KR102489738B1 - Polycarbonate resin composition with excellent chemical resistance and blackness and molded articles comprising the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition having excellent chemical resistance and blackness and a molded product including the same, and more particularly, to a polycarbonate resin, a polysiloxane-polycarbonate resin, a polyester resin, a carbon black master batch, and a zinc acetate dihydrate It relates to a polycarbonate resin composition having excellent expression of high blackness and improved chemical resistance and mechanical properties by including a water catalyst in a specific amount, and a molded article including the same.

Description

Polycarbonate resin composition with excellent chemical resistance and blackness and molded articles comprising the same

The present invention relates to a polycarbonate resin composition having excellent chemical resistance and blackness and a molded product including the same, and more particularly, to a polycarbonate resin, a polysiloxane-polycarbonate resin, a polyester resin, a carbon black master batch, and a zinc acetate dihydrate It relates to a polycarbonate resin composition having excellent expression of high blackness and improved chemical resistance and mechanical properties by including a water catalyst in a specific amount, and a molded article including the same.

Polycarbonate resin compositions are widely used in various fields because of their excellent impact resistance, heat resistance and mechanical properties.

Recently, demand for polycarbonate resin compositions with excellent impact resistance without going through a painting treatment process is increasing in order to reduce costs in interior parts in the automobile field, but the situation is that they are not commercialized as unpainted automobile parts due to their vulnerability to everyday chemicals. to be.

In particular, attempts have been made to improve the chemical resistance of polycarbonate by blending other thermoplastic resins with polycarbonate (PC) resin having excellent mechanical properties, impact resistance and heat resistance. This is presented in Patent Publication No. 10-2020-0066480, but due to the problem that the colored particles added to implement visual sensibility do not sufficiently appear due to poor compatibility of the resin, the composition becomes opaque and consequently the blackness is lowered there is a problem.

Therefore, it is possible to improve chemical resistance while using existing polycarbonate, and at the same time, maintain mechanical properties such as impact resistance, while realizing high blackness, such as a non-painting polycarbonate resin composition that can be used for applications such as automotive interior materials for non-painting. is in need of development.

An object of the present invention is to provide excellent expression of high blackness, improved chemical resistance and To provide a polycarbonate resin composition having mechanical properties and a molded article including the same.

In order to solve the above technical problem, the present invention, based on 100% by weight of the total composition, (1) 15 to 70% by weight of a polycarbonate resin; (2) 6 to 45% by weight of a polysiloxane-polycarbonate resin; (3) 6 to 45% by weight of a polyester resin; (4) 1.5 to 10% by weight of a carbon black master batch; and (5) 0.006 to 0.19% by weight of a zinc acetate dihydrate catalyst.

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

The thermoplastic resin composition of the present invention has not only excellent blackness, but also excellent chemical resistance, mechanical properties and processability, so it can be widely applied to housings of electric and electronic products, interior materials of automobiles, and parts.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention is a polycarbonate resin; polysiloxane-polycarbonate resins; polyester resin; carbon black master batch; and zinc acetate dihydrate catalysts.

(1) Polycarbonate resin

The polycarbonate resin included in the thermoplastic resin composition of the present invention is preferably an aromatic polycarbonate resin, but as long as it can implement the technical idea of the present invention, the type is not particularly limited thereto, and thermoplastics commonly used in the art Aromatic polycarbonate resins can be used.

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

[Formula 1]

In Formula 1,

X is an alkylene group, a straight, branched or cyclic alkylene group without a functional group, or a straight, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, isobutylphenyl represents a flag. Preferably, X may be a straight, branched or cyclic alkylene group having 1 to 10 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 cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms).

n and m independently represent an integer of 0 to 4;

Non-limiting examples of the dihydric 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); Bisphenol A is preferably used.

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

As the molecular weight modifier, a material already known in the art, that is, a monofunctional compound similar to a monomer used in preparing a thermoplastic aromatic polycarbonate resin may be used. Non-limiting examples of the molecular weight regulator include phenol-based derivatives (e.g., para-isopropylphenol, para-tert-butylphenol (PTBP), para-cumylphenol, para-isooctylphenol, para-isononylphenol, etc.), aliphatic alcohols, and the like. Preferably, para-tert-butylphenol (PTBP) may be used.

Examples of aromatic polycarbonate resins prepared from divalent phenols, carbonate precursors and molecular weight modifiers 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, when 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 greatly reduced, and if it is 40,000, problems may arise in processing the resin due to an increase in melt viscosity.

The content of the polycarbonate resin is 15 wt% or more, 20 wt% or more, 30 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, or 55 wt% or more based on 100 wt% of the composition of the present invention. It may be 70 wt% or less, 69 wt% or less, 68 wt% or less, 67 wt% or less, 66 wt% or less, or 65 wt% or less, for example, 15 to 70 wt%, 15 to 15 wt% 65 wt%, 20 to 65 wt%, 30 to 65 wt%, 40 to 65 wt%, 45 to 65 wt%, 50 to 65 wt%, or 55 to 65 wt%. If 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 insignificant. It can be.

(2) polysiloxane-polycarbonate resin

The resin composition of the present invention includes a polysiloxane-polycarbonate resin to improve impact resistance. 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-terminated siloxane of Formula 2 and a polycarbonate block of Formula 3 below as repeating units.

[Formula 2]

In Formula 2,

R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxyl 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 having 1 to 13 carbon atoms or a hydroxy group. For example, R ₂ is an alkyl group or 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 aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or 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, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group (e.g., a cycloalkylene group having 3 to 6 carbon atoms), or a halogen atom, an alkyl group, or an alkoxy group. group, a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, substituted or unsubstituted with an aryl group or a carboxyl group. For example, X is an aliphatic group which is unsubstituted or substituted with a halogen atom, an aliphatic group containing oxygen, nitrogen or sulfur atoms in the main chain, or an aryl which can be derived from bisphenol A, resorcinol, hydroquinone or diphenylphenol. It may be a rene group, and may be represented, for example, by the following Chemical Formulas 2a to 2h.

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

[Formula 2e]

[Formula 2f]

[Formula 2g]

[Formula 2h]

m is independently 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 Formula 2 may be a reaction product of a hydroxy-terminated siloxane of Formula 2-1 and an acyl compound (ie, 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.

The hydroxy-terminated siloxane of Formula 2-1 is, for example, a compound of Formula 2-2 having a hydroxyl group and a double bond and a compound of Formula 2-3 containing silicon using a platinum catalyst 2: It can be prepared by synthesizing at a molar ratio of 1.

[Formula 2-2]

In Formula 2-2, R ₁ and m are as defined in Formula 2 above, and k represents an integer from 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, as the hydroxy-terminated siloxane of Formula 2-1, Dow Corning's siloxane monomer (

) can be used, but is not necessarily limited thereto. Also, reference may be made to US Patent US 6,072,011 regarding the preparation of the hydroxy-terminated siloxane of Chemical Formula 2-1.

The acyl compound used in preparing the hydroxy-terminated siloxane of Chemical Formula 2 may have, for example, an aromatic, aliphatic, or mixed structure including both aromatic and aliphatic compounds. 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, hydroxy-terminated siloxane having a urethane bond).

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

The polysiloxane-polycarbonate resin included in the resin composition according to the present invention includes a polycarbonate block represented by the following Chemical Formula 3 as a repeating unit in addition to the hydroxy-terminated siloxane represented by the above-described Chemical Formula 2.

[Formula 3]

In Formula 3,

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

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

[Formula 3a]

In Formula 3a,

X is an alkylene group, a straight, branched or cyclic alkylene group without a functional group, or a straight, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, isobutylphenyl represents a flag. Preferably, X may be a straight, branched or cyclic alkylene group having 1 to 10 carbon atoms.

Each R ₆ independently represents a hydrogen atom, a halogen atom, or an alkyl group, such as a straight, branched or cyclic alkyl group having 3 to 20 (preferably 3 to 6) carbon atoms, such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

n and m independently represent an integer of 0 to 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, hydroquinone, 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-hydroxy hydroxyphenyl)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, but is not limited thereto. Representative of these is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols may be referred to US Patents US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used alone or in combination of two or more. can be used

In a preferred embodiment, the polysiloxane-polycarbonate copolymer has a structure represented by Formula 4a or 4b below.

[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 from 1 to 20.

In the polysiloxane-polycarbonate resin, the content ratio of hydroxy-terminated siloxane:polycarbonate block is preferably 50 to 99:50 to 1 in a medium ratio. If the relative content of the siloxane part in the resin is less than this, flame retardancy and low-temperature impact strength may be lowered. Manufacturing costs may increase.

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

The polysiloxane-polycarbonate resin may be a homopolymer, a copolymer, or a blend thereof. In addition, the polysiloxane-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, or a copolycarbonate obtained by copolymerization of a silicone-based resin. .

The content of the polysiloxane-polycarbonate resin may be 6% by weight or more, 7% by weight or more, 8% by weight or more, 9% by weight or more or 10% by weight or more based on the total 100% by weight of the composition of the present invention, 45% by weight % or less, 40 wt% or less, 30 wt% or less, or 20 wt% or less, and may be, for example, 6 to 45 wt%, 8 to 30 wt%, or 10 to 20 wt%. If the content of the polysiloxane-polycarbonate resin in the composition is less than 6% by weight, the effect of improving physical properties such as chemical resistance and impact strength may be insignificant. this may deteriorate.

(3) polyester resin

The thermoplastic resin composition of the present invention may include a polyester resin to improve 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 and at least one aliphatic or alicyclic glycol. Preferably, aromatic dicarboxylic acids consist of 6 to 20 carbon atoms, aliphatic or cycloaliphatic dicarboxylic acids consist of 3 to 20 carbon atoms, and aliphatic or cycloaliphatic glycols consist of 2 to 20 carbon atoms.

A polyester resin can be synthesized using a dicarboxylic acid compound and a glycol compound as described above. The production of a polyester resin using a dicarboxylic acid compound and a glycol compound is usually performed in two steps of an esterification reaction and a polycondensation reaction, and the production 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'-dibenzyldicarboxylic acid A boxylic acid or the like may be used, but is not necessarily limited thereto. Preferably, terephthalic acid, isophthalic acid or a mixture thereof is used. Examples of the glycol compound 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. may be used, but must be limited thereto. it is not going to be Preferably, ethylene glycol, cyclohexanedimethanol or a mixture thereof is used.

As the polyester resin, one selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, and mixtures thereof may be used, but is not necessarily limited thereto. Preferably, a polybutylene terephthalate (PBT) resin is used, which is excellent in heat resistance, chemical resistance, electrical properties, mechanical strength and molding processability and is advantageous in terms of economy.

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

The content of the polyester resin may be 6% by weight or more, 8% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more based on 100% by weight of the total composition of the present invention, and 45% by weight or less , 40 wt% or less, 35 wt% or less, 30 wt% or less, or 25 wt% or less, for example, 6 to 45 wt%, 10 to 35 wt%, or 20 to 25 wt%. When the content of the polyester resin in the composition is less than 6% by weight, the effect of improving chemical resistance may be insignificant, and on the contrary, when the content of the polyester resin is greater than 45% by weight, mechanical properties and color reproducibility may be deteriorated.

(4) Carbon black master batch

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

The carbon black master batch refers to a mixture in which carbon black is dispersed in a thermoplastic resin, preferably in the above-described polycarbonate resin. By using a carbon black master batch 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. The particle size of the carbon black is preferably in the range of 10 nm to 40 nm. The nitrogen adsorption specific surface area (NSA) of the carbon black is not particularly limited, but 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 obtained by measuring the amount of nitrogen adsorption on the surface of carbon black according to JIS K6217-2: 2001 "Part 2: Method for obtaining specific surface area - Nitrogen adsorption method - Disadvantage method".

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

The content of the carbon black master batch may be 1.5% by weight or more, 2% by weight or more, 3% by weight or more, 4% by weight or more, or 5% by weight or more based on 100% by weight of the total composition of the present invention, and 10% by weight Or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, or 6 wt% or less, for example, 1.5 to 10 wt%, 2 to 9 wt%, or 4 to 6 wt%. When the content of the carbon black master batch in the composition is less than 1.5% by weight, the effect of improving light resistance may be insignificant, and on the contrary, when the content of the carbon black master batch exceeds 10% by weight, mechanical properties such as impact strength may be deteriorated.

(5) zinc acetate dihydrate catalyst

The thermoplastic resin composition of the present invention may include a zinc acetate dihydrate catalyst to induce transesterification and increase compatibility of the resin. Polycarbonate and polyester used in the thermoplastic resin composition have poor compatibility, making it difficult to achieve high blackness. The present invention promotes the exchange reaction of ester bonds included in the base resin by including a catalyst to impart compatibility to the resin. This increases the transmittance of the base resin, enabling high blackness to be realized.

In general, zinc-based catalysts include zinc carboxylic salt, zinc oxide, zinc acetate, zinc acetate dihydrate, and the like. It is most preferred to use a dihydrate catalyst.

The content of the zinc acetate dihydrate catalyst may be 0.006 wt% or more, 0.007 wt% or more, 0.008 wt% or more, 0.009 wt% or more, or 0.01 wt% or more based on 100 wt% of the composition of the present invention, and 0.19 wt% or more % or less, 0.17 wt% or less, 0.15 wt% or less, 0.13 wt% or less, or 0.1 wt% or less, for example, 0.006 to 0.19 wt%, 0.008 to 0.18 wt%, or 0.01 to 0.1 wt%. If the content of the zinc acetate dihydrate catalyst in the composition is less than 0.006% by weight, the effect of implementing high blackness may be insufficient, and if the content of the catalyst is greater than 0.19% by weight, the compound is decomposed and bubbles are generated, resulting in poor appearance and heat resistance and the impact strength decreases.

(6) MBS-based impact modifier

The thermoplastic resin composition of the present invention may further include an MBS-based impact modifier to improve impact resistance among mechanical properties.

According to one embodiment of the present invention, the impact modifier may be an MBS-based impact modifier having a core/shell structure. The MBS-based impact modifier of the core/shell structure is a core/shell graft copolymer serving as an additive to enhance the impact strength of the polycarbonate resin composition.

The core/shell graft copolymer is a core/shell graft copolymer in which a hard shell is formed by grafting a vinyl monomer to a rubber core, and the rubber core may preferably be polybutadiene. Preferably, it may be an alkyl methacrylate or an alkyl acrylate.

Compared to 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 cores having a silicone rubber structure, and the cycle time during injection molding is reduced. It has the advantage of being able to shorten the .

The content of the MBS-based impact modifier of the core/shell structure may be 1% by weight or more, 2% by weight or more, 3% by weight or more, or 5% by weight or more based on 100% by weight of the total composition of the present invention, and 10% by weight Or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, or 6 wt% or less, for example, 1 to 10 wt%, 2 to 9 wt%, or 4 to 6 wt%. 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 insignificant. Conversely, if the content of the impact modifier exceeds 10% by weight, the reinforcing agent particles are white, so the brightness is high and the blackness is poor. It happens.

(7) Other additives

In addition to the components described above, other additives may be added to the thermoplastic resin composition of the present invention as needed within a range capable of achieving the object of the present invention.

The type and content 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, release agents, colorants, UV stabilizers, antistatic agents, conductivity imparting agents, magnetic imparting agents, crosslinking agents, antibacterial agents, processing aids, antifriction agents, antiwear agents And a 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 A metal salt of , montanic acid ester wax or polyethylene wax may be used. In addition, benzophenone or benzotriazole and amine-type UV stabilizers may be used as the UV stabilizer, and dyes or pigments may be used as the colorant.

In addition, other additives generally available on the market may be used.

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 and purpose of use, and may be preferably used within the range of 2 to 5% by weight. there is.

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

The molded article according to an embodiment of the present invention is not particularly limited and may be manufactured by a method commonly known in the art, for example, melting and extruding the thermoplastic resin composition in an extruder and preparing it in the form of pellets, injection molding, Molded articles 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, the scope of the present invention is not limited thereto.

[Example]

The configurations used in Examples and Comparative Examples are 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) Core/shell structure MBS-based impact modifier: KANEKA M732

(E) carbon black master batch

It was prepared by dispersing carbon black (Raven 2350 Ultra (Birla Carbon Co.) (NSA surface area: 203 m ² /g, average particle diameter: 15 nm) in the above-mentioned (A) polycarbonate resin, (A) polycarbonate: carbon black As a carbon black master batch having a weight ratio of 70:30, it was specifically prepared as follows.

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

(F) Catalyst: Zinc acetate dehydrate (Sigma Aldrich)

(F-1) catalyst: zinc acetate (Sigma Aldrich)

The zinc acetate has an insoluble property, and zinc acetate dihydrate is characterized by melting at 237° C. or uniformly dispersed in a polar solvent.

Polycarbonate resin, polysiloxane-polycarbonate resin, polyester resin, impact modifier, carbon black master batch, and catalyst as ingredients and contents of Examples and Comparative Examples shown in Tables 1 and 2 below are L/D=48 and Φ biaxial In a melt-kneading extruder, extrusion was performed under conditions of a melt temperature of 230 to 250° C., a screw rotation speed of 150 rpm, a first vent pressure of about -600 mmHg, and a self-feed rate of 20 kg/h. After cooling the extruded strand in water, it was cut with a rotary cutter to produce pellets.

The prepared pellets were dried in hot air at 80 ° C to 100 ° C for 4 hours, and then injection molded at a cylinder temperature of 250 ° C to 280 ° C and a mold temperature of 80 ° C to prepare specimens. method, and the results are shown in Tables 1 and 2.

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

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

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

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

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

(5) Blackness: The lightness L* value of a rectangular specimen (60 x 60 x 3 mm) was measured using X-rite's spectrophotometer CI 7800SE. The lower the brightness, the higher the blackness was evaluated.

(6) Chemical resistance: A band strip test (7 days) of the coating material was conducted using a tensile specimen based on ASTM D638. The evaluation intensity is 1 to 5, and the criteria are as follows.

[Table 1]

[Table 2]

As can be seen from Table 1, in Examples 1 to 7, which are the thermoplastic resin compositions of the present invention, while maintaining mechanical properties and chemical resistance appropriate for use in automotive interior parts, at the same time, to realize visual sensibility, blackness was obtained. It was confirmed that an improved polycarbonate resin composition is provided.

On the other hand, as can be seen from Table 2, if the (C) polyester resin was not included as in Comparative Examples 1 and 2, or if a small amount was included as in Comparative Example 3, the chemical resistance was poor, and as in Comparative Example 4 ( C) When the polyester resin is included in an excessive amount, the lightness becomes bright and sufficient blackness is not realized.

In addition, when a small amount of (E) carbon black masterbatch was included as in Comparative Example 5, the color was also faded and high blackness was not realized, and as in Comparative Example 6, (E) when an excessive amount of carbon black masterbatch was included In this case, the impact strength is relatively low.

As in Comparative Examples 7 and 8, when the (F) zinc acetate dihydrate catalyst was not included or included in a very small amount, the brightness was brightened and high blackness of 5.5 or less was not implemented. On the other hand, when the zinc acetate dihydrate catalyst (F) was included in an excessive amount as in Comparative Example 9, the compound in the composition was decomposed, resulting in bubbles and significantly reduced impact strength.

On the other hand, as in Comparative Examples 10 and 11, when using a catalyst different from the (F) zinc acetate dihydrate catalyst used in the present invention, even if a zinc acetate molecule that functions to induce a transesterification reaction is included, the corresponding It was confirmed that there was no catalytic effect if the material did not melt and had low compatibility with the resin system.

Claims (8)

Based on 100% by weight of the total composition,
(1) 15 to 70% by weight of a polycarbonate resin;
(2) 6 to 45% by weight of a polysiloxane-polycarbonate resin;
(3) 6 to 45% by weight of a polyester resin;
(4) 1.5 to 10% by weight of a carbon black master batch; and
(5) 0.01 to 0.1% by weight of a zinc acetate dihydrate catalyst;
Thermoplastic resin composition. The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin has a viscosity average molecular weight of 15,000 to 40,000. The thermoplastic resin composition of claim 1, wherein the polysiloxane-polycarbonate resin comprises a hydroxy-terminated siloxane of Formula 2 and a polycarbonate block of Formula 3 below as repeating units:
[Formula 2]

In Formula 2,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, or an aryl group having 6 to 10 carbon atoms;
R ₂ is independently an alkyl group or 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, or an alkenyloxy group having 2 to 13 carbon atoms. Representing an aralkyl group or aralkoxy group of 7 to 13, or an alkaryl group or alkaryloxy group of 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, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms; A cycloalkylene group having 3 to 6 carbon atoms; Or represents a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, unsubstituted or substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group,
m is independently an integer from 0 to 4;
n is an integer from 30 to 200;
[Formula 3]

In Formula 3, R ₄ is unsubstituted or substituted with 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 nitro. represents an aromatic hydrocarbon group having 6 to 30 carbon atoms. The thermoplastic resin composition according to claim 1, wherein the polyester resin is selected from polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene terephthalate resin, and mixtures thereof. The thermoplastic resin composition according to claim 1, wherein the content of carbon black in the carbon black master batch is 10 to 40% by weight based on the total weight of the master batch. The thermoplastic resin composition according to claim 1, further comprising an MBS-based impact modifier. The method of claim 1, inorganic filler, lubricant, antioxidant, light stabilizer, hydrolysis stabilizer, mold release agent, colorant, UV stabilizer, antistatic agent, conductivity imparting agent, magnetic imparting agent, crosslinking agent, antibacterial agent, processing aid, anti-friction agent, A thermoplastic resin composition further comprising an additive selected from an antiwear agent and a coupling agent and combinations thereof. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 7.