KR20200036718A - Thermoplastic resin composition and molded article using the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition comprising, based on 100 parts by weight of a base resin including (A) 80 to 90 wt% of polycarbonate resin; (B) 5 to 10 wt% of aromatic vinyl-cyanide vinyl based copolymer; (C) 3 to 7 wt% of acrylonitrile-butadiene-styrene graft copolymer; and (D) 2 to 8 wt% of methyl methacrylate-butadiene-styrene graft copolymer, (E) 0.1 to 0.3 parts by weight of a phosphate-based heat stabilizer; and (F) 5 to 25 parts by weight of an inorganic filler having an average particle diameter (D50) of 1 to 5 μm. The present invention also relates to a molded article using the thermoplastic resin composition.

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.

Polycarbonate resin is one of the engineering plastics and is widely used in the plastics industry.

The polycarbonate resin has a glass transition temperature (Tg) of about 150 ° C due to its bulky molecular structure such as bisphenol-A, showing high heat resistance, and the carbonyl group of the carbonate group is highly flexible in polycarbonate resin due to its high rotational mobility And gives stiffness. In addition, it is an amorphous polymer and has excellent transparency.

Not only that, it has excellent impact resistance and compatibility with other resins, but polycarbonate resins have the disadvantage of low fluidity, so they are often used in an alloy form with various resins to supplement formability and post-processing properties. do.

 Among them, polycarbonate / acrylonitrile-butadiene-styrene copolymer (PC / ABS) alloy is excellent in durability, moldability, heat resistance, impact resistance, dimensional stability, etc., so that it is in the electric / electronic field, automobile field, construction field, and other life. It is applied to a wide range of fields such as materials.

On the other hand, the PC / ABS alloy is sometimes added with an inorganic filler to further enhance dimensional stability. The appearance of the PC / ABS alloy is caused by the decomposition of the PC resin by the metal ion component contained in the inorganic filler. There is a fear that impact resistance is deteriorated.

Therefore, in order to solve the above problems, it is necessary to develop a thermoplastic resin composition having excellent impact resistance, appearance, and dimensional stability compared to a conventional PC / ABS alloy.

It is to provide a thermoplastic resin composition having excellent impact resistance, appearance and dimensional stability, and a molded article using the same.

According to one embodiment, (A) 80 to 90% by weight of a polycarbonate resin; (B) 5 to 10% by weight of an aromatic vinyl-cyanide copolymer; (C) 3 to 7% by weight of acrylonitrile-butadiene-styrene graft copolymer; And (D) methyl methacrylate-butadiene-styrene graft copolymer 2 to 8 parts by weight based on 100 parts by weight of the basic resin (E) phosphate-based heat stabilizer 0.1 to 0.3 parts by weight; And (F) 5 to 25 parts by weight of an inorganic filler having an average particle diameter (D50) of 1 to 5 μm.

The polycarbonate resin (A) may have a melt flow index (Melt flow index) of 15 to 25 g / 10min measured under a load condition of 300 ° C and 1.2 kg according to ASTM D1238.

The (B) aromatic vinyl-vinyl cyanide copolymer may be a copolymer of a monomer mixture containing 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyanide compound.

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

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

The (C) acrylonitrile-butadiene-styrene graft copolymer may be a core-shell structure including a core made of a butadiene-based rubbery polymer, and a shell formed by graft polymerization of acrylonitrile and styrene on the core. .

The (C) acrylonitrile-butadiene-styrene graft copolymer may include 30 to 60 wt% of the core, and 40 to 70 wt% of the shell, based on 100 wt% of the graft copolymer. .

The (C) acrylonitrile-butadiene-styrene graft copolymer may have an average particle diameter of butadiene-based rubbery polymer of 200 to 400 nm.

The (D) methyl methacrylate-butadiene-styrene graft copolymer is a core-shell comprising a core made of a butadiene-based rubbery polymer, and a shell formed by graft polymerization of the methyl methacrylate and / or styrene to the core. It can be a structure.

The (E) phosphate-based heat stabilizer may include dihydrogen phosphate, stearyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, or combinations thereof.

The inorganic filler (F) may include montmorillonite, talc, kaolin, zeolite, vermiculite, aluminum oxide, silica, magnesium hydroxide, aluminum hydroxide, glass flake, or a combination thereof.

The thermoplastic resin composition may further include at least one additive selected from flame retardants, nucleating agents, coupling agents, glass fibers, plasticizers, lubricants, antibacterial agents, mold release agents, antioxidants, ultraviolet stabilizers, antistatic agents, pigments, and dyes.

Meanwhile, a molded article using a thermoplastic resin composition according to one embodiment may be provided.

The thermoplastic resin composition according to one embodiment and the molded article using the same can be widely applied to molding of various products used for painting and uncoating, as they have excellent impact resistance, appearance, and dimensional stability, in particular, automobile interior / exterior materials, etc. It can be usefully applied to the use of.

1 to 3 are images for indicating the initial appearance evaluation criteria of molded article specimens using a thermoplastic resin composition according to one embodiment, respectively, grade 1 (Figure 1), grade 2 (Figure 2), grade 3 (Figure 3) ), Respectively,
4 to 6 are images for showing the evaluation criteria of the appearance of the thermal stability of the molded article specimens using the thermoplastic resin composition according to one embodiment, 1st grade (FIG. 4), 2nd grade (FIG. 5), 3rd grade (FIG. 6) 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 invention, unless otherwise specified, the average particle diameter of the rubbery polymer is the volume average diameter, and means the Z-average particle diameter measured using a dynamic light scattering analysis equipment.

According to one embodiment, (A) 80 to 90% by weight of a polycarbonate resin; (B) 5 to 10% by weight of an aromatic vinyl-cyanide copolymer; (C) 3 to 7% by weight of acrylonitrile-butadiene-styrene graft copolymer; And (D) methyl methacrylate-butadiene-styrene graft copolymer 2 to 8 parts by weight based on 100 parts by weight of the basic resin (E) phosphate-based heat stabilizer 0.1 to 0.3 parts by weight; And (F) 5 to 25 parts by weight of an inorganic filler having an average particle diameter (D50) of 1 to 5 μm.

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

(A) Polycarbonate resin

The polycarbonate resin is a polyester having a carbonate bond, and its type is not particularly limited, and any polycarbonate resin available in the resin composition field can be used.

For example, it may be prepared by reacting a compound selected from the group consisting of diphenols represented by the following Chemical Formula 1 and phosgene, a halogen acid ester, a carbonic acid ester, and combinations thereof.

[Formula 1]

In Chemical 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 alkylene 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 acid ester group, CO, S and SO ₂ is a linking group selected from the group consisting of, R ¹ and R ² are each independently substituted or unsubstituted C1 to C30 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, n1 and n2 are each independently an integer of 0 to 4.

The diphenols represented by Chemical Formula 1 may be combined with two or more kinds 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, And bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, and the like. 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 can be used.

The polycarbonate resin may be a mixture of copolymers prepared from two or more diphenols.

In addition, the polycarbonate resin may be used a linear polycarbonate resin, branched (branched) polycarbonate resin, polyester carbonate copolymer resin and the like.

A specific example of the linear polycarbonate resin may be 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 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 here may be diaryl carbonate such as diphenyl carbonate or ethylene carbonate.

It is preferable to use the polycarbonate resin having a weight average molecular weight of 10,000 to 200,000 g / mol, and it is effective to use, for example, 14,000 to 40,000 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 polycarbonate resin may be included in 80 to 90% by weight based on 100% by weight of the base resin, for example, it may be included in 83 to 87% by weight. When the polycarbonate resin is less than 80% by weight, the mechanical strength is poor, and when it exceeds 90% by weight, moldability may be deteriorated.

The polycarbonate resin may have a melt flow index (Melt flow index) measured under a load condition of 300 ° C and 1.2 kg according to ASTM D1238, for example, 15 g / 10min or more, for example, 16 g / 10min or more, for example For example, it may be 25 g / 10min or less, for example, 20 g / 10min or less, for example, 15-25 g / 10min, for example 16-20 g / 10min. When using a polycarbonate resin having a melt flow index within the above range, excellent impact resistance and fluidity can be obtained.

However, one implementation is not necessarily limited thereto. For example, the polycarbonate resin may be used by mixing two or more polycarbonate resins having different weight average molecular weights or flow indexes. It is easy to control the thermoplastic resin composition to have a desired fluidity by mixing and using polycarbonate resins having different weight average molecular weights or flow indexes.

(B) aromatic vinyl-vinyl cyanide copolymer

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer serves to improve the fluidity of the thermoplastic resin composition and maintain the compatibility between components to a certain level.

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

In the present invention, the weight average molecular weight is measured by dissolving a powder sample in tetrahydrofuran (THF), and then using 1200 series gel permeation chromatography (GPC) from Agilent Technologies (columns are Shodex LF-804, The standard sample is made of polystyrene using Shodex).

The aromatic vinyl compound may be at least one selected from styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, and vinylnaphthalene.

The vinyl cyanide compound may be at least one selected from acrylonitrile, methacrylonitrile, and fumaronitrile.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be a copolymer of an aromatic vinyl compound and a monomer mixture comprising a vinyl cyanide compound.

In this case, with respect to 100% by weight of the aromatic vinyl-vinyl cyanide copolymer, the aromatic vinyl compound may be included, for example, 60% by weight or more, for example, 65% by weight or more, for example, 70% by weight or more, , For example, 80% by weight or less, for example, 75% by weight or less, and for example, 60 to 80% by weight, for example, 65 to 75% by weight.

In addition, with respect to the aromatic vinyl-vinyl cyanide copolymer 100% by weight, the vinyl cyanide compound may include, for example, 20% by weight or more, for example, 25% by weight or more, for example, 40% by weight or less, For example, 30% by weight or less may be included, for example, 20 to 40% by weight, for example, 25 to 35% by weight.

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer (SAN).

In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may include 5% by weight or more, for example, 6% by weight or more, for example, 10% by weight or less, for example 9% by weight, based on 100% by weight of the base resin Hereinafter, it may be included, for example, 8% by weight or less, for example, 5 to 10% by weight, for example, 6 to 8% by weight.

When the content of the aromatic vinyl-vinyl cyanide copolymer is less than 5% by weight, the moldability of the thermoplastic resin composition may be deteriorated, and when it exceeds 10% by weight, the impact resistance of the thermoplastic resin composition may be deteriorated.

(C) Acrylonitrile-butadiene-styrene graft copolymer

The acrylonitrile-butadiene-styrene graft copolymer according to one embodiment imparts impact resistance to the thermoplastic resin composition. In one embodiment, the acrylonitrile-butadiene-styrene graft copolymer is a core (core, core) made of a butadiene-based rubbery polymer component, and a graft polymerization reaction of acrylonitrile and styrene around the center of the shell (shell) ) May have a core-shell structure.

The rubbery polymer component constituting the core particularly improves the impact strength at low temperatures, and the shell component can lower the interfacial tension to improve the adhesion at the interface.

The acrylonitrile-butadiene-styrene graft copolymer according to one embodiment may be prepared by adding styrene and acrylonitrile to a butadiene-based rubbery polymer and graft copolymerizing through conventional polymerization methods such as emulsion polymerization and bulk polymerization. .

The butadiene rubber polymer may be selected from the group consisting of butadiene rubber polymer, butadiene-styrene rubber polymer, butadiene-acrylonitrile rubber polymer, butadiene-acrylate rubber polymer, and mixtures thereof.

The acrylonitrile-butadiene-styrene graft copolymer may have an average particle diameter of butadiene-based rubbery polymer, for example, 200 to 400 nm, for example, 200 to 350 nm, for example, 250 to 350 nm.

The acrylonitrile-butadiene-styrene graft copolymer may be included in 3 to 7% by weight, for example 4 to 7% by weight, for example 5 to 7% by weight based on 100% by weight of the base resin.

With respect to 100% by weight of the acrylonitrile-butadiene-styrene graft copolymer, the butadiene-based rubbery polymer core may be included in 30 to 60% by weight, and the shell in 40 to 70% by weight. Meanwhile, the shell may be a styrene-acrylonitrile copolymer having a weight ratio of styrene and the acrylonitrile of 6: 4 to 8: 2.

When the acrylonitrile-butadiene-styrene graft copolymer is contained in an amount of less than 3% by weight, there is a fear that the impact resistance of the thermoplastic resin composition is lowered, and when it exceeds 7% by weight, the heat resistance and the appearance of the molded product may be lowered. .

(D) Methyl methacrylate-butadiene-styrene graft copolymer

The methyl methacrylate-butadiene-styrene graft copolymer according to one embodiment provides impact resistance of the thermoplastic resin composition together with the acrylonitrile-butadiene-styrene graft copolymer described above, while the molded article using the thermoplastic resin composition It also contributes to the improvement of dimensional stability and appearance characteristics.

In one embodiment, the methyl methacrylate-butadiene-styrene graft copolymer is a graft polymerization reaction of a central portion (core, core) made of a butadiene-based rubbery polymer component and a central portion of the methyl methacrylate and / or styrene around it. It may have a core-shell structure in which a shell is formed.

The methyl methacrylate-butadiene-styrene graft copolymer according to an embodiment is obtained by adding methyl methacrylate and / or styrene to a butadiene-based rubbery polymer and graft copolymerizing it through conventional polymerization methods such as emulsion polymerization and bulk polymerization. Can be manufactured.

The butadiene rubber polymer may be selected from the group consisting of butadiene rubber polymer, butadiene-styrene rubber polymer, butadiene-acrylonitrile rubber polymer, butadiene-acrylate rubber polymer, and mixtures thereof.

The methyl methacrylate-butadiene-styrene graft copolymer may be included in 2 to 8% by weight, for example, 2 to 6% by weight based on 100% by weight of the base resin.

With respect to 100% by weight of the methyl methacrylate-butadiene-styrene graft copolymer, the butadiene-based rubbery polymer core may be included in an amount of 20 to 80% by weight, and a shell in an amount of 20 to 80% by weight.

In addition, the methyl methacrylate-butadiene-styrene graft copolymer preferably has an average particle diameter of 100-400 nm of butadiene-based rubbery polymer, for example, it may be effective that it is 120-380 nm.

When the methyl methacrylate-butadiene-styrene graft copolymer is included in an amount of less than 2% by weight, the impact resistance of the thermoplastic resin composition may be deteriorated, and when it exceeds 8% by weight, there is a fear that dimensional stability and appearance characteristics are deteriorated. have.

(E) Phosphate heat stabilizer

The phosphate-based thermal stabilizer according to one embodiment prevents the thermal decomposition reaction of the polycarbonate resin by heat in the manufacturing process of the thermoplastic resin composition and / or the manufacturing process of the molded article using the thermoplastic resin composition. In addition, when the inorganic filler is added to further enhance the dimensional stability to the thermoplastic resin composition, it is prevented that the thermal decomposition of the polycarbonate resin is accelerated by the metal ion component contained in the inorganic filler. The thermal decomposition reaction of the polycarbonate resin is not preferable because it may cause deterioration of various properties (impact resistance, dimensional stability, appearance) of the thermoplastic resin composition. That is, the phosphate-based thermal stabilizer suppresses thermal decomposition of the polycarbonate resin to impart thermal stability to the thermoplastic resin composition.

In one embodiment, the phosphate-based thermal stabilizer may include dihydrogen phosphate, stearyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, or a combination thereof, specifically stearyl phosphate. Can be used.

The phosphate-based thermal stabilizer may be contained in a relatively small amount relative to 100 parts by weight of the base resin. Specifically, it may be included in 0.1 to 0.3 parts by weight, for example, 0.1 to 0.2 parts by weight.

When the phosphate-based thermal stabilizer is out of the above range, various properties such as impact resistance and appearance characteristics of the thermoplastic resin composition and a molded product using the same may be deteriorated, and there is a fear that it is difficult to balance the target properties. .

(F) Weapon filler

The inorganic filler according to one embodiment may improve dimensional stability of the thermoplastic resin composition. The inorganic filler may be, for example, particulate or flake type. As a non-limiting example, mica, quartz powder, titanium dioxide, silicate, aluminosilicate can be used. In addition, for example, chalk, wollastonite, mica layered clay minerals, montmorillonite, in particular, ion exchange modified montmorillonite, talc, kaolin, zeolite, vermiculite, aluminum oxide, silica, magnesium hydroxide, aluminum hydroxide, glass flakes, etc. Can be used. Mixtures of different inorganic fillers can also be used.

A preferred example according to an embodiment may be talc, mica, and combinations thereof, and more preferably talc.

The inorganic filler may have an average particle diameter (D50) measured by a laser particle size analyzer (Malvern Panalytical, Mastersizer 3000) of 1 μm or more, for example 2 μm or more, for example 3 μm or more, for example For example, it may be 5 µm or less, for example, 4 µm or less, for example, 1 to 5 µm, for example, 2 to 4 µm. When the average particle diameter of the inorganic filler is outside the above range, there is a fear that mechanical strength and appearance characteristics are deteriorated.

The inorganic filler may be included, for example, 5 parts by weight or more, for example, 10 parts by weight or more, for example, 15 parts by weight or more, and for example, 25 parts by weight or less, , For example, 5 parts by weight to 25 parts by weight, for example, 10 parts by weight to 25 parts by weight, for example, 10 parts by weight to 20 parts by weight. When the content of the inorganic filler is outside the above range, the dimensional stability, heat resistance, mechanical strength, and appearance characteristics of the thermoplastic resin composition and the molded article using the same may be deteriorated.

(G) Other additives

The thermoplastic resin composition according to one embodiment, in addition to the components (A) to (F), in order to balance the properties under the conditions of maintaining excellent heat resistance, impact resistance, dimensional stability, and appearance properties, or the thermoplastic Depending on the end use of the resin composition, one or more additives may be further included.

Specifically, as the additives, flame retardants, nucleating agents, coupling agents, glass fibers, plasticizers, lubricants, antibacterial agents, mold release agents, antioxidants, ultraviolet stabilizers, antistatic agents, pigments, dyes, etc. can be used, and these may be used alone or in combination of two or more. Can be used as

These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, specifically 20 parts by weight or less based on 100 parts by weight of the base resin, but is not limited thereto.

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

For example, the thermoplastic resin composition according to the present invention may be prepared in the form of pellets by mixing and kneading the components of the present invention and other additives simultaneously in an extruder.

The molded article according to an embodiment of the present invention may be prepared from the above-described thermoplastic resin composition. The thermoplastic resin composition is excellent in heat resistance, impact resistance, dimensional stability, and appearance, and has excellent moldability, and is widely applicable to molding of various products used for painting and uncoating, and specifically for interior / exterior materials of automobiles, etc. It can be usefully applied to applications.

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

Example 1, Example 2 and Comparative Examples 1 to 6

The thermoplastic resin compositions of Example 1, Example 2 and Comparative Examples 1 to 6 were prepared according to the component content ratios shown in Table 1 below.

In Table 1, (A), (B), (C), (D) is included in the base resin is represented by weight percent based on the total weight of the base resin, (E), (F), (F ' ) Is added to the base resin and is expressed in parts by weight relative to 100 parts by weight of the base resin.

The components listed in Table 1 were dry mixed and quantitatively continuously charged and melted / kneaded into the feed section of a twin-screw extruder (L / D = 29, φ = 45 mm). At this time, the barrel temperature of the twin-screw extruder was set to 250 ° C. Subsequently, after drying the pelletized thermoplastic resin composition through a twin-screw extruder at about 100 ° C. for about 2 hours, a specimen for impact resistance measurement using a 6 oz injection molding machine set at a cylinder temperature of about 270 ° C. and a mold temperature of about 60 ° C. , 50 mm (horizontal) x 200 mm (vertical) specimens that can verify the appearance of 2 mm thickness, and 10 mm (horizontal) x 15 mm (vertical) specimens that can verify the dimensional stability of 3 mm thickness, respectively It was injected.

division Example
One Example
2 Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 Comparative example
6 Basic resin (A) 85 85 85 85 85 85 85 85 (B) 6 6 6 7 6 6 6 6 (C) 5 5 9 - 5 5 5 5 (D) 4 4 - 8 4 4 4 4 (E) 0.1 0.2 0.1 0.1 - 0.4 0.1 15 (F) 21 21 20 22 21 21 - 21 (F ') - - - - - - 21 -

Description of each configuration described in Table 1 is as follows.

(A) Polycarbonate resin

Polycarbonate resin with a melt flow index of about 18 g / 10min measured at 300 ° C and 1.2 kg load conditions according to ASTM D1238 standard (Lotte Advanced Materials Co., Ltd.)

(B) aromatic vinyl-vinyl cyanide copolymer

Styrene-acrylonitrile copolymer having a weight average molecular weight of about 100,000 g / mol copolymerized from a monomer mixture containing 28% by weight of acrylonitrile and 72% by weight of styrene (Lotte Advanced Materials Co., Ltd.)

(C) Acrylonitrile-butadiene-styrene graft copolymer

Acrylonitrile, a styrene-acrylonitrile copolymer consisting of a styrene-acrylonitrile weight ratio of 7: 3, consists of a core of 45 wt% of a butadiene rubbery polymer having an average particle diameter of about 300 nm and a shell of 55 wt%. Butadiene-styrene graft copolymer (Lotte Advanced Materials Co., Ltd.)

(D) Methyl methacrylate-butadiene-styrene graft copolymer

Methyl methacrylate-butadiene-styrene graft copolymer of core-shell structure forming a shell by graft polymerization of methyl methacrylate on a butadiene-styrene rubber polymer core (Dow, PARALOID)

(E) Phosphate heat stabilizer

Stearyl Phosphate (Adeka, ADK STAB)

(F) Weapon filler (type-I)

Talc with an average particle diameter (D50) of 3.9 μm measured by a laser particle size analyzer (Malvern Pnalytical, Mastersizer 3000) (Imerys, JETFINE)

(F ') Weapon Filler (type-II)

Talc with an average particle diameter (D50) of 6.5 μm measured by a laser particle size analyzer (Malvern Panalytical, Mastersizer 3000) (Koch, KCM-6300C)

Experimental example

Table 2 shows the experimental results.

(1) Impact resistance (kgf · cm / cm): Notched Izod impact strength was measured at room temperature (23 ° C) and low temperature (-30 ° C) according to ASTM D256 for 1/8 "thick specimens. .

(2) Dimensional stability (㎛ / m · ℃): After removing the stress in the -50 ℃ to 130 ℃ section using a thermomechanical analyzer (TA Instruments, Q400) in the resin flow direction for the specimen for dimensional stability verification,- The linear expansion coefficient was measured in a temperature range of 40 ° C to 40 ° C.

(3) Initial appearance: As shown in the images shown in Figs. 1 to 3, the specimen for verification of the appearance of the gas generated in the standard area (width 50 mm x height 50 mm) centered on the injection gate located at the center of the specimen top Judging by area. Specifically, it was classified into 1st class when no gas in the standard area occurs, 2nd class if it is less than 1/4 of the standard area, and 3rd class if it exceeds 1/4 of the standard area.

1 to 3 are images for showing the initial appearance evaluation criteria of molded article specimens using a thermoplastic resin composition according to one embodiment, respectively, grade 1 (Figure 1), grade 2 (Figure 2), grade 3 (Figure 3) ).

(4) Late appearance: After the resin composition pellet was stayed in the injection molding machine cylinder set to a cylinder temperature of 290 ° C. for 4 minutes, the injection gate (gate) located in the center of the specimen as shown in FIGS. The area of the gas generated in one standard area (50 mm horizontal x 50 mm vertical) is determined. Specifically, it was classified into 1 class when no gas in the standard area occurs, 2 class if it is less than 1/2 of the standard area, and 3 class when it exceeds 1/2 of the standard area.

4 to 6 are images for showing the evaluation criteria of the appearance of the thermal stability of the molded article specimens using the thermoplastic resin composition according to one embodiment, 1st grade (FIG. 4), 2nd grade (FIG. 5), 3rd grade (FIG. 6) respectively.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Izod (23 ℃) 12 18 12 8 9 18 8 4 Izod (-30 ℃) 7 9 6 5 6 9 5 3 Coefficient of linear expansion 43 43 40 45 43 43 44 55 Early appearance One One 2 One 3 3 2 3 Late appearance One One 2 One 3 3 2 3

From Table 1 and Table 2, polycarbonate resin, aromatic vinyl-vinyl cyanide copolymer, acrylonitrile-butadiene-styrene graft copolymer, methyl methacrylate-styrene-acrylonitrile graft copolymer, phosphate series By using the stabilizer and the inorganic filler in an optimum content, it can be confirmed that the thermoplastic resin composition and the molded article using the same can exhibit excellent impact resistance, dimensional stability, and appearance characteristics.

Although the present invention has been described through preferred embodiments as described above, 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 skilled in the art to which the invention pertains will readily understand.

Claims (13)

(A) 80 to 90% by weight of polycarbonate resin;
(B) 5 to 10% by weight of an aromatic vinyl-cyanide copolymer;
(C) 3 to 7% by weight of acrylonitrile-butadiene-styrene graft copolymer; And
(D) Methyl methacrylate-butadiene-styrene graft copolymer 2 to 8 parts by weight based on 100 parts by weight of the basic resin
(E) 0.1 to 0.3 parts by weight of a phosphate-based heat stabilizer; And
(F) A thermoplastic resin composition comprising 5 to 25 parts by weight of an inorganic filler having an average particle diameter (D50) of 1 to 5 μm. In claim 1,
The polycarbonate resin (A) is a thermoplastic resin composition having a melt flow index (Melt flow index) of 15 to 25 g / 10min measured under a load condition of 300 ° C and 1.2 kg according to ASTM D1238. In claim 1,
The (B) aromatic vinyl-vinyl cyanide copolymer is a copolymer of a monomer mixture containing 60 to 80% by weight of an aromatic vinyl compound and 20 to 40% by weight of a vinyl cyanide compound, a thermoplastic resin composition. In claim 1,
The weight average molecular weight of the (B) aromatic vinyl-vinyl cyanide copolymer is 80,000 to 200,000 g / mol, a thermoplastic resin composition. In claim 1,
The (B) aromatic vinyl-vinyl cyanide copolymer is a styrene-acrylonitrile copolymer, a thermoplastic resin composition. In claim 1,
The (C) acrylonitrile-butadiene-styrene graft copolymer is
Core made of butadiene-based rubbery polymer, and
A thermoplastic resin composition having a core-shell structure comprising a shell formed by graft polymerization of acrylonitrile and styrene on the core. In claim 6,
The (C) acrylonitrile-butadiene-styrene graft copolymer based on 100% by weight of the core containing 30 to 60% by weight, the shell 40 to 70% by weight of the thermoplastic resin composition comprising the. In claim 1,
The (C) acrylonitrile-butadiene-styrene graft copolymer is a thermoplastic resin composition having an average particle diameter of the rubbery polymer is 200 to 400 nm. In claim 1,
The (D) acrylonitrile-butadiene-styrene graft copolymer is
Core made of butadiene-based rubbery polymer, and
A thermoplastic resin composition having a core-shell structure comprising a shell formed by graft polymerization of methyl methacrylate and / or styrene on the core. In claim 1,
The (E) phosphate-based thermal stabilizer is a thermoplastic resin composition comprising dihydrogen phosphate, stearyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, or a combination thereof. In claim 1,
The (F) inorganic filler is a montmorillonite, talc, kaolin, zeolite, vermiculite, aluminum oxide, silica, magnesium hydroxide, aluminum hydroxide, glass flakes, or a thermoplastic resin composition comprising a combination thereof. In claim 1,
A thermoplastic resin composition further comprising at least one additive selected from flame retardants, nucleating agents, coupling agents, glass fibers, plasticizers, lubricants, antibacterial agents, release agents, antioxidants, ultraviolet stabilizers, antistatic agents, pigments, dyes. A molded article using the thermoplastic resin composition according to any one of claims 1 to 12.

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