KR102227121B1 - Thermoplastic resin composition and molded article using the same - Google Patents

Abstract

(A) 20% to 50% by weight of the first polycarbonate resin having a weight average molecular weight of 15,000 to 27,000 g/mol; (B) 20% to 50% by weight of a second polycarbonate resin having a weight average molecular weight of more than 27,000 and 40,000 g/mol or less; (C) 9% to 20% by weight of an acrylic graft copolymer; And (D) 10% to 20% by weight of an aromatic vinyl-vinyl cyanide copolymer, and the weight average molecular weight of the (A) first polycarbonate resin with respect to the weight average molecular weight of the (B) second polycarbonate resin The ratio (Mw _A /Mw _B ) of 0.3 to 0.6 relates to a thermoplastic resin composition and a molded article using the same.

Description

Thermoplastic resin composition and molded article using the same {THERMOPLASTIC RESIN COMPOSITION AND MOLDED ARTICLE USING THE SAME}

It relates to a thermoplastic resin composition and a molded article using the same.

Acrylate-styrene-acrylonitrile (ASA) resin has excellent weather resistance and is widely used in outdoor building materials and automobile interior/exterior materials. However, in order to apply the ASA resin to applications requiring high impact strength due to poor impact resistance, etc., the content of the acrylic rubber polymer of the ASA resin must be increased. However, if the content of the acrylic rubber polymer is increased, the heat resistance, etc. /There is a limit in application to applications requiring high heat resistance such as exterior materials.

As an alternative to this, a method of supplementing heat resistance and impact resistance by alloying ASA resin and polycarbonate (PC) resin having excellent heat resistance has been proposed, and such PC/ASA resin is an interior/exterior material for various vehicles. Can be applied to

In the case of applying PC/ASA resin to automobile interior/exterior materials as described above, a beautiful appearance may be required depending on the part to be applied. In order to secure the excellent appearance of the PC/ASA resin, a method of using an ASA resin containing an acrylic rubber polymer having a relatively small particle diameter in combination with a PC resin has been proposed, but in this case, there is a concern that the impact resistance of the final product will be greatly reduced. have.

Meanwhile, there are attempts to improve the injection moldability and the appearance of the final molded product by improving the flowability of the existing PC/ASA resin. However, in this case, it was pointed out that it is difficult to improve problems such as a chronic weld line occurrence during injection molding.

Accordingly, there is a need for a way to improve the appearance characteristics without deteriorating the basic physical properties of the PC/ASA resin.

It is to provide a thermoplastic resin composition excellent in both impact resistance, fluidity, heat resistance, and appearance characteristics, and a molded article using the same.

According to one embodiment, (A) 20% to 50% by weight of the first polycarbonate resin having a weight average molecular weight of 15,000 to 27,000 g/mol; (B) 20% to 50% by weight of a second polycarbonate resin having a weight average molecular weight of more than 27,000 and 40,000 g/mol or less; (C) 9% to 20% by weight of an acrylic graft copolymer; And (D) 10% to 20% by weight of an aromatic vinyl-vinyl cyanide copolymer, and the weight average molecular weight of the (A) first polycarbonate resin with respect to the weight average molecular weight of the (B) second polycarbonate resin _A thermoplastic resin composition having a ratio of (Mw A /Mw _B ) of 0.3 to 0.6 is provided.

The (B) second polycarbonate resin may have a terminal hydroxyl group content of more than 0 and 15 mol% or less.

Based on the total weight of the thermoplastic resin composition, the sum of the content of the (A) first polycarbonate resin and the content of the (B) second polycarbonate resin may be 60% by weight to 80% by weight.

The (C) acrylic graft copolymer may have a grafting rate of 15% to 40%.

The (C) acrylic graft copolymer may have an average particle diameter of 100 nm to 300 nm of the acrylic rubber polymer.

The (C) acrylic graft copolymer may be an acrylonitrile-styrene-acrylate graft copolymer.

The (D) aromatic vinyl-vinyl cyanide copolymer may be a copolymer of a monomer mixture including 60% to 85% by weight of an aromatic vinyl compound and 15% to 40% by weight of a vinyl cyanide compound.

The weight average molecular weight of the (D) aromatic vinyl-vinyl cyanide copolymer may be 80,000 g/mol to 200,000 g/mol.

In the (D) aromatic vinyl-vinyl cyanide copolymer, the vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.

Among the (D) aromatic vinyl-cyanide vinyl copolymers, the aromatic vinyl compound may be selected from the group consisting of styrene unsubstituted or substituted with a halogen or C1 to C10 alkyl group, α-methyl styrene, and combinations thereof.

The (D) aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer.

The thermoplastic resin composition is at least one additive selected from flame retardants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, release agents, heat stabilizers, antioxidants, inorganic additives, ultraviolet stabilizers, antistatic agents, pigments, and dyes. It may further include.

Among the thermoplastic resin compositions, a polydispersity index (PDI) of a mixture of the first polycarbonate resin and the second polycarbonate resin separable by a wet precipitation method may be 2.5 to 5.5.

_{The weight average molecular weight (Mw B} , unit: g/mol) of the second polycarbonate resin, defined as the weight ratio weighted dispersion index _{, multiplied by the used weight ratio (Wt B} , unit: wt%) of the second polycarbonate resin. _{The ratio of the value obtained by multiplying the weight average molecular weight (Mw A} , unit: g/mol) of the first polycarbonate resin to the value by the weight _{ratio (Wt A} , unit: wt%) used of the first polycarbonate resin [(Mw _A × Wt _A ) / (Mw _B × Wt _B )] may be greater than 0.2 to less than 0.8.

Meanwhile, according to another embodiment, a molded article manufactured from the above-described thermoplastic resin composition is provided.

The notched Izod impact strength of the molded article measured according to ASTM D256 may be 40 kgf·cm/cm to 80 kgf·cm/cm.

According to ASTM D1238, the melt flow index of the molded article measured at 250° C. and 10 kg may range from 30 g/10min to 60 g/10min.

The Vicat softening temperature of the molded article measured at 50N condition according to ASTM D1525 may be 120°C or higher.

As it satisfies excellent impact resistance, fluidity, and heat resistance and exhibits improved appearance characteristics, it can be widely applied to molding various products used for painting or non-painting, especially for molding interior/exterior materials for automobiles. It is possible to provide a thermoplastic resin composition that can be applied, and a molded article manufactured therefrom.

1 and 2 are images photographing the appearance of molded articles according to Example 1 and Comparative Example 1, respectively.

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

In the present specification, “copolymerization” means block copolymerization or random copolymerization, and “copolymer” means block copolymer or random copolymer.

In the present specification, unless otherwise specified, the average particle diameter refers to a volume average diameter, and refers to a Z-average mean particle diameter measured using a dynamic light scattering analyzer.

Unless otherwise defined herein, the term'substituted' means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, or an amino group. Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, vinyl group, C1 to C20 alkyl group, C2 to C20 alke Nyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C6 to C30 allyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group , C3 to C15 cycloalkenyl group, C6 to C15 cycloalkynyl group, C3 to C30 heterocycloalkyl group, and a combination thereof.

In addition, "unsubstituted" means that a hydrogen atom remains a hydrogen atom without being substituted with another substituent.

In addition, unless otherwise defined in the specification,'hetero' means containing 1 to 3 heteroatoms selected from N, O, S, P, and Si.

One embodiment provides a thermoplastic resin composition excellent in all of impact resistance, fluidity, heat resistance, and appearance characteristics.

The thermoplastic resin composition includes (A) 20% to 50% by weight of the first polycarbonate resin having a weight average molecular weight of 15,000 to 27,000 g/mol; (B) 20% to 50% by weight of a second polycarbonate resin having a weight average molecular weight of more than 27,000 and 40,000 g/mol or less; (C) 9% to 20% by weight of an acrylic graft copolymer; And (D) 10% to 20% by weight of an aromatic vinyl-vinyl cyanide copolymer, and the weight average molecular weight of the (A) first polycarbonate resin with respect to the weight average molecular weight of the (B) second polycarbonate resin The ratio of (Mw _A /Mw _B ) satisfies 0.3 to 0.6.

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

(A, B) 1st, 2nd polycarbonate resin

In the thermoplastic resin composition, both the first and second polycarbonate resins are polyesters having a carbonate bond.

For example, the first and second polycarbonate resins according to an embodiment may be prepared by reacting diphenols represented by the following Formula 1 with a compound selected from the group consisting of phosgene, halogen acid esters, carbonate esters, and combinations thereof. have.

[Formula 1]

In Formula 1,

A is 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 haloalkyl A ene 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 alkoxyl group, a halogen acid ester group, a carbonic ester group, _{a linking group selected from the group consisting of CO, S and SO 2} , and R1 and R2 are each independently 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 an integer of 0 to 4.

Two or more diphenols represented by Formula 1 may be combined to form a repeating unit of a polycarbonate resin.

Specific examples of the diphenols include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also referred to as'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. are mentioned. Among the diphenols, preferably 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 used. More preferably, 2,2-bis (4-hydroxyphenyl) propane may be used.

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 prepared by reacting a polyfunctional aromatic compound such as trimellatic anhydride and trimellitic acid with diphenols and carbonates. The polyester carbonate copolymer resin may be prepared by reacting a difunctional carboxylic acid with diphenols and carbonates, and the carbonate used herein may be a diaryl carbonate such as diphenyl carbonate or ethylene carbonate.

The first and second polycarbonate resins may be prepared using two methods of interfacial polymerization (also referred to as a solvent method or a phosgene method) and a melt polymerization method.

In one embodiment, the first polycarbonate resin may be prepared using an interfacial polymerization method and/or a melt polymerization method.

In one embodiment, at least one of the first and second polycarbonate resins may be prepared by an interfacial polymerization method. Specifically, at least the second polycarbonate resin may be prepared by an interfacial polymerization method. In this case, the second polycarbonate resin may have a relatively small terminal hydroxyl group content compared to the first polycarbonate resin. In one embodiment, the second polycarbonate resin may have a terminal hydroxyl group content of more than 0 and 15 mol% or less, for example, more than 0 and 12 mol% or less, for example, more than 0 and 10 mol% or less.

In one embodiment, the first and second polycarbonate resins have different weight average molecular weights.

In one embodiment, the first polycarbonate resin has a weight average molecular weight of 15,000 g/mol to 27,000 g/mol, for example 16,000 g/mol to 27,000 g/mol, for example 17,000 g/mol to 26,000 g/mol It is preferable to use a phosphorus.

In one embodiment, the second polycarbonate resin has a greater weight average molecular weight compared to the first polycarbonate resin. For example, the second polycarbonate resin has a weight average molecular weight of more than 27,000 g/mol and 40,000 g/mol, for example, 28,000 g/mol to 40,000 g/mol, for example, 28,000 g/mol to 38,000 g/mol. It is preferable to use it.

In one embodiment, the ratio of the weight average molecular weight of the first polycarbonate resin to the weight average molecular weight of the second polycarbonate resin (Mw _A / Mw _B ) is preferably 0.3 to 0.6, for example 0.4 to 0.6.

In one embodiment, the polydispersity index (PDI) of the mixture of the first polycarbonate resin and the second polycarbonate resin separable by a wet precipitation method in the thermoplastic resin composition is, for example, 2.5 or more, for example, 3.0. It may be greater than or equal to 3.3, for example less than or equal to 5.5, for example less than or equal to 5.0, for example less than or equal to 4.5, and may be, for example, from 2.5 to 5.5, such as from 3.3 to 4.5. The polydispersity index is a parameter representing a molecular weight distribution, and means a value obtained by dividing a weight average molecular weight (Mw) by a number average molecular weight (Mn) (Mw/Mn).

When the polydispersity index of the thermoplastic resin composition according to one embodiment satisfies the above range, a thermoplastic resin composition having excellent appearance without causing weld lines, etc., without deteriorating the impact resistance, fluidity, and heat resistance of the thermoplastic resin composition Can provide.

The method of measuring the polydispersity index may use a known method. For example, a thermoplastic resin composition sample is dissolved, acetone, etc. are added to the dissolved sample to precipitate only a mixture of the first and second polycarbonate resins, and the precipitated mixture is separated, filtered, and concentrated, followed by a known weight average molecular weight. An analysis method (eg, gel permeation chromatography, etc.) can be used to measure the polydispersity index of the first and second polycarbonate resin mixtures described above.

_{Meanwhile, in one embodiment, the weight ratio (Wt B} , unit _{) of the second polycarbonate to the weight average molecular weight (Mw B} , unit: g/mol) of the second polycarbonate resin, defined as “weight ratio weighted dispersion index” : The weight average molecular weight (Mw _A , unit: g/mol) of the first _{polycarbonate resin multiplied by the weight ratio (Wt A} , unit: wt%) of the first polycarbonate resin to the value multiplied by wt%) The ratio [(Mw _A ×Wt _A )/(Mw _B ×Wt _B )] may be greater than 0.2 and less than 0.8.

When the weight-ratio-weighted dispersion index satisfies the above range, the thermoplastic resin composition may exhibit excellent appearance characteristics while satisfying excellent impact resistance, fluidity, and heat resistance.

The first polycarbonate resin may be included, for example, 20% by weight or more, for example, 22% by weight or more, for example, 25% by weight or more, based on the total weight of the thermoplastic resin composition, for example, 50% by weight or less, For example, 48% by weight or less, such as 45% by weight or less, may be included, for example 20% to 50% by weight, such as 20% to 45% by weight, such as 25% to 45% by weight % Can be included. If the first polycarbonate resin is contained in less than 20% by weight, the flowability of the thermoplastic resin composition decreases, which negatively affects the moldability of the final product, and if it exceeds 50% by weight, the target physical properties are reduced by the impact resistance of the thermoplastic resin composition. Cannot be achieved.

The second polycarbonate resin may be included, for example, 20% by weight or more, such as 25% by weight or more, for example, 27% by weight or more, based on the total weight of the thermoplastic resin composition, for example, 50% by weight or less, For example, 47% by weight or less may be included, for example, 20% by weight to 50% by weight, such as 25% by weight to 50% by weight, for example, 27% by weight to 47% by weight. If the second polycarbonate resin is contained in less than 20% by weight, there is a concern that the impact resistance of the thermoplastic resin composition may be greatly reduced, and if it exceeds 50% by weight, there is a concern that fluidity and appearance characteristics may be deteriorated.

In addition, it is preferable that the sum of the content of the first polycarbonate resin and the content of the second polycarbonate resin satisfies 60% by weight to 80% by weight based on the total weight of the thermoplastic resin composition. If the sum of the contents of the first and second polycarbonate resins is less than 60% by weight, the heat resistance of the thermoplastic resin composition may be greatly reduced, and if it exceeds 80% by weight, weld lines, etc., are generated in the final product. There is a fear that the appearance characteristics may be deteriorated.

That is, when the sum of the contents of each of the first and second polycarbonate resins and the contents of the first and second polycarbonate resins based on the total weight of the thermoplastic resin composition satisfies the above ranges, impact resistance and heat resistance , It is possible to provide a thermoplastic resin composition excellent in both fluidity and appearance characteristics.

(C) Acrylic Graft Copolymer

In one embodiment, the acrylic graft copolymer performs a function of enhancing the weather resistance and impact resistance of the thermoplastic resin composition by alloying with the first and second polycarbonate resins described above.

In one embodiment, the acrylic graft copolymer may be prepared by graft polymerization of a monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound on an acrylic rubber polymer.

The acrylic graft copolymer may be prepared according to any manufacturing method known to a person skilled in the art.

As the production method, conventional polymerization methods, for example, emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization may be used. As a non-limiting example, an acrylic rubber polymer is prepared, and a monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound is graft-polymerized on a core formed with one or more layers of the acrylic rubber polymer to form one or more shell layers. It can be manufactured by a method.

The acrylic rubber polymer may be prepared using an acrylic monomer as a main monomer. The acrylic monomer may be one or more selected from the group consisting of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and hexyl acrylate, but is not limited thereto.

The acrylic monomer may be copolymerized with one or more radically polymerizable other monomers. When copolymerized, the amount of the one or more radically polymerizable other monomers may be 5% to 30% by weight, specifically 10% to 20% by weight, based on the total weight of the acrylic rubber polymer.

The aromatic vinyl compound included in the shell layer may be at least one selected from styrene, α-methyl styrene, and combinations thereof unsubstituted or substituted with halogen or C1 to C10 alkyl groups, but is not limited thereto.

The vinyl cyanide compound included in the shell layer may be at least one selected from acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof, but is not limited thereto.

In one embodiment, the acrylic graft copolymer may be an acrylate-styrene-acrylonitrile graft copolymer (g-ASA).

In one embodiment, the grafting rate of the acrylic graft copolymer may be, for example, 15% or more, for example, 20% or more, and may be, for example, 50% or less, such as 35% or less, for example It may be between 15% and 50%.

When the acrylic graft copolymer according to an embodiment satisfies the grafting ratio range within the above range, the thermoplastic resin composition may exhibit excellent impact resistance and appearance characteristics.

In one embodiment, the acrylic graft copolymer has an average particle diameter of the acrylic rubber polymer of 100 nm or more, such as 120 nm or more, and, for example, 300 nm or less, such as 200 nm or less, such as 150 nm or less, for example 100 nm to 300 nm, for example 120 nm to 200 nm, for example 120 nm to 150 nm.

If the average particle diameter of the acrylic rubber polymer in the acrylic graft copolymer is less than 100 nm, the overall mechanical properties such as impact resistance and tensile strength of the thermoplastic resin composition may be deteriorated.If the average particle diameter exceeds 300 nm, the thermoplastic resin composition There is a concern that fluidity and gloss characteristics may be deteriorated.

The acrylic graft copolymer may be 9% by weight or more, for example 10% by weight or more, based on the total amount of the thermoplastic resin composition, for example 20% by weight or less, for example 19% by weight or less, such as 18% by weight. It may be contained in% or less, for example, it may be 9% by weight to 20% by weight.

If the acrylic graft copolymer is less than 9% by weight, the impact resistance of the thermoplastic resin composition may be deteriorated, and if it exceeds 20% by weight, the mechanical stiffness, colorability, and heat resistance of the thermoplastic resin composition may be lowered.

(D) aromatic vinyl-vinyl cyanide copolymer

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer performs a function of maintaining compatibility between components of the thermoplastic resin composition at a certain level.

In one embodiment, the aromatic vinyl-cyanide vinyl copolymer may be a copolymer of an aromatic vinyl compound and a vinyl cyanide compound. The aromatic vinyl-cyanide vinyl copolymer has a weight average molecular weight of 80,000 g/mol or more, such as 85,000 g/mol or more, such as 90,000 g/mol or more, for example, 200,000 g/mol or less, for example 150,000 g/mol, for example 80,000 g/mol to 200,000 g/mol, for example 80,000 g/mol to 150,000 g/mol may be used.

In the present invention, the weight average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF) and then using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) (column is Shodex LF-804, The standard sample is Shodex's polystyrene).

Among the aromatic vinyl-cyanide vinyl copolymers, the aromatic vinyl compound may be one or more selected from the group consisting of styrene, α-methyl styrene, and combinations thereof unsubstituted or substituted with halogen or C1 to C10 alkyl groups.

Among the aromatic vinyl-cyanide vinyl copolymers, the vinyl cyanide may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer (SAN) having a weight average molecular weight of 80,000 g/mol to 200,000 g/mol.

In one embodiment, based on 100% by weight of the aromatic vinyl-vinyl cyanide copolymer, the vinyl cyanide compound may be contained in an amount of 10% by weight or more, such as 15% by weight or more, for example, 20% by weight or more, and , For example, 50% by weight or less, for example 40% by weight or less, may be included, for example, 10% by weight to 50% by weight, such as 15% by weight to 40% by weight, such as 20% by weight % To 40% by weight may be included.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be included in an amount of 10% by weight or more, such as 12% by weight or more, such as 14% by weight or more, based on the total weight of the thermoplastic resin composition, for example, 20% by weight. Hereinafter, for example, it may be included in an amount of 18% by weight or less, for example, 16% by weight or less, and may be included in an amount of, for example, 10% to 20% by weight, for example, 12% to 18% by weight.

If the content of the aromatic vinyl-vinyl cyanide copolymer is less than 10% by weight, the mechanical stiffness and heat resistance of the thermoplastic resin composition may be reduced, and if it exceeds 20% by weight, the impact resistance and weather resistance of the thermoplastic resin composition may be reduced. There is.

(E) additive

In addition to the components (A) to (D), in the thermoplastic resin composition according to an embodiment, in order to balance the physical properties under conditions capable of expressing excellent appearance characteristics without deteriorating impact resistance, heat resistance, and fluidity, Alternatively, one or more additives required according to the final use of the thermoplastic resin composition may be further included.

Specifically, as the additive, a flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, an impact modifier, a lubricant, an antibacterial agent, a release agent, a heat stabilizer, an antioxidant, an inorganic additive, an ultraviolet stabilizer, an antistatic agent, a pigment, a dye, etc. may be used. These may be used alone or in combination of two or more.

These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less based on 100 parts by weight of the total amount of components (A) to (D). It is not limited.

Meanwhile, the thermoplastic resin composition according to an embodiment may be mixed with other resins or other rubber components and used together.

On the other hand, another embodiment provides a molded article including the thermoplastic resin composition according to the embodiment. The molded article may be manufactured by various methods known in the art, such as injection molding and extrusion molding, using the thermoplastic resin composition.

The molded article may have a notched Izod impact strength measured according to ASTM D256 of 40 kgf·cm/cm to 80 kgf·cm/cm.

The molded article may have a melt flow index of 30 g/10min to 60 g/10min measured under conditions of 250°C and 10 kg according to ASTM D1238.

The molded article may have a Vicat softening temperature of 120° C. or higher measured under 50N condition according to ASTM D1525.

As described above, in the molded article according to another embodiment, even if the above-described thermoplastic resin composition is manufactured by extrusion molding or injection molding, while maintaining excellent impact resistance, fluidity, and heat resistance, appearance characteristics such as weld lines do not deteriorate. Therefore, the molded article can be advantageously used not only for various electric and electronic parts, building materials, sports goods, etc. used outdoors, but also for interior/exterior parts of automobiles. Specifically, the molded article may be used in a satellite antenna, a door panel, an automobile radiator grill, a side mirror housing, etc., but is not limited thereto.

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

Examples 1 to 6 and Comparative Examples 1 to 7

Polycarbonate resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 7 were prepared according to the component content ratios shown in Table 1 below.

Each component shown in Table 1 was mixed in the amount shown in Table 1, melted and extruded to prepare a thermoplastic resin composition in the form of a pellet. For the extrusion, a twin screw extruder having L/D=44 and a diameter of 35 mm was used, and the barrel temperature was set to 260°C.

Polycarbonate resin (C) g-ASA
(weight%) (D) SAN
(weight%) (A) First polycarbonate resin (% by weight) (B) second poly
Carbonate resin
(weight%) Weight average molecular weight ratio
(Mw _A /Mw _B ) Weight ratio weighted dispersion index
(Mw _A ×Wt _A )
/
(Mw _B ×Wt _B ) (A-1) (A-2) (A-3) (B-1) (B-2) (C-1) (C-2) Example 1 40 - - 32 - 0.45 0.56 14 - 14 Example 2 40 - - 36 - 0.45 0.50 10 - 14 Example 3 40 - - 28 - 0.45 0.64 18 - 14 Example 4 25 - - 47 - 0.45 0.24 14 - 14 Example 5 45 - - 27 - 0.45 0.75 14 - 14 Example 6 40 - - - 32 0.61 0.76 14 - 14 Comparative Example 1 40 - 32 - - 0.65 0.82 14 - 14 Comparative Example 2 40 32 - - - 0.81 1.01 14 - 14 Comparative Example 3 55 - - 17 - 0.45 1.45 14 - 14 Comparative Example 4 15 - - 57 - 0.45 0.12 14 - 14 Comparative Example 5 46 - - 35 - 0.45 0.59 5 - 14 Comparative Example 6 34 - - 24 - 0.45 0.63 28 - 14 Comparative Example 7 40 - - 32 - 0.45 0.56 - 14 14

A description of each configuration described in Table 1 is as follows.

(A) First polycarbonate resin

(A-1)

Polycarbonate resin with a weight average molecular weight of about 17,000 g/mol (Lotte Advanced Materials)

(A-2)

Polycarbonate resin with a weight average molecular weight of about 21,000 g/mol (Lotte Advanced Materials)

(A-3)

Polycarbonate resin with a weight average molecular weight of about 26,000 g/mol (Lotte Advanced Materials)

(B) 2nd polycarbonate resin

(B-1)

Polycarbonate resin with a weight average molecular weight of about 38,000 g/mol (Samyang)

(B-2)

Polycarbonate resin with a weight average molecular weight of about 28,000 g/mol (Lotte Advanced Materials)

(C) acrylic graft copolymer (g-ASA)

(C-1)

Acrylonitrile-styrene-acrylate graft copolymer with an average particle diameter of about 138 nm and a grafting rate of about 35% of a rubber polymer (Lotte Advanced Materials)

(C-2)

Acrylonitrile-styrene-acrylate graft copolymer with an average particle diameter of about 175 nm and a grafting rate of about 70% (Lotte Advanced Materials)

(D) Aromatic vinyl-vinyl cyanide copolymer (SAN)

Styrene-acrylonitrile copolymer with a weight ratio of styrene and acrylonitrile of about 72:28 and a weight average molecular weight of about 95,000 g/mol (Lotte Advanced Materials)

Experimental example

The experimental results are shown in Table 2 below.

(1) Impact resistance (kgf·cm/cm): Notched Izod impact strength was measured at room temperature according to ASTM D256 standard for a 1/8" thick specimen.

(2) Fluidity (g/10min): The melt flow index was measured at 250° C. and 10 kg according to ASTM D1238 standard.

(3) Heat resistance (℃): Vicat softening temperature was measured under 50N condition according to ASTM D1525 standard.

(4) Appearance characteristics: After visually checking the presence or absence of occurrence of weld lines on the surface of the molded article, each appearance characteristic was evaluated according to the following evaluation criteria.

○: No weld line was observed

△: A faint weld line recognizable with the naked eye is observed

X: A clear weld line recognizable with the naked eye is observed

Impact resistance
(Kgf*cm/cm) liquidity
(g/10min) Heat resistance
(℃) Appearance characteristics Example 1 55.4 42.6 123.5 ○ Example 2 48.7 39.8 124.3 ○ Example 3 66.2 41.2 122.8 ○ Example 4 69.5 31.2 123.7 ○ Example 5 52.3 45.2 122.5 ○ Example 6 47.2 46.0 123.1 ○ Comparative Example 1 32.7 52.3 122.5 X Comparative Example 2 21.5 62.4 121.1 X Comparative Example 3 23.6 65.0 122.5 △ Comparative Example 4 71.2 12.1 125.7 X Comparative Example 5 28.4 21.3 126.7 X Comparative Example 6 39.2 37.6 112.3 △ Comparative Example 7 31.2 39.9 123.1 X

1 is an image photographing the appearance of a molded article according to Example 1, and FIG. 2 is an image photographing the appearance of a molded article according to Comparative Example 1.

From Tables 1 to 2 and FIGS. 1 to 2, when using a thermoplastic resin composition in which the first and second polycarbonate resins satisfying a _{specific weight average molecular weight ratio (Mw A} / Mw _{B) are alloyed with an ASA resin} , It can be seen that a molded article exhibiting excellent appearance characteristics can be manufactured without deterioration in impact resistance, fluidity, and heat resistance.

In the above, the present invention has been described through preferred embodiments as described above, but the present invention is not limited thereto, and various modifications and variations are possible without departing from the concept and scope of the following claims. Those who work in the technical field to which the invention belongs will easily understand.

Claims (18)

(A) 20% to 50% by weight of the first polycarbonate resin having a weight average molecular weight of 15,000 to 27,000 g/mol;
(B) 20% to 50% by weight of a second polycarbonate resin having a weight average molecular weight of more than 27,000 and 40,000 g/mol or less;
(C) 10% to 18% by weight of an acrylic graft copolymer; And
(D) containing 10% to 20% by weight of an aromatic vinyl-cyanide vinyl copolymer,
_{The ratio (Mw A} /Mw _B ) of the weight average molecular weight of the (A) first polycarbonate resin to the weight average molecular weight of the (B) second polycarbonate resin is 0.3 to 0.6,
The (C) acrylic graft copolymer is a thermoplastic resin composition having a grafting ratio of 15% to 35%. In claim 1,
The (B) second polycarbonate resin has a terminal hydroxyl group content of more than 0 and 15 mol% or less, a thermoplastic resin composition. In claim 1,
Based on the total weight of the thermoplastic resin composition, the sum of the content of the (A) first polycarbonate resin and the content of the (B) second polycarbonate resin is 60% by weight to 80% by weight, thermoplastic resin composition. delete In claim 1,
The (C) acrylic graft copolymer has an average particle diameter of an acrylic rubber polymer of 100 nm to 300 nm, a thermoplastic resin composition. In claim 1,
The (C) acrylic graft copolymer is an acrylonitrile-styrene-acrylate graft copolymer, a thermoplastic resin composition. In claim 1,
The (D) aromatic vinyl-vinyl cyanide copolymer is a copolymer of a monomer mixture comprising 60% to 85% by weight of an aromatic vinyl compound and 15% to 40% by weight of a vinyl cyanide compound, a thermoplastic resin composition. In claim 1,
The weight average molecular weight of the (D) aromatic vinyl-vinyl cyanide copolymer is 80,000 g/mol to 200,000 g/mol, a thermoplastic resin composition. In claim 1,
In the (D) aromatic vinyl-vinyl cyanide copolymer, the vinyl cyanide compound is selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof. In claim 1,
In the (D) aromatic vinyl-vinyl cyanide copolymer, the aromatic vinyl compound is selected from the group consisting of styrene unsubstituted or substituted with a halogen or C1 to C10 alkyl group, α-methyl styrene, and combinations thereof. In claim 1,
The (D) aromatic vinyl-vinyl cyanide copolymer is a styrene-acrylonitrile copolymer, a thermoplastic resin composition. In claim 1,
A flame retardant, a nucleating agent, a coupling agent, a filler, a plasticizer, an impact modifier, a lubricant, an antibacterial agent, a release agent, a heat stabilizer, an antioxidant, an inorganic additive, an ultraviolet stabilizer, an antistatic agent, a pigment, and a dye. Thermoplastic resin composition. In claim 1,
Of the thermoplastic resin composition, a polydispersity index (PDI) of the mixture of the first polycarbonate resin and the second polycarbonate resin, which can be separated by a wet precipitation method, is 2.5 to 5.5, a thermoplastic resin composition. In claim 1,
Of the first polycarbonate resin to a value obtained by multiplying _{the weight average molecular weight (Mw B} ) of the second polycarbonate resin by the weight ratio (Wt _B ) used of the second polycarbonate resin, defined as a weight-ratio-weighted dispersion index The ratio [(Mw _A ×Wt _A )/(Mw _B ×Wt _B )] of the value obtained by multiplying the weight average molecular weight (Mw _A ) by the used weight ratio (Wt _B ) of the first polycarbonate resin is greater than 0.2 and less than 0.8, Thermoplastic resin composition. A molded article manufactured from the thermoplastic resin composition according to any one of claims 1 to 3 and 5 to 14. In paragraph 15,
Notched Izod impact strength of the molded article measured according to ASTM D256 is 40 kgf·cm/cm to 80 kgf·cm/cm, a molded article. In paragraph 15,
According to ASTM D1238, the melt flow index of the molded article measured at 250° C., 10 kg condition is 30 g/10min to 60 g/10min, a molded article. In paragraph 15,
According to ASTM D1525, the Vicat softening temperature of the molded article measured at 50N condition is 120°C or higher.

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