KR102175714B1 - Polycarbonate resin composition and molded articles thereof - Google Patents

Abstract

In the present invention, a copolycarbonate comprising an aromatic polycarbonate-based repeating unit and an aromatic polycarbonate-based repeating unit having at least one siloxane bond; And by including the polyarylate in an optimum mixing ratio, there is provided a polycarbonate-based resin composition and a molded article thereof having excellent weather resistance and improved appearance characteristics.

Description

Polycarbonate resin composition and its molded article TECHNICAL FIELD [POLYCARBONATE RESIN COMPOSITION AND MOLDED ARTICLES THEREOF}

The present invention relates to a polycarbonate-based resin composition and a molded article thereof having excellent weather resistance and improved appearance properties.

Polycarbonate-based resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and have excellent mechanical and thermal properties, high transparency and impact resistance, and are used as engineering plastic materials in various fields.

However, the polycarbonate-based resin is poor in chemical resistance and lacks scratch resistance and weather resistance, so it is limited to be applied to fields requiring the above characteristics. In addition, since interest in environment-friendly environment has recently increased and demand for non-painting materials is increasing due to cost reduction issues, etc., it is difficult to apply the polycarbonate resin itself.

On the other hand, a method of blending with polymethyl methacrylate (hereinafter referred to as PMMA), which is transparent and has excellent scratch resistance, has been proposed, but there is still a problem due to the low impact strength of PMMA.

Accordingly, an object of the present invention is to provide a polycarbonate-based resin composition having excellent weather resistance and improved appearance properties, and a molded article manufactured using the same.

According to an embodiment of the present invention, a weight ratio of 50:50 to 95:5 of a copolycarbonate including an aromatic polycarbonate-based repeating unit, an aromatic polycarbonate-based repeating unit having at least one siloxane bond, and a polyarylate It provides a polycarbonate-based resin composition comprising as.

In addition, according to another embodiment of the present invention, a molded article comprising the polycarbonate-based resin composition, specifically, an automobile part is provided.

The polycarbonate-based resin composition according to the present invention exhibits excellent weather resistance and appearance characteristics, and thus can be usefully used in electric and electronic parts, automobile parts, general miscellaneous goods, and the like that require such characteristics.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprises", "includes" or "have" are intended to designate the existence of a feature, step, component, or combination of the implemented features, one or more other features or steps, It is to be understood that the possibility of the presence or addition of components, or combinations thereof, is not excluded in advance.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form disclosed, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a polycarbonate-based resin composition according to a specific embodiment of the present invention and a molded article manufactured using the same will be described in more detail.

In the present invention, when the polycarbonate resin composition is prepared, a polysiloxane structure is introduced into the main chain of the polycarbonate, so that a copolycarbonate having better weather resistance compared to a conventional polycarbonate is used, and the gloss according to the use of the copolycarbonate In order to compensate for the deterioration of appearance characteristics in painting and color, by using a polyarylate having excellent transparency, heat resistance and mechanical strength characteristics and excellent UV stability by itself, the weatherability and appearance characteristics of the polycarbonate resin composition are greatly improved. Can be improved.

Specifically, the polycarbonate-based resin composition according to an embodiment of the present invention,

(a) a copolycarbonate comprising an aromatic polycarbonate-based repeating unit and an aromatic polycarbonate-based repeating unit having at least one siloxane bond; And

(b) polyarylate; and 50:50 to 95:5 in a weight ratio.

Hereinafter, each component will be described in more detail.

(a) copolycarbonate

In the present invention, the term'copolycarbonate' means a copolymer including a polycarbonate-based repeating unit in which a polysiloxane structure is not introduced into the main chain and a polycarbonate-based repeating unit in which a polysiloxane structure is introduced into the main chain.

Specifically, the copolycarbonate includes an aromatic polycarbonate-based first repeating unit having no siloxane bond represented by the following Formula 1; As the aromatic polycarbonate-based second repeating unit having one or more siloxane bonds, the repeating units respectively represented by the following Formulas 2 and 3 may be included, and optionally a repeating unit represented by the following Formula 4 may be further included:

[Formula 1]

In Formula 1,

R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is Beach and unsubstituted or phenyl-substituted C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, or CO, the

[Formula 2]

In Chemical Formula 2,

Each X ₁ is independently C _1-10 alkylene,

Each R ₅ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, C _1-10 alkoxy substituted with oxiranyl, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,

m is an integer from 1 to 200,

[Formula 3]

In Chemical Formula 3,

Each X ₂ is independently C _1-10 alkylene,

Each Y ₁ is independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,

Each R ₆ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, C _1-10 alkoxy substituted with oxiranyl, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,

n is an integer from 1 to 200,

[Formula 4]

In Chemical Formula 4,

Z ₂ is unsubstituted or substituted phenyl or a C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted by a ,

l is an integer from 1 to 10.

The copolycarbonate can simultaneously improve several physical properties by controlling the content of each repeating unit. Specifically, the weight ratio of the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 may be 1:99 to 99:1. It is preferably 3:97 to 97:3, and more preferably 5:95 to 95:5. By including the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 having a polyorganosiloxane structure in the above content ratio, the low-temperature impact strength and YI (Yellow Index) of the copolycarbonate can be simultaneously improved. The weight ratio of the repeating unit corresponds to a weight ratio of a siloxane compound, for example, a siloxane compound represented by the following formula 2-1 and a siloxane compound represented by the following formula 3-1.

In addition, the weight ratio of the total weight of the repeating unit represented by Formula 1, the repeating unit represented by Formula 2, and the repeating unit represented by Formula 3 (Chemical Formula 1: (Formula 2+ Formula 3)) is 1: 0.001 to 1:0.2, more preferably 1:0.01 to 1:0.1. By including the repeating unit represented by Formula 1, the repeating unit represented by Formula 2, and the repeating unit represented by Formula 3 at the above content ratio, the room temperature impact strength and weather resistance of the copolycarbonate may be improved. The weight ratio of the repeating unit corresponds to the weight ratio of the aromatic diol compound used to form the repeating unit of Formula 1 and the siloxane compound used to form the repeating unit of Formulas 2 and 3.

In addition, when the copolycarbonate further includes a repeating unit represented by Formula 4, the weight ratio between the repeating unit represented by Formula 1 and the repeating unit represented by Formula 4 may be 1:99 to 99:1. have. It is preferably 2:98 to 98:2, and more preferably 3:97 to 97:3. By further including the repeating unit represented by Chemical Formula 4 in the above content ratio, the fluidity of the copolycarbonate may be improved. The weight ratio of the repeating unit represented by Formula 4 corresponds to the weight ratio of the aromatic diol compound and the compound represented by Formula 4-1 below.

Specifically, the repeating unit represented by Formula 1 forms the basic skeleton of the copolycarbonate according to the present invention, and is formed by reacting an aromatic diol compound and a carbonate precursor.

In Formula 1, preferably, R ₁ to R ₄ are each independently hydrogen, methyl, chloro, or bromo.

Also preferably, Z is a linear or branched C _1-10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, Butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, Z is cyclohexane-1,1-diyl, O, S, SO, SO ₂ , or CO.

Preferably, the repeating unit represented by Formula 1 is bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl) )Sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, bisphenol A, 2,2-bis(4-hydroxyl) Roxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4- Hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2 ,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1 -From any one or more aromatic diol compounds selected from the group consisting of phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and a,ω-bis[3-(ο-hydroxyphenyl)propyl]polydimethylsiloxane It can be derived.

The meaning of “derived from an aromatic diol compound” means that the hydroxy group of the aromatic diol compound reacts with the carbonate precursor to form the repeating unit represented by Formula 1.

For example, when bisphenol A as an aromatic diol compound and triphosgene as a carbonate precursor are polymerized, the first repeating unit represented by Formula 1 is represented by Formula 1-1 below.

[Formula 1-1]

In addition, as the carbonate precursor, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl At least one selected from the group consisting of carbonate, bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformate may be used. Preferably, triphosgene or phosgene may be used.

In addition, the repeating units represented by Chemical Formulas 2 and 3 have a polyorganosiloxane structure, and are introduced into copolycarbonate to improve various physical properties, particularly low-temperature impact strength and YI.

Specifically, in Formula 2, each of X ₁ is independently C _2-10 alkylene, more preferably C _2-4 alkylene, and most preferably propane-1,3-diyl.

Also preferably, R ₅ is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxyranylmethoxy)propyl, fluoro, chloro, bromo, iodo, Methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each R ₅ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C _1-3 alkyl, and most preferably methyl.

Also preferably, m is an integer of 10 to 50. More preferably, n is 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 31 or more, or 32 or more, 50 or less, 45 or less, 40 or less, 39 or less, 38 or less, 37 or less, or It is an integer of 35 or less.

Further, in Formula 3, preferably, each of X ₂ is independently C _2-10 alkylene, more preferably C _2-6 alkylene, and most preferably isobutylene.

Also preferably, Y ₁ is hydrogen.

Also preferably, R ₆ is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxyranylmethoxy)propyl, fluoro, chloro, bromo, iodo, Methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each R ₆ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C _1-3 alkyl, and most preferably methyl.

Also preferably, n is an integer of 40 to 100. More preferably, m is 40 or more, 45 or more, 50 or more, 55 or more, 56 or more, 57 or more, or 58 or more, and 100 or less, 80 or less, 75 or less, 70 or less, 65 or less, 64 or less, 63 Or an integer of 62 or less.

The repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 are derived from a siloxane compound represented by Formula 2-1 and a siloxane compound represented by Formula 3-1, respectively:

[Formula 2-1]

In Formula 2-1, the definitions of X ₁ , R ₅ and m are as previously defined.

[Formula 3-1]

In Formula 3-1, the definitions of X ₂ , Y ₁ , R ₆ and n are as previously defined.

The meaning of'derived from a siloxane compound' means that the hydroxy group of each of the siloxane compounds reacts with the carbonate precursor to form a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 . In addition, the carbonate precursor that can be used to form the repeating unit of Formulas 2 and 3 is as described in the carbonate precursor that can be used to form the repeating unit of Formula 1 described above.

Preferably, the repeating unit represented by Formula 2 is represented by the following Formula 2-2:

[Formula 2-2]

In Formula 2-2, R ₅ and m are as defined above. Preferably, R ₅ is methyl.

Also preferably, the repeating unit represented by Formula 3 is represented by the following Formula 3-2:

[Chemical Formula 3-2]

In Formula 3-2, R ₆ and n are as defined above. Preferably, R ₆ is methyl.

Meanwhile, the repeating unit represented by Chemical Formula 4 has a Sebacoyl structure and may be introduced into copolycarbonate to improve fluidity.

In Formula 4, preferably, Z ₂ is a straight or branched C _1-10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, or propane-2 ,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, Z ₂ is cyclohexane-1,1-diyl, O, S, SO, SO ₂ , or CO.

Preferably, the repeating unit represented by Formula 4 is represented by the following Formula 4-1.

[Formula 4-1]

The repeating unit represented by Formula 4 is formed by reacting a composition comprising a compound represented by Formula 4-2, an aromatic diol compound, and a carbonate precursor:

[Formula 4-2]

In Formula 4-2,

R And R'is each independently hydrogen, OH, C _1-10 alkyl, or halogen, and l is as defined above.

In addition, the aromatic diol compound and the carbonate precursor are the same as described above in the aromatic diol compound and carbonate precursor that can be used to form the repeating unit of Formula 1.

The copolycarbonate according to the present invention has a weight average molecular weight of 1,000 to 100,000 g/mol, preferably 10,000 to 70,000 g/mol, and more preferably 30,000 to 60,000 g/mol. By satisfying the weight average molecular weight range of the above range, excellent processability can be exhibited without deteriorating mechanical strength.

The copolycarbonate having the above structure may be prepared by polymerizing the aromatic diol compound, the siloxane compound represented by Formulas 2-1 and 3-1, and the carbonate precursor, for example, and the content and polymerization of each repeating unit The above-described physical properties can be implemented through the control of conditions.

(b) polyarylate

The polyarylate is a polyester composed of repeating units derived from aromatic dicarboxylic acids and repeating units derived from bisphenols, and has excellent transparency, heat resistance, and mechanical strength characteristics. In addition, since it has UV stability itself, it has excellent weather resistance.

The polyarylate according to the present invention can be prepared by known methods such as melt polymerization or interfacial polymerization of aromatic dicarboxylic acids and bisphenols.

As the aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5 -Naphthalene dicarboxylic acid, methyl terephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyl ether dicarboxylic acid, 4,4 '-Diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl isopropylidene dicarboxylic acid, 1,2-bis(4-carboxyphenoxy ) Ethane, or 5-sodium sulfoisophthalic acid, and the like, and any one or a mixture of two or more of them may be used. Among the above compounds, terephthalic acid or isophthalic acid may be preferable, and a mixture of terephthalic acid and isophthalic acid may be used in consideration of the effect of improving melt processability and mechanical properties.

In addition, examples of the bisphenol include 2,2-bis(4-hydroxyphenyl) propane (bisphenol A), 4,4'-(3,3,5-trimethyl cyclohexylidene) diphenol, 2, 2-bis(4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis(4-hydroxy -3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4' -Dihydroxybenzophenone (diphenyl ketone), 4,4'-dihydroxy diphenylmethane, or 1,1-bis(4-hydroxyphenyl) cyclohexane, and the like, any one of them or Mixtures of two or more may be used. Among the above compounds, 2,2-bis(4-hydroxyphenyl) propane may be used when considering excellent polymerizability, and 4,4'-(3,3,5-trimethyl cyclohexyl) may be used when considering the effect of improving heat resistance. Silidene) diphenol can be used.

The polyarylate having the above structure has a weight average molecular weight of 12,000 to 30,000 g/mol, preferably 15,000 to 30,000 g/mol, and more preferably 20,000 to 25,000 g/mol. By having a weight average molecular weight in the above range, it exhibits excellent weatherability and excellent compatibility with the copolycarbonate described above.

In the polycarbonate-based resin composition according to an embodiment of the present invention, the copolycarbonate and polyarylate may be included in a weight ratio of 50:50 to 95:5. If the amount of polycarbonate is less than 50 parts by weight, there is a concern that impact resistance may decrease, and if it exceeds 90 parts by weight, weather resistance, scratch resistance, and chemical resistance may decrease. Preferably, the copolycarbonate and polyarylate may be included in a weight ratio of 50:50 to 80:20, more preferably 70:30 to 80:20.

(c) additive

The polycarbonate-based resin composition according to an embodiment of the present invention may further include one or more additives selected from the group consisting of a heat stabilizer, an ultraviolet stabilizer, and a lubricant.

The heat stabilizer serves to improve appearance characteristics by preventing discoloration of the polycarbonate-based resin composition, and specifically, a diphosphite-based compound may be used.

Specifically, as the diphosphite compound, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite (Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol -di-phosphite), or bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Bis (2,4-dicumylphenyl) pentaerythritol di-phosphite), and the like, any one or two or more Mixtures can be used. Among them, it has excellent thermal stability and hydrolysis resistance compared to various heat stabilizers used in conventional resin compositions, shows better weather resistance in a high temperature and high humidity environment, and has better compatibility with the above-described copolycarbonate and polyarylate. Bis(2,4-dicumylphenyl)pentaerythritol diphosphite can be more preferably used because it can exhibit the effect of improving the appearance characteristics of the resin composition.

The heat stabilizer may be included in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of the total weight of the copolycarbonate and polyarylate described above. When the content of the heat stabilizer is included within the above range, it may exhibit an effect of improving appearance characteristics in addition to excellent weatherability. More preferably, it may be included in an amount of 0.5 to 1.5 parts by weight based on 100 parts by weight of the total weight of the copolycarbonate and polyarylate.

In addition, as the ultraviolet stabilizer, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-, which exhibits the maximum absorption wavelength (λmax) in the wavelength range of 380nm to 270nm. tert-butyl-2'-hydroxyphenyl) benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2-(2-hydroxy-5-(1,1) ,3,3,tetramethylbutyl)phenyl) benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-benzotriazole, 2-(3'- tert-butyl-2'-hydroxyphenyl-5'-methylphenyl)-5-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole , 2-(2'-hydroxy-4'-octyloxyphenylphenyl)-5-benzotriazole or 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole Benzotriazole-based compounds such as; Or a triazine type such as 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine Compounds, and any one or a mixture of two or more of these may be used. These UV stabilizers exhibit excellent UV stabilizer effects and excellent compatibility with the above-described copolycarbonates and polyarylates, thereby further improving the weather resistance of the resin composition.

According to an embodiment of the present invention, it may be preferable to mix and use two types of UV-absorption wavelength bands different among the above-described ultraviolet stabilizers, and specifically, the maximum absorption wavelength (λmax) in the wavelength range of 350 nm and 310 nm. Weather resistance can be further improved by mixing and using the benzotriazole-based compound shown and a triazine-based compound exhibiting the maximum absorption wavelength (λmax) in the wavelength range of 340 nm and 270 nm. More specifically, the benzotriazole-based compound and the triazine-based compound may be mixed and used in a weight ratio of 1:1 to 2:1, and when mixed at the mixing ratio described above, weather resistance can be further improved without deteriorating physical properties of the resin composition.

The ultraviolet stabilizer may be included in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the total weight of the copolycarbonate and polyarylate, and more preferably 0.5 to 2.5 parts by weight. When included in the above content range, weather resistance can be further improved without deteriorating physical properties of the resin composition.

In addition, as the lubricant, an ester-based lubricant, more specifically an aliphatic ester-based lubricant, which exhibits excellent compatibility with the above-described copolycarbonate and polyarylate and can further improve the appearance characteristics of the resin composition, may be used. As the ester-based lubricant, Octadecanoic acid, 2,2-bis[(1-oxooctadecyl)oxy]methyl]1,3-propanediyl ester, etc. may be used, and may be commercially obtained and used such as NOF's Unister H-476. have.

The lubricant may be included in an amount of 0.5 to 5.0 parts by weight based on 100 parts by weight of the total weight of the copolycarbonate and polyarylate, more preferably 2.0 to 4.0 parts by weight. When included in the above content range, it is possible to further improve the scratch resistance of the resin composition.

In addition to the above additives, the polycarbonate-based resin composition according to an embodiment of the present invention, as long as the physical properties of the resin are not damaged, other additives such as flame retardants, inorganic fillers, colorants, Or it may further include one or more other additives such as a hydrolysis resistant agent. The above additives may be included in an appropriate amount according to the use within a range that does not impair the physical properties of the resin composition, specifically 20 parts by weight or less based on 100 parts by weight of the total weight of the copolycarbonate and polyarylate, More preferably, it may be included in an amount of 1 to 10 parts by weight.

Specifically, the flame retardant may include phosphorus-based flame retardants such as phosphoric acid ester, halogen-containing phosphoric acid ester, condensed phosphoric acid ester, polyphosphate, red phosphorus, and the like; Or brominated polystyrene, brominated polyphenylene ether, brominated bisphenol-type epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromo biphenyl, brominated polycarbonate, park And halogen-based flame retardants such as rorocopentadecane, brominated crosslinked aromatic polymer, and the like, and any one or a mixture of two or more of them may be used.

In addition, the inorganic fillers include zinc sulfate, potassium hydrogen sulfate, aluminum sulfate, antimony sulfate, sulfate ester, potassium sulfate, cobalt sulfate, sodium hydrogen sulfate, iron sulfate, copper sulfate, sodium sulfate, nickel sulfate, barium sulfate, magnesium sulfate, and sulfuric acid. Metal sulfate compounds such as ammonium; Titanium compounds such as titanium oxide; carbonate compounds such as potassium carbonate; Metal hydroxide compounds such as aluminum hydroxide and magnesium hydroxide; Alternatively, silica-based compounds such as synthetic silica and natural silica may be used. In addition, calcium aluminate, gypsum dihydrate, zinc borate, barium borate, sodium acetate, molybdenum compound, zirconium compound, antimony compound and its modified products, silicon dioxide Or composite fine particles of aluminum oxide, and any one or a mixture of two or more of them may be used.

As the colorant, a dye or a pigment may be used.

Specifically, the polycarbonate-based resin composition according to an embodiment of the present invention comprises an aromatic polycarbonate-based repeating unit, a copolycarbonate including an aromatic polycarbonate-based repeating unit having at least one siloxane bond, and a polyarylate 50: Included in a weight ratio of 50 to 80:20, and selected from the group consisting of 0.5 to 1.5 parts by weight of a diphosphite thermal stabilizer, benzotriazole and triazine based on 100 parts by weight of the total weight of the copolycarbonate and polyarylate 0.5 to 2.5 parts by weight of an ultraviolet stabilizer and 2.0 to 4.0 parts by weight of an ester-based lubricant may be further included. As described above, as the constituent components and their content ranges are optimized, the improvement in weather resistance and appearance properties of the resin composition may be further improved.

The polycarbonate-based resin composition according to an embodiment of the present invention is prepared by mixing the above-described components, and may be melt-kneaded to produce a molded product, thereby producing pellets. The melt-kneading is carried out by a conventional method in the technical field to which the present invention belongs, such as a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a coneder, a multi-screw extruder, etc. Can be. The temperature of the melt-kneading may be appropriately adjusted as necessary, and preferably may be adjusted to 200 to 300°C.

The polycarbonate-based resin composition having the configuration as described above may exhibit excellent weather resistance and appearance characteristics.

Specifically, the resin composition has a glossiness (20°) of 92% or more, a blackness (L*) of 4.5 or less, and a scratch resistance (dL*) of 6.0 or less. More specifically, the glossiness (20°) is 92 to 100%, the blackness (L*) is 3.0 to 4.0, and the scratch resistance (dL*) is 0.5 to 4.0.

As described above, the polycarbonate-based resin composition exhibiting excellent weather resistance and external appearance characteristics can be usefully used for various electric and electronic parts, automobile parts, and general miscellaneous goods that require such characteristics.

Accordingly, according to another embodiment of the present invention, a molded article manufactured using a polycarbonate-based resin composition is provided.

The molded article may be manufactured by extruding the above-described polycarbonate resin composition into various shapes such as various molded extrusion molded articles, extrusion molded sheets, and films. The above-described various extrusion molding methods include injection compression molding, injection press molding, gas assisted injection molding, foam molding (including supercritical fluid injection), insert molding, in-mold coating molding as well as cold runner molding and hot runner molding. , Injection molding methods such as thermal insulation mold molding, rapid heating cooling mold molding, dichroic molding, sandwich molding, and ultra-high speed injection molding. In addition, an inflation method, a calender method, a casting method, or the like can be used for forming a sheet or film. Further, it is also possible to form a heat-shrinkable tube by subjecting it to a specific stretching operation. Further, by molding the resin composition of the present invention by rotational molding or blow molding, it is also possible to obtain a hollow molded article.

Hereinafter, preferred embodiments are presented to aid understanding of the invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

The compounds used in the following examples and comparative examples are as follows:

a) Copolycarbonate (Si-PC):

PC 8000-05™ manufactured by LG Chemical Co., Ltd., which is a copolycarbonate having a weight average molecular weight of 30,500 g/mol and containing the repeating units of Formulas 1-1, 2-2, and 3-2, was used.

b) Polyarylate (PAr): U-100™ manufactured by Unitika was used (Mw: 51,400 g/mol).

c) Polymethyl methacrylate (PMMA): IH830™ of LG MMA was used.

d) heat stabilizer:

d1) As bis(2,6-di-t-butyl-4-phenyl) pentaerythritol diphosphite, ADK Stab PEP 36™ manufactured by ADEKA Corp. was used.

d2) As bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite, Doverphos S-9228™ manufactured by Dover Chemical Corp. was used.

e) UV stabilizer:

e1) Benzotriazole-based UV stabilizer: 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (Tinuvin 234™, manufactured by BASF, maximum absorption wavelength 300nm and 340nm) Was used.

e2) Benzotriazole-based UV stabilizer: 2-2'-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3,-tetramethylbutyl)phenol] (Tinuvin 360™, manufactured by BASF , Maximum absorption wavelengths 310 nm and 350 nm) were used.

e3) Triazine UV stabilizer: 2-(4,6-Diphenyl-1,3,5-triazin-2-yl)5-[(hexyl)oxy]-phenol (Tinuvin 1577™, manufactured by BASF, maximum absorption wavelength 270 nm) And 340nm) was used.

f) Lubricant: Ocatadecanoic acid, 2,2-bis[(1-oxooctadecyl)oxy]methyl]1,3-proanediyl ester (PETS-AHS™, manufactured by FACI) was used as an ester-based lubricant.

Example 1 to 8, and Comparative example 1 to 5

After mixing each component in the composition as shown in Table 1 below on a PC, using a twin-screw extruder, L/D = 42, Φ = 40, under the conditions of 270 ~ 300 ℃ barrel temperature Pellets were prepared at a rate of 50 kg per hour.

(weight%) Example Comparative example One 2 3 4 5 6 7 8 One 2 3 4 5 Si-PC 78.5 77.5 76.5 56.5 75.5 75.5 75.5 75.0 98.5 - - 78.5 46.5 PAr 20.0 20.0 20.0 40.0 20.0 20.0 20.0 20.0 - 98.5 - - 50.0 PMMA - - - - - - - - - - 98.5 20.0 - Heat stabilizer
(d1) 0.5 0.5 0.5 0.5 1.5 - - - 0.5 0.5 0.5 0.5 0.5 Thermal stabilizer (d2) - - - - - 1.5 1.5 1.5 - - - - - UV stabilizer (e1) 0.5 0.5 0.5 0.5 0.5 0.5 - - 0.5 0.5 0.5 0.5 0.5 UV stabilizer (e2) - - - - - - 0.5 1.0 - - - - - UV stabilizer (e3) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Lubricant - 1.0 2.0 2.0 2.0 2.0 2.0 2.0 - - - - 2.0

Test example

The pellets of the polycarbonate-based resin compositions prepared in Examples and Comparative Examples were dried at 100° C. for 4 hours or more, and then injection-molded and left at room temperature for 48 hours or more. Physical properties were measured in the following manner for the manufactured molded article, and the results are shown in Table 2.

1) Scratch resistance: measured by the Ericshen test method, and expressed as dL*. The lower the dL* value, the better the scratch resistance.

2) Glossiness (20°): It was measured according to ASTM D2457 method.

3) Blackness (Color): After measurement with COLOR-EYE 7000 Series (CE 7000A), it is expressed as L*. (SCE mode) The lower the L* value, the better the blackness.

4) Impact resistance: After measuring at room temperature (23° C.) and low temperature (-30° C.) according to ASTM D3763 method, it is expressed as ductility (%). At this time, the ductility should not be separated into two or more specimens, and no cracks of 10 mm or more should occur in the middle of the impact point.

5) Weather resistance: After measuring according to the ASTM D7869 method, it is expressed as dE*. The lower the dE* value, the better the weather resistance.

6) Chemical resistance: After deeping the plating solution, gloss was measured by ASTM D2457 method.

Example Comparative example One 2 3 4 5 6 7 8 One 2 3 4 5 Scratch resistance (dL*) 5.7 2.5 0.9 0.9 0.9 0.9 0.9 0.9 9.5 6.4 1.5 4.5 0.9 Gloss
(20°, %) 96 95 95 100 95 95 95 95 95 105 105 88 100 Blackness (L*) 4.0 4.0 4.0 3.3 4.0 4.0 4.0 4.1 4.5 2.4 2.7 5.0 4.1 Impact resistance (%) Room temperature 100 100 100 100 100 100 100 100 100 100 20 100 80 -30℃ 80 80 80 80 80 80 80 80 80 0 0 0 0 Weather resistance (2250hrs, dE*) 9.5 9.4 9.3 8.4 8.8 7.5 6.3 5.0 11.6 5.1 2.4 8.4 8.0 Chemical resistance
(Glossiness, %) 90 90 90 94 90 90 90 90 75 94 20 39 95

In the case of the resin composition of Comparative Example 1 containing only Si-PC as in Comparative Example 1, the impact resistance at room temperature and low temperature was excellent, but scratch resistance, weather resistance, and chemical resistance were low. In addition, the resin composition of Comparative Example 2 containing only polyarylate exhibited more improved scratch resistance, weather resistance and chemical resistance than Comparative Example 1, but the impact resistance at low temperatures was greatly reduced. In addition, the resin composition of Comparative Example 3 containing only PMMA exhibited significantly improved scratch resistance and weather resistance compared to Comparative Examples 1 and 2, but the impact resistance at room temperature and low temperature, including chemical resistance, was significantly reduced. In addition, the resin composition of Comparative Example 4 containing Si-PC having excellent impact resistance and PMMA having excellent scratch resistance, weather resistance, and chemical resistance, improved scratch resistance compared to Comparative Example 1 containing only Si-PC and Although it exhibited weather resistance, it exhibited significantly deteriorated characteristics in terms of impact resistance, chemical resistance, and gloss at low temperatures.

On the other hand, in the case of Example 1 including Si-PC and PAr, compared to Comparative Examples 1 and 2 including Si-PC or PAr, respectively, while showing improved scratch resistance, excellent impact resistance, weather resistance, chemical resistance, and glossiness And blackness, and as the content of the lubricant in the resin composition increased as in Examples 2 to 3, while maintaining excellent impact resistance, chemical resistance, gloss and blackness, scratch resistance and weather resistance were further improved.

On the other hand, in the case of Examples 3 and 4 containing Si-PC and PAr in a weight ratio of 79.3:20.7 and 58.5:41.5, respectively, excellent scratch resistance and impact resistance were exhibited, and in particular, glossiness and black color with an increase in PAr Also, the weather resistance and chemical resistance showed a more improved effect.

However, in the case of Comparative Example 5 containing Si-PC and PAr in a weight ratio of 48.2:51.8, scratch resistance, weather resistance, and chemical resistance showed the same level of effect as Example 3, but Si-PC and PAr As the optimal mixing ratio condition was not satisfied, the impact resistance at room temperature and low temperature was greatly reduced. From these results, it can be confirmed that the content range of Si-PC and PAr should be optimized in order to realize the effect according to the present invention.

In addition, from the results of Examples 5 and 6, it was confirmed that when bis(2,4-di-t-butylphenyl) pentaerythritol diphosphite was used as a heat stabilizer, it was more excellent in terms of weather resistance. From the results, weather resistance when using a mixture of a benzotriazole compound that exhibits the maximum absorption wavelength (λmax) in the wavelength range of 350nm and 310nm and a triazine compound that exhibits the maximum absorption wavelength (λmax) in the wavelength range of 340nm and 270nm It was confirmed that a better effect can be obtained in terms of. In addition, from the results of Examples 7 and 8, it was confirmed that as the content of the ultraviolet stabilizer increased, an effect of more increased weatherability could be obtained.

Claims (17)

Copolycarbonate comprising an aromatic polycarbonate-based repeating unit and an aromatic polycarbonate-based repeating unit having at least one siloxane bond, and
Including polyarylate in a weight ratio of 50:50 to 80:20,
Based on 100 parts by weight of the total weight of the copolycarbonate and polyarylate,
0.5 to 1.5 parts by weight of a heat stabilizer containing a diphosphite compound,
0.5 to 2.5 parts by weight of an ultraviolet stabilizer, and
It further comprises 2.0 to 4.0 parts by weight of an ester-based lubricant,
The ultraviolet stabilizer is a benzotriazole-based compound exhibiting a maximum absorption wavelength (λmax) in the wavelength region of 350nm and 310nm, and a triazine-based compound exhibiting the maximum absorption wavelength (λmax) in the wavelength region of 340nm and 270nm 1:1 to 2: A polycarbonate resin composition containing in a weight ratio of 1.
The method of claim 1,
The copolycarbonate includes a repeating unit represented by the following formula 1 as the aromatic polycarbonate repeating unit, and a repeating unit represented by the following formula 2 as the aromatic polycarbonate repeating unit having at least one siloxane bond, and the following formula: Polycarbonate-based resin composition comprising a repeating unit represented by 3:
[Formula 1]

In Formula 1,
R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is Beach and unsubstituted or phenyl-substituted C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, or CO, the
[Formula 2]

In Chemical Formula 2,
Each X ₁ is independently C _1-10 alkylene,
Each R ₅ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, C _1-10 alkoxy substituted with oxiranyl, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,
m is an integer from 10 to 200,
[Formula 3]

In Chemical Formula 3,
Each X ₂ is independently C _1-10 alkylene,
Each Y ₁ is independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,
Each R ₆ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, C _1-10 alkoxy substituted with oxiranyl, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,
n is an integer from 10 to 200.
The method of claim 2,
The repeating unit represented by Formula 1 is represented by the following Formula 1-1, a polycarbonate resin composition:
[Formula 1-1]

The method of claim 2,
The repeating unit represented by Formula 2 is represented by the following Formula 2-2, a polycarbonate-based resin composition:
[Formula 2-2]

In Formula 2-2, m is an integer of 10 to 50, and R ₅ is methyl.
The method of claim 2,
The repeating unit represented by Formula 3 is represented by the following Formula 3-2, a polycarbonate resin composition:
[Chemical Formula 3-2]

In Formula 3-2, n is an integer of 40 to 100, and R ₆ is methyl.
The method of claim 1,
The copolycarbonate has a weight average molecular weight of 1,000 to 100,000 g/mol, a polycarbonate-based resin composition.
The method of claim 1,
The polyarylate includes a bisphenol-derived repeating unit and an aromatic dicarboxylic acid-derived repeating unit.
The method of claim 1,
The polyarylate has a weight average molecular weight of 12,000 to 30,000 g/mol, a polycarbonate-based resin composition.
delete delete The method of claim 1,
The heat stabilizer is bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and bis(2, 4-di-tert-butyl phenyl) pentaerythritol diphosphite, comprising at least one diphosphite-based compound selected from the group consisting of, polycarbonate resin composition.
delete delete delete The method of claim 1,
The ester-based lubricant is octadecanoic acid 2,2-bis[(1-oxooctadecyl)oxy]methyl]1,3-propanediyl ester (Octadecanoic acid, 2,2-bis[(1-oxooctadecyl)oxy] methyl]1,3-propanediyl ester), a polycarbonate-based resin composition containing.
delete A molded article comprising the polycarbonate-based resin composition of any one of claims 1 to 8, 11 and 15.