KR20240131121A - Thermoplastic resin composition and molded article manufactured by the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising, relative to 100 parts by weight of a base resin comprising (A) 50 to 70 wt% of a polycarbonate resin; (B) 10 to 30 wt% of a polysiloxane-polycarbonate copolymer resin; and (C) 10 to 20 wt% of a polybutylene terephthalate resin, (D) 1 to 3 wt% of a siloxane-modified polyester; (E) 1 to 3 wt% of a syndiotactic polystyrene; and (F) 0.5 to 2 wt% of a benzotriazole-based UV stabilizer.

Description

Thermoplastic resin composition and molded article manufactured therefrom {THERMOPLASTIC RESIN COMPOSITION AND MOLDED ARTICLE MANUFACTURED BY THE SAME}

The present invention relates to a thermoplastic resin composition and a molded article manufactured therefrom.

Thermoplastic resins have lower specific gravity than glass or metal and have advantages such as excellent formability and impact resistance. Recently, with the trend toward lower cost, larger size, and lighter weight of electrical and electronic products, plastic products using thermoplastic resins have rapidly replaced the areas of existing glass and metal, and are expanding their areas of use from electrical and electronic products to automobile parts.

Among thermoplastic resins, polycarbonate (PC) resin is widely used in electrical and electronic products and automobile parts due to its excellent impact resistance, heat resistance, and rigidity.

However, these polycarbonate resins lack resistance to chemicals such as cosmetics and air fresheners, so there are problems such as breakage and discoloration when used as automobile interior materials.

To solve these problems, there have been attempts to introduce polyester resins with excellent chemical resistance into polycarbonate resins, but as polyester resins are mixed in, the heat resistance and impact resistance of the resin decrease, so there is a problem that the benefits of using polycarbonate resins cannot be obtained.

Meanwhile, when using polycarbonate resin in an unpainted state, scratch resistance, light resistance, and impact resistance must be secured to a certain level, and excellent coloring properties are also required because the desired color must be implemented by the resin itself.

Accordingly, much research is being conducted on thermoplastic resin compositions that have excellent chemical resistance and colorability while maintaining excellent impact resistance, scratch resistance, and light resistance.

The present invention provides a thermoplastic resin composition having excellent impact resistance, scratch resistance, light resistance, and chemical resistance, and excellent colorability to the extent that a piano black color can be realized, and a molded article manufactured from the same.

According to one embodiment, a thermoplastic resin composition is provided, comprising: (A) 50 to 70 wt% of a polycarbonate resin; (B) 10 to 30 wt% of a polysiloxane-polycarbonate copolymer resin; and (C) 10 to 20 wt% of a polybutylene terephthalate resin, relative to 100 wt% of a base resin; (D) 1 to 3 wt% of a siloxane-modified polyester; (E) 1 to 3 wt% of a syndiotactic polystyrene; and (F) 0.5 to 2 wt% of a benzotriazole-based UV stabilizer.

The above (A) polycarbonate resin may have a melt flow index of 5 to 30 g/10 min as measured under conditions of 300°C and 1.2 kg load according to ASTM D1238.

The above (B) polysiloxane-polycarbonate copolymer resin may include a polycarbonate block and a polysiloxane block, and may include 1 to 50 wt% of a polysiloxane block including a structural unit represented by the following chemical formula 2:

[Chemical formula 2]

(In the above chemical formula 2, R ³ and R ⁴ are the same as or different from each other, and each independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryloxy group, or NRR' (wherein R and R' are the same as or different from each other and are a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group).)

The above (B) polysiloxane-polycarbonate copolymer resin may have a weight average molecular weight of 10,000 to 100,000 g/mol.

The above (C) polybutylene terephthalate resin may have an intrinsic viscosity of 0.7 to 1.5 dl/g as measured according to ASTM D2857.

The above (D) siloxane modified polyester can be represented by the following chemical formula 3:

[Chemical Formula 3]

(In the above chemical formula 3, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a C1 to C5 alkylene group, R ⁹ is a C1 to C4 alkyl group or a phenyl group, R ¹⁰ is hydrogen, a hydroxyl group or a methyl group, and l, m and n are each independently an integer of 1 or more.)

In the above chemical formula 3, R ⁵ and R ⁶ are each -(CH ₂ ) ₃ -, R ⁷ and R ⁸ are each -(CH ₂ ) ₅ -, R ⁹ is a methyl group, and l, m and n can be integers of 1 or more that satisfy l + m : n = 15 to 20 : 25 to 35.

The syndiotacticity of the above (E) syndiotactic polystyrene can be 97 to 100%.

The above (F) benzotriazole-based UV stabilizer can be used together with a triazine-based UV stabilizer.

The thermoplastic resin composition may further include at least one additive selected from a flame retardant, a nucleating agent, a coupling agent, glass fiber, a plasticizer, a lubricant, a mineral filler, an antibacterial agent, a release agent, a heat stabilizer, an antioxidant, a pigment, a dye, and an antistatic agent.

Meanwhile, a molded product manufactured from a thermoplastic resin composition according to one embodiment can be provided.

The above molded article may have a notched Izod impact strength of greater than or equal to 40 kgf·cm/cm at 1/4 inch thickness as measured in accordance with ASTM D256.

The above molded product may have a brightness change (ΔL) of 5.0 or less before and after scratch resistance evaluation measured using Erichsen Scratch Hardness Tester 430 P-I.

The above molded product may have a color change (ΔE) of 2.0 or less before and after the light resistance evaluation measured by continuously irradiating the product with light having a wavelength of 300 to 400 nm until the irradiation amount reaches 84 MJ/ ^m2 according to Hyundai Motor Company MS210-05.

A thermoplastic resin composition according to one embodiment and a molded article manufactured therefrom have excellent impact resistance, chemical resistance, light resistance and scratch resistance, and excellent coloring properties to the extent that a piano black color can be realized.

Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples, and the present invention is not limited thereby, and the present invention is defined only by the appended claims.

Unless specifically stated herein, “copolymerization” means block copolymerization, random copolymerization, and graft copolymerization, and “copolymer” means block copolymer, random copolymer, and graft copolymer.

In the present invention, unless otherwise specified, the average particle diameter of a rubber polymer is a volume average diameter and means the Z-average particle diameter measured using a dynamic light scattering analysis device.

Unless otherwise specified herein, the weight average molecular weight is measured by dissolving a powder sample in an appropriate solvent and using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) (Shodex polystyrene is used as the standard sample).

According to one embodiment, a thermoplastic resin composition is provided, comprising (A) 50 to 70 wt% of a polycarbonate resin; (B) 10 to 30 wt% of a polysiloxane-polycarbonate copolymer resin; and (C) 10 to 20 wt% of a polybutylene terephthalate resin, relative to 100 wt% of a base resin, (D) 1 to 3 wt% of a siloxane-modified polyester; (E) 1 to 3 wt% of a syndiotactic polystyrene; and (F) 0.5 to 2 wt% of a benzotriazole-based UV stabilizer.

Hereinafter, each component included in the thermoplastic resin composition will be described in detail.

(A) Polycarbonate resin

(A) Polycarbonate (PC) resin is a polyester having a carbonate bond, and its type is not particularly limited, and any polycarbonate resin available in the field of resin compositions can be used.

For example, (A) a polycarbonate resin can be produced by reacting a compound selected from the group consisting of a diphenol represented by the following chemical formula 1 and phosgene, a halogen acid ester, a carbonic ester, and combinations thereof.

[Chemical Formula 1]

In the above chemical formula 1,

A is a linking group selected from the group consisting of a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkylidene group, a substituted or unsubstituted C1 to C30 haloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkenylene group, a substituted or unsubstituted C5 to C10 cycloalkylidene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C1 to C20 alkoxylene group, a halogen acid ester group, a carbonic acid ester group, C=O, S and SO ₂ , R ¹ and R ² are each independently a substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and n1 and n2 are each independently 0 to It is an integer of 4.

Two or more diphenols represented by the above chemical formula 1 may be combined to form a repeating unit of a polycarbonate resin.

Specific examples of the above diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also called 'bisphenol-A'), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, Bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ether, etc. can be mentioned. Among the above diphenols, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl)cyclohexane can be preferably used. 2,2-bis(4-hydroxyphenyl)propane can be more preferably used.

The above (A) polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols. In addition, the polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, a polyester carbonate copolymer resin, or the like.

A specific example of the linear polycarbonate resin may be a bisphenol-A based polycarbonate resin. A specific example of the branched polycarbonate resin may be a resin produced by reacting a polyfunctional aromatic compound, such as trimellitic anhydride or trimellitic acid, with diphenols and carbonates. The polyester carbonate copolymer resin may be produced by reacting a difunctional carboxylic acid with diphenols and carbonates, and the carbonate used here may be a diaryl carbonate, such as diphenyl carbonate, or ethylene carbonate.

The above (A) polycarbonate resin may have a weight average molecular weight of 10,000 to 100,000 g/mol, for example, 10,000 to 50,000 g/mol. When the weight average molecular weight of the polycarbonate resin is within the above range, excellent impact resistance and fluidity can be obtained.

The above (A) polycarbonate resin may be included in an amount of 50 to 70 wt%, for example, 50 to 60 wt%, for example, 60 to 70 wt%, based on 100 wt% of the base resin including (A) polycarbonate resin, (B) polysiloxane-polycarbonate copolymer resin to be described later, and (C) polybutylene terephthalate resin. In the above weight range, the thermoplastic resin composition of the present invention and the molded article manufactured therefrom may exhibit excellent mechanical properties.

The above (A) polycarbonate resin may have a melt flow index of 5 to 30 g/10 min, for example, 5 to 10 g/10 min, as measured under conditions of 300° C. and 1.2 kg load according to ASTM D1238. When a polycarbonate resin having a melt flow index in the above range is used, the thermoplastic resin composition and a molded article manufactured therefrom may exhibit excellent moldability and excellent impact resistance.

Meanwhile, the polycarbonate resin (A) above can be used by mixing two or more polycarbonate resins having different weight average molecular weights or melt flow indices. By mixing and using polycarbonate resins having different weight average molecular weights or melt flow indices, it is easy to control the thermoplastic resin composition to have the desired fluidity.

(B) Polysiloxane-polycarbonate copolymer resin

(B) The polysiloxane-polycarbonate copolymer (Si-PC) resin can be used together with the (A) polycarbonate resin and the (D) siloxane-modified polyester described below to improve the compatibility of the components in the thermoplastic resin composition.

In the past, in order to improve the scratch resistance of a polycarbonate resin composition, a silicone-based surface modifier was added to the polycarbonate resin and used. In this case, although the scratch resistance of the polycarbonate resin composition could be improved, there was a problem in that the mechanical properties were deteriorated or the colorability was deteriorated due to poor compatibility between the polycarbonate resin and the silicone-based surface modifier.

The present invention can solve the above problem by improving the compatibility of each component by including the (B) polysiloxane-polycarbonate copolymer resin in the resin composition comprising the (A) polycarbonate resin and (D) siloxane-modified polyester.

The above (B) polysiloxane-polycarbonate copolymer resin may include a polycarbonate block and a polysiloxane block.

The above polycarbonate block may include the same carbonate structural unit as that included in the above-described (A) polycarbonate resin.

The above polysiloxane block may include a structural unit represented by the following chemical formula 2.

[Chemical formula 2]

(In the above chemical formula 2, R ³ and R ⁴ are the same as or different from each other, and each independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryloxy group, or NRR' (wherein R and R' are the same as or different from each other and are a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group).)

The polysiloxane block may be included in an amount of 1 to 50 wt%, for example, 1 to 40 wt%, for example, 1 to 30 wt%, for example, 1 to 20 wt%, for example, 1 to 10 wt%, based on 100 wt% of the (B) polysiloxane-polycarbonate copolymer resin, but is not limited thereto.

By including the polysiloxane block in the above (B) polysiloxane-polycarbonate copolymer resin within the above weight range, the impact resistance of the thermoplastic resin composition and the molded article manufactured therefrom can be excellent, and processing such as extrusion and injection molding can be facilitated.

The above (B) polysiloxane-polycarbonate copolymer resin may have a weight average molecular weight of 10,000 to 100,000 g/mol, for example, 10,000 to 50,000 g/mol, for example, 15,000 to 30,000 g/mol. In the above range, the impact resistance of the thermoplastic resin composition and the molded article manufactured therefrom may be excellent.

The above (B) polysiloxane-polycarbonate copolymer resin may be included in an amount of 10 to 30 wt% based on 100 wt% of the base resin, for example, 10 to 20 wt%, for example, 20 to 30 wt%. In the above range, the impact resistance of the thermoplastic resin composition and the molded article manufactured therefrom may be excellent, and the compatibility between the components in the composition may be excellent.

(C) Polybutylene terephthalate resin

(C) Polybutylene terephthalate resin can impart excellent chemical resistance to a thermoplastic resin composition.

The above (C) polybutylene terephthalate resin is generally a resin obtained by a polycondensation reaction from terephthalic acid or a derivative thereof and 1,4-butanediol or a derivative thereof, but a resin copolymerized with other dicarboxylic acids or glycols, etc., may also be used as long as the purpose of the present invention is not impaired.

Here, examples of copolymerizable dicarboxylic acids include isophthalic acid, 2-chloro terephthalic acid, 2,5-dichloro terephthalic acid, 2-methyl terephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. These copolymerizable dicarboxylic acids may be appropriately selected from the compounds illustrated, and may be used alone or in combination of two or more.

Meanwhile, examples of copolymerizable glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis(2-hydroxyethyl ether), etc. These copolymerizable glycols may be appropriately selected from the exemplified compounds and used alone or in combination of two or more.

In addition, the polybutylene terephthalate resin (C) may have an intrinsic viscosity of 0.7 to 1.5 dl/g as measured according to ASTM D2857 in order to sufficiently secure impact resistance of a molded product using the thermoplastic resin composition.

According to one embodiment, the (C) polybutylene terephthalate resin may be included in an amount of 10 to 20 wt% based on 100 wt% of the base resin, for example, 15 to 20 wt%. By including the (C) polybutylene terephthalate resin within the above range, the thermoplastic resin composition has excellent chemical resistance.

(D) Siloxane modified polyester

(D) The siloxane-modified polyester can improve the scratch resistance and colorability of the thermoplastic resin composition of the present invention.

The above (D) siloxane modified polyester can be represented by the following chemical formula 3:

[Chemical Formula 3]

(In the above chemical formula 3, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a C1 to C5 alkylene group, R ⁹ is a C1 to C4 alkyl group or a phenyl group, R ¹⁰ is hydrogen, a hydroxyl group or a methyl group, and l, m and n are each independently an integer of 1 or more.)

In the above chemical formula 3, all siloxane structural units are shown as being positioned at the center of the polymer, and ester structural units are positioned at both ends, but this does not specify the positions of the structural units. That is, the (D) siloxane-modified polyester according to one embodiment may be a random copolymer as well as a block copolymer. Therefore, in the above chemical formula 3, the ester structural units and the siloxane structural units are shown to be included in the polymer in numbers of l + m and n, respectively, and each structural unit is not limited to being present at a specific position in the form of a block.

In one embodiment, R ⁵ and R ⁶ of the chemical formula 3 are each -(CH ₂ ) ₃ -, R ⁷ and R ⁸ are each -(CH ₂ ) ₅ -, R ⁹ is a methyl group, and l, m and n can be integers of 1 or more satisfying l + m : n = 15 to 20 : 25 to 35.

The above (D) siloxane-modified polyester may be included in an amount of 1 to 3 parts by weight based on 100 parts by weight of the base resin, for example, 1 to 2 parts by weight, for example, 2 to 3 parts by weight. In the above range of parts by weight, the scratch resistance and colorability of the thermoplastic resin composition and the molded article manufactured therefrom may be excellent.

(E) Syndiotactic polystyrene

(E) Syndiotactic polystyrene can improve the impact resistance of the thermoplastic resin composition of the present invention. In particular, in the present invention, by using (E) syndiotactic polystyrene together with the component (B) polysiloxane-polycarbonate copolymer resin and (D) siloxane-modified polyester, the thermoplastic resin composition according to one embodiment can realize excellent impact resistance.

Polystyrene is generally divided into atactic, isotactic, and syndiotactic structures depending on the position of the benzene rings in the side chain. Atactic polystyrene has the benzene rings arranged irregularly, while isotactic polystyrene has the benzene rings arranged on one side of the polymer main chain. On the other hand, syndiotactic polystyrene has the benzene rings arranged regularly and alternately.

Among these, syndiotactic polystyrene can be produced by using a catalyst system comprising a metallocene catalyst and a cocatalyst, a styrene monomer. The metallocene catalyst has a structure in which one or two cycloalkane dienyl groups (cyclopentadienyl groups, indenyl groups, fluorenyl groups, and derivatives thereof) are linked to a group Ⅳ transition metal complex of the periodic table, such as Ti, Zr, or Hf.

As a prior art for polystyrene having high stereoregularity, high melting point and excellent molecular weight distribution, U.S. Patent No. 6,010,974 discloses a method for polymerizing styrene monomer using a new alkyl-bridged dinuclear metallocene catalyst, a silyl-bridged dinuclear metallocene catalyst, and an alkyl-silyl bridged dinuclear metallocene catalyst, and U.S. Patent No. 6,284,700 discloses a method for producing syndiotactic polystyrene using a catalyst system comprising a metallocene catalyst and a cocatalyst. The disclosures of these patents are incorporated herein by reference in their entirety.

The syndiotacticity of the above (E) syndiotactic polystyrene can be 97 to 100%.

The above (E) syndiotactic polystyrene may be included in an amount of 1 to 3 parts by weight, for example, 1 to 2 parts by weight, for example, 2 to 3 parts by weight, based on 100 parts by weight of the base resin. Within the above range of parts by weight, the thermoplastic resin composition and the molded article manufactured therefrom may have excellent impact resistance.

(F) Benzotriazole UV stabilizer

(F) A benzotriazole-based UV stabilizer prevents decomposition and discoloration of the thermoplastic resin composition according to the present invention due to ultraviolet rays, thereby improving light resistance.

The type of the above (F) benzotriazole-based UV stabilizer is not particularly limited, and various commercially available benzotriazole-based UV stabilizers can be used.

In one embodiment, the (F) benzotriazole-based UV stabilizer may be used in combination with a triazine-based UV stabilizer. The type of the triazine-based UV stabilizer is not particularly limited, and various commercially available triazine-based UV stabilizers may be used.

The above (F) benzotriazole-based UV stabilizer may be included in an amount of 0.5 to 2 parts by weight, for example, 0.5 to 1 part by weight, for example, 1 to 2 parts by weight, based on 100 parts by weight of the base resin. In the above weight range, the thermoplastic resin composition and the molded article manufactured therefrom may have excellent light resistance.

(G) Additive

A thermoplastic resin composition according to one embodiment may further include, in addition to the components (A) to (F), one or more additives necessary to balance the properties under conditions of maintaining excellent scratch resistance, impact resistance, light resistance, chemical resistance, and colorability, or depending on the final use of the thermoplastic resin composition.

Specifically, the additive may include at least one additive selected from among flame retardants, nucleating agents, coupling agents, glass fibers, plasticizers, lubricants, mineral fillers, antibacterial agents, release agents, heat stabilizers, antioxidants, pigments, dyes, and antistatic agents.

These additives may be appropriately included within a range that does not impair the properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less with respect to 100 parts by weight of the base resin, but is not limited thereto.

The thermoplastic resin composition of the present invention can be produced by a known method for producing a thermoplastic resin composition.

For example, the thermoplastic resin composition of the present invention can be manufactured in the form of pellets by mixing the components of the present invention and other additives and then melting/mixing them in an extruder.

A molded article according to one embodiment of the present invention can be manufactured from the thermoplastic resin composition described above.

The above molded article may have a notched Izod impact strength of greater than or equal to 40 kgf·cm/cm at 1/4 inch thickness as measured in accordance with ASTM D256.

The above molded product may have a brightness change (ΔL) of 5.0 or less before and after scratch resistance evaluation measured using Erichsen Scratch Hardness Tester 430 P-I.

The above molded product may have a color change (ΔE) of 2.0 or less before and after the light resistance evaluation measured by continuously irradiating the product with light having a wavelength of 300 to 400 nm until the irradiation amount reaches 84 MJ/ ^m2 according to Hyundai Motor Company MS210-05.

A molded product manufactured by appropriately adding a black pigment or dye mixture to the thermoplastic resin composition described above can realize a piano black color, which is a high-quality, deep black color, due to the synergistic effect of each component of the thermoplastic resin composition.

Hereinafter, preferred embodiments of the present invention will be described. However, the following embodiments are only preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

Examples 1 to 6 and Comparative Examples 1 to 9

The thermoplastic resin compositions of Examples 1 to 6 and Comparative Examples 1 to 9 were prepared according to the component content ratios described in Table 1 below.

A mixture of the components described in Table 1 and a quinone dye exhibiting a black color was added in an amount of 0.5 parts by weight to 100 parts by weight of the base resin, dry-mixed, and quantitatively and continuously fed into the feed section of a twin-screw extruder (L/D = 59, diameter = 45 mm) to melt/knead. At this time, the barrel temperature of the twin-screw extruder was set to about 270°C. Subsequently, the pelletized thermoplastic resin composition through the twin-screw extruder was dried at about 100°C for about 2 hours, and then a specimen for measuring physical properties was injection-molded using a 6 oz injection molding machine having a cylinder temperature of about 260°C and a mold temperature of about 60°C.

In Table 1, (A) to (C) represent the weight % of each component among 100 weight % of the base resin, and (D) to (F) represent the weight parts based on 100 weight parts of the base resin ((A) + (B) + (C)).

division Example Comparative example 1 2 3 4 5 6 1 2 3 4 5 6 7 8 9 (A) 60 70 50 65 60 60 80 60 60 60 60 60 60 60 30 (B) 20 10 30 20 20 20 20 20 20 20 20 20 20 10 50 (C) 20 20 20 15 20 20 - 20 20 20 20 20 20 30 20 (D) 2 2 2 2 1 2 2 - 2 2 4 2 2 2 2 (E) 2 2 2 2 2 2 2 2 - 2 2 4 2 2 2 (F) 1 1 1 1 1 2 1 1 1 - 1 1 4 1 1

A description of each component listed in Table 1 above is as follows.

(A) Polycarbonate resin

Polycarbonate resin from Lotte Chemical Co., Ltd. was used, which has a melt flow index of approximately 8 g/10 min measured under conditions of 300°C and 1.2 kg load according to ASTM D1238.

(B) Polysiloxane-polycarbonate copolymer resin

A polysiloxane-polycarbonate copolymer resin from Samyang Corporation was used, having a weight average molecular weight of about 24,000 g/mol and containing about 98 to 99 wt% of polycarbonate blocks and about 1 to 2 wt% of polysiloxane blocks.

(C) Polybutylene terephthalate resin

Shinkong's DHK011, which has an intrinsic viscosity of approximately 1.2 dl/g as measured according to ASTM D2857, was used.

(D) Siloxane modified polyester

H-Si 6441 P from Evonik Industries was used.

(E) Syndiotactic polystyrene

Idemitsu Kosan's 130ZC was used.

(F) Benzotriazole UV stabilizer

Adeka's LA-300K was used.

Experimental example

The experimental results are shown in Table 2 below.

(1) Impact strength (unit: kgf cm/cm): Notched Izod impact strength was measured on 1/4 inch thick specimens according to ASTM D256.

(2) Colorability: The brightness (L) value in the specular elimination mode (SCE Mode) was measured using Konica Minolta CM-3700D. The lower the brightness, the better the black color implementation, so it was judged that the colorability was good.

(3) Scratch resistance: Using an Erichsen Scratch Hardness Tester 430 P-I, a test tip with a diameter of 1 mm was used to apply scratches to the specimen at 2 mm intervals for 20 times in a grid pattern under the conditions of a load of 10 N and a scratch speed of 1 m/min. The change in brightness (ΔL) of the specimen before and after the scratch evaluation was measured using a Konica Minolta CM-3700D in the specular emission elimination mode (SCE Mode). When scratches are applied, microcracks occur on the surface of the specimen, creating flaws that increase the brightness of the specimen. Therefore, it was determined that the higher the change in brightness (ΔL), the more damage caused by the scratches, and thus the lower the scratch resistance.

(4) Chemical resistance: The ASTM D638 type I specimen was placed on a jig with a critical strain of 2.1%, P&G's Febreze Clear Sky Wind for vehicles was applied, and the chemical resistance was evaluated by visually inspecting the appearance after leaving it at room temperature for 168 hours. If cracks occurred in the specimen, it was judged as X, and if no cracks occurred, it was judged as O.

(5) Lightfastness: According to the MS210-05, which is the lightfastness evaluation standard for plastic molded products for interior parts of Hyundai Motor Company, a Weather-O-meter equipped with a xenon arc lamp consisting of a combination of a borosilicate inner filter and a soda lime outer filter was used under the conditions of a black panel temperature of 89±3℃ and an internal chamber humidity of 50±5%. Light with a wavelength of 300 to 400 nm was continuously irradiated to the evaluation specimen until the irradiance reached 84 MJ/ ^m2 , and then the color change (ΔE) of the specimen was calculated to evaluate the lightfastness. The smaller the color change (ΔE) of the specimen, the better the lightfastness was determined to be.

Physical properties Example Comparative example 1 2 3 4 5 6 1 2 3 4 5 6 7 8 9 Izod
Impact strength 50 45 55 55 45 40 65 16 12 55 21 11 15 11 65 Brightness (L) 0.9 0.8 1.0 0.8 0.8 1.0 1.0 1.0 1.0 0.9 4.5 1.2 1.5 0.9 1.2 Change in brightness (ΔL) 3.5 3.3 3.6 3.5 4.2 3.5 3.6 8.4 3.5 3.3 2.8 4.5 4.0 3.8 4.0 Whether cracks occur O O O O O O X O O O O O O O O Color change (ΔE) 1.6 1.5 1.9 1.5 1.4 1.0 1.6 1.7 1.6 4.2 3.8 3.6 1.1 3.7 3.6

From the above Tables 1 and 2, it can be seen that by using a thermoplastic resin composition including a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, a polybutylene terephthalate resin, a siloxane-modified polyester, a syndiotactic polystyrene, and a benzotriazole-based UV stabilizer in an optimal amount, a thermoplastic resin composition having excellent impact resistance, scratch resistance, light resistance, chemical resistance, and colorability, and a molded article manufactured from the same can be realized.

Although the present invention has been described above through preferred embodiments as described above, the present invention is not limited thereto, and those engaged in the technical field to which the present invention pertains will easily understand that various modifications and variations are possible without departing from the concept and scope of the patent claims described below.

Claims (14)

(A) 50 to 70 wt% of polycarbonate resin;
(B) 10 to 30 wt% of polysiloxane-polycarbonate copolymer resin; and
(C) For 100 parts by weight of a base resin containing 10 to 20 wt% of polybutylene terephthalate resin
(D) 1 to 3 parts by weight of siloxane-modified polyester;
(E) 1 to 3 parts by weight of syndiotactic polystyrene; and
(F) 0.5 to 2 parts by weight of benzotriazole-based UV stabilizer
A thermoplastic resin composition comprising: In paragraph 1,
The above (A) polycarbonate resin is a thermoplastic resin composition having a melt flow index of 5 to 30 g/10 min as measured under conditions of 300°C and 1.2 kg load according to ASTM D1238. In paragraph 1,
The above (B) polysiloxane-polycarbonate copolymer resin is a thermoplastic resin composition comprising a polycarbonate block and a polysiloxane block, and comprising 1 to 50 wt% of a polysiloxane block comprising a structural unit represented by the following chemical formula 2:
[Chemical formula 2]

(In the above chemical formula 2, R ³ and R ⁴ are the same as or different from each other, and each independently represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group, a substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C6 to C30 aryl group, or NRR' (wherein R and R' are the same as or different from each other, and are a hydrogen atom, or a substituted or unsubstituted C1 to C20 alkyl group).) In paragraph 1,
The above (B) polysiloxane-polycarbonate copolymer resin is a thermoplastic resin composition having a weight average molecular weight of 10,000 to 100,000 g/mol. In paragraph 1,
The above (C) polybutylene terephthalate resin is a thermoplastic resin composition having an intrinsic viscosity of 0.7 to 1.5 dl/g as measured according to ASTM D2857. In paragraph 1,
The above (D) siloxane modified polyester is a thermoplastic resin composition represented by the following chemical formula 3:
[Chemical Formula 3]

(In the above chemical formula 3, R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkylene group having 1 to 5 carbon atoms, R ⁹ is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R ¹⁰ is hydrogen, a hydroxyl group or a methyl group, and l, m and n are each independently an integer of 1 or more.) In Article 6,
A thermoplastic resin composition, wherein R ⁵ and R ⁶ of the above chemical formula 3 are each -(CH ₂ ) ₃ -, R ⁷ and R ⁸ are each -(CH ₂ ) ₅ -, R ⁹ is a methyl group, and l, m and n are integers of 1 or more satisfying l + m : n = 15 to 20 : 25 to 35. In paragraph 1,
A thermoplastic resin composition, wherein the syndiotactic degree of the above (E) syndiotactic polystyrene is 97 to 100%. In paragraph 1,
A thermoplastic resin composition in which the above (F) benzotriazole-based UV stabilizer is used together with a triazine-based UV stabilizer. In paragraph 1,
A thermoplastic resin composition further comprising at least one additive selected from a flame retardant, a nucleating agent, a coupling agent, glass fiber, a plasticizer, a lubricant, a mineral filler, an antibacterial agent, a release agent, a heat stabilizer, an antioxidant, a pigment, a dye, and an antistatic agent. A molded product manufactured from a thermoplastic resin composition according to any one of claims 1 to 10. In Article 11,
The above molded product is a molded product having a notched Izod impact strength of 40 kgf·cm/cm or more as measured in accordance with ASTM D256 at 1/4 inch thickness. In Article 11,
The above molded product is a molded product in which the brightness change (ΔL) before and after the scratch resistance evaluation measured using Erichsen Scratch Hardness Tester 430 PI is 5.0 or less. In Article 11,
The above molded product is a molded product in which the color change (ΔE) before and after the light resistance evaluation, measured by continuously irradiating the molded product with light having a wavelength of 300 to 400 nm until the irradiation amount reaches 84 MJ/ ^m2 according to Hyundai Motor Company MS210-05, is 2.0 or less.