KR20200066480A - High-gloss polycarbonate resin composition with excellent chemical resistance, mechanical properties and light resistance, and product comprising the same - Google Patents

Abstract

The present invention relates to a high-gloss polycarbonate resin composition excellent in chemical resistance, mechanical properties and light resistance, and a molded article comprising the same. The present invention, particularly, relates to a polycarbonate resin composition for non-coating parts, which can be used for applications such as automotive interior materials for non-coating parts. The polycarbonate resin composition comprises a polycarbonate resin, a polysiloxane-polycarbonate copolymer, a polyester resin, an MBS-based impact modifier having a core/shell structure, and a carbon black masterbatch.

Description

High-gloss polycarbonate resin composition with excellent chemical resistance, mechanical properties and light resistance, and product comprising the same}

The present invention relates to a high-gloss polycarbonate resin composition having excellent chemical resistance, mechanical properties, and light resistance, and a molded article comprising the same, and more particularly, to a non-coating polycarbonate resin composition that can be used for applications such as automotive interior materials for uncoating.

Since the polycarbonate resin composition exhibits improved processability while maintaining excellent impact resistance, heat resistance, and mechanical strength, it is generally used widely in automotive parts, computer housings, or other office equipment housings, and due to the characteristics of these applications, paint properties and excellent processability Is required.

In recent years, in the fields of automobiles, electrical and electronics, and industrial materials, there is an increasing demand for materials that are lightweight and have various functionalities, and the utilization of resins such as plastic parts in conventional metal and crosslinked rubber parts is increasing.

In particular, there have been attempts to improve the physical properties of polycarbonates by blending other thermoplastic resins with polycarbonate (PC) resins having excellent mechanical properties, impact resistance and heat resistance.

For example, U.S. Patent No. 3,218,372 discloses a resin composition in which polycarbonate and polyalkylene terephthalate are mixed to lower melt viscosity and improve ductility than polyalkylene terephthalate, but the composition has poor compatibility with resins. There is a problem that it becomes opaque and the impact strength decreases.

In addition, U.S. Patent No. 4,391,954 discloses a resin composition composed of a copolyester consisting essentially of repeat units derived from a mixture of polycarbonate and isophthalic acid, terephthalic acid and 1,4-cyclohexanedimethanol, Sufficient impact strength cannot be obtained with the composition.

In addition, U.S. Patent No. 4,634,737 discloses a resin composition composed of an ester-bonded copolymerized polycarbonate and a copolyester composed of isophthalic acid, terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol and an olefin-acrylate copolymer. However, it also does not provide sufficient impact strength.

In addition, U.S. Patent No. 4,188,314 discloses a sheet molding comprising polycarbonate and copolyester derived from isophthalic acid, terephthalic acid and 1,4-cyclohexanedimethanol, and having improved chemical resistance. Again, it does not provide sufficient impact strength.

In addition, PC/ABS (polycarbonate/acrylonitrile butadiene styrene) resins have weak chemical resistance to external chemicals, and when they come into contact with chemicals such as fragrances and sunscreens, physical and chemical reactions between chemicals and PC/ABS resins Through this, surface damage and product damage may occur. To compensate for this, attempts have been made to enhance the chemical resistance of PC/ABS resins by adding crystalline resins, but in this case, the mechanical/physical properties requirements for use as interior materials for vehicles, such as PC/ABS stiffness, impact resistance and heat resistance, are not satisfied. Did not.

Therefore, while using the existing polycarbonate, while improving the chemical resistance, and at the same time, while maintaining mechanical properties such as impact resistance, and exhibits excellent light resistance and high gloss, the uncoated polycarbonate resin composition can be used for applications such as automotive interior materials for uncoating Development of the situation is necessary.

The present invention is intended to solve the problems of the prior art as described above, while satisfying mechanical properties such as impact resistance, heat resistance, and mechanical strength, has improved chemical resistance, exhibits light resistance and high gloss, and has excellent injection appearance. It is a technical problem to provide a non-coating polycarbonate resin composition that can be used for such purposes.

The present inventors studied to solve the above technical problems, and as a result, polysiloxane-polycarbonate copolymer and polyester resin were alloyed with polycarbonate resin, and core/shell structured MBS-based impact modifier and carbon black masterbatch were prepared. When added, the chemical resistance can be improved, and the present invention was completed by knowing that it exhibits light resistance and high gloss properties without deteriorating mechanical properties.

Therefore, the present invention is (A) 15 to 65% by weight of polycarbonate resin, (B) 10 to 45% by weight of polysiloxane-polycarbonate copolymer, (C) 10 to 45% by weight of polyester resin, (D) core/shell structure It provides a polycarbonate resin composition, comprising 1 to 10% by weight of MBS-based impact modifier, (E) 1.5 to 8.5% by weight of the carbon black masterbatch.

According to another aspect of the present invention, a molded article comprising the polycarbonate resin composition is provided.

The polycarbonate resin composition according to the present invention satisfies mechanical properties such as impact resistance, heat resistance, and mechanical strength, and has improved chemical resistance, exhibits light resistance and high gloss, and also satisfies injection appearance, thereby exhibiting excellent physical property balance.

Therefore, the polycarbonate resin composition according to the present invention and the molded article containing the same are widely used in the fields of electric and electronic, industrial materials, and automobile interior parts, and are particularly suitable for use in automotive interior materials for uncoating.

The present invention (A) 15 to 65% by weight of polycarbonate resin, (B) 10 to 45% by weight of polysiloxane-polycarbonate copolymer, (C) 10 to 45% by weight of polyester resin, (D) core/shell structure MBS-based impact modifier 1 to 10% by weight, (E) a carbon black master batch containing 1.5 to 8.5% by weight, relates to a polycarbonate resin composition.

According to another aspect of the present invention, a molded article comprising the polycarbonate resin composition is provided.

As used herein, the term "reaction product" refers to a substance formed by the reaction of two or more reactants.

In addition, the English letter "R" used to represent hydrogen, halogen atoms, and/or hydrocarbon groups, etc. in the formulas described herein has a subscript represented by a number, but the "R" is a subscript. It is not limited by. The "R" represents, independently of each other, hydrogen, a halogen atom, and/or a hydrocarbon group. For example, regardless of whether two or more "R"s have the same or different numbers of subscripts, these "Rs" may represent the same hydrocarbon group or different hydrocarbon groups.

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

(A) Polycarbonate resin

Aromatic polycarbonate resin is preferable as the polycarbonate resin that can be included in the resin composition of the present invention, but if the technical idea of the present invention can be realized, the type is not particularly limited, and the thermoplastic aromatic commonly used in the art Polycarbonate resins can be used.

In one embodiment, the aromatic polycarbonate resin may be prepared from divalent phenols, carbonate precursors, and molecular weight modifiers. The divalent phenols are one of the monomers constituting the aromatic polycarbonate resin, and may be represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

X is an alkylene group, a straight, branched or cyclic alkylene group having no functional group, or a straight, branched or cyclic alkylene including functional groups such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, and isobutylphenyl. Group. Preferably, X may be a linear, branched or cyclic alkylene group having 3 to 6 carbon atoms.

R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, such as a straight, branched, or 3 to 20 carbon atoms (preferably 3-6) cyclic alkyl group.

n and m independently represent the integer of 0-4.

Non-limiting examples of the divalent phenols include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxy Phenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1, 1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis (4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), and the like. Preferably, bisphenol A can be used.

The carbonate precursor is another monomer constituting the aromatic polycarbonate resin, and non-limiting examples include carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate, and dimethyl carbonate. . Preferably, carbonyl chloride (phosgene) can be used.

As the molecular weight modifier, a monofunctional compound similar to a monomer used in the production of a thermoplastic aromatic polycarbonate resin may be used. Non-limiting examples of the molecular weight modifier include phenol-based derivatives (eg, para-isopropylphenol, para-tert-butylphenol (PTBP), para-cumyl phenol, para-isooctylphenol, Para-isononyl phenol, etc.), aliphatic alcohols, and the like. Preferably, para-tert-butylphenol (PTBP) can be used.

Examples of such aromatic polycarbonate resins prepared from divalent phenols, carbonate precursors, and molecular weight regulators include linear polycarbonate resins, branched polycarbonate resins, copolycarbonate resins, and polyester carbonate resins. , These may be used alone or in combination of two or more.

The aromatic polycarbonate resin may have a preferred viscosity average molecular weight (Mv, measured in a 25°C methylene chloride solution) of 15,000 to 40,000, more preferably 17,000 to 30,000, and most preferably 20,000 to 30,000. If the viscosity average molecular weight of the aromatic polycarbonate resin is 15,000, mechanical properties such as impact strength and tensile strength may be significantly reduced, and if 40,000, the melt viscosity may increase, resulting in problems in processing of the resin.

The polycarbonate resin is included in an amount of 15 to 65% by weight based on the total weight of the composition of the present invention, more preferably 15 to 60% by weight, even more preferably 15 to 50% by weight Can be. When the content of the polycarbonate resin in the composition is less than 15% by weight, the effect of improving physical properties such as transparency, fluidity, heat resistance, and impact strength at room temperature may be negligible. Conversely, when the content of the polycarbonate resin exceeds 65% by weight, flame retardancy and low temperature impact Strength may be lowered.

(B) Polysiloxane -Polycarbonate copolymer

The resin composition of the present invention comprises a polysiloxane-polycarbonate copolymer. According to a preferred embodiment of the present invention, the polysiloxane-polycarbonate resin included in the resin composition of the present invention includes a hydroxy terminal siloxane of Formula 2 and a polycarbonate block of Formula 3 as repeating units.

[Formula 2]

In Chemical Formula 2,

R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or an aryl group. For example, the halogen atom may be Cl or Br, the alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, It may be ethoxy or propoxy, and the aryl group may be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl.

R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms. For example, R ₂ is an alkyl group or an alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, It may be an aralkyl group or an aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or an alkaryloxy group having 7 to 13 carbon atoms.

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms.

A is X or NH-X-NH, where X is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group (for example, a cycloalkylene group having 3 to 6 carbon atoms), or a halogen atom, an alkyl group, an alkoxy A mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, which is unsubstituted or substituted with a group, an aryl group, or a carboxyl group. For example, X is an aliphatic group substituted or unsubstituted with a halogen atom, an aliphatic group containing oxygen, nitrogen or sulfur atoms in the main chain, or aryl which may be derived from bisphenol A, lesocinol, hydroquinone or diphenylphenol. It may be a Ren group, for example, it may be represented by the following formulas 2a to 2h.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Formula 2g]

[Formula 2h]

m independently represents an integer of 0 to 10, preferably an integer of 0 to 4.

n independently represents an integer of 2 to 1,000, preferably an integer of 2 to 500, more preferably an integer of 5 to 100.

In one embodiment, the hydroxy-terminated siloxane of Chemical Formula 2 may be a reaction product of a hydroxy-terminated siloxane of Chemical Formula 2-1 and an acyl compound (ie, a hydroxy-terminated siloxane having an ester bond).

[Formula 2-1]

In Formula 2-1, R ₁ , R ₂ , R ₃ , m and n are as defined in Formula 2 above.

For the hydroxy-terminated siloxane of Formula 2-1, for example, a compound of Formula 2-2 having a double bond with a hydroxy group and a compound of Formula 2-3 containing silicon are used by using a platinum catalyst: It can be prepared by synthesis in a molar ratio of 1.

[Formula 2-2]

In Formula 2-2, R ₁ and m are the same as defined in Formula 2 above, and k represents an integer of 1 to 7.

[Formula 2-3]

In Formula 2-3, R ₂ and n are as defined in Formula 2 above.

)를 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다. 또한 상기 화학식 2-1의 히드록시 말단 실록산의 제조와 관련하여 미국특허 US 6,072,011호를 참조할 수 있다.Specifically, Dow Corning's siloxane monomer as the hydroxy-terminated siloxane of Formula 2-1 (

) May be used, but is not limited thereto. Also, reference may be made to US Pat. No. 6,072,011 in connection with the preparation of the hydroxy-terminated siloxane of Formula 2-1.

The acyl compound used in the preparation of the hydroxy-terminated siloxane of Formula 2 may have, for example, an aromatic, aliphatic or mixed structure containing both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms, and when it is aliphatic, it may have 1 to 20 carbon atoms. In addition, the acyl compound may further include a halogen, oxygen, nitrogen or sulfur atom.

In another embodiment, the hydroxy-terminated siloxane of Formula 2 may be a reaction product of the hydroxy-terminated siloxane of Formula 2-1 and a diisocyanate compound (ie, a hydroxy-terminated siloxane having a urethane bond).

Here, the diisocyanate compound is, for example, 1,4-phenylenediisocyanate (1,4-phenylenediisocyanate), 1,3-phenylenediisocyanate (1,3-phenylenediisocyanate) or 4,4'- methylenediphenyl di It may be an isocyanate (4,4'-methylenediphenyl diisocyanate).

The polysiloxane-polycarbonate resin included in the resin composition according to the present invention is to include a polycarbonate block of the following formula 3 as a repeating unit in addition to the hydroxy-terminated siloxane of the above-mentioned formula (2).

[Formula 3]

In Chemical Formula 3,

R ₄ is an alkyl group having 1 to 20 carbon atoms (eg, an alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (eg, cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (eg, alkenyl group having 2 to 13 carbon atoms), An alkoxy group (for example, an alkoxy group having 1 to 13 carbon atoms), a halogen atom, or an aromatic hydrocarbon group having 6 to 30 carbon atoms substituted or unsubstituted with nitro.

Here, the aromatic hydrocarbon group may be derived from a compound having the structure of Formula 3a.

[Formula 3a]

In Chemical Formula 3a,

X is an alkylene group, a straight, branched or cyclic alkylene group having no functional group, or a straight, branched or cyclic alkylene including functional groups such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, and isobutylphenyl. Group. Preferably, X may be a linear, branched or cyclic alkylene group having 3 to 6 carbon atoms.

Each R ₆ independently represents a hydrogen atom, a halogen atom, or an alkyl group, such as a linear, branched or 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms), a cyclic alkyl group.

n and m independently represent the integer of 0-4.

The compound of Formula 3a is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl) )-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1 -Bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis( 4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy Phenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)nonane, 2,2- Bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-fluoro-4-hydroxyphenyl)propane, 4-methyl-2,2-bis(4-hydroxyphenyl)pentane , 4,4-bis(4-hydroxyphenyl)heptane, diphenyl-bis(4-hydroxyphenyl)methane, Resorcinol, Hydroquine, 4,4'-dihydroxyphenyl ether [Bis(4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether , Bis(3,5-dimethyl-4-hydroxyphenyl) ether, bis(3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1, 4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4- Hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis (4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,4-bis(4-hydroxyphenyl)butane , 1,4-bis(4-hydr Oxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxy) Phenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5- Dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methyl-butane , 4,4'-thiodiphenol [bis(4-hydroxyphenyl)sulfone], bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3-chloro-4-hydroxyphenyl)sulfone , Bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4-hydroxyphenyl) Sulfide, bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4,4'- Dihydroxybenzophenone, 4,4'-dihydroxy diphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. Representative of these is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols (dihydric phenol) may refer to U.S. Pat. Can be used.

In one preferred embodiment, the polysiloxane-polycarbonate copolymer has a structure of the following formula 4a or 4b.

[Formula 4a]

[Formula 4b]

In Formulas 4a and 4b, R ₁ , R ₂ , R ₃ , m and n are as defined in Formula 2 above, R ₄ is as defined in Formula 3 above, and l represents an integer of 1 to 20.

In the polysiloxane-polycarbonate resin, the content ratio of the hydroxy-terminated siloxane:polycarbonate block is preferably 50 to 99:50 to 1 in a neutral ratio. If the relative content of the siloxane portion in the resin is less than this, flame retardancy and low-temperature impact strength may be lowered. Conversely, if it is more than this, physical properties such as transparency, fluidity, heat resistance, and room temperature impact strength are reduced due to a decrease in the relative content of the polycarbonate portion in the resin. Manufacturing costs may increase.

The polysiloxane-polycarbonate resin, when measured in a methylene chloride solution, preferably has a viscosity average molecular weight (M _v ) of 15,000 to 200,000, more preferably 15,000 to 70,000. If the viscosity average molecular weight of the polysiloxane-polycarbonate resin is less than 15,000, mechanical properties may be remarkably deteriorated, and if it exceeds 200,000, a problem may occur in the processing of the resin due to an increase in melt viscosity.

The polysiloxane-polycarbonate resin may be a homopolymer, a copolymer, or a blend form thereof. In addition, the polysiloxane-polycarbonate resin may be partially or completely replaced by copolycarbonate copolymerized with an aromatic polyester-carbonate resin or a silicone-based resin obtained by polymerization in the presence of an ester precursor, such as a bifunctional carboxylic acid. .

The polysiloxane-polycarbonate resin is included in an amount of 10 to 45% by weight based on the total weight of the composition of the present invention, more preferably 10 to 40% by weight, even more preferably 15 to 40% by weight It can be included as When the content of the polysiloxane-polycarbonate resin in the composition is less than 10% by weight, the effect of improving physical properties such as chemical resistance and impact strength may be insignificant. Conversely, when the content of the polysiloxane-polycarbonate resin exceeds 45% by weight, heat resistance and color reproducibility This can degrade.

(C) Polyester resin

The resin composition of the present invention includes a polyester resin for improving physical properties such as fluidity and chemical resistance.

According to one embodiment of the present invention, the polyester resin may be prepared by condensation polymerization of at least one aromatic, aliphatic or alicyclic dicarboxylic acid with at least one aliphatic or alicyclic glycol. Preferably, the aromatic dicarboxylic acid is composed of 6 to 20 carbon atoms, the aliphatic or alicyclic dicarboxylic acid is composed of 3 to 20 carbon atoms, and the aliphatic or alicyclic glycol is composed of 2 to 20 carbon atoms.

The polyester resin can be synthesized using the dicarboxylic acid compound and glycol compound as described above. The production of a polyester resin using a dicarboxylic acid compound and a glycol compound is usually carried out in two stages of an ester reaction and a polycondensation reaction, and the manufacturing process is well known in the art. Dicarboxylic acid compounds include terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, (1, 4-, 1,5-, 2,3-, 2,6- or 2,7-)naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-dibenzyldicar Acidic acids and the like can be used, but are not limited thereto. Preferably, terephthalic acid, isophthalic acid or mixtures thereof are used. Glycol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexanediol, ( 1,2-, 1,3- or 1,4-)cyclohexanedimethanol, neopentyl glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, etc. can be used, but must be limited thereto It does not work. Preferably, ethylene glycol, cyclohexanedimethanol or mixtures thereof are used.

The polyester resin may be selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, and mixtures thereof, but is not limited thereto. Preferably, a polybutylene terephthalate (PBT) resin is used which is excellent in heat resistance, chemical resistance, electrical properties, mechanical strength, and moldability, and is economical.

In the present invention, polybutylene terephthalate (PBT) is a polymer polycondensed through a direct esterification reaction or transesterification reaction using butane-1,4-diol and terephthalic acid or dimethyl terephthalate as a monomer, and the melting temperature is 215 to 235 ℃, the intrinsic viscosity (IV) is preferably 0.45 to 1.6 dl/g, more preferably 0.80 to 1.3 dl/g.

The polyester resin is included in an amount of 10 to 45% by weight based on the total weight of the composition of the present invention, more preferably 10 to 40% by weight, even more preferably 15 to 40% by weight Can be. When the content of the polyester resin in the composition is less than 10% by weight, the effect of improving chemical resistance may be insignificant, whereas, when the content of the polyester resin exceeds 45% by weight, mechanical properties and color reproducibility may be deteriorated.

(D) Core/shell structure MBS series Impact modifier

The resin composition of the present invention includes an MBS-based impact modifier having a core/shell structure to improve impact resistance among mechanical properties.

The MBS-based impact modifier of the core/shell structure is a core/shell graft copolymer serving as an additive for enhancing the impact strength of the polycarbonate resin composition.

The core-shell graft copolymer is a core-shell graft copolymer having a hard shell in which a vinyl monomer is grafted on a rubber core, preferably as a rubber core, and may be polybutadiene, preferably as the vinyl monomer It may be an alkyl methacrylate or an alkyl acrylate.

Compared with silicone-based impact modifiers commonly used in alloys of polycarbonate resins, MBS-based impact modifiers have relatively higher color reproducibility and thermal stability than silicone-based impact modifiers with a silicone rubber structure, and cycle time during injection molding. It has the advantage of being able to shorten.

The core/shell structure MBS-based impact modifier is included in an amount of 1 to 10% by weight based on the total weight of the composition of the present invention, more preferably 3 to 10% by weight, even more preferably 5 to 10 It may be included in an amount of weight percent. If the content of the impact modifier in the composition is less than 1% by weight, the effect of improving the impact strength may be negligible. Conversely, when the content of the impact modifier is more than 10% by weight, mechanical properties may be deteriorated.

(E) Carbon black masterbatch

The resin composition of the present invention includes a carbon black master batch to improve light resistance.

The carbon black master batch means a mixture in which carbon black is dispersed in a thermoplastic resin, preferably in the aforementioned polycarbonate resin. By using a carbon black masterbatch in a form in which carbon black is dispersed in a polycarbonate resin, the carbon black is easily dispersed, and light resistance can be effectively improved.

The carbon black contained in the carbon black master batch is not particularly limited, and for example, ketjen black, acetylene black, channel black, or a combination thereof may be used. It is preferable that the particle diameter of the carbon black is in the range of 10 nm to 40 nm. Although the nitrogen adsorption specific surface area (NSA) of the carbon black is not particularly limited, it is preferably 150 to 250 m ² /g, and more preferably 180 to 240 m ² /g. Here, the nitrogen adsorption specific surface area (NSA) is a value measured according to JIS K6217-2: 2001'Part 2: Determination of specific surface area-nitrogen adsorption method-single point method' for nitrogen adsorption amount on carbon black surface.

The content of carbon black in the carbon black masterbatch may be 10 to 40% by weight, preferably 15 to 40% by weight, even more preferably 15 to 30% by weight based on the total weight of the masterbatch. When the content of carbon black in the carbon black master batch is less than 10% by weight, the content of carbon black is too small to expect a synergistic effect of light resistance, and when it exceeds 40% by weight, workability may be poor.

The carbon black masterbatch is included in an amount of 1.5 to 8.5% by weight based on the total weight of the composition of the present invention, more preferably 3 to 8.5% by weight, even more preferably included in an amount of 3.5 to 6.5% by weight Can be. When the content of the carbon black master batch in the composition is less than 1.5% by weight, the light fastness improving effect may be insignificant, whereas, when the content of the carbon black master batch is greater than 8.5% by weight, mechanical properties may be deteriorated.

(F) other optional additional ingredients

To the resin composition of the present invention, other additives may be added as necessary within the range capable of achieving the object of the present invention in addition to the above-described components.

The types and contents of the other additives can be easily selected by those skilled in the art according to various purposes. In one embodiment, inorganic fillers, lubricants, antioxidants, light stabilizers, hydrolysis stabilizers, mold release agents, colorants, UV stabilizers, antistatic agents, conductive additives, magnetic additives, crosslinking agents, antibacterial agents, processing aids, anti-friction agents, abrasion resistance agents And the coupling agent may be added to the composition alone or in combination of two or more.

As the antioxidant, a phenol-type, phosphite-type, thioether-type or amine-type antioxidant may be used, and the release agent may include a fluorine-containing polymer, silicone oil, a metal salt of stearic acid, and montanic acid. Metal salts of, Montan acid ester wax or polyethylene wax can be used. In addition, a benzophenone or benzotriazole and an amine type ultraviolet stabilizer may be used as the ultraviolet stabilizer, and a dye or pigment may be used as the colorant.

The content of other additives is not particularly limited, and is included in an amount of 1 to 5% by weight, based on the total weight of the composition of the present invention, depending on the purpose of use and use, preferably 2 to 5% by weight have.

According to another aspect of the present invention, a molded article comprising the resin composition of the present invention described above is provided. The molded article satisfies mechanical properties such as impact resistance, heat resistance, and mechanical strength, and has improved chemical resistance, exhibits light resistance and high gloss, and also satisfies injection appearance, thereby exhibiting excellent physical property balance. Therefore, the molded article according to the present invention can be widely used in the field of electric and electronic, industrial materials, and automotive interior parts, and is particularly suitable as an automotive interior material for uncoating, but is not limited thereto.

The molded article according to an embodiment of the present invention is not particularly limited and can be prepared by a method commonly known in the art, for example, melt-extruding the thermoplastic resin composition in an extruder and producing pellets, or injection molding, A molded article can be manufactured by various processes such as blow molding, extrusion molding, and thermoforming.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, these examples are only for understanding the present invention, and the scope of the present invention is not limited to these examples in any sense.

[ Example And Comparative example ]

The components used in the examples and comparative examples are specifically as follows.

(A) Polycarbonate resin: Samyang Corporation 3020 PJ (Mv: 21,000)

(B) Polysiloxane-polycarbonate resin: Samyang Corporation ST4-3022 PJ (Mv: 26,000)

(C) Polyester resin: Polybutylene terephthalate having an intrinsic viscosity of 1.1 dl/g

(D-1) Core-shell type MBS impact modifier: KANEKA M732

(D-2) Core-shell type silicone impact modifier: Mitsubishi Rayon S-2001

(D-2) Core-shell type acrylic impact modifier: R & Hass EXL 2313

(E-1) Carbon black

Raven 2350 Ultra (Birla Carbon) (NSA surface area: 203 m ² /g, average particle diameter: 15 nm)

(E-2) Carbon Black Masterbatch

Prepared by dispersing the above-described carbon black in the above-mentioned (A) polycarbonate resin, (A) as a carbon black masterbatch having a weight ratio of polycarbonate: carbon black of 70:30, specifically prepared as follows.

The (A) polycarbonate resin and carbon black in a weight ratio of 70:30, L/D=48 and Φ=25mm in a twin-screw melt-kneading extruder, melt temperature 230-250°C, screw rotation speed 150 rpm, first vent ( vent) Extruded under the conditions of a pressure of about -600 mmHg and a self-feeding rate of 20 kg/h, the extruded strand was cooled in water, and then cut with a rotary cutter to prepare a carbon black masterbatch.

The polycarbonate resin, polysiloxane-polycarbonate resin, polyester resin, impact modifier, carbon black masterbatch L/D=48 and Φ=25mm as the components and contents of Examples and Comparative Examples shown in Tables 1 and 2 below It was extruded in a melt-kneading extruder under conditions of a melting temperature of 230 to 250°C, a screw rotation speed of 150 rpm, a first vent pressure of about -600 mmHg, and a self-feeding rate of 20 kg/h. The extruded strand was cooled in water, and then cut with a rotary cutter to prepare pellets.

After the hot pellets were dried at 80°C to 100°C for 4 hours, the pellets were prepared by injection molding at a cylinder temperature of 250°C to 280°C and a mold temperature of 80°C to prepare specimens, and the physical properties of each prepared sample were specified below. It was measured by the method, and the results are shown in Table 3 and Table 4.

The properties of each prepared specimen were measured by the following method.

(1) Tensile strength: evaluated according to ASTM D638.

(2) Flexural strength and modulus of elasticity: evaluated according to ASTM D790.

(3) Impact strength: evaluated according to ASTM D256 (1/4 inch thick, notch-izod).

(4) Heat deflection temperature (HDT): evaluated according to ASTM D648 with a load of 18.6 kg/cm 2.

(5) Surface impact: evaluated according to ISO 6603. (Sample thickness: 2T, drop speed: 4.4 m/s)

(6) Light resistance: Samyang company's own measurement (based on ATLAS CI 4000, irradiation amount 1,050 KJ/m ² )

(7) Glossiness: 20° specular glossiness was evaluated according to ASTM D523.

(8) Chemical resistance: ASTM D638 standard tensile specimens were tested for band strip test (7day). The evaluation strength is 1-5, and the criteria are as follows.

The polycarbonate resin composition according to the present invention can obtain improved chemical resistance, light resistance, glossiness, mechanical properties, etc. without going through a separate post-treatment process to improve the chemical resistance of the molded article. As can be seen from Table 3, the resin composition according to the embodiment of the present invention has increased chemical resistance compared to the resin composition presented in the comparative example, and at the same time, mechanical properties such as tensile strength, flexural strength, impact strength and surface impact, light resistance and gloss. All of the figures show excellent balanced properties, specifically, excellent lightfastness of 3 or less and excellent glossiness of 80 or more were realized in all compositions.

Such a polycarbonate resin composition can be suitably used as a molded article for automobiles, electrical and electronic applications, and particularly as a vehicle interior material for uncoating.

On the other hand, as can be seen in Table 4, Comparative Examples 1 and 2 can be seen that the light resistance and gloss is reduced by using a different type of impact modifier other than the MBS system. Comparative Examples 3 and 5 show very low chemical resistance and are insufficient to be applied as a non-coating material. In Comparative Example 7, impact strength was not significantly reduced because an impact modifier was not added. In the case of Comparative Examples 4 and 8, it can be seen that the content of the polysiloxane-polycarbonate resin and the impact modifier is high, so that the tensile strength, flexural strength, and flexural modulus are very low, and Comparative Example 6 has a higher polyester resin content than Example 1 It can be seen that the impact strength and light resistance are reduced. In Comparative Example 10, dispersibility was lowered by adding carbon black, not in the form of a masterbatch, so that the overall mechanical properties, light resistance, and glossiness could be reduced. In Comparative Example 9, the light resistance was lowered because the carbon black masterbatch was not added, and in Comparative Example 11, the carbon black masterbatch was added in an excessive amount, thereby showing overall low mechanical properties.

Claims (10)

(A) 15 to 65% by weight of polycarbonate resin;
(B) 10 to 45% by weight of polysiloxane-polycarbonate copolymer;
(C) 10 to 45% by weight of a polyester resin;
(D) 1 to 10% by weight of an MBS-based impact modifier having a core/shell structure; And
(E) comprising a carbon black master batch 1.5 to 8.5% by weight,
Polycarbonate resin composition. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin is an aromatic polycarbonate having a viscosity average molecular weight (Mv) of 15,000 to 40,000 when measured in a 25°C methylene chloride solution. The polycarbonate resin composition according to claim 1, wherein (B) the polysiloxane-polycarbonate copolymer comprises a hydroxy-terminated siloxane represented by Formula 2 and a polycarbonate block represented by Formula 3 as repeating units:
[Formula 2]

In Chemical Formula 2,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or an aryl group;
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms;
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms;
A is X or NH-X-NH, where X is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group, or substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group Represents a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms;
m is an integer from 0 to 4 independently;
n is independently an integer from 2 to 1,000;

[Formula 3]

In Chemical Formula 3,
R ₄ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a halogen atom, or 6 to 30 carbon atoms unsubstituted or substituted with nitro. Represents an aromatic hydrocarbon group. The polycarbonate resin composition according to claim 1, wherein the polyester resin (C) is polybutylene terephthalate. The polycarbonate resin composition according to claim 4, wherein the polybutylene terephthalate has an intrinsic viscosity (IV) of 0.45 to 1.6 dl/g. According to claim 1, (D) MBS-based impact modifier having a core/shell structure is characterized in that an alkyl methacrylate or an alkyl acrylate is grafted to a polybutadiene core, a polycarbonate resin composition. According to claim 1, (E) carbon black master batch is characterized in that the content of carbon black is 10 to 40% by weight, based on the total weight of the master batch, polycarbonate resin composition. The polycarbonate resin composition according to claim 1, wherein the specimen injection-molded from the composition exhibits light resistance of 3 or less at an irradiation amount of 1,050 KJ/m ² , and exhibits gloss of 80 or more when evaluating 20° mirror gloss. . A molded article comprising the polycarbonate resin composition of claim 1. The molded article according to claim 9, which is an automotive interior material for uncoating.