KR20190036916A - Polyoxymethylene Resin Composition and Molding Produced from the Same - Google Patents

Abstract

The present invention relates to a polyoxymethylene resin composition and a molded product manufactured from the same, wherein the polyoxymethylene resin composition, based on 100 parts by weight of polyoxymethylene, comprises: 10 to 20 parts by weight of an aliphatic thermoplastic polyurethane; 2.0 to 5.0 parts by weight of an ethylene-butyl acrylate copolymer; 2.0 to 5.0 parts by weight of a thermoplastic polyester elastomer; 0.2 to 0.4 parts by weight of an aliphatic isocyanate compound; 0.1 to 0.5 parts by weight of a hindered phenolic antioxidant; 0.1 to 0.5 parts by weight of an ultraviolet absorber; and 0.1 to 0.5 parts by weight of a hindered amine-based photostabilizer. Specifically, the present invention provides the polyoxymethylene resin composition having excellent impact strength characteristics and light resistant characteristics at the same time, and the molded product manufactured by using the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyoxymethylene resin composition and a molded article produced therefrom,

The present invention relates to a polyoxymethylene resin composition and a molded article produced using the same.

Polyoxymethylene (POM) resin is known as crystalline engineering plastic with excellent mechanical properties, rigidity, creep resistance, chemical resistance, friction / wear characteristics, long term durability, and high crystallinity. Utilizing this feature, POM is used in a wide range of fields such as electronic parts, automobile parts, and industrial parts.

However, since it is difficult to apply to polyoxymethylene pure resin which requires impact characteristics, it is necessary to modify the physical properties by adding an impact resistant agent. In addition, there is a demand for lightfastness as the demand for products requiring lightfastness is increased by continuously receiving automobile interior materials or ultraviolet rays.

As a conventional technique for improving the impact strength of a polyoxymethylene resin, there have been proposed a method of adding a plasticizer, an impact modifier and a coupling agent to a polyoxymethylene resin (refer to Japanese Patent Publication No. 2013-0117794) A method of adding a compatibilizing agent and an impact modifier (US Patent Publication No. 2007-0276064) has been proposed.

However, in the case of the above-mentioned prior arts, only the impact characteristics can be modified, and in the case of light resistance, modification is very difficult due to the intrinsic properties of the impactor. Accordingly, there is a need to develop a technology for a polyoxymethylene resin that simultaneously alters impact characteristics and satisfies light resistance characteristics.

Accordingly, it is an object of the present invention to provide a polyoxymethylene resin composition having excellent impact strength characteristics and light fastness properties, and a molded article produced using the same.

A first preferred embodiment of the present invention for solving the above problems is a polyoxymethylene; And 10 to 20 parts by weight of an aliphatic thermoplastic polyurethane, 2.0 to 5.0 parts by weight of an ethylene-butyl acrylate copolymer, 2.0 to 5.0 parts by weight of a thermoplastic polyester elastomer, and 0.2 to 0.5 parts by weight of an aromatic isocyanate compound per 100 parts by weight of the polyoxymethylene 0.1 to 0.5 parts by weight of a hindered phenolic antioxidant, 0.1 to 0.5 parts by weight of an ultraviolet absorber and 0.1 to 0.5 parts by weight of a hindered amine light stabilizer.

The aliphatic thermoplastic polyurethane has a number average molecular weight of 20,000 to 60,000 g / mol and a Shore A hardness of 80 to 90.

The ethylene-butyl acrylate copolymer contains 5 to 35 mol% of butyl acrylate repeating units and 65 to 95 mol% of ethylene repeating units based on the total molar amount of the polymer ethylene-butyl acrylate copolymer, and the melting point (T _m ) Deg.] C and 80 to 100 [deg.] C.

The thermoplastic polyester elastomer has a Shore A hardness of 75 to 85 and a number average molecular weight of 20,000 to 50,000 g / mol. The aromatic isocyanate compound may be selected from the group consisting of methylene diphenyl diisocyanate (MDI); 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI); Toluene diisocyanate (TDI); Polymeric MDI; Carbodiimide modified liquid 4,4'-diphenylmethane diisocyanate; Paraphenylene diisocyanate (PPDI); Meta-phenylene diisocyanate (MPDI); Polyphenylene polymethylene polyisocyanate (PMDI); A mixture of MDI and PMDI; A mixture of PMDI and TDI; m-phenylene diisocyanate, m-xylylene diisocyanate; m-tetramethylxylylene diisocyanate, p, p'-biphenyl diisocyanate; 3,3'-dimethyl-4,4'-biphenylene diisocyanate; 3,3'-dimethoxy-4,4'-biphenylene diisocyanate; 3,3'-diphenyl-4,4'-biphenylene diisocyanate; 4,4'-biphenylene diisocyanate; 3,3'-dichloro-4,4'-biphenylene diisocyanate; 1,5-naphthalene diisocyanate; 4-chloro-1,3-phenylene diisocyanate; 1,5-tetrahydronaphthalene diisocyanate; 2,4-chlorophenylene diisocyanate; And a mixture thereof.

The hindered phenol-based antioxidant has a molecular weight of 500 to 1,500 g / mol and a melting point of 40 to 200 ° C.

The ultraviolet absorber has a molecular weight of 200 to 500 g / mol and a melting point of 50 to 160 ° C.

The hindered amine light stabilizer has a weight average molecular weight of 1,000 to 4,500 g / mol.

The composition described above is characterized by having a melt index (MI) of 5.5 g / 10 min or more as measured by ISO 1133.

A second preferred embodiment of the present invention is to provide a molded article produced from the above-mentioned polyoxymethylene resin composition.

The molded product has a Charpy notched impact strength of not less than 12 kJ / m 2 at a room temperature of 23 캜 measured at ISO 179/1 eA, a light resistance test (SAE J2412: 2015) Measurement standard 601.6 kJ After the energy irradiation, it is characterized by having a grade of 4 or higher and a color change (Delta E) of 2.5 or less.

According to the present invention, there is provided a polyoxymethylene resin composition having an excellent impact strength and at the same time, a sun visor-related part, a seat belt-related part, and an electric / electronic exterior part, which have a light resistance characteristic and are required to be exposed to ultraviolet rays for a long time It can be suitably applied to the purpose.

As a preferred embodiment of the present invention, polyoxymethylene; And 10 to 20 parts by weight of an aliphatic thermoplastic polyurethane, 2.0 to 5.0 parts by weight of an ethylene-butyl acrylate copolymer, 2.0 to 5.0 parts by weight of a thermoplastic polyester elastomer, and 0.2 to 0.5 parts by weight of an aromatic isocyanate compound per 100 parts by weight of the polyoxymethylene , 0.1 to 0.5 parts by weight of a hindered phenol-based antioxidant, 0.1 to 0.5 parts by weight of an ultraviolet absorber and 0.1 to 0.5 parts by weight of a hindered amine light stabilizer, and the polyoxymethylene resin composition To provide a molded article.

In the present invention, the aliphatic thermoplastic polyurethane can obtain excellent light resistance compared to the aromatic thermoplastic polyurethane at the same time as improving impact resistance. Further, by improving the impact resistance through the ethylene-butyl acrylate copolymer and the thermoplastic polyester elastomer and by including an aromatic isocyanate compound as a coupling agent, the compatibility of the polyoxymethylene resin and the aliphatic thermoplastic polyurethane resin can be improved .

In addition, the hindered phenol-based antioxidant, ultraviolet absorber and hindered amine-based light stabilizer each have an effect of improving the light resistance of the polyoxymethylene resin.

 Ultimately, the polyoxymethylene resin composition comprising the above-mentioned composition has a melt index (MI) of 5.5 g / 10 min or more as measured by ISO 1133, and the molded article produced therefrom has a tensile strength of 40 (SAE J2412: 2015) measurement standard 601.6 kJ after irradiating with energy, and a Charpy notched impact strength of not less than 12 kJ / m 2 at a temperature of 23 캜 at an ISO 179 / Gray Scale) grade 4 or higher and color change (Delta E) 2.5 or less.

In addition, the molded article produced from the resin composition of the present invention exhibits light resistance characteristics while exhibiting impact properties, and can be usefully used for interior parts of automobiles and exterior parts of electronic devices which are continuously exposed to ultraviolet rays.

Hereinafter, each component of the polyoxymethylene resin composition of the present invention will be described in more detail.

Polyoxymethylene

The polyoxymethylene of the present invention is an oxymethylene homopolymer containing an oxymethylene- (OCH ₂ ) n - group as a repeating unit, an end group of which is blocked with an ester or an ether group, or a polymer chain comprising oxymethylene monomer units An oxymethylene-based copolymer in which an oxyalkylene unit having 2 to 8 carbon atoms is randomly inserted into the main chain and both ends of the polymer are blocked with an ester or an ether group, or a terpolymer.

The polyoxymethylene of the present invention serves as a base resin of the resin composition, secures the basic mechanical and chemical properties of the resin, and particularly performs a function important for abrasion resistance. In the present invention, the polyoxymethylene is not particularly limited as long as it is a commonly used polyoxymethylene, but it is more preferable that the melting point (T _m ) measured by differential scanning calorimetry (DSC) is 160 to 180 ° C .

Although the present invention is not particularly limited thereto, the oxymethylene homopolymer and the oxymethylene-based copolymer may be prepared by the following method. First, the above-mentioned oxymethylene homopolymer is polymerized by introducing anhydrous formaldehyde into an organic solvent containing a basic polymerization catalyst such as, for example, an organic amine, an organic or inorganic tin compound, or a metal hydroxide, filtering the polymer, By heating in acetic anhydride in the presence of sodium to acetylate the end.

The oxymethylene-based copolymer may be obtained by copolymerization of a cyclic oligomer of formaldehyde such as, for example, anhydrous trioxane or tetraoxane and a cyclic oligomer of formaldehyde such as ethylene oxide, propylene oxide, 1,3-dioxolane, But are not limited to, for example, 1,4-butane diol, 1,4-butane diol, 1,4-butane diol, 1,5- Trioxomethane or the like is dissolved or suspended in an organic solvent such as cyclohexane or benzene, and then a Lewis acid catalyst such as boron triflate diethylether is added to polymerize to decompose and remove the unstable terminal have.

In the present invention, it may be preferable to select an oxymethylene copolymer from the viewpoint of balance of heat resistance, mechanical strength and impact resistance. From the viewpoint of improving the thermal stability of the polymer and improving the degree of crystallization of the polymer, the oxymethylene-based copolymer preferably contains 0.4 to 15 mol% of oxyethylene repeating units and 85 to 99.6 mol% of oxymethylene repeating units based on the total molar amount of the oxymethylene copolymer %. ≪ / RTI >

Aliphatic thermoplastic polyurethane

The aliphatic thermoplastic polyurethane resin includes an isocyanate, an ether-containing polyester polyol and a chain extender in a molecular structure. Preferably, the aliphatic thermoplastic polyurethane of the present invention has a number average molecular weight of 20,000 to 60,000 g / mol and a Shore A hardness of 80 to 88. The aliphatic thermoplastic polyurethane resin is a polyester-polyether-based aliphatic thermoplastic polyurethane.

The isocyanate compound used herein may be the same as or similar to those used in the production of conventional polyurethanes, preferably aromatic isocyanates, aliphatic isocyanates or cycloaliphatic isocyanates, more preferably diphenylmethane diisocyanate A group consisting of diphenyl methane diisocyanate (MDI), tolunene diisocyanate (TDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI) May be used.

The ether-containing polyester polyol may be selected from the group consisting of adipic acid, sbelic acid, abelic acid, azelic acid, sebacic acid, dodecanedioic acid, , Trimeric acid or a mixture of two or more thereof and a polyfunctional carboxylic acid compound selected from the group consisting of diols such as ethylene glycol, butane diol and hexane diol ; Triols such as trimethylol propane; Or polytetramethylene ether glycol (PTMG), which is a polyfunctional alcohol compound selected from the group consisting of a mixture of two or more thereof.

The chain extender may be selected from the group consisting of diols such as ethylene glycol, diethylene glycol, butane diol, and hexane diol; Triols such as trimethylol propane; Polytetramethylene ether glycol; Or a mixture of two or more thereof.

In the present invention, the aliphatic thermoplastic polyurethane is mixed with the base resin, polyoxymethylene, and is present between the resins to absorb and absorb external shocks. Unlike aromatic thermoplastic polyurethanes, they have excellent resistance to light. In this respect, the thermoplastic polyurethane is preferably contained in an amount of 10 to 20 parts by weight based on 100 parts by weight of polyoxymethylene. When the amount of the thermoplastic polyurethane is less than 10 parts by weight, improvement in tensile elongation and impact strength may be insufficient, The tensile strength and the bending strength characteristics may be lowered.

Ethylene-butyl acrylate copolymer

In the present invention, the ethylene-butyl acrylate copolymer also functions as an impact modifier to absorb and absorb impact from the outside while being mixed with polyoxymethylene and existing between the resins. The ethylene-butyl acrylate copolymer Butyl acrylate copolymer is not particularly limited as far as it is a commercially available ethylene-butylacrylate copolymer, but the content of ethylene-butyl acrylate copolymer is 5 to 35 mol% and the content of ethylene repeating unit is 65 to 95 mol %, And the melting point is preferably 80 to 100 ° C.

The content of the ethylene-butyl acrylate copolymer is preferably 2.0 to 5.0 parts by weight based on 100 parts by weight of polyoxymethylene. When the content is less than 2.0 parts by weight, the content thereof is too small to serve as an impact reinforcing agent. When the content exceeds 5.0 parts by weight, the tensile strength and bending strength characteristics may be deteriorated.

Thermoplastic polyester elastomer

In the present invention, the thermoplastic polyester elastomer also mixes with polyoxymethylene and functions as an impact modifier to absorb and absorb impact from the outside while being present between the resins, and has a Shore A hardness of 75 to < RTI ID = 0.0 > 85A, and a number average molecular weight of 20,000 to 50,000 g / mol.

The content of the thermoplastic polyester elastomer is preferably 2.0 to 5.0 parts by weight based on 100 parts by weight of polyoxymethylene. When the content is less than 2.0 parts by weight, the content thereof is too small to serve as an impact reinforcing agent. When the content exceeds 5.0 parts by weight, the tensile strength and bending strength characteristics may be deteriorated.

Aromatic isocyanate compound

In the present invention, the aromatic isocyanate compound serves as a coupling agent for increasing the compatibility of the polyoxymethylene and the aliphatic thermoplastic polyurethane. The content of the aromatic isocyanate compound is preferably 0.2 to 0.5 parts by weight based on 100 parts by weight of the polyoxymethylene. When the content is less than 0.2 part by weight, it is not sufficient to perform the role of a coupling agent. When the content is more than 0.5 part by weight, the content thereof is excessively high, and the flowability of the resin can be greatly reduced.

The aromatic isocyanate compound may be selected from the group consisting of methylene diphenyl diisocyanate (MDI); 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI); Toluene diisocyanate (TDI); Polymeric MDI; Carbodiimide modified liquid 4,4'-diphenylmethane diisocyanate; Paraphenylene diisocyanate (PPDI); Meta-phenylene diisocyanate (MPDI); Polyphenylene polymethylene polyisocyanate (PMDI); A mixture of MDI and PMDI; A mixture of PMDI and TDI; m-phenylene diisocyanate, m-xylylene diisocyanate; m-tetramethylxylylene diisocyanate, p, p'-biphenyl diisocyanate; 3,3'-dimethyl-4,4'-biphenylene diisocyanate; 3,3'-dimethoxy-4,4'-biphenylene diisocyanate; 3,3'-diphenyl-4,4'-biphenylene diisocyanate; 4,4'-biphenylene diisocyanate; 3,3'-dichloro-4,4'-biphenylene diisocyanate; 1,5-naphthalene diisocyanate; 4-chloro-1,3-phenylene diisocyanate; 1,5-tetrahydronaphthalene diisocyanate; 2,4-chlorophenylene diisocyanate; And mixtures thereof. Among them, it is particularly preferable to use methylenediphenyl diisocyanate, which is the raw material of the thermoplastic polyurethane and has the highest reactivity, as the polyoxymethylene and the aliphatic thermoplastic polyurethane Which may be most suitable for improving the compatibility of

Hindered phenolic antioxidants

In the present invention, the hindered phenol-based antioxidant plays a role of capturing radicals generated in the resin broken by heat. That is, the polymer bonds are broken due to heat, and the generated radicals must be taken out because the bonds of the polymers present in the surrounding are continuously destroyed. The hindered phenol antioxidant plays a role in this.

The hindered phenol-based antioxidant preferably has a molecular weight of 500 to 1,500 g / mol and a melting point of 45 to 200 ° C.

Examples of the hindered phenolic antioxidant include tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3- Bis (tert-butyl-4-hydroxyphenyl) propionate, tris (3,5-di- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydroxyamide) and 1,3,5-tris (2,6-dimethyl- And anthraquinone.

The content of the hindered phenol antioxidant is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of polyoxymethylene. If the content is less than 0.1 parts by weight, the antioxidant does not sufficiently act. If the content is more than 0.5 parts by weight, the effect of impurities may be increased, thereby deteriorating the mechanical properties.

Ultraviolet absorber

In the present invention, the ultraviolet absorber is mixed with polyoxymethylene and has a molecular weight of 200 to 500 g / mol and a melting point of 50 to 500 g / mol. The ultraviolet absorber is mixed with polyoxymethylene to absorb ultraviolet rays in advance to prevent decomposition by ultraviolet rays. 160 < 0 > C.

Examples of the ultraviolet absorber include 2- [2-hydroxy-3'-t-butyl-butyl (2-hydroxybenzoyl) -5'-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) Benzotriazole-2-yl) -4- (1, 1, 3,3'-tetramethylbutyl) phenol , 2-ethyl-2'-ethoxy-oxanilide and 2- (4,6-diphenyl-1,3,5- 5-triazin-2-yl) -5-hexylosylphenol.

The content of the ultraviolet absorber is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of polyoxymethylene. When the content is less than 0.1 part by weight, the content of the ultraviolet absorber is too small to serve as an ultraviolet absorber. If the content of the ultraviolet absorber is more than 0.5 parts by weight, the ultraviolet absorber can not be further added.

Hindered amine light stabilizer

In the present invention, the hindered amine light stabilizer performs a secondary function of mixing with polyoxymethylene to prevent decomposition by ultraviolet rays not absorbed by the ultraviolet absorber, and has a weight average molecular weight of 1,000 to 4,500 g / mol.

As the hindered amine light stabilizer, Cas No. 1 represented by the following general formula (1) is used. : 192268-64-7, a compound represented by the following formula (2); : 65447-77-0, a compound represented by the following formula (3); : 82451-48-7, a compound represented by the following formula (4). : ≪ / RTI >70624-18-9; : ≪ / RTI > 106990-43-6.

≪ Formula 1 >

(2)

(3)

≪ Formula 4 >

≪ Formula 5 >

The content of the hindered amine light stabilizers is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of polyoxymethylene. When the content is less than 0.1 part by weight, the amount of the photo-stabilizer is too small to serve as a light stabilizer. If the content exceeds 0.5 part by weight, the photo-stabilizer can not be further added.

The polyoxymethylene resin composition according to the present invention may further contain a release agent and a colorant in addition to the above-described components. The above releasing agent and coloring agent are specifically described below.

Release agent

In the present invention, the release agent is added for the purpose of imparting stability in the production process and securing the injection property, and the content thereof is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of polyoxymethylene. When the content is less than 0.1 parts by weight, the effect of securing the injection property is insignificant. When the content is more than 0.5 parts by weight, it acts as an impurity and may cause deterioration of mechanical properties.

As the release agent, one selected from the group consisting of paraffin wax, paraffin wax oxide, polyethylene wax, low molecular weight ethylene vinyl acetate, ethylene bisstearamide, erucamide, and oleamide may be used.

The composition of the present invention may contain a formaldehyde capturing agent such as a colorant, a nucleating agent, a plasticizer, a melamine, a guanidine, a Dicyan diamide, etc., , Lubricants, and the like may be additionally included, but the present invention is not limited thereto.

As a preferred embodiment of the present invention, there is provided a molded article produced from the above-mentioned polyoxymethylene resin composition.

The molded article has a tensile strength of 40 MPa or more, preferably 40 to 45 MPa, a Charpy notched impact strength at 23 ° C at room temperature of 12 kJ / m 2 or more, preferably 12 to 18 kJ / m 2, After the kJ energy irradiation, it is preferable to have a Gray scale of 4 or more, preferably 4 to 5, and a color change (Delta E) of 2.5 or less, preferably 0 to 2.3.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for the purpose of illustrating the present invention more specifically, and the present invention is not limited thereto.

Example 1

After the polyoxymethylene resin (Kocetal K300, Kolon Plastics) was dried at 80 DEG C for 4 hours, an aliphatic thermoplastic polyurethane resin (Neostane 9180AP, Dongsung Corp.), an ethylene-butyl acrylate copolymer (Elvoyoy 3427AC, Dupont), thermoplastic polyester elastomer (KOPEL, KP3328), aromatic isocyanate compound (4,4'-diphenylmethane diisocyanate, Junsei Chemical), hindered phenolic antioxidant (Songnox 2450, (Songsorb 2340, Songwon Industry), hindered amine light stabilizer (SABO STAB UV62, Songwon Industry), release agent (HI-LUBE 500P, Shinwon Chemical) and coloring agent (Kocetal KM002GR, Kolon Plastics) Respectively. The mixed mixture was poured into a primary inlet of a twin-screw extruder and melt-kneaded at 190 ° C to prepare a polyoxymethylene resin composition.

The polyoxymethylene resin composition was discharged through a die into spaghetti, cooled, and then formed into chips in a pelletizer.

Examples 2 to 5

The content of aliphatic thermoplastic polyurethane resin, ethylene-butyl acrylate copolymer, thermoplastic polyester elastomer and aromatic isocyanate compound and hindered phenolic antioxidant / ultraviolet absorber / hindered amine light stabilizer is varied , The resin composition was prepared in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 5

The aromatic polyurethane was added as an impact resistant agent instead of the aliphatic thermoplastic polyurethane. And the contents of ethylene-butyl acrylate copolymer, thermoplastic polyester elastomer, aromatic isocyanate compound and hindered phenol antioxidant / ultraviolet absorber / hindered amine light stabilizer were changed as shown in the following Table 1, 1, a resin composition was prepared.

Comparative Examples 6 to 11

The contents of aliphatic thermoplastic polyurethane, ethylene-butyl acrylate copolymer, thermoplastic polyester elastomer, methylenediphenyl diisocyanate and hindered phenolic antioxidant / ultraviolet absorber / hindered amine light stabilizer were varied as described in Table 1 below A resin composition was prepared in the same manner as in Example 1, except that

Classification (parts by weight) (end) (I) (All) (la) (hemp) (bar) (four) (Ah) (character) (car) (K) Example 1 100.0 14.0 - 3.0 3.0 0.3 0.4 0.2 0.1 0.1 2.0 Example 2 100.0 12.0 - 5.0 3.0 0.3 0.4 0.2 0.1 0.1 2.0 Example 3 100.0 12.0 - 3.0 5.0 0.3 0.4 0.2 0.1 0.1 2.0 Example 4 100.0 14.0 - 3.0 3.0 0.3 0.5 0.5 0.5 0.1 2.0 Example 5 100.0 14.0 - 3.0 3.0 0.5 0.4 0.2 0.1 0.1 2.0 Comparative Example 1 100.0 - 20.0 - - - - - - 0.1 2.0 Comparative Example 2 100.0 17.0 3.0 - - - - - 0.1 2.0 Comparative Example 3 100.0 17.0 - 3.0 - - - - 0.1 2.0 Comparative Example 4 100.0 20.0 - - 0.3 - - - 0.1 2.0 Comparative Example 5 100.0 20.0 - - - 0.3 0.3 0.3 0.1 2.0 Comparative Example 6 100.0 14.0 3.0 3.0 0.3 0.3 0.3 0.3 0.1 2.0 Comparative Example 7 100.0 20.0 - - - - - - - 0.1 2.0 Comparative Example 8 100.0 17.0 - 3.0 - - - - - 0.1 2.0 Comparative Example 9 100.0 17.0 - - 3.0 - - - - 0.1 2.0 Comparative Example 10 100.0 20.0 - - - 0.3 - - - 0.1 2.0 Comparative Example 11 100.0 20.0 - - - - 0.3 0.3 0.3 0.1 2.0

(A) Polyoxymethylene: Kocetal K300 (Kolon Plastics)

(B) Aliphatic thermoplastic polyurethane: Neostane 9180AP (Synthesis Corporation, having a number average molecular weight of 40,000 g / mol and a Shore A hardness of 84)

(C) Thermoplastic polyurethane: Neothane 5080AP (Dongsung Corporation)

(D) Ethylene-butyl acrylate copolymer: Elvaloy 3427AC (Dupont) (containing 27 mol% of butyl acrylate repeating units and 73 mol% of ethylene repeating units and having a melting point (T _m ) of 94 ° C.)

(E) Thermoplastic polyester elastomer: KOPEL KP3328 (Kolon Plastics) (Shore A having a hardness of 80 and a number average molecular weight of 35,000 g / mol)

(F) An aromatic isocyanate compound: 4,4'-diphenylmethane diisocyanate (Junsei Chemical)

(G) Hindered phenolic antioxidant: Songnox 2450 (Songwon Industrial Co., Ltd.) having a molecular weight of 587 g / mol and a melting point of 78 캜

(A) Ultraviolet absorber: Songsorb 2340 (Songwon Industrial Co., Ltd.) (molecular weight is 3,500 g / mol, melting point is 139 캜)

Hindered amine light stabilizer: SABO STAB UV62 (Songwon Industrial Co., Ltd.) (weight average molecular weight is 3,500 g / mol)

(Tea) Releasing agent: HI-LUBE 500P (Shinwon Chemical)

(K) Colorant: Kocetal KM002GR (Kolon Plastic)

< Measurement example >

The resin compositions prepared in Examples and Comparative Examples were made into specimens and subjected to a melt index, a tensile test, a Charpy notched room temperature (23 ° C) impact test, a light resistance test (SAE J2412: 2015) And the results are shown in Table 2.

(1) Melt index (MI): According to ISO 1133, a melt index (g / 10 min) was obtained by adding 2.16 Kg of another mass at 190 캜.

(2) Tensile strength: The tensile strength (MPa) of the test piece was measured according to ISO 527-1 / 2.

(3) Impact Strength (Charpy Notched Impact Test): The impact strength (kJ / m 2) at room temperature (23 ° C) of Charpyp notched specimens was determined according to ISO 179 / 1eA.

(4) Light resistance test (SAE J2412: 2015): Gray scale and color change (Delta E) were measured after 601.6 kJ energy irradiation according to SAE J21412: 2015 test method.

MI (g / 10 min) Tensile strength (MPa) Impact strength (kJ / m 2) Gray Scale Delta E Example 1 7.5 41.5 13.5 4 2.26 Example 2 7.6 41.2 13.9 4 2.29 Example 3 7.5 41.3 13.7 4 2.31 Example 4 7.5 41.4 13.4 4 1.97 Example 5 6.4 41.6 14.1 4 2.35 Comparative Example 1 9.5 44.8 14.9 2 10.32 Comparative Example 2 9.3 44.6 15.2 2 10.28 Comparative Example 3 9.4 44.6 15.1 2 10.44 Comparative Example 4 7.4 45 15.3 2 11.45 Comparative Example 5 9.3 44.7 14.9 2 9.86 Comparative Example 6 7.3 45.2 15.6 2 10.04 Comparative Example 7 9.2 40.2 9.2 4.5 1.67 Comparative Example 8 9.2 39.9 9.6 4.5 1.71 Comparative Example 9 9.3 40.0 9.5 4.5 1.80 Comparative Example 10 7 40.4 9.7 4.5 2.37 Comparative Example 11 9.1 40.2 9.1 4.5 1.48

As can be seen from the results of Table 2, in Comparative Examples 1 to 6 in which an aromatic thermoplastic polyurethane was added (an aliphatic thermoplastic polyurethane in general), the light resistance was inferior due to the Gray Scale and Detla E values Respectively. Further, even when the hindered phenol-based antioxidant / ultraviolet absorber / hindered amine-based light stabilizer is added as in Comparative Example 6, it can be seen that there is no large variation in light resistance characteristics due to the intrinsic properties of the aromatic thermoplastic polyurethane.

In addition, in the case of Comparative Examples 7 to 11, it was confirmed that the impact strength characteristics were lowered in the absence of one or more impact resistant agent and aromatic isocyanate compound.

In addition, it can be confirmed that the light resistance characteristics are disadvantageous in the absence of the hindered phenol-based antioxidant / ultraviolet absorber / hindered amine-based light stabilizer additive.

Claims (11)

Polyoxymethylene; And 10 to 20 parts by weight of an aliphatic thermoplastic polyurethane, 2.0 to 5.0 parts by weight of an ethylene-butyl acrylate copolymer, 2.0 to 5.0 parts by weight of a thermoplastic polyester elastomer, and 0.2 to 0.5 parts by weight of an aromatic isocyanate compound per 100 parts by weight of the polyoxymethylene 0.1 to 0.5 parts by weight of a hindered phenol antioxidant, 0.1 to 0.5 parts by weight of an ultraviolet absorber and 0.1 to 0.5 parts by weight of a hindered amine light stabilizer. The polyoxymethylene resin composition according to claim 1, wherein the aliphatic thermoplastic polyurethane has a number average molecular weight of 20,000 to 60,000 g / mol and a Shore A hardness of 80 to 90. The ethylene-butyl acrylate copolymer according to claim 1, wherein the ethylene-butyl acrylate copolymer contains 5 to 35 mol% of butyl acrylate repeating units and 65 to 95 mol% of ethylene repeating units, based on the total molar amount of ethylene- ( _Tm ) of the polyoxymethylene resin composition is 80 to 100 占 폚. The polyoxymethylene resin composition according to claim 1, wherein the thermoplastic polyester elastomer has a Shore A hardness of 75 to 85 and a number average molecular weight of 20,000 to 50,000 g / mol. The method of claim 1, wherein the aromatic isocyanate compound is selected from the group consisting of methylene diphenyl diisocyanate (MDI); 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TODI); Toluene diisocyanate (TDI); Polymeric MDI; Carbodiimide modified liquid 4,4'-diphenylmethane diisocyanate; Paraphenylene diisocyanate (PPDI); Meta-phenylene diisocyanate (MPDI); Polyphenylene polymethylene polyisocyanate (PMDI); A mixture of MDI and PMDI; A mixture of PMDI and TDI; m-phenylene diisocyanate, m-xylylene diisocyanate; m-tetramethylxylylene diisocyanate, p, p'-biphenyl diisocyanate; 3,3'-dimethyl-4,4'-biphenylene diisocyanate; 3,3'-dimethoxy-4,4'-biphenylene diisocyanate; 3,3'-diphenyl-4,4'-biphenylene diisocyanate; 4,4'-biphenylene diisocyanate; 3,3'-dichloro-4,4'-biphenylene diisocyanate; 1,5-naphthalene diisocyanate; 4-chloro-1,3-phenylene diisocyanate; 1,5-tetrahydronaphthalene diisocyanate; 2,4-chlorophenylene diisocyanate; And mixtures thereof. The polyoxymethylene resin composition according to claim 1, The polyoxymethylene resin composition according to claim 1, wherein the hindered phenol-based antioxidant has a molecular weight of 500 to 1,500 g / mol and a melting point of 45 to 200 ° C. The polyoxymethylene resin composition according to claim 1, wherein the ultraviolet absorber has a molecular weight of 200 to 500 g / mol and a melting point of 50 to 160 ° C. The polyoxymethylene resin composition according to claim 1, wherein the hindered amine light stabilizer has a molecular weight of 1,000 to 4,500 g / mol. The polyoxymethylene resin composition according to claim 1, wherein the composition has a melt index (MI) of 5.5 g / 10 min or more as measured by ISO 1133. A molded article produced from the resin composition of any one of claims 1 to 9. The molded article according to claim 10, wherein the molded article has a tensile strength of not less than 40 MPa according to ISO 527-1 / 2 measurement, a Charpy notched impact strength of not less than 12 kJ / m 2 at room temperature of 23 캜 according to ISO 179 / , And has a gray scale rating of 4 or more and a color change (Delta E) of 2.5 or less after irradiation of 601.6 kJ energy of a light resistance test (SAE J2412: 2015) measurement standard.