KR101868672B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

[화학식 2]

[화학식 3]

상기 화학식 3에서, R₁ 및 R₂는 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 6의 알킬기이며, m 및 n은 각각 독립적으로 0 내지 4의 정수이다.The thermoplastic resin composition of the present invention comprises a polycarbonate resin and a polysiloxane-polycarbonate copolymer resin comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula Basic resin; And an impact modifier. The thermoplastic resin composition is excellent in impact resistance, scratch resistance, physical properties and the like.
[Chemical Formula 1]

(2)

(3)

In Formula 3, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and m and n are each independently an integer of 0 to 4.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoplastic resin composition and a molded article formed from the thermoplastic resin composition.

The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a polycarbonate-based thermoplastic resin composition excellent in impact resistance, scratch resistance, physical properties and the like, and a molded article formed from the polycarbonate-based thermoplastic resin composition.

BACKGROUND ART [0002] In recent years, thermoplastic resins having low specific gravity and excellent formability as compared with glass or metal have been widely used as exterior materials for electric and electronic products and office equipment. As a result, the function and appearance of the outer cover material become important, and the importance of the impact resistance and scratch resistance, which indicates the property that the thermoplastic resin can withstand external impacts or scratches, is increasing.

The polycarbonate resin is a typical thermoplastic material having a heat distortion temperature of 135 DEG C or higher and is widely used for electric and electronic products, office equipment, and automobile parts because of its excellent transparency, impact resistance, self-extinguishing property, dimensional stability and heat resistance.

However, the polycarbonate resin and the resin composition containing the polycarbonate resin are poor in scratch resistance, and thus they are problematic in that they are used as exterior materials and optical films for notebooks, mobile phones, and the like. Therefore, in order to compensate the scratch resistance of the polycarbonate resin, a separate scratch film may be coated on the polycarbonate film, but this method is expensive and scratch film of the polycarbonate resin is expensive, There is a disadvantage.

Accordingly, in addition to the film coating method, various methods for improving the scratch resistance of the polycarbonate resin and the resin composition have been studied. Among the methods for improving the scratch resistance of the polycarbonate resin composition, the most commonly used method is to blend the polycarbonate resin with a resin having scratch resistance such as an acrylic resin.

However, when the polycarbonate resin is blended with an acrylic resin or the like in order to improve the scratch resistance of the polycarbonate resin, excellent physical properties inherent in the polycarbonate resin such as impact resistance and transparency may be reduced due to lower compatibility between the two components.

Therefore, development of a thermoplastic resin composition excellent in scratch resistance, physical properties and the like, while retaining excellent inherent impact resistance and appearance characteristics inherent in the polycarbonate resin has been demanded.

The background art of the present invention is disclosed in U.S. Published Patent Application No. 2008-0004426.

An object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance, scratch resistance, physical properties and the like.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition comprises a polycarbonate resin and a polysiloxane-polycarbonate copolymer resin comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula ; And an impact modifier.

[Chemical Formula 1]

(2)

(3)

In Formula 3, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and m and n are each independently an integer of 0 to 4.

In an embodiment, the polycarbonate resin is comprised in 20 to 80 wt% of the total basis resin, and the polysiloxane-polycarbonate copolymer resin is comprised in 20 to 80 wt% of the total base resin, 1 to 10 parts by weight based on 100 parts by weight of the resin.

In one embodiment, the repeating unit represented by the formula (1) is contained in an amount of 1 to 69 mol% in the polycarbonate resin, and the repeating unit represented by the formula (2) is contained in the polycarbonate resin in an amount of 30 to 98 mol% The repeating unit repeating unit represented by the formula (3) may be contained in an amount of 1 to 50 mol% of the polycarbonate resin.

In an embodiment, the polysiloxane-polycarbonate copolymer resin may be prepared by reacting a siloxane compound represented by the following formula (7), an aromatic dihydroxy compound, and a carbonate precursor:

(7)

In Formula 7, R ₁₃ and R ₁₄ are each independently a C 1 -C 10 alkyl group, a C 6 -C 18 aryl group, a C 1 -C 10 alkyl group having a halogen atom or an alkoxy group, or a C 6 -C 18 aryl group, A substituted or unsubstituted C2-C20 hydrocarbon group independently substituted or unsubstituted, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, each Y is independently a hydrogen atom, a halogen atom, a C1 A halogenated alkyl group having 1 to 18 carbon atoms, a cyano group (-CN) or an ester group, and the average value of m is 2 to 1,000.

In an embodiment, the impact modifier is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, styrene, Acrylate, acrylonitrile, methacrylonitrile, maleic anhydride, and alkyl or phenyl nucleus-substituted maleimide may be graft copolymerized with at least one monomer.

In a specific example, the thermoplastic resin composition may have a scratch width of 260 占 퐉 or less by BSP (Ball Scratch Profile) test.

In a specific example, the thermoplastic resin composition may have a notch Izod impact strength of 30 kgf · cm / cm or more in a 1/8 "thick specimen measured according to ASTM D256.

Another aspect of the present invention relates to a molded article formed from the thermoplastic resin composition.

The present invention has the effect of providing a thermoplastic resin composition excellent in impact resistance, scratch resistance, physical properties and the like, and a molded article formed from the composition.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a base resin comprising (A1) a polycarbonate resin and (A2) a polysiloxane-polycarbonate copolymer resin; And (B) an impact modifier.

(A) Base resin

(A1) Polycarbonate resin

The polycarbonate resin according to one embodiment of the present invention is a ternary copolymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3).

[Chemical Formula 1]

(2)

(3)

In Formula 3, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and m and n are each independently an integer of 0 to 4.

In the present specification, the term "substituted" means that the hydrogen atom is a halogen group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, ≪ / RTI >

In a specific example, the repeating unit represented by the formula (1) may be contained in an amount of 1 to 69 mol%, for example, 2 to 59 mol% in 100 mol% of the polycarbonate resin, May be contained in an amount of 30 to 98 mol%, for example, 40 to 96 mol% in 100 mol% of the polycarbonate resin, and the repeating unit represented by the above-mentioned formula (3) may be contained in the polycarbonate resin in an amount of 1 to 50 mol% For example, from 2 to 30 mol%. Within the above range, the thermoplastic resin composition may have excellent physical properties such as scratch resistance and impact resistance.

In an embodiment, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 16,000 to 100,000 g / mol, for example, 16,500 to 75,000 g / mol. In the above range, the thermoplastic resin composition may have excellent impact resistance, scratch resistance, and the like.

In an embodiment, the polycarbonate resin may be produced by a conventional polycarbonate resin production method. For example, bisphenol A (BPA) represented by the following formula (4), 3,3'- (Condensation reaction, transesterification reaction, etc.) of a diol mixture comprising dimethyl bisphenol A (DMBPA) and a biphenol compound represented by the following formula (6) with a carbonate precursor.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Formula 6, R _1, R ₂ , m and n are as defined in Formula 3.

In specific examples, the biphenol compound represented by Formula 6 may be 4,4'-biphenol, 2,2'-dimethyl-4,4'-biphenol, 3,3'-dimethyl- Biphenol, 2,2 ', 6,6'-tetramethyl-4,4'-biphenol, and the like, but are not limited thereto. For example, 4,4'-biphenol can be used.

In an embodiment, the bisphenol A (BPA, Formula 4) may comprise from 1 to 69 mol%, such as from 2 to 59 mol%, of the diol mixture, and the 3,3'-dimethyl bisphenol A DMBPA (Formula 5) may be contained in an amount of 30 to 98 mol%, for example, 40 to 96 mol% in 100 mol% of the diol mixture, and the biphenol compound represented by Formula 6 may include 1 To 50 mol%, for example, 2 to 30 mol%. Within the above range, the thermoplastic resin composition may have excellent physical properties such as scratch resistance and impact resistance.

In the specific examples, examples of the carbonate precursor include phosgene, triphosgene, diaryl carbonate, mixtures thereof, and the like. Examples of the diaryl carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl Carbonate, dicyclohexyl carbonate, and the like, but the present invention is not limited thereto. These may be used alone or in combination of two or more. For example, diphenyl carbonate and the like may be used.

In embodiments, the molar ratio of the diol mixture to the carbonate precursor (diol mixture / carbonate precursor) may be 0.5 to 2.0, such as 0.7 to 1.5. And the mechanical strength and the like of the polycarbonate resin in the above range can be excellent.

In an embodiment, the reaction of the diol mixture and the carbonate precursor may be an ester exchange reaction and may proceed under reduced pressure at 150 to 360 ° C, for example 160 to 330 ° C, specifically 170 to 320 ° C. The above temperature range is preferable for decreasing the reaction rate and the side reaction of the transesterification reaction.

The transesterification reaction is carried out at a reduced pressure of not more than 750 torr, for example not more than 600 torr, specifically not more than 300 torr, more specifically not more than 100 torr, for at least 10 minutes, for example 15 minutes to 24 hours, For 15 minutes to 12 hours is preferable in reducing the reaction rate and the side reaction.

In an embodiment, the transesterification reaction may be carried out in the presence of a catalyst. As the catalyst, a catalyst used for a common ester exchange reaction can be used. For example, an alkali metal catalyst, an alkaline earth metal catalyst, or the like can be used. Examples of the alkali metal catalyst include, but are not limited to, LiOH, NaOH, and KOH. These may be used alone or in combination of two or more. The catalyst may be used in the range of 1 × 10 ^-8 to 1 × 10 ^-3 mol, for example, 1 × 10 ^-7 to 1 × 10 ^-4 mol per mol of the diol mixture. In the above range, sufficient reactivity can be obtained in the transesterification reaction, and generation of by-products by side reactions can be minimized.

In an embodiment, the polycarbonate resin may comprise 20 to 80 wt%, for example 30 to 70 wt%, of 100 wt% of the total base resin. In the above range, the thermoplastic resin composition may have excellent impact resistance, scratch resistance, and the like.

(A2) Polysiloxane-polycarbonate copolymer resin

The polysiloxane-polycarbonate copolymer resin according to one embodiment of the present invention comprises a polycarbonate block and a polysiloxane block. But is not limited to, for example, a triblock copolymer of polycarbonate block / polysiloxane block / polycarbonate block. For example, the polysiloxane-polycarbonate copolymer resin may be a polysiloxane-polycarbonate copolymer resin prepared by reacting a siloxane compound represented by the following formula (7), an aromatic dihydroxy compound, and a carbonate precursor.

(7)

In Formula 7, R ₁₃ and R ₁₄ are each independently a C 1 -C 10 alkyl group, a C 6 -C 18 aryl group, a C 1 -C 10 alkyl group having a halogen atom or an alkoxy group, or a C 6 -C 18 aryl group, A substituted or unsubstituted C2-C20 hydrocarbon group independently substituted or unsubstituted, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, each Y is independently a hydrogen atom, a halogen atom, a C1 (-CN), or an ester group, and the average value of m may be from 2 to 1,000, for example, from 4 to 120, specifically from 10 to 100.

In an embodiment, aromatic dihydroxy compounds (diphenols) may be aromatic dihydroxy compounds used in the preparation of conventional polycarbonate resins, for example, 4,4'-biphenol, 2,2- (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2- -Chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and the like. Specific examples thereof include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, Hexane and the like can be used, and 2,2-bis (4-hydroxyphenyl) propane, also referred to as bisphenol A, can be preferably used.

In the specific examples, examples of the carbonate precursor include phosgene, triphosgene, diaryl carbonate, mixtures thereof, and the like. Examples of the diaryl carbonate include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl Carbonate, dicyclohexyl carbonate, and the like, but the present invention is not limited thereto. These may be used alone or in combination of two or more. For example, diphenyl carbonate and the like may be used.

In an embodiment, the polycarbonate-polysiloxane copolymer comprises from 1 to 99% by weight, for example from 40 to 97% by weight, of a polycarbonate block derived from the aromatic dihydroxy compound and from 1 to 99 polysiloxane blocks derived from the siloxane compound By weight, for example 3 to 60% by weight. In the above range, the thermoplastic resin composition may be excellent in impact resistance, scratch resistance, appearance, and physical properties thereof.

In embodiments, the polycarbonate-polysiloxane copolymer may have a weight average molecular weight (Mw) as measured by gel permeation chromatography (GPC) of from 10,000 to 50,000 g / mol, such as from 15,000 to 30,000 g / mol. The polycarbonate-polysiloxane copolymer has a melt index (MI) of 5 to 40 g / 10 min, for example, 10 to 30 g / 10 min (measured at 300 ° C under a load of 1.2 kg) according to ISO 1133 Lt; / RTI > In the above range, a thermoplastic resin composition having excellent mechanical properties, injection fluidity, and physical properties balance thereof can be obtained.

In embodiments, the polycarbonate-polysiloxane copolymer may be prepared by conventional methods. For example, the aromatic dihydroxy compound, the carbonate precursor, and the siloxane compound can be copolymerized using interfacial condensation polymerization, emulsion polymerization, or the like. As the polycarbonate-polysiloxane copolymer, for example, commercially available products such as TARFLON FG-1700 and TARFLON RC-1700 available from Idemitsu may be used.

In an embodiment, the polysiloxane-polycarbonate copolymer resin may comprise 20 to 80 wt%, for example 30 to 70 wt%, of 100 wt% of the total base resin. In the above range, the thermoplastic resin composition may be excellent in impact resistance, scratch resistance, appearance, and physical properties thereof.

(B) impact modifier

The impact modifier according to one embodiment of the present invention may be a core-shell graft copolymer. The core-shell graft copolymer is formed by forming a shell by graft-copolymerizing a vinyl polymer monolith with a rubber polymer core. (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, propyl (meth) acrylate and the like can be obtained by polymerizing at least one of an acrylate monomer, a silicone monomer and a diene monomer, At least one monomer selected from the group consisting of butyl (meth) acrylate, styrene, alpha-methylstyrene, alkyl substituted styrene, acrylonitrile, methacrylonitrile, maleic anhydride and alkyl or phenyl core substituted maleimide is graft copolymerized with a rubbery polymer It may be manufactured.

In an embodiment, the acrylate-based monomer is at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, And the like. Examples of the silicon-based monomer include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetra And cyclosiloxanes such as cyclopentylsiloxane, octylphenylcyclotetrasiloxane, and the like, but not limited thereto. Examples of the curing agent used in polymerizing the rubbery polymer include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate or 1,4-butylene glycol dimethacrylate, Allyl methacrylate, triallyl cyanurate, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane and the like can be used.

In the specific example, the rubbery polymer may be a silicone-acrylate rubber such as polydimethylsiloxane / butyl acrylate rubber (PDMS / BA) or the like, but is not limited thereto.

In an embodiment, the average particle size (Z-average) of the rubbery polymer may be from 0.05 to 6 탆, for example from 0.1 to 1 탆. In the above range, an impact modifier capable of exhibiting excellent polymerization efficiency upon graft polymerization and exhibiting excellent impact resistance and appearance characteristics can be obtained.

In the specific examples, the monomer forming the shell is preferably a (meth) acrylate monomer such as methylmethacrylate (MMA), ethyl methacrylate or propyl methacrylate, and specifically, methyl methacrylate Can be used.

In an embodiment, the impact modifier may be one obtained by graft copolymerizing 50 to 200 parts by weight, for example, 60 to 150 parts by weight of the shell component with respect to 100 parts by weight of the rubbery polymer (core). An impact modifier capable of realizing excellent impact resistance, fluidity and appearance characteristics in the above range can be obtained.

In an embodiment, the content of the impact modifier may be 1 to 10 parts by weight, for example, 2 to 8 parts by weight, based on 100 parts by weight of the base resin. In the above range, the impact resistance, fluidity, appearance and the like of the thermoplastic resin composition can be excellent.

The thermoplastic resin composition according to one embodiment of the present invention may further contain conventional additives as required. Examples of the additives include, but are not limited to, a flame retardant, a filler, an antioxidant, a dripping inhibitor, a lubricant, a releasing agent, a nucleating agent, an antistatic agent, a stabilizer, a pigment, a dye and mixtures thereof. When the additive is used, the content thereof may be 0.001 to 10 parts by weight based on 100 parts by weight of the base resin, but is not limited thereto.

The thermoplastic resin composition according to one embodiment of the present invention may have a scratch width of 260 탆 or less, for example, 200 to 260 탆, specifically 210 to 258 탆, according to BSP (Ball Scratch Profile) test, and according to ASTM D256 The notched Izod impact strength of the 1/8 "thick specimen measured by the above method may be 30 kgf · cm / cm or more, for example, 30 to 90 kgf · cm / cm, specifically 30 to 70 kgf · cm / cm.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition of the present invention can be produced by a known method for producing a thermoplastic resin composition. For example, after mixing the above components and other additives as necessary, they may be melt-extruded in an extruder to produce pellets. The produced pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. The molded article is excellent in impact resistance, scratch resistance, flowability (molding processability), appearance, balance of physical properties thereof, and is thus useful as an automobile part or an interior / exterior material of an electric / electronic product. In particular, it can be used for interior / exterior materials such as mobile phones and notebooks.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Example

The specifications of each component used in the following examples and comparative examples are as follows.

(A) Base resin

(A1) Polycarbonate resin

A polycarbonate resin (ternary copolymer) prepared by the following method was used.

, 0.3 kg of 2,2-bis (4-hydroxyphenyl) propane (BPA), 2.70 kg of 3,3'-dimethyl bisphenol A (DMBPA), 0.28 kg of 4,4'-biphenol, 2.92 kg of diphenyl carbonate, After 200 ppb (relative to 1 mol of BPA) was added to the reactor in turn, nitrogen was used to remove oxygen in the reactor. Next, the temperature of the reactor was raised to 160 캜, held for 2 hours, and reacted at 190 캜 for 6 hours. The temperature was raised again to 210 ° C and held at a pressure of 100 torr for 1 hour. Next, the temperature of the reactor was raised to 260 占 폚, held at a pressure of 20 torr for 1 hour, maintained at a pressure of 0.5 torr for 1 hour to prepare a molten polycarbonate resin. (Weight average molecular weight: 30,000 g / mol) using a pelletizer.

(A2) Polysiloxane-polycarbonate copolymer resin

Polysiloxane-polycarbonate copolymer resin (Si-PC, trade name: Idemitsu, product name: TARFLON FG-1700) was used.

(A3) Acrylic resin

NCF-30, a modified acrylic copolymer resin obtained by copolymerizing a mixture of phenyl methacrylate and methyl methacrylate with butyl methacrylate and divinyltetramethyldisilonic acid was used.

(A4) Polycarbonate resin

A polycarbonate resin (binary copolymer) prepared by the following method was used.

0.3 kg of 2,2-bis (4-hydroxyphenyl) propane (BPA), 2.70 kg of 3,3'-dimethyl bisphenol A (DMBPA), 2.92 kg of diphenyl carbonate, and 200 ppb of KOH , And then nitrogen was used to remove oxygen in the reactor. Next, the temperature of the reactor was raised to 160 캜, held for 2 hours, and reacted at 190 캜 for 6 hours. The temperature was raised again to 210 ° C and held at a pressure of 100 torr for 1 hour. Next, the temperature of the reactor was raised to 260 占 폚, held at a pressure of 20 torr for 1 hour, maintained at a pressure of 0.5 torr for 1 hour to prepare a molten polycarbonate resin. (Weight average molecular weight: 30,000 g / mol) using a pelletizer.

(A5) Polycarbonate resin

A polycarbonate resin (binary copolymer) prepared by the following method was used.

2.70 kg of 2,2-bis (4-hydroxyphenyl) propane (BPA), 0.3 kg of 4,4'-biphenol, 2.92 kg of diphenyl carbonate and 200 ppb of KOH (relative to 1 mol of BPA) After that, nitrogen was used to remove oxygen in the reactor. Next, the temperature of the reactor was raised to 160 캜, held for 2 hours, and reacted at 190 캜 for 6 hours. The temperature was raised again to 210 ° C and held at a pressure of 100 torr for 1 hour. Next, the temperature of the reactor was raised to 260 占 폚, held at a pressure of 20 torr for 1 hour, maintained at a pressure of 0.5 torr for 1 hour to prepare a molten polycarbonate resin. (Weight average molecular weight: 30,000 g / mol) using a pelletizer.

(B) impact modifier

An impact modifier (manufactured by Mitsubishi Rayon Corporation, product name: S-2100) having a core (rubbery polymer) of PDMS / BA and a shell of MMA was used.

Example  1 to 3 and Comparative Example  1 to 3: Preparation of Thermoplastic Resin Composition

The above components were added to a twin screw type extruder having an L / D of 36 and a diameter of 45 mm according to the composition and content of the following Table 1, and then melted and extruded at 230 to 240 ° C and a stirring speed of 250 rpm To prepare pellets. The prepared pellets were dried at 90 DEG C for 3 hours or more and then ejected from a screw extruder (150 tons single injector) at 240 to 280 DEG C to prepare specimens. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Melt-flow index (MI, unit: g / 10 min): Measured under a load of 10 kg at 250 占 폚 according to the evaluation method specified in ASTM D1238.

(2) Notched Izod Impact Strength (Unit: kgf · cm / cm): The notched Izod impact strength of a 1/8 "thick specimen was measured based on the evaluation method specified in ASTM D256.

(3) Evaluation of scratch resistance (unit: 占 퐉) Using a Ball Scratch Profile (BSP) test method, a 2.5 mm thick specimen was subjected to a load of 1 kg and a spherical metal having a diameter of 0.7 mm The surface of the applied scratches was subjected to a scratch with a length of 10 mm to 20 mm using a tip of a surface profiler (manufacturer: Ambios Co., Ltd., device name: XP-1) The profile of the scratch was measured through a surface scan using a tip of a metal stylus having a diameter of 탆 and a scratch width (unit: 占 퐉) as a measure of scratch resistance was determined from the measured scratch profile. At this time, as the measured scratch width decreases, the scratch resistance is superior.

(4) Evaluation of Appearance Characteristic: After a cell phone bracket specimen having two gates of 5 cm × 10 cm × 0.7 cm was injected, oblique welds were observed in the middle of the specimen, And the presence or absence of a different color was confirmed.

Example Comparative Example One 2 3 One 2 3 4 5 (A)
(weight%) (A1) 40 60 65 - - 60 - - (A2) 60 40 35 54 35 40 40 40 (A3) - - - 46 65 - - - (A4) - - - - - - 60 - (A5) - - - - - - - 60 (B) (parts by weight) 3 3 7 7 7 - 3 3 Melt flow index 17.5 24.2 23.1 74.8 90.1 25.0 25.0 25.0 Notch Izod impact strength 40 32 51 10 3 4 2 70 Scratch width 252 250 257 274 258 243 241 320 Whether it is welded or not Not occurring Not occurring Not occurring Occur Occur Not occurring Not occurring Not occurring

Parts by weight based on 100 parts by weight of the base resin (A)

From the above results, it can be seen that the thermoplastic resin composition according to the present invention is excellent in impact resistance, scratch resistance, flowability (molding processability) and appearance characteristics.

On the other hand, when the acrylic copolymer was used in place of the polycarbonate resin (ternary copolymer) of the present invention (Comparative Examples 1 and 2), it was found that the impact resistance and appearance characteristics were lowered. When the impact modifier was not included Comparative Example 3), the impact resistance is greatly reduced. Further, in the case of using a polycarbonate resin (binary copolymer) containing only the repeating units of the formulas (1) and (2) instead of the polycarbonate resin (ternary copolymer) containing the repeating units of the formulas (1), (Comparative Example 4), impact resistance and the like were lowered. In the case of using the polycarbonate resin (binary copolymer) containing only the repeating units of the formulas (1) and (3) (Comparative Example 5) Able to know.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (8)

A base resin comprising a polycarbonate resin and a polysiloxane-polycarbonate copolymer resin comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3); And
An impact modifier,
The thermoplastic resin composition according to ASTM D1238, wherein the melt flow index measured at 250 占 폚 under a load of 10 kg is 17.5 to 24.2 g / 10 min.
[Chemical Formula 1]

(2)

(3)

In Formula 3, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and m and n are each independently an integer of 0 to 4.
The method of claim 1, wherein the polycarbonate resin is contained in an amount of 20 to 80% by weight based on the total weight of the base resin, the polysiloxane-polycarbonate copolymer resin is included in 20 to 80% by weight of the total base resin, And 1 to 10 parts by weight based on 100 parts by weight of the base resin.
The polycarbonate resin according to claim 1, wherein the repeating unit represented by Formula 1 is contained in 1 to 69 mol% of the polycarbonate resin, and the repeating unit represented by Formula 2 is contained in the polycarbonate resin in an amount of 30 to 98 mol% , And the repeating unit repeating unit represented by the formula (3) is contained in an amount of 1 to 50 mol% in the polycarbonate resin.
The thermoplastic resin composition according to claim 1, wherein the polysiloxane-polycarbonate copolymer resin is prepared by reacting a siloxane compound represented by the following formula (7), an aromatic dihydroxy compound, and a carbonate precursor:
(7)

In Formula 7, R ₁₃ and R ₁₄ are each independently a C 1 -C 10 alkyl group, a C 6 -C 18 aryl group, a C 1 -C 10 alkyl group having a halogen atom or an alkoxy group, or a C 6 -C 18 aryl group, A substituted or unsubstituted C2-C20 hydrocarbon group independently substituted or unsubstituted, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, each Y is independently a hydrogen atom, a halogen atom, a C1 A halogenated alkyl group having 1 to 18 carbon atoms, a cyano group (-CN) or an ester group, and the average value of m is 2 to 1,000.
The impact modifier according to claim 1, wherein the impact modifier is one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, styrene, Wherein the thermoplastic resin composition is a graft copolymer obtained by graft copolymerizing at least one monomer selected from styrene, acrylonitrile, methacrylonitrile, maleic anhydride, and alkyl or phenyl nucleus-substituted maleimide.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a scratch width of 260 占 퐉 or less by BSP (Ball-type Scratch Profile) test.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of not less than 30 kgf · cm / cm in a 1/8 "thick specimen measured according to ASTM D256.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 7.