KR102543266B1 - Thermoplastic resin composition and article produced therefrom - Google Patents

Abstract

The thermoplastic resin composition of the present invention includes 100 parts by weight of a polycarbonate resin; 0.1 to 2 parts by weight of a phosphite compound represented by Formula 1 below; 0.1 to 1.2 parts by weight of a hindered phenol compound represented by Formula 2 below; and 1.5 to 9 parts by weight of a silicone-based rubber-modified vinyl-based graft copolymer. The thermoplastic resin composition is excellent in (high temperature) chemical resistance, impact resistance, stiffness, balance of physical properties thereof, and the like.

Description

Thermoplastic resin composition and molded article formed therefrom

The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in (high temperature) chemical resistance, impact resistance, rigidity, balance of physical properties thereof, and the like, and a molded article formed therefrom.

For the low price and stability of mobile phones, thermoplastic resin is applied to batteries and rear covers. In particular, in the case of mobile phone back covers (existing battery covers), thin film formability and high gloss appearance are required, so inorganic materials are not reinforced. High-impact polycarbonate-based products are mainly applied.

Polycarbonate resin, which is widely used as a mobile phone material, must undergo a clear coating to realize various colors and prevent scratches, or a painting process after injection to secure the appearance. In this case, after diluting the coating solution and paint using various organic solvents, the coating solution is applied to the surface of the resin product and then dried. However, organic solvents used as diluents in this process penetrate into the polycarbonate resin and act as a cause of lowering mechanical properties such as impact resistance and rigidity. Decomposition may be accelerated.

Therefore, there is a need to develop a thermoplastic resin composition having excellent chemical resistance, impact resistance, stiffness, balance of physical properties thereof, and the like.

The background art of the present invention is disclosed in Korean Patent Publication No. 10-2010-0076643 and the like.

An object of the present invention is to provide a thermoplastic resin composition excellent in (high temperature) chemical resistance, impact resistance, rigidity, balance of physical properties thereof, 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 all be achieved by the present invention described below.

1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition is polycarbonate resin 100 parts by weight; 0.1 to 2 parts by weight of a phosphite compound represented by Formula 1 below; 0.1 to 1.2 parts by weight of a hindered phenol compound represented by Formula 2 below; and 1.5 to 9 parts by weight of a silicone-based rubber-modified vinyl-based graft copolymer:

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is a sulfur atom or an oxygen atom am;

[Formula 2]

In Formula 2, R ₉ is a linear or branched alkyl group having 8 to 22 carbon atoms, and n is 0 or 1.

2. In the first embodiment, at least one of R ₁ , R ₂ , R ₃ and R ₄ includes a branched alkyl group having 4 to 10 carbon atoms, and one of R ₅ , R ₆ , R ₇ and R ₈ The above may include a branched alkyl group having 4 to 10 carbon atoms.

3. In the embodiment 1 or 2, the phosphite compound may include a compound represented by Formula 1a below.

[Formula 1a]

4. In the above 1 to 3 embodiments, the silicone-based rubber-modified vinyl-based graft copolymer may be obtained by graft polymerization of an alkyl (meth)acrylate-based monomer to a silicone-based rubbery polymer.

5. In embodiments 1 to 4, the weight ratio of the phosphite compound and the hindered phenol compound may be 1:0.1 to 1:3.

6. In the embodiments 1 to 5, the thermoplastic resin composition may further include a maleic anhydride-modified olefin-based copolymer.

7. In the embodiments 1 to 6, the thermoplastic resin composition may include 0.1 to 2 parts by weight of the maleic anhydride-modified olefin-based copolymer based on 100 parts by weight of the polycarbonate resin.

8. In the embodiments 1 to 7, the maleic anhydride-modified olefin-based copolymer may include a maleic anhydride-modified alkylene-α-olefin copolymer obtained by polymerizing maleic anhydride into an alkylene-α-olefin copolymer. can

9. In the embodiments 1 to 8, the maleic anhydride-modified olefin-based copolymer may include at least one of a maleic anhydride-modified ethylene-butene copolymer and a maleic anhydride-modified ethylene-octene copolymer.

10. In the embodiments 1 to 9, the thermoplastic resin composition is prepared by immersing a specimen having a thickness of 1 mm in a thinner solution for 2 minutes and 30 seconds, drying it at 80 ° C. for 20 minutes, leaving it at room temperature for 24 hours, and then weighing 1 kg of The height at which the specimen is destroyed may be 70 to 100 cm, as measured by impact with a drop evaluation equipment of a DuPont drop test method using a weight.

10. In the embodiments 1 to 9, the thermoplastic resin composition may have a weight average molecular weight difference of 500 or less between the polycarbonate resins according to Formula 1 below:

[Equation 1]

Weight average molecular weight difference = Mw1 - Mw2

In Equation 1, Mw1 is the weight average molecular weight of the polycarbonate resin measured by GPC after immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds and drying it at 80 ° C. for 20 minutes, and Mw2 is the weight average molecular weight of the specimen. This is the weight average molecular weight of the polycarbonate resin measured by GPC after being allowed to stand at °C for 24 hours.

12. In the embodiments 1 to 11, the thermoplastic resin composition may have a notched Izod impact strength of 70 kgf·cm/cm or more of a 1/8″ thick specimen measured according to ASTM D256.

13. In the embodiments 1 to 12, the thermoplastic resin composition may have a flexural modulus of 20,000 kgf/cm ² or more measured for a 1/4" thick specimen under a condition of 2.8 mm/min according to ASTM D790.

14. Another aspect of the invention relates to molded articles. The molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of 1 to 13 above.

The present invention has the effect of providing a thermoplastic resin composition excellent in (high temperature) chemical resistance, impact resistance, rigidity, physical property balance thereof, and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail as follows.

The thermoplastic resin composition according to the present invention includes (A) a polycarbonate resin; (B) phosphite compounds; (C) a hindered phenolic compound; and (D) a silicone-based rubber-modified vinyl-based graft copolymer.

In this specification, "a to b" representing a numerical range is defined as "≥a and ≤b".

(A) polycarbonate resin

Polycarbonate resins used in conventional thermoplastic resin compositions may be used as the polycarbonate resin according to one embodiment of the present invention. For example, an aromatic polycarbonate resin produced by reacting diphenols (aromatic diol compounds) with precursors such as phosgene, halogen formate, and diester carbonate can be used.

In a specific embodiment, the diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1 ,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl) Propane and the like may be exemplified, but are not limited thereto. For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 1,1-bis(4-hydroxyphenyl) ) Cyclohexane can be used, and specifically, 2,2-bis(4-hydroxyphenyl)propane called bisphenol-A can be used.

In a specific embodiment, the polycarbonate resin may be used having a branched chain, for example, 0.05 to 2 mol% of a trivalent or higher multifunctional compound, specifically, 3 A branched polycarbonate resin prepared by adding a compound having two or more phenolic groups may also be used.

In embodiments, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, for example, a bifunctional carboxylic acid.

In embodiments, the polycarbonate resin may have a weight average molecular weight (Mw) of 10,000 to 50,000 g/mol, for example, 15,000 to 40,000 g/mol, as measured by gel permeation chromatography (GPC). Within the above range, the fluidity (processability) of the thermoplastic resin composition may be excellent.

(B) phosphite compounds

The phosphite compound of the present invention is applied together with a specific hindered phenolic compound, a silicone-based rubber-modified vinyl-based graft copolymer, and the like to improve (high-temperature) chemical resistance, impact resistance, and stiffness of the thermoplastic resin composition without the application of an inorganic filler. , As a thing that can improve the balance of these physical properties, etc., a phosphite compound represented by the following formula (1) can be used.

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is a sulfur atom or an oxygen atom am.

In embodiments, at least one of R ₁ , R ₂ , R ₃ and R ₄ may include a branched alkyl group having 4 to 10 carbon atoms, and at least one of R ₅ , R ₆ , R ₇ and R ₈ is It may contain a branched alkyl group having 4 to 10 carbon atoms.

In embodiments, the phosphite compound may include a compound represented by Formula 1a below.

[Formula 1a]

In embodiments, the phosphite compound may be included in an amount of 0.1 to 2 parts by weight, for example, 0.2 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. If the content of the phosphite compound is less than 0.1 part by weight based on 100 parts by weight of the polycarbonate resin, there is a concern that the (high temperature) chemical resistance of the thermoplastic resin composition may decrease, and if it exceeds 2 parts by weight, the thermoplastic resin composition There is a risk that the chemical resistance and impact resistance of the

(C) hindered phenol compounds

The hindered phenolic compound of the present invention is applied together with the phosphate compound, silicone-based rubber-modified vinyl-based graft copolymer, and the like to improve (high temperature) chemical resistance, impact resistance, stiffness, A hindered phenol compound represented by the following formula (2) can be used as a thing capable of improving the balance of physical properties thereof.

[Formula 2]

In Formula 2, R ₉ is a linear or branched alkyl group having 8 to 22 carbon atoms, and n is 0 or 1.

In embodiments, the hindered phenol compound may include alkyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate having n of 8 to 22 carbon atoms and the like.

In embodiments, the hindered phenol compound may be included in an amount of 0.1 to 1.2 parts by weight, for example, 0.1 to 1 part by weight, based on 100 parts by weight of the polycarbonate resin. When the content of the hindered phenol compound is less than 0.1 part by weight based on 100 parts by weight of the polycarbonate resin, there is a risk of deterioration in (high temperature) chemical resistance of the thermoplastic resin composition, and when it exceeds 1.2 parts by weight, the thermoplastic resin There is a possibility that the chemical resistance, impact resistance, rigidity, etc. of the composition may decrease.

In embodiments, the weight ratio (B:C) of the phosphite compound (B) and the hindered phenol compound (C) may be 1:0.1 to 1:3, for example, 1:0.2 to 1:2. Within the above range, the (high temperature) chemical resistance of the thermoplastic resin composition may be more excellent.

(D) Silicone-based rubber-modified vinyl-based graft copolymer

The silicone-based rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention is applied together with the phosphate compound, hindered phenolic compound, etc., to improve (high temperature) chemical resistance, As one capable of improving impact resistance, rigidity, balance of physical properties thereof, etc., it may be obtained by graft polymerization of a vinyl-based monomer (alkyl (meth)acrylate-based monomer, etc.) to a silicone-based rubbery polymer. The polymerization may be performed by a known polymerization method such as emulsion polymerization or suspension polymerization. In addition, the silicone-based rubber-modified vinyl-based graft copolymer may form a core (silicone-based rubbery polymer)-shell (polymer of vinyl-based monomers) structure.

In a specific embodiment, the silicone-based rubbery polymer may be prepared by polymerizing a rubbery monomer including a silicone-based monomer such as cyclosiloxane. Examples of the cyclosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrosiloxane, Octaphenylcyclotetrasiloxane and the like may be used, and as the curing agent used at this time, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, or tetraethoxysilane may be exemplified. For example, a polydimethylsiloxane (PDMS) rubbery polymer may be used as the silicone-based rubbery polymer.

In embodiments, the silicone-based rubbery polymer (rubber particle) may have an average particle size (D50) of 30 to 200 nm, for example, 50 to 100 nm, as measured by a particle size analyzer, and the silicone-based rubber-modified vinyl-based graft air The coalescence may have an average particle size (D50) of 100 to 300 nm, for example 150 to 250 nm, as measured by a particle sizer. Within this range, the thermoplastic resin composition may have excellent (low-temperature) impact resistance and appearance characteristics. Here, the average particle size was measured using a Mastersizer 2000E series (Malvern) instrument in a dry method according to a known method.

In a specific example, an alkyl (meth)acrylate-based monomer, an aromatic vinyl-based monomer, or a combination thereof may be used as the vinyl-based monomer.

In a specific embodiment, the alkyl (meth) acrylate-based monomer may be graft polymerized to the rubbery polymer, and methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, ) acrylate, etc., and epoxy group-containing alkyl (meth) acrylate-based monomers such as glycidyl (meth) acrylate and the like can be exemplified. These may be used alone or in combination of two or more.

In embodiments, the aromatic vinyl-based monomer may be graft polymerized onto the rubbery polymer, and may be selected from styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene, ethylstyrene, vinylxylene, Monochloro styrene, dichloro styrene, dibromo styrene, vinyl naphthalene, etc. can be illustrated. These may be used alone or in combination of two or more.

In a specific embodiment, the silicone-based rubber-modified vinyl-based graft copolymer is graft polymerized with an alkyl (meth)acrylate-based monomer (eg, butyl acrylate and/or methyl methacrylate) on a silicone-based rubbery polymer. A copolymer etc. can be illustrated.

In embodiments, the content of the silicone-based rubbery polymer may be 20 to 85% by weight, for example, 40 to 85% by weight, based on 100% by weight of the total amount of the silicone-based rubber-modified vinyl-based graft copolymer, and the content of the vinylic monomer is It may be 15 to 80% by weight, for example, 15 to 60% by weight, based on 100% by weight of the entire silicone-based rubber-modified vinyl-based graft copolymer. Within the above range, the thermoplastic resin composition may have excellent chemical resistance.

In embodiments, the silicone-based rubber-modified vinyl-based graft copolymer may be included in an amount of 1.5 to 9 parts by weight, for example, 2 to 8 parts by weight, based on 100 parts by weight of the polycarbonate resin. When the content of the silicone-based rubber-modified vinyl-based graft copolymer is less than 1.5 parts by weight based on 100 parts by weight of the polycarbonate resin, chemical resistance and impact resistance of the thermoplastic resin composition may deteriorate, and exceeds 9 parts by weight In the case of doing so, there is a fear that the chemical resistance, impact resistance, rigidity, etc. of the thermoplastic resin composition may decrease.

In a specific embodiment, the weight ratio (B:D) of the phosphite compound (B) and the silicone-based rubber-modified vinyl-based graft copolymer (D) is 1: 1 to 1: 25, for example 1: 4 to 1: may be 20 Within the above range, the thermoplastic resin composition may have better chemical resistance, impact resistance, and stiffness.

The thermoplastic resin composition according to one embodiment of the present invention may further include a maleic anhydride-modified olefin-based copolymer in order to further improve (high temperature) chemical resistance.

In a specific embodiment, the maleic anhydride-modified olefin-based copolymer may be a reactive olefin-based copolymer obtained by polymerizing maleic anhydride, which is a reactive functional group, to the olefin-based copolymer. For example, the maleic anhydride-modified olefin-based copolymer may be obtained by polymerizing maleic anhydride with an olefin-based copolymer in which two or more types of alkylene monomers are copolymerized. As the alkylene monomer, an alkylene having 2 to 10 carbon atoms may be used, and examples thereof may include ethylene, propylene, isopropylene, butylene, isobutylene, octene, and combinations thereof.

In a specific embodiment, the maleic anhydride-modified olefin-based copolymer may include a maleic anhydride-modified alkylene-α-olefin copolymer obtained by polymerizing maleic anhydride with an alkylene-α-olefin copolymer.

In embodiments, the maleic anhydride modified olefin-based copolymer may include a maleic anhydride modified ethylene-butene copolymer, a maleic anhydride modified ethylene-octene copolymer, a combination thereof, and the like. can

In embodiments, the maleic anhydride-modified olefin-based copolymer has a melt-flow index of 0.5 to 20 g/10 min, for example, measured under the condition of 190° C. and 2.16 kg, according to ASTM D1238. 1 to 10 g/10 min.

In embodiments, the maleic anhydride-modified olefin-based copolymer may be included in an amount of 0.1 to 2 parts by weight, for example, 0.2 to 1.5 parts by weight, based on 100 parts by weight of the polycarbonate resin. Within the above range, the thermoplastic resin composition may have better chemical resistance and high-temperature chemical resistance.

The thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of the additive include flame retardants, anti-drip agents, lubricants, nucleating agents, stabilizers, release agents, pigments, dyes, mixtures thereof, and the like, but are not limited thereto. When using the additive, the amount thereof may be 0.001 to 40 parts by weight, for example, 0.1 to 10 parts by weight, based on 100 parts by weight of the polycarbonate resin.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of pellets obtained by mixing the components and melt-extruding them at 200 to 280° C., for example, 220 to 260° C., using a conventional twin-screw extruder.

In an embodiment, the thermoplastic resin composition is prepared by immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds, drying it at 80 ° C. for 20 minutes, leaving it at room temperature for 24 hours, and then performing a DuPont drop test using a 1 kg weight. The height at which the specimen is destroyed, measured by impact with a Dupont drop test type drop evaluation equipment, may be 70 to 100 cm, for example, 72 to 98 cm.

In embodiments, the thermoplastic resin composition may have a weight average molecular weight difference of 500 or less, for example, 400 or less, between the polycarbonate resins according to Formula 1 below.

[Equation 1]

Weight average molecular weight difference = Mw1 - Mw2

In Equation 1, Mw1 is the weight average molecular weight of the polycarbonate resin measured by GPC after immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds and drying it at 80 ° C. for 20 minutes, and Mw2 is the weight average molecular weight of the specimen. This is the weight average molecular weight of the polycarbonate resin measured by GPC after being allowed to stand at °C for 24 hours.

In embodiments, the thermoplastic resin composition may have a notched Izod impact strength of 70 kgf cm/cm or more, for example, 75 to 90 kgf cm/cm of a 1/8" thick specimen measured according to ASTM D256. .

In an embodiment, the thermoplastic resin composition has a flexural modulus of 20,000 kgf/cm ² or more, for example, 20,000 to 30,000 kgf/cm, measured for a 1/4" thick specimen under the condition of 2.8 mm/min, according to ASTM D790. can be ²

A molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known to those skilled in the art to which the present invention belongs. The molded product is excellent in (high temperature) chemical resistance, impact resistance, rigidity, balance of physical properties thereof, and is useful as interior/exterior materials for electric/electronic products, interior/exterior materials for automobiles, and exterior materials for construction. In particular, it can be used for interior/exterior materials such as mobile phones and notebooks, which include painting processes such as clear coating.

Hereinafter, the present invention will be described in more detail through examples, but these examples are only for the purpose of explanation and should not be construed as limiting the present invention.

Example

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) polycarbonate resin

A bisphenol-A type polycarbonate resin having a weight average molecular weight (Mw) of 22,000 g/mol was used.

(B) phosphite compounds

(B1) A phosphite compound represented by Formula 1a was used.

[Formula 1a]

(B2) A triphenylphosphite compound was used.

(B3) A tri(2,4-di-tert-butylphenyl) phosphite compound was used.

(B4) A tri(4-methoxyphenyl)phosphite compound was used.

(C) hindered phenol compounds

(C1) Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was used.

(C2) 3,9-bis[1,1-dimethyl-2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy], which is different in structure from the phenolic compound of the present invention. Ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (manufacturer: Smitomo, product name: Sumilizer GA-80) was used.

(D) rubber-modified vinyl-based graft copolymer

(D1) A silicone rubber-modified vinyl-based graft copolymer (manufacturer: Mitsubishi Chemical, product name: Metablen S-2100) obtained by graft polymerization of acrylic monomers (BA/MMA) on a silicone-based rubber polymer (PDMS) was used.

(D2) g-ABS obtained by graft copolymerization of 55% by weight of styrene and acrylonitrile (weight ratio: 75/25) to 45% by weight of butadiene rubber having a Z-average of 310 nm was used.

(E) A maleic anhydride-modified ethylene-butene copolymer (manufacturer: Mitsui Chemicals, product name: TAFMER MH-7020) was used.

Examples 1 to 8 and Comparative Examples 1 to 11

After adding each of the above components in an amount as shown in Tables 1, 2 and 3 below, pellets were prepared by extrusion at 250 ° C. For extrusion, a twin-screw extruder with L/D = 36 and a diameter of 45 mm was used, and the pellets were dried at 100 ° C for more than 4 hours and then injected in a 10 Oz extruder (injection temperature 300 ° C) to prepare a specimen. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1, 2 and 3 below.

How to measure physical properties

(1) Evaluation of chemical resistance (impact resistance after painting): A specimen with a thickness of 1 mm was immersed in a thinner solution for 2 minutes and 30 seconds, dried at 80 ° C for 20 minutes, left at room temperature for 24 hours, and then weighed 1 kg. The height (unit: cm) at which the specimen was destroyed was measured by impact with a drop evaluation equipment of the Dupont drop test method used.

(2) High-temperature chemical resistance evaluation: According to the following formula 1, the difference in weight average molecular weight of the polycarbonate resin (whether or not the molecular weight of the resin is reduced under high temperature conditions after painting) was measured.

[Equation 1]

Weight average molecular weight difference = Mw1 - Mw2

In Equation 1, Mw1 is the weight average molecular weight of the polycarbonate resin measured by GPC after immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds and drying it at 80 ° C. for 20 minutes, and Mw2 is the weight average molecular weight of the specimen. This is the weight average molecular weight of the polycarbonate resin measured by GPC after being allowed to stand at °C for 24 hours.

(3) Notched Izod impact strength (unit: kgf cm/cm): In accordance with ASTM D256, the notched Izod impact strength of a 1/8" thick specimen was measured.

(4) Flexural modulus (FM, unit: kgf/cm ² ): According to the evaluation method specified in ASTM D790, it was measured for a 1/4" thick specimen under the condition of 2.8 mm/min.

Example One 2 3 4 5 6 7 8 (A) (parts by weight) 100 100 100 100 100 100 100 100 (B1) (parts by weight) 0.2 0.5 1.0 0.5 0.5 0.5 0.5 0.5 (B2) (parts by weight) - - - - - - - - (B3) (parts by weight) - - - - - - - - (B4) (parts by weight) - - - - - - - - (C1) (parts by weight) 0.2 0.2 0.2 0.1 1.0 0.2 0.2 0.2 (C2) (parts by weight) - - - - - - - - (D1) (parts by weight) 4 4 4 4 4 2 8 4 (D2) (parts by weight) - - - - - - - - (E) (parts by weight) - - - - - - - 0.5 Specimen fracture height (cm) 90 85 80 85 78 72 95 98 Weight average molecular weight difference 100 0 400 300 100 0 100 0 Notched Izod impact strength (kgf cm/cm) 80 79 80 81 78 80 79 82 Flexural modulus (kgf/cm ² ) 21,000 21,000 21,000 21,000 21,000 21,500 20,000 20,800

comparative example One 2 3 4 5 (A) (parts by weight) 100 100 100 100 100 (B1) (parts by weight) 0.05 2.5 - - - (B2) (parts by weight) - - 0.5 - - (B3) (parts by weight) - - - 0.5 - (B4) (parts by weight) - - - - 0.5 (C1) (parts by weight) 0.2 0.2 0.2 0.2 0.2 (C2) (parts by weight) - - - - - (D1) (parts by weight) 4 4 4 4 4 (D2) (parts by weight) - - - - - (E) (parts by weight) - - - - - Specimen fracture height (cm) 44 56 57 39 38 Weight average molecular weight difference 900 100 800 1,100 1,100 Notched Izod impact strength (kgf cm/cm) 78 69 80 80 80 Flexural modulus (kgf/cm ² ) 21,000 21,000 21,000 21,000 21,000

comparative example 6 7 8 9 10 11 (A) (parts by weight) 100 100 100 100 100 100 (B1) (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.5 (B2) (parts by weight) - - - - - - (B3) (parts by weight) - - - - - - (B4) (parts by weight) - - - - - - (C1) (parts by weight) 0.05 1.5 - 0.2 0.2 0.2 (C2) (parts by weight) - - 0.2 - - - (D1) (parts by weight) 4 4 4 One 10 - (D2) (parts by weight) - - - - - 4 (E) (parts by weight) - - - - - - Specimen fracture height (cm) 62 41 65 60 58 62 Weight average molecular weight difference 800 300 600 200 100 900 Notched Izod impact strength (kgf cm/cm) 79 68 80 72 69 70 Flexural modulus (kgf/cm ² ) 21,000 19,500 21,000 22,500 18,000 19,000

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in chemical resistance (impact resistance after painting), high temperature chemical resistance (heat stability under high temperature conditions after painting), impact resistance, stiffness, balance of physical properties thereof, and the like. there is.

On the other hand, in the case of Comparative Example 1 in which a small amount of the phosphite compound of the present invention was applied, it can be seen that chemical resistance, high temperature chemical resistance, etc. are reduced, and in the case of Comparative Example 2 in which an excessive amount of the phosphite compound of the present invention is applied, chemical resistance, It can be seen that the impact resistance is reduced, and in the case of Comparative Examples 3, 4 and 5 in which the phosphite compound (B2), (B3) or (B4) is applied instead of the phosphite compound of the present invention, chemical resistance and high temperature chemical resistance, etc. This degradation can be seen. In the case of Comparative Example 6 in which a small amount of the hindered phenol compound of the present invention was applied, it can be seen that chemical resistance and high-temperature chemical resistance were deteriorated, and in the case of Comparative Example 7 in which an excessive amount of the hindered phenol compound of the present invention was applied, chemical resistance, It can be seen that impact resistance, stiffness, etc. are reduced, and in the case of Comparative Example 8 in which the hindered phenol compound (C2) is applied instead of the hindered phenol compound of the present invention, chemical resistance and high-temperature chemical resistance are reduced. In the case of Comparative Example 9, in which a small amount of the silicone-based rubber-modified vinyl-based graft copolymer of the present invention was applied, it was found that chemical resistance, etc., was lowered. In the case of Comparative Example 11 in which g-ABS (D2) was applied instead of the silicone-based rubber-modified vinyl-based graft copolymer of the present invention, chemical resistance, high-temperature resistance It can be seen that chemical properties, stiffness, etc. are lowered.

So far, the present invention has been looked at mainly through embodiments. Those skilled in the art to which the present invention pertains will be able to understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a limiting sense. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the equivalent scope will be construed as being included in the present invention.

Claims (15)

100 parts by weight of polycarbonate resin;
0.1 to 2 parts by weight of a phosphite compound represented by Formula 1 below;
0.1 to 1.2 parts by weight of a hindered phenol compound represented by Formula 2 below; and
1.5 to 9 parts by weight of a silicone-based rubber-modified vinyl-based graft copolymer;
A specimen with a thickness of 1 mm is immersed in a thinner solution for 2 minutes and 30 seconds, dried at 80 ° C for 20 minutes, left at room temperature for 24 hours, and then evaluated by a Dupont drop test using a 1 kg weight. A thermoplastic resin composition, characterized in that the height at which the specimen is destroyed, measured by impact with the equipment, is 70 to 100 cm:
[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is a sulfur atom or an oxygen atom am;
[Formula 2]

In Formula 2, R ₉ is a linear or branched alkyl group having 8 to 22 carbon atoms, and n is 0 or 1.
The method of claim 1, wherein at least one of R ₁ , R ₂ , R ₃ and R ₄ includes a branched alkyl group having 4 to 10 carbon atoms, and at least one of R ₅ , R ₆ , R ₇ and R ₈ is A thermoplastic resin composition comprising a branched alkyl group having 4 to 10 carbon atoms.
The thermoplastic resin composition according to claim 1, wherein the phosphite compound comprises a compound represented by Formula 1a below.
[Formula 1a]

The thermoplastic resin composition according to claim 1, wherein the silicone-based rubber-modified vinyl-based graft copolymer is obtained by graft polymerization of an alkyl (meth)acrylate-based monomer onto a silicone-based rubbery polymer.
The thermoplastic resin composition according to claim 1, wherein a weight ratio of the phosphite compound and the hindered phenol compound is 1:0.1 to 1:3.
The thermoplastic resin composition according to claim 1, further comprising a maleic anhydride-modified olefin-based copolymer.
The thermoplastic resin composition according to claim 6, wherein the thermoplastic resin composition comprises 0.1 to 2 parts by weight of the maleic anhydride-modified olefin copolymer based on 100 parts by weight of the polycarbonate resin.
7. The method of claim 6, wherein the maleic anhydride-modified olefin-based copolymer comprises a maleic anhydride-modified alkylene-α-olefin copolymer obtained by polymerizing maleic anhydride into an alkylene-α-olefin copolymer. Thermoplastic resin composition.
The thermoplastic resin composition according to claim 6, wherein the maleic anhydride-modified olefin-based copolymer includes at least one of a maleic anhydride-modified ethylene-butene copolymer and a maleic anhydride-modified ethylene-octene copolymer.
delete The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a weight average molecular weight difference of 500 or less between the polycarbonate resins according to the following formula 1:
[Equation 1]
Weight average molecular weight difference = Mw1 - Mw2
In Equation 1, Mw1 is the weight average molecular weight of the polycarbonate resin measured by GPC after immersing a 1 mm thick specimen in a thinner solution for 2 minutes and 30 seconds and drying it at 80 ° C. for 20 minutes, and Mw2 is the weight average molecular weight of the specimen. This is the weight average molecular weight of the polycarbonate resin measured by GPC after being allowed to stand at °C for 24 hours.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of 70 kgf·cm/cm or more of a 1/8″ thick specimen measured according to ASTM D256.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a flexural modulus of 20,000 kgf/cm ² or more measured for a 1/4" thick specimen under a condition of 2.8 mm/min according to ASTM D790.
A molded article characterized in that it is formed from the thermoplastic resin composition according to any one of claims 1 to 9 and 11 to 13.
100 parts by weight of polycarbonate resin;
0.1 to 2 parts by weight of a phosphite compound represented by Formula 1 below;
0.1 to 1.2 parts by weight of a hindered phenol compound represented by Formula 2 below; and
1.5 to 9 parts by weight of a silicone-based rubber-modified vinyl-based graft copolymer;
A specimen with a thickness of 1 mm is immersed in a thinner solution for 2 minutes and 30 seconds, dried at 80 ° C for 20 minutes, left at room temperature for 24 hours, and then evaluated by a Dupont drop test using a 1 kg weight. The height at which the specimen is destroyed, measured by impact with the equipment, is 70 to 100 cm,
The notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 is 70 kgf cm/cm or more,
In accordance with ASTM D790, cell phone interior/exterior materials characterized in that the flexural modulus measured for a 1/4" thick specimen under the condition of 2.8 mm/min is 20,000 kgf/cm ² or more:
[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and A is a sulfur atom or an oxygen atom am;
[Formula 2]

In Formula 2, R ₉ is a linear or branched alkyl group having 8 to 22 carbon atoms, and n is 0 or 1.