Polycarbonate resin composition and molded article produced therefrom

Abstract

A polycarbonate resin composition of the present invention comprises: about 100 parts by weight of a base resin containing about 45 to about 85 wt% of a polycarbonate resin and about 15 to about 55 wt% of a polysiloxane-polycarbonate copolymer resin; about 1.5 to about 4 parts by weight of a phosphazene compound; about 0.3 to about 1.5 parts by weight of siloxane-modified polyester; about 0.3 to about 3 parts by weight of syndiotactic polystyrene; and about 0.3 to about 1.5 parts by weight of a benzotriazole-based ultraviolet stabilizer. The polycarbonate resin composition exhibits excellent scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, and the like.

Description

Polycarbonate resin composition and molded article manufactured therefrom

[0001] The present invention relates to a polycarbonate resin composition and a molded article manufactured therefrom. More specifically, the present invention relates to a polycarbonate resin composition having excellent scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc., and a molded article manufactured therefrom.

[0002]

[0003] Resin compositions containing polycarbonate resins exhibit excellent impact resistance, toughness, transparency, thermal stability, self-extinguishing properties, and dimensional stability, making them suitable for applications in electrical / electronic products, automotive components, lenses, and glass replacement materials. However, conventional polycarbonate resins have issues such as significantly lower scratch resistance compared to glass when applied to products requiring transparency.

[0004] To solve these problems, research has been conducted to improve scratch resistance by applying a silicone-based surface modifier. However, in this case, the compatibility between the polycarbonate resin and the silicone-based surface modifier is not good, so there is a concern that mechanical properties and colorability may deteriorate.

[0005] In addition, in order to use a polycarbonate resin composition in an unpainted state, it is necessary to secure a certain level of scratch resistance, impact resistance, flame retardancy, weather resistance, etc., and colorability that can implement a desired color with the resin composition itself without painting is required.

[0006] Therefore, there is a need to develop a polycarbonate resin composition that has excellent scratch resistance, impact resistance, flame retardancy, weather resistance, and colorability (especially, deep black color).

[0007] The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2010-0076643, etc.

[0008]

[0009] The purpose of the present invention is to provide a polycarbonate resin composition having excellent scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc.

[0010] Another object of the present invention is to provide a molded product formed from the polycarbonate resin composition.

[0011] The above and other objects of the present invention can all be achieved by the present invention described below.

[0012]

[0013] 1. One aspect of the present invention relates to a polycarbonate resin composition. The polycarbonate resin composition comprises: about 100 parts by weight of a base resin comprising about 45 to about 85 weight percent of a polycarbonate resin and about 15 to about 55 weight percent of a polysiloxane-polycarbonate copolymer resin; about 1.5 to about 4 weight parts of a phosphazene compound; about 0.3 to about 1.5 weight parts of a siloxane-modified polyester; about 0.3 to about 3 weight parts of a syndiotactic polystyrene; and about 0.3 to about 1.5 weight parts of a benzotriazole-based UV stabilizer.

[0014] 2. In the above 1 specific example, the polycarbonate resin may have a melt flow index of about 5 to about 50 g / 10 min measured under conditions of 300°C and 1.2 kg according to ASTM D1238.

[0015] 3. In the above 1 or 2 specific examples, the polysiloxane-polycarbonate copolymer resin may include about 1 to about 50 wt% of a polysiloxane block and about 50 to about 99 wt% of a polycarbonate block.

[0016] 4. In the above 1 to 3 specific examples, the weight average molecular weight of the polysiloxane-polycarbonate copolymer resin may be about 10,000 to about 100,000 g / mol.

[0017] 5. In the above 1 to 4 specific examples, the phosphazene compound may be a compound represented by the following chemical formula 2:

[0018] [Chemical Formula 2]

[0019]

[0020] In the above chemical formula 2, R1, R2, R3, R4, R5 and R6 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group or a hydroxy group.

[0021] 6. In the above 1 to 5 specific examples, the siloxane-modified polyester may be a compound represented by the following chemical formula 3:

[0022] [Chemical Formula 3]

[0023]

[0024] In the above chemical formula 3, R1, R2, R3 and R4 are each independently an alkylene group having 1 to 5 carbon atoms, R5 is an alkyl group or phenyl group having 1 to 4 carbon atoms, R6 is a hydrogen atom, a hydroxy group or a methyl group, and l, m and n are each independently an integer of 1 or more.

[0025] 7. In the above 1 to 6 specific examples, R1 and R2 of the above chemical formula 3 are each -(CH2)3-, R3 and R4 are each -(CH2)5-, R5 is a methyl group, and l, m and n may be integers of 1 or more satisfying l + m : n = 15 to 20 : 25 to 35.

[0026] 8. In the above specific examples 1 to 7, the syndiotacticity of the syndiotactic polystyrene may be about 97 to about 100%.

[0027] 9. In the above 1 to 8 specific examples, the benzotriazole-based UV stabilizer can be used together with a triazine-based UV stabilizer.

[0028] 10. In the above 1 to 9 specific examples, the polycarbonate resin composition is a black quinone dye mixture applied at 0.5 parts by weight to 100 parts by weight of the base resin, and the change in brightness (ΔL) before / after the scratch resistance evaluation is measured with a colorimeter according to ISO 2409. * ) may be less than or equal to about 6.

[0029] 11. In the above 1 to 10 specific examples, the polycarbonate resin composition may have a notched Izod impact strength of about 40 to about 90 kgf·cm / cm for a 1 / 4" thick specimen measured according to ASTM D256.

[0030] 12. In the above 1 to 11 specific examples, the polycarbonate resin composition may have a total combustion time of about 30 seconds or less for a 1.5 mm thick specimen measured by the UL-94 vertical test method.

[0031] 13. In the above 1 to 12 specific examples, the polycarbonate resin composition is applied with 0.5 parts by weight of a black quinone dye mixture per 100 parts by weight of the base resin, and the initial color (L0) is measured by a colorimeter on a 50 mm × 90 mm × 3 mm sized specimen. * , a0 *, b0 * ) was measured, and the above specimens were subjected to a weathering test for 3,000 hours according to SAE J 1960, and the color (L1) was tested with a colorimeter. * , a1 * , b1 * ) is measured, and the color change (ΔE) calculated according to the following equation 1 may be about 3.8 or less:

[0032] [Formula 1]

[0033] Color change (ΔE) =

[0034] In the above equation 1, ΔL * L before and after the test * Difference in value (L1 * -L0 * ) and Δa * a before and after the test * Difference in value (a1 * - a0 * ) and Δb * b before and after the test * Difference in value (b1 * - b0 * )am.

[0035] 14. In the above 1 to 13 specific examples, the polycarbonate resin composition has a blackness (L) measured by a colorimeter for a specimen to which 0.5 parts by weight of a black quinone dye mixture was applied to 100 parts by weight of the base resin. * ) may be less than or equal to about 2.

[0036] 15. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from a polycarbonate resin composition according to any one of 1 to 14.

[0037]

[0038] The present invention has the effect of providing a polycarbonate resin composition having excellent scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc., and a molded article formed therefrom.

[0039]

[0040] Hereinafter, the present invention will be described in detail as follows.

[0041] A polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin; (B) a polysiloxane-polycarbonate copolymer resin; (C) a phosphazene compound; (D) a siloxane-modified polyester; (E) a syndiotactic polystyrene; and (F) a benzotriazole-based UV stabilizer.

[0042] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0043]

[0044] (A) Polycarbonate resin

[0045] According to one specific example of the present invention, a polycarbonate resin can be applied together with a polysiloxane-polycarbonate copolymer resin, a phosphazene compound, a siloxane-modified polyester, syndiotactic polystyrene, and a benzotriazole-based UV stabilizer to improve the scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc. of a polycarbonate resin composition, and a polycarbonate resin used in a typical thermoplastic resin composition can be used. For example, an aromatic polycarbonate resin produced by reacting a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, or carbonic diester can be used.

[0046] In specific examples, the diphenols may include, but are not limited to, 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, etc. For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane can be used, and specifically, 2,2-bis(4-hydroxyphenyl)propane, also called bisphenol-A, can be used.

[0047] In a specific example, the polycarbonate resin may be one having a branched chain, and for example, a branched polycarbonate resin may be used that is prepared by adding about 0.05 to about 2 mol% of a trivalent or higher polyfunctional compound, specifically, a compound having a trivalent or higher phenol group, to the total diphenols used in the polymerization.

[0048] In specific examples, the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, such as a difunctional carboxylic acid.

[0049] In a specific example, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 100,000 g / mol, for example, about 10,000 to about 50,000 g / mol. Within this range, the polycarbonate resin composition may have excellent impact resistance, fluidity (processability), etc.

[0050] In a specific example, the polycarbonate resin may have a melt flow index (MI) of about 5 to about 50 g / 10 min, for example, about 5 to about 30 g / 10 min, measured under conditions of 300° C. and 1.2 kg according to ASTM D1238. Within this range, the polycarbonate resin composition may have excellent impact resistance, fluidity (processability), etc. In addition, the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indices.

[0051] In a specific example, the polycarbonate resin may be included in an amount of about 45 to about 85 wt%, for example, about 50 to about 80 wt%, of the total 100 wt% of the base resin including the polycarbonate resin and the polysiloxane-polycarbonate copolymer resin. When the content of the polycarbonate resin is less than about 45 wt%, of the 100 wt% of the base resin, there is a concern that the weather resistance, etc. of the polycarbonate resin composition may be reduced, and when it exceeds about 85 wt%, there is a concern that the impact resistance, etc. of the polycarbonate resin composition may be reduced.

[0052]

[0053] (B) Polysiloxane-polycarbonate copolymer resin

[0054] A polysiloxane-polycarbonate copolymer resin according to one specific example of the present invention can be applied together with a polycarbonate resin, a phosphazene compound, a siloxane-modified polyester, syndiotactic polystyrene, and a benzotriazole-based UV stabilizer to improve scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc. of a polycarbonate resin composition, and a polysiloxane-polycarbonate copolymer resin used in a typical thermoplastic resin composition can be used.

[0055] In a specific example, the polysiloxane-polycarbonate copolymer resin comprises a polysiloxane block and a polycarbonate block. The polycarbonate block may comprise a structural unit derived from a conventional polycarbonate resin, and the polysiloxane block may comprise a structural unit represented by the following chemical formula 1.

[0056] [Chemical Formula 1]

[0057]

[0058] In the above chemical formula 1, R1 and R2 are each independently a hydrogen atom, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C1 to C20 alkoxy group, a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C3 to C30 cycloalkynyl group, a C6 to C30 aryl group, a C6 to C30 aryloxy group, or NRR' (wherein, R and R' are each independently a hydrogen atom or a C1 to C20 alkyl group).

[0059] In a specific example, the average polymerization degree of the polysiloxane block may be 30 to 50. If the average polymerization degree of the polysiloxane block is less than 30, there is a concern that the chemical resistance of the polycarbonate resin composition may be reduced, and if it exceeds 50, there is a concern that the transparency of the polycarbonate resin composition may be reduced.

[0060] In a specific example, the polysiloxane-polycarbonate copolymer resin can be produced according to a conventional method for producing a polycarbonate-polysiloxane copolymer. For example, it can be produced by reacting a polysiloxane including a structural unit represented by the above chemical formula 1 and a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, or carbonic diester. The reaction can be performed by a conventional polymerization method such as interfacial polymerization or melt polymerization, and for example, it can be performed by an interfacial polymerization method using phosgene.

[0061] In a specific example, the polysiloxane-polycarbonate copolymer resin may include, but is not limited to, about 1 to about 50 wt%, for example, about 1 to about 40 wt%, specifically about 1 to about 30 wt%, of a polysiloxane block and about 50 to about 99 wt%, for example, about 60 to about 99 wt%, specifically about 70 to about 99 wt%, of a polycarbonate block. Within this range, the impact resistance, moldability, etc. of the polycarbonate resin composition may be excellent.

[0062] In a specific example, the polysiloxane-polycarbonate copolymer resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 100,000 g / mol, for example, about 10,000 to about 50,000 g / mol, specifically about 15,000 to about 30,000 g / mol. Within this range, the polycarbonate resin composition may have excellent impact resistance, moldability, and the like.

[0063] In a specific example, the polysiloxane-polycarbonate copolymer resin may be included in an amount of about 15 to about 55 wt%, for example, about 20 to about 50 wt%, based on 100 wt% of the total base resin including the polycarbonate resin and the polysiloxane-polycarbonate copolymer resin. When the content of the polysiloxane-polycarbonate copolymer resin is less than about 15 wt%, based on 100 wt% of the base resin, there is a concern that the impact resistance, etc. of the polycarbonate resin composition may be reduced, and when it exceeds about 55 wt%, there is a concern that the weather resistance, etc. of the polycarbonate resin composition may be reduced.

[0064]

[0065] (C) Phosphazene compound

[0066] A phosphazene compound according to one specific example of the present invention can be applied together with a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, a siloxane-modified polyester, a syndiotactic polystyrene, and a benzotriazole-based UV stabilizer, etc., to improve the scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc. of the polycarbonate resin composition. For example, a cyclic phosphazene can be used.

[0067] In a specific example, the phosphazene compound may be a compound represented by the following chemical formula 2.

[0068] [Chemical Formula 2]

[0069]

[0070] In the above chemical formula 2, R1, R2, R3, R4, R5 and R6 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group or a hydroxy group.

[0071] Here, the above “substitution” means that a hydrogen atom is replaced with a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a heterocycloalkyl group having 3 to 10 carbon atoms, a heteroaryl group having 4 to 10 carbon atoms, or a combination thereof.

[0072] In addition, the substituents including the above "alkyl", "alkoxy" and other "alkyl" moieties include both straight-chain and branched forms, "alkenyl" includes both straight-chain and branched forms having 2 to 8 carbon atoms and containing at least one double bond, and the above "cycloalkyl" includes all saturated monocyclic or saturated bicyclic ring structures having 3 to 20 carbon atoms. The above "aryl" is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen atom, and includes a single or fused ring system, suitably containing 4 to 7, preferably 5 or 6 ring atoms in each ring. Specifically, examples thereof include, but are not limited to, phenyl, naphthyl, biphenyl, tolyl, etc.

[0073] The above "heterocycloalkyl" means a cycloalkyl group having 1 to 3 heteroatoms selected from N, O, and S as saturated cyclic hydrocarbon skeletal atoms, and the remaining saturated monocyclic or bicyclic ring skeletal atoms are carbon, and is selected from pyrrolidinyl, azetidinyl, pyrazolidinyl, oxazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, hydantoinyl, valerolactamyl, oxiranyl, oxetanyl, dioxolanyl, dioxanyl, oxathiolanyl, oxathianyl, dithianyl, dihydrofuranyl, tetrahydrofuranyl, dihydropyranyl, tetrahydropyranyl, tetrahydropyridinyl, tetrahydropyrimidinyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, diazepanyl, Examples include azepanil.

[0074] The above "heteroaryl" refers to an aryl group having 1 to 3 heteroatoms selected from N, O, and S as aromatic ring skeletal atoms, and the remaining aromatic ring skeletal atoms are carbon, and the heteroaryl group includes a divalent aryl group in which the heteroatom in the ring is oxidized or quaternized to form, for example, an N-oxide or a quaternary salt. Specifically, examples thereof include, but are not limited to, furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and the like.

[0075] In a specific example, the phosphazene compound may be included in an amount of about 1.5 to about 4 parts by weight, for example, about 1.5 to about 3 parts by weight, relative to about 100 parts by weight of the base resin. If the content of the phosphazene compound is less than about 1.5 parts by weight relative to about 100 parts by weight of the base resin, there is a concern that the flame retardancy, etc. of the polycarbonate resin composition may be reduced, and if it exceeds about 4 parts by weight, there is a concern that the impact resistance, heat resistance, etc. of the polycarbonate resin composition may be reduced.

[0076]

[0077] (D) Siloxane modified polyester

[0078] According to one specific example of the present invention, a siloxane-modified polyester can be applied together with a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, a phosphazene compound, a syndiotactic polystyrene, and a benzotriazole-based UV stabilizer, thereby improving the scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc. of a polycarbonate resin composition.

[0079] In a specific example, the siloxane-modified polyester may be a compound represented by the following chemical formula 3.

[0080] [Chemical Formula 3]

[0081]

[0082] In the above chemical formula 3, R1, R2, R3 and R4 are each independently an alkylene group having 1 to 5 carbon atoms, R5 is an alkyl group or phenyl group having 1 to 4 carbon atoms, R6 is a hydrogen atom, a hydroxy group or a methyl group, and l, m and n are each independently an integer of 1 or more.

[0083] In the above chemical formula 3, it is shown that all siloxane structural units are located in the center of the polymer, and ester structural units are located at both ends, but this does not specify the positions of the structural units. That is, the siloxane-modified polyester according to one specific example of the present invention may be a random copolymer as well as a block copolymer. Therefore, in the above chemical formula 3, the ester structural units and the siloxane structural units are intended to indicate that l + m and n may be included in the polymer, respectively, and each structural unit is not limited to being present at a specific position in a block form.

[0084] In a specific example, R1 and R2 of the above chemical formula 3 are each -(CH2)3-, R3 and R4 are each -(CH2)5-, R5 is a methyl group, and l, m and n may be integers of 1 or more satisfying l + m : n = 15 to 20 : 25 to 35.

[0085] In a specific example, the siloxane-modified polyester may be included in an amount of about 0.3 to about 1.5 parts by weight, for example, about 0.5 to about 1 part by weight, relative to about 100 parts by weight of the base resin. If the content of the siloxane-modified polyester is less than about 0.3 parts by weight relative to about 100 parts by weight of the base resin, there is a concern that the scratch resistance, etc. of the polycarbonate resin composition may be reduced, and if it exceeds about 1.5 parts by weight, there is a concern that the weather resistance, colorability, etc. of the polycarbonate resin composition may be reduced.

[0086]

[0087] (E) syndiotactic polystyrene

[0088] According to one specific example of the present invention, syndiotactic polystyrene can be applied together with a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, a phosphazene compound, a siloxane-modified polyester, and a benzotriazole-based UV stabilizer, thereby improving the scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc. of a polycarbonate resin composition.

[0089] Polystyrene is generally classified into atactic, isotactic, and syndiotactic structures based on the position of the benzene rings in the side chain. Atactic polystyrene has an irregular arrangement of the benzene rings, while isotactic polystyrene has the benzene rings arranged along one side of the polymer backbone. In contrast, syndiotactic polystyrene has a structure in which the benzene rings are arranged in a regular, alternating pattern.

[0090] Among these, syndiotactic polystyrene can be produced using a catalyst system comprising a metallocene catalyst and a cocatalyst, using a styrene monomer. The metallocene catalyst has a structure in which one or two cycloalkane dienyl groups (cyclopentadienyl groups, indenyl groups, fluorenyl groups, and derivatives thereof) are linked to a group Ⅳ transition metal complex of the periodic table, such as Ti, Zr, or Hf.

[0091] As a prior art for polystyrene having high stereoregularity, high melting point, and excellent molecular weight distribution, U.S. Patent No. 6,010,974 discloses a method for polymerizing styrene monomer using a new alkyl-bridged dinuclear metallocene catalyst, a silyl-bridged dinuclear metallocene catalyst, and an alkyl-silyl bridged dinuclear metallocene catalyst, and U.S. Patent No. 6,284,700 discloses a method for producing syndiotactic polystyrene using a catalyst system comprising a metallocene catalyst and a cocatalyst. The disclosures of these patents are incorporated by reference in their entirety into the present specification.

[0092] In specific examples, the syndiotacticity of the syndiotactic polystyrene may be about 97 to about 100%.

[0093] In a specific example, the syndiotactic polystyrene may be included in an amount of about 0.3 to about 3 parts by weight, for example, about 0.5 to about 1 part by weight, relative to about 100 parts by weight of the base resin. If the amount of the syndiotactic polystyrene is less than about 0.3 parts by weight relative to about 100 parts by weight of the base resin, there is a concern that the impact resistance, etc. of the polycarbonate resin composition may be reduced, and if it exceeds about 3 parts by weight, there is a concern that the flame retardancy, weather resistance, etc. of the polycarbonate resin composition may be reduced.

[0094]

[0095] (F) Benzotriazole UV stabilizer

[0096] A benzotriazole-based UV stabilizer according to one specific example of the present invention can be applied together with a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, a phosphazene compound, a siloxane-modified polyester, and syndiotactic polystyrene, etc., to improve the scratch resistance, impact resistance, flame retardancy, weather resistance, colorability, etc. of a polycarbonate resin composition. Various commercially available benzotriazole-based UV stabilizers used in conventional thermoplastic resin compositions can be used.

[0097] In a specific example, the benzotriazole-based UV stabilizer may be used together with a triazine-based UV stabilizer. The type of the triazine-based UV stabilizer is not particularly limited, and various commercially available triazine-based UV stabilizers may be used.

[0098] In a specific example, the benzotriazole-based UV stabilizer may be included in an amount of about 0.3 to about 1.5 parts by weight, for example, about 0.5 to about 1 part by weight, relative to about 100 parts by weight of the base resin. If the content of the benzotriazole-based UV stabilizer is less than about 0.3 parts by weight relative to about 100 parts by weight of the base resin, there is a concern that the weather resistance, etc. of the polycarbonate resin composition may be reduced, and if it exceeds about 1.5 parts by weight, there is a concern that the impact resistance, flame retardancy, etc. of the polycarbonate resin composition may be reduced.

[0099]

[0100] A polycarbonate resin composition according to one embodiment of the present invention may further include additives such as a flame retardant, a nucleating agent, a coupling agent, glass fiber, a plasticizer, a lubricant, a mineral filler, an antibacterial agent, a release agent, a heat stabilizer, an antioxidant, a pigment, a dye, an antistatic agent, or a mixture thereof, within a range that does not impair physical properties.

[0101] In a specific example, when applying the additive, the content may be included in an amount of about 40 parts by weight or less, for example, about 20 parts by weight or less, based on about 100 parts by weight of the base resin, but is not limited thereto.

[0102]

[0103] A polycarbonate resin composition according to one specific example of the present invention may be in the form of pellets obtained by mixing the above components and melt-extruding them at about 200 to about 290°C, for example, about 250 to about 280°C, using a conventional twin-screw extruder.

[0104] In a specific example, the polycarbonate resin composition is a black quinone dye mixture applied at 0.5 parts by weight to 100 parts by weight of the base resin, and the change in brightness (ΔL) before and after the scratch resistance evaluation is measured with a colorimeter according to ISO 2409. * ) may be about 6 or less, for example, about 4 to about 5.8.

[0105] In a specific example, the polycarbonate resin composition may have a notched Izod impact strength of about 40 to about 90 kgf·cm / cm, for example, about 43 to about 80 kgf·cm / cm, of a 1 / 4" thick specimen measured according to ASTM D256.

[0106] In a specific example, the polycarbonate resin composition may have a total burning time of about 30 seconds or less, for example, about 10 to about 28 seconds, of a 1.5 mm thick specimen measured by the UL-94 vertical test method.

[0107] In a specific example, the polycarbonate resin composition is applied with 0.5 parts by weight of a black quinone dye mixture per 100 parts by weight of the base resin, and the initial color (L0) is measured by a colorimeter on a 50 mm × 90 mm × 3 mm sized specimen. * , a0 * , b0 * ) was measured, and the above specimens were subjected to a weathering test for 3,000 hours according to SAE J 1960, and the color (L1) was tested with a colorimeter. * , a1 * , b1 * ) is measured, and the color change (ΔE) calculated according to the following equation 1 may be about 3.8 or less, for example, about 2 to about 3.6.

[0108] [Formula 1]

[0109] Color change (ΔE) =

[0110] In the above equation 1, ΔL * L before and after the test * Difference in value (L1 * -L0 * ) and Δa * a before and after the test * Difference in value (a1 * - a0 * ) and Δb * b before and after the test * Difference in value (b1* - b0 * )am.

[0111] In a specific example, the polycarbonate resin composition has a blackness (L) measured by a colorimeter for a specimen to which 0.5 parts by weight of a black quinone dye mixture was applied to 100 parts by weight of the base resin. * ) may be about 2 or less, for example, about 0.5 to about 1.6.

[0112]

[0113] The molded article according to the present invention is formed from the polycarbonate resin composition. For example, the molded article can be manufactured from the polycarbonate resin composition through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention pertains. The molded article has excellent scratch resistance, impact resistance, flame retardancy, weather resistance, colorability (particularly, deep black color), and a balance of these physical properties, and is therefore useful as automobile parts, automobile interior / exterior materials, or interior / exterior materials for electrical and electronic products.

[0114]

[0115] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0116]

[0117] Example

[0118] Below, the specifications of each component used in the examples and comparative examples are as follows.

[0119] (A) Polycarbonate resin

[0120] Bisphenol-A polycarbonate resin (manufacturer: Lotte Chemical, melt flow index (MI): approximately 19 g / 10 min measured at 300°C and 1.2 kg according to ASTM D1238) was used.

[0121] (B) Polysiloxane-polycarbonate copolymer resin

[0122] Polysiloxane-polycarbonate copolymer resin (manufacturer: Samyang Corporation, polysiloxane block: about 1.5 wt%, polycarbonate block: about 98.5 wt%, weight average molecular weight: about 24,000 g / mol) was used.

[0123] (C) Phosphazene compound

[0124] Cyclic phosphazene (manufacturer: Fushimi Pharmaceutical Co., Ltd., product name: Rabitle FP-110) was used.

[0125] (D) Siloxane modified polyester

[0126] Siloxane-modified polyester (manufacturer: Evonik Industries AG, product name: TEGOMER H-Si 6441 P) was used.

[0127] (E) syndiotactic polystyrene

[0128] Syndiotactic polystyrene (Manufacturer: Idemitsu Kosan Co., Ltd., Product name: XAREC SP130) was used.

[0129] (F) Benzotriazole UV stabilizer

[0130] Benzotriazole-based UV stabilizer (Manufacturer: Adeka Corp., Product name: ADK STAB LA-31G) was used.

[0131]

[0132] Examples 1 to 6 and Comparative Examples 1 to 10

[0133] Each of the above components was added in the amounts shown in Tables 1, 2, and 3 below, and then extruded at about 270°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 59 and a diameter of 45 mm. The manufactured pellets were dried at about 100°C for about 2 hours or more, and then injected using a 6 oz injection molding machine (cylinder temperature: about 260°C, mold temperature: about 60°C) to produce test pieces. The physical properties of the manufactured test pieces were evaluated using the following methods, and the results are shown in Tables 1, 2, and 3 below.

[0134]

[0135] Method of measuring physical properties

[0136] (1) Scratch resistance evaluation: After preparing a 100 mm × 100 mm × 3 mm sized specimen by applying 0.5 parts by weight of a quinone dye mixture that represents black color to 100 parts by weight of the base resin, scratches were applied to the specimen in a grid pattern at 2 mm intervals 20 times with a test tip having a diameter of 1 mm under the conditions of a load of 10 N and a scratch speed of 1 m / min, using an Erichsen Scratch Hardness Tester 430 PI according to ISO 2409, and then the change in brightness (ΔL) of the specimen before and after the scratch evaluation was measured. * ) was measured in the specular emission elimination mode (SCE Mode) using a colorimeter (manufacturer: Konica Minolta Inc., model number: CM-3700D). When a scratch is applied, microcracks occur on the surface of the specimen, creating flaws, which increases the brightness of the specimen. Therefore, the brightness change (ΔL * ) was judged to be higher, the more damage caused by scratches, and thus the lower the scratch resistance.

[0137] (2) Impact resistance evaluation: The notched Izod impact strength (unit: kgf·cm / cm) of a 1 / 4" thick specimen was measured according to ASTM D256.

[0138] (3) Flame retardancy evaluation: The total burning time (sum of the burning time after the first contact (T1) and the burning time after the second contact (T2), unit: seconds) of a 1.5 mm thick specimen was measured using the UL-94 vertical test method.

[0139] (4) Weatherability evaluation: The initial color (L0) was measured using a colorimeter (manufacturer: Konica Minolta Inc., model number: CM-3700D) on a 50 mm × 90 mm × 3 mm sized specimen to which 0.5 parts by weight of a quinone dye mixture that indicates black was applied to 100 parts by weight of the base resin. * , a0 * , b0 * ) was measured, and the above specimens were tested for weatherability for 3,000 hours according to SAE J 1960, and the color (L1) after testing using a colorimeter * , a1 * , b1 * ) was measured, and the color change (ΔE) was calculated according to Equation 1 below.

[0140] [Formula 1]

[0141] Color change (ΔE) =

[0142] In the above equation 1, ΔL * L before and after the test * Difference in value (L1 * -L0 * ) and Δa * a before and after the test * Difference in value (a1 * - a0 * ) and Δb * b before and after the test * Difference in value (b1 * - b0 * )am.

[0143] (5) Colorability evaluation: After preparing a specimen in which 0.5 parts by weight of a quinone dye mixture that exhibits black color was applied to 100 parts by weight of the base resin, the blackness (brightness, L) of the specimen was measured in the specular reflection elimination mode (SCE Mode) using a colorimeter (manufacturer: Konica Minolta Inc., model name: CM-3700D). * ) was measured. The lower the brightness, the better the black color implementation, so it was judged that the coloring property was excellent.

[0144]

[0145] Example 123456 (A) (weight%) 608050606060 (B) (weight%) 402050404040 (C) (weight parts) 222222 (D) (weight parts) 0.50.50.510.50.5 (E) (weight parts) 0.50.50.50.510.5 (F) (weight parts) 0.50.50.50.50.51 Brightness change (ΔL) * )5.35.55.64.85.35.4Notched Izod impact strength594465686652Total burning time222124222326Color change before / after weathering test (ΔE)2.92.63.33.53.32.4Blackness (L) * )1.11.21.31.21.21.3

[0146] * Weight parts: Weight parts per 100 weight parts of base resin (A+B)

[0147]

[0148] Comparative Example 12345 (A) (weight%) 90 10 60 60 60 (B) (weight%) 10 90 40 40 40 (C) (weight parts) 22 012 (D) (weight parts) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0 (E) (weight parts) 0.5 ... * )5.45.65.05.09.8Notch Izod impact strength2988656349Total burning time2127Drip4522Color change before / after weathering test (ΔE)2.54.52.22.62.6Blackness (L) * )1.11.41.01.00.9

[0149] * Weight parts: Weight parts per 100 weight parts of base resin (A+B)

[0150]

[0151] Comparative Example 678910(A) (weight%)8080806060(B) (weight%)2020204040(C) (weight part)22222(D) (weight part)20.50.50.50.5(E) (weight part)0.5050.50.5(F) (weight part)0.50.50.503Change in brightness(ΔL * )3.85.45.65.25.5Notched Izod impact strength6228556433Total burning time2720362342Color change before / after weathering test (ΔE)4.42.84.05.42.1Blackness (L) * )2.51.21.40.91.3

[0152] * Weight parts: Weight parts per 100 weight parts of base resin (A+B)

[0153]

[0154] From the above results, the polycarbonate resin composition of the present invention has scratch resistance (brightness change (ΔL * )), impact resistance (notched Izod impact strength), flame retardancy (total burning time), weather resistance (color change before / after weather resistance evaluation (ΔE)), colorability (blackness (L * )), it can be seen that their physical properties are excellent in balance.

[0155] On the other hand, in the case of Comparative Example 1, where polycarbonate resin was applied in excess and polysiloxane-polycarbonate copolymer resin was applied in small amounts, it can be seen that impact resistance, etc. were reduced, and in the case of Comparative Example 2, where polycarbonate resin was applied in small amounts and polysiloxane-polycarbonate copolymer resin was applied in excess, it can be seen that weather resistance, etc. were reduced. In the case of Comparative Examples 3 and 4, where phosphazene compounds were not applied or were applied in small amounts, it can be seen that flame retardancy, etc. were reduced, and in the case of Comparative Example 5, where siloxane-modified polyester was not applied, it can be seen that scratch resistance, etc. were reduced, and in the case of Comparative Example 6, where siloxane-modified polyester was applied in excess, it can be seen that weather resistance, colorability, etc. were reduced. In the case of Comparative Example 7, where syndiotactic polystyrene was not applied, it can be seen that impact resistance, etc. were reduced, and in the case of Comparative Example 8, where syndiotactic polystyrene was applied in excessive amounts, it can be seen that flame retardancy, weather resistance, etc. were reduced. In addition, in the case of Comparative Example 9, where a benzotriazole-based UV stabilizer was not applied, it can be seen that weather resistance, etc. were reduced, and in the case of Comparative Example 10, where a benzotriazole-based UV stabilizer was applied in excessive amounts, it can be seen that impact resistance, flame retardancy, etc. were reduced.

[0156]

[0157] The present invention has been described with reference to exemplary embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. About 100 parts by weight of a base resin comprising about 45 to about 85 wt% of a polycarbonate resin and about 15 to about 55 wt% of a polysiloxane-polycarbonate copolymer resin; About 1.5 to about 4 parts by weight of a phosphazene compound; About 0.3 to about 1.5 parts by weight of siloxane modified polyester; About 0.3 to about 3 parts by weight of syndiotactic polystyrene; and A polycarbonate resin composition characterized by comprising about 0.3 to about 1.5 parts by weight of a benzotriazole-based UV stabilizer.

2. A polycarbonate resin composition according to claim 1, characterized in that the polycarbonate resin has a melt flow index of about 5 to about 50 g / 10 min, measured under conditions of 300°C and 1.2 kg according to ASTM D1238.

3. A polycarbonate resin composition according to claim 1 or 2, characterized in that the polysiloxane-polycarbonate copolymer resin comprises about 1 to about 50 wt% of a polysiloxane block and about 50 to about 99 wt% of a polycarbonate block.

4. A polycarbonate resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the polysiloxane-polycarbonate copolymer resin is about 10,000 to about 100,000 g / mol.

5. A polycarbonate resin composition according to any one of claims 1 to 4, wherein the phosphazene compound is a compound represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R1, R2, R3, R4, R5 and R6 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 7 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a heteroaryl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted carbonylalkyl group having 2 to 10 carbon atoms, an amino group or a hydroxy group.

6. A polycarbonate resin composition according to any one of claims 1 to 5, wherein the siloxane-modified polyester is a compound represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, R1, R2, R3 and R4 are each independently an alkylene group having 1 to 5 carbon atoms, R5 is an alkyl group or phenyl group having 1 to 4 carbon atoms, R6 is a hydrogen atom, a hydroxy group or a methyl group, and l, m and n are each independently an integer of 1 or more.

7. A polycarbonate resin composition characterized in that in the 6th paragraph, R1 and R2 of the chemical formula 3 are each -(CH2)3-, R3 and R4 are each -(CH2)5-, R5 is a methyl group, and l, m and n are integers of 1 or more satisfying l + m : n = 15 to 20 : 25 to 35.

8. A polycarbonate resin composition according to any one of claims 1 to 7, wherein the syndiotactic polystyrene has a syndiotacticity of about 97 to about 100%.

9. A polycarbonate resin composition according to any one of claims 1 to 8, characterized in that the benzotriazole-based UV stabilizer is used together with a triazine-based UV stabilizer.

10. In any one of the first to 9th clauses, the polycarbonate resin composition is a black quinone dye mixture applied at 0.5 parts by weight to 100 parts by weight of the base resin, and the change in brightness (ΔL) before and after the scratch resistance evaluation is measured with a colorimeter according to ISO 2409. * ) is about 6 or less.

11. A polycarbonate resin composition according to any one of claims 1 to 10, characterized in that the polycarbonate resin composition has a notched Izod impact strength of about 40 to about 90 kgf·cm / cm of a 1 / 4" thick specimen measured according to ASTM D256.

12. A polycarbonate resin composition according to any one of claims 1 to 11, characterized in that the total combustion time of a 1.5 mm thick specimen measured by the UL-94 vertical test method is about 30 seconds or less.

13. In any one of the first to 12th clauses, the polycarbonate resin composition is a 50 mm × 90 mm × 3 mm sized specimen to which 0.5 parts by weight of a black quinone dye mixture is applied to 100 parts by weight of the base resin, and the initial color (L0) is measured by a colorimeter. * , a0 * , b0 * ) was measured, and the injection molded specimen was subjected to a weathering test for 3,000 hours according to SAE J 1960, and the color (L1) was tested with a colorimeter. * , a1 * , b1 * ) and then a polycarbonate resin composition characterized in that the color change (ΔE) calculated according to the following formula 1 is about 3.8 or less: [Formula 1] Color change (ΔE) = In the above equation 1, ΔL * L before and after the test * Difference in value (L1 * -L0 * ) and Δa * a before and after the test * Difference in value (a1 * - a0 * ) and Δb * b before and after the test * Difference in value (b1 * - b0 * )am.

14. In any one of claims 1 to 13, the polycarbonate resin composition has a blackness (L) measured by a colorimeter for a specimen to which 0.5 parts by weight of a black quinone dye mixture is applied to 100 parts by weight of the base resin. * ) is about 2 or less.

15. A molded product characterized by being formed from a polycarbonate resin composition according to any one of claims 1 to 14.

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