D648 (4.6 kg / cm 2). 6. The product of claim 5, wherein the product is selected from the group consisting of wheel caps, wheel covers, door handles, and grill products.