Polycarbonate resin composition, method for preparing same, and molded article comprising same

Abstract

The present invention relates to a polycarbonate resin composition, a method for preparing the same, and a molded article comprising the same, and, according to the present invention, provides a polycarbonate resin composition capable of achieving excellent high heat resistance, high flow characteristics, and impact resistance characteristics, a method for preparing the same, and the like.

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin composition, a method for preparing the same, and a molded article containing the same, and more particularly, to a polycarbonate resin composition capable of achieving excellent high heat resistance, high flowability, and impact resistance, and a method for preparing the same, etc. Background Art

[0002] Polycarbonate resin (PC) is transparent and has excellent impact strength, and thus is widely used as various industrial resins including electrical and electronic parts.

[0003] Recently, as electronic devices are increasingly used in daily life, the requirements for high heat resistance capable of withstanding external heat and impact resistance for preventing breakage of polycarbonate resin for electronic devices are increasing, but are not satisfactory.

[0004] It is known that methods for solving such problems in the past include mixing a metal-based flame retardant into polycarbonate resin, or mixing an impact modifier such as an acrylic or styrene-based one together with a metal salt-based flame retardant, or mixing an impact modifier and a phosphorus-based flame retardant, etc.

[0005] However, it is difficult to sufficiently ensure the required physical properties only by mixing a metal-based flame retardant. When an impact modifier is mixed together with a metal salt-based flame retardant, it is difficult to sufficiently ensure high heat resistance and the like. When an impact modifier is mixed together with a phosphate-based flame retardant, an excessive amount of flame retardant must be mixed to ensure sufficient high heat resistance. Therefore, there is a problem in that high flowability or impact resistance is reduced.

[0006] Therefore, there is a need to develop a flame-retardant polycarbonate resin composition with enhanced high heat resistance, high flowability, and impact resistance, etc.

[0007] Prior Art Documents

[0008] Patent Document: Korean Patent Publication No. 2023-0053076 Summary of the Invention

[0009] Technical Problem

[0010] In order to solve the problems in the prior art as described above, an object of the present invention is to provide a polycarbonate resin composition that can satisfy high heat resistance, high flowability, and impact resistance, and is used for various purposes such as household electronic devices, chargers, and adapter housings in addition to electrical and electronic parts or industrial uses.

[0011] In addition, an object of the present invention is to provide a method for preparing the polycarbonate resin composition and a molded article, the molded article comprising the polycarbonate resin composition, and thus having excellent flame retardancy and enhanced high heat resistance, high flowability, and impact resistance characteristics.

[0012] The above object of the present invention and many other objects can be fully achieved by the present invention described below.

[0013] Technical Solution

[0014] To achieve the above object, (I), the present invention provides a polycarbonate resin composition comprising a polycarbonate resin, a heat stabilizer, a metal salt flame retardant, and an anti-dripping agent, wherein the melting point of the heat stabilizer is higher than the melting point of the polycarbonate resin.

[0015] (II), in the above (I), as an example, the polycarbonate resin may be a linear polycarbonate resin.

[0016] (III), in the above (I) to (II), as an example, the melting point (Tm) of the polycarbonate resin may be 285 to 315 °C.

[0017] (IV), in the above (I) to (III), as an example, the heat stabilizer may be an organic basic phosphate containing a fatty acid.

[0018] (V), in the above (I) to (IV), as an example, the melting point of the heat stabilizer may be 350 °C or higher.

[0019] (VI), in the above (I) to (V), as an example, relative to 100 parts by weight of the polycarbonate resin, the content of the heat stabilizer may be 0.01 to 5.5 parts by weight.

[0020] (VII), in the above (I) to (VI), as an example, the metal salt flame retardant may be one or more selected from perfluoroalkyl sulfonates, diphenyl sulfone sulfonates, alkyl sulfonates, benzene sulfonates, sulfosulfonates, and alkyl benzene sulfonates.

[0021] (VIII), in the above (I) to (VII), as an example, the metal ion of the salt may be lithium, sodium, or potassium.

[0022] (IX), in the above (I) to (VIII), as an example, relative to 100 parts by weight of the polycarbonate resin, the content of the metal salt flame retardant may be 0.01 to 3 parts by weight.

[0023] (X), among the above (I) to (IX), as an example, the anti-dripping agent may be a mixed anti-dripping agent, a coated anti-dripping agent, or a combination thereof.

[0024] (XI), among the above (I) to (X), as an example, relative to 100 parts by weight of the polycarbonate resin, the content of the anti-dripping agent may be 0.1 to 5 parts by weight.

[0025] (XII), among the above (I) to (XI), as an example, according to the ASTM D1238 (300 °C, 1.2 kg) standard, the melt index difference between the melt index measured after the polycarbonate resin composition is retained at 300 °C for 5 minutes and the melt index measured after being retained for 10 minutes may be 0.1 to 5 g / 10 min.

[0026] (XIII), among the above (I) to (XII), as an example, the difference between the impact strength measured according to the ASTM D256 standard for a specimen (with a thickness of 1 / 8 inch) of the polycarbonate resin composition retained at 300 °C for 5 minutes and the impact strength measured according to the ASTM D256 standard for a specimen (with a thickness of 1 / 8 inch) retained at 300 °C for 10 minutes may be 5 kgf·cm / cm or less.

[0027] (XIX), the present invention provides a polycarbonate resin composition, which comprises 100 parts by weight of a polycarbonate resin, 0.01 to 5.5 parts by weight of a heat stabilizer, 0.01 to 3 parts by weight of a metal salt flame retardant, and 0.1 to 5 parts by weight of an anti-dripping agent, wherein the melting point of the heat stabilizer is higher than the melting point of the polycarbonate resin.

[0028] (XX), the present invention provides a method for preparing a polycarbonate resin composition, which comprises the steps of kneading and extruding a mixture containing 100 parts by weight of a polycarbonate resin, 0.01 to 5.5 parts by weight of a heat stabilizer, 0.01 to 3 parts by weight of a metal salt flame retardant, and 0.1 to 5 parts by weight of an anti-dripping agent, wherein the melting point of the heat stabilizer is higher than the melting point of the polycarbonate resin.

[0029] (XXI), the present invention provides a method for preparing a polycarbonate resin composition, which comprises the steps of kneading and extruding a mixture containing a polycarbonate resin, a heat stabilizer, a metal salt flame retardant, and an anti-dripping agent under the conditions of 200 to 330 °C and 100 to 400 rpm, wherein the melting point of the heat stabilizer is higher than the melting point of the polycarbonate resin.

[0030] (XXII), the present invention provides a molded article, which comprises the above polycarbonate resin composition.

[0031] Beneficial effects

[0032] According to the present invention, a polycarbonate resin composition can be provided, which has more excellent high heat resistance characteristics, impact resistance characteristics, and flame retardant characteristics than known polycarbonate resin compositions. In particular, even when staying at a high temperature, the high flow characteristics and impact resistance characteristics can be significantly improved.

[0033] Furthermore, the polycarbonate resin composition of the present invention can simultaneously satisfy high heat resistance characteristics, flame retardant characteristics, high flow characteristics, and impact resistance characteristics. Therefore, in addition to parts of industrial electrical and electronic products, it is also used for various purposes such as household electronic devices, chargers, and adapter housings. Detailed implementation manners

[0034] Hereinafter, the polycarbonate resin composition of the present invention will be described in detail.

[0035] The inventor of the present invention mixed a heat stabilizer with a melting point higher than that of the polycarbonate resin into the polycarbonate resin to meet the high heat resistance characteristics of the polycarbonate resin composition. Further preferably, the existing core-shell structure impact enhancer was excluded to achieve impact resistance characteristics, high flame retardant characteristics, and ensure stability. It has been confirmed that the flame retardant characteristics of the polycarbonate resin composition of this combination are excellent, and the high heat resistance characteristics, high flow characteristics, and impact resistance characteristics are enhanced, and the present invention has been completed based on this.

[0036] As an example, the polycarbonate resin composition of the present invention may include a polycarbonate resin, a heat stabilizer, a metal salt flame retardant, and a dripping inhibitor, and the heat stabilizer is an organic basic phosphate containing fatty acid.

[0037] As another example, the polycarbonate resin composition of the present invention may include 100 parts by weight of a polycarbonate resin, 0.01 to 5.5 parts by weight of a heat stabilizer, 0.01 to 3 parts by weight of a metal salt flame retardant, and 0.1 to 5 parts by weight of a dripping inhibitor, and the heat stabilizer is an organic basic phosphate containing fatty acid.

[0038] In addition, the polycarbonate resin composition of the present invention may not contain a core-shell structure impact enhancer.

[0039] As another example, the polycarbonate resin composition of the present invention may exclude impact enhancers including acrylic rubber, conjugated diene rubber, or both of them. At this time, the advantages of excellent heat resistance characteristics, flow characteristics, and impact resistance characteristics of the flame retardant polycarbonate resin composition are provided.

[0040] The terms "exclude" or "not contain" used in the present invention mean intentionally not adding a specific component.

[0041] As a specific example, the impact enhancer of the core-shell structure includes (meth)acrylic acid alkyl ester-vinyl aromatic compound-acrylonitrile compound copolymer (ASA resin), acrylonitrile compound-conjugated diene compound-vinyl aromatic compound copolymer (ABS resin), methyl methacrylate-conjugated diene compound-vinyl aromatic compound copolymer (MBS resin), acrylic impact modifier, etc. The polycarbonate resin composition of the present invention can be a polycarbonate resin composition without such a component and without a core-shell structure impact enhancer. At this time, the advantages of excellent heat resistance, flowability, and impact resistance of the flame-retardant polycarbonate resin composition are provided.

[0042] As a preferred example, the polycarbonate resin composition of the present invention may contain 100 parts by weight of polycarbonate resin, 0.01 to 5.5 parts by weight of heat stabilizer, 0.01 to 3 parts by weight of metal salt flame retardant, and 0.1 to 5 parts by weight of anti-dripping agent. At this time, the effects of excellent flame retardancy and impact resistance of the finished product and improved heat resistance and flowability are provided.

[0043] As another example, the polycarbonate resin composition of the present invention may contain 100 parts by weight of polycarbonate resin, 0.01 to 1 part by weight of heat stabilizer, 0.01 to 1 part by weight of metal salt flame retardant, and 0.1 to 3 parts by weight of anti-dripping agent. At this time, the advantages of excellent flame retardancy and impact resistance of the polycarbonate resin composition and improved heat resistance, flowability, etc. are provided.

[0044] As another example, the polycarbonate resin composition of the present invention may contain 100 parts by weight of polycarbonate resin, 0.01 to 0.5 part by weight of heat stabilizer, 0.01 to 0.5 part by weight of metal salt flame retardant, and 0.1 to 1 part by weight of anti-dripping agent. At this time, the impact resistance, flame retardancy, heat resistance, and flowability of the polycarbonate resin composition can be satisfied simultaneously.

[0045] Hereinafter, the polycarbonate resin composition will be described according to each component.

[0046] Polycarbonate resin

[0047] As an example, the polycarbonate resin may be a resin polymerized from an aromatic diol compound and a carbonate precursor.

[0048] As an example, the aromatic diol compound may be selected from 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-hydroxyphenyl)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-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, etc. Among them, bisphenol A is preferably used.

[0049] As an example, the carbonate precursor may be selected from dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, xylenyl carbonate, bis(chlorophenyl) carbonate, di-m-tolyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, carbonyl bromide, bis(haloformate), etc. In terms of preparation efficiency and physical properties, triphosgene or phosgene is preferably used.

[0050] As a specific example, the polycarbonate resin formed by polymerizing the aromatic diol compound and the carbonate precursor contains a repeating unit represented by Chemical Formula 1.

[0051] Chemical Formula 1:

[0052]

[0053] In Chemical Formula 1, R'1 to R'4 are each independently hydrogen, C 1-10 alkyl, C 1-10 alkoxy or halogen, and Z' is unsubstituted or substituted by C 1-6 alkyl or C 6-20 aryl-substituted C 1-10 alkylene, unsubstituted or substituted by C 1-10 alkyl-substituted C 3-15 cycloalkylene, O, S, SO, SO2 or CO.

[0054] As a preferred example, in Chemical Formula 1, R'1 to R'4 may each independently be hydrogen or C 1-3 alkyl, and Z' may be unsubstituted or substituted by methyl or phenyl C 1-6 alkylene.

[0055] As an example, the polycarbonate resin may be a virgin polycarbonate resin.

[0056] The virgin polycarbonate resin in the present invention refers to a polycarbonate resin that has not been subjected to molding processes such as injection molding after polymerization preparation, and can represent a polycarbonate resin that does not contain recycled polycarbonate resin.

[0057] The polycarbonate resin is preferably a linear polycarbonate resin.

[0058] As an example, the melt index (at 300 °C with a load of 1.2 kg) of the polycarbonate resin may be 10 - 30 g / 10 min, 10 - 25 g / 10 min, 10 - 22 g / 10 min, 10 - 20 g / 10 min, or 20 - 25 g / 10 min. Within this range, the polycarbonate resin composition has the advantages of being easy to mold and process, and having improved physical properties such as impact resistance characteristics.

[0059] As another example, the polycarbonate resin may be a mixture of two or more polycarbonate resins with different melt indices. Specifically, it may be a mixture of a polycarbonate resin with a melt index of 10 - 15 g / 10 min and a polycarbonate resin with a melt index of 20 - 25 g / 10 min.

[0060] As an example, the weight-average molecular weight of the polycarbonate resin may be 1,000 - 100,000 g / mol, 5,000 - 50,000 g / mol, 20,000 - 40,000 g / mol, 20,000 - 35,000 g / mol, and is preferably 22,000 - 31,000 g / mol. Within this range, the polycarbonate resin composition has the advantages of excellent processing and moldability, and excellent balance of physical properties such as flame retardancy characteristics, impact resistance characteristics, and heat resistance characteristics.

[0061] In the present invention, unless otherwise specifically mentioned, the weight-average molecular weight is measured by gel permeation chromatography (GPC) method after calibration using the polycarbonate resin as a standard material.

[0062] As an example, the melting point (Tm) of the polycarbonate resin may be 285 - 315 °C, 270 - 330 °C, and is preferably 280 - 300 °C. Within this range, the polycarbonate resin composition has the advantages of excellent processing and moldability, and excellent balance of physical properties such as flame retardancy characteristics, impact resistance characteristics, and heat resistance characteristics.

[0063] In the present invention, the melting point can be measured using a differential scanning calorimeter (DSC; Differential Scanning Calorimeter 2920) manufactured by TA Instruments. As a specific measurement example, after equilibrating the DSC at a temperature of 0°C, the temperature can be increased to 180°C at a rate of 20°C per minute, then decreased to -60°C at a rate of 20°C per minute, and then increased to 180°C at a rate of 10°C per minute to measure the melting point. Among them, the melting point is obtained by taking the top region of the endothermic curve during the second temperature rise.

[0064] Heat stabilizer

[0065] The melting point (Tm) of the heat stabilizer can be higher than the melting point (Tm) of the polycarbonate resin. As an example, it can be 350°C or higher, preferably 500°C or higher, and more preferably 700 - 1800°C. Within this range, even when exposed to high temperatures for a long time, it has excellent flow characteristics and impact resistance characteristics.

[0066] The heat stabilizer is preferably an organic phosphate containing a fatty acid, more preferably an organic basic phosphate containing a fatty acid, and even more preferably sodium organic phosphate containing a fatty acid. At this time, the heat stabilizer is uniformly dispersed in the polycarbonate resin composition. Therefore, even when exposed to high temperatures for a long time, it has the effect of improving flow characteristics and impact resistance characteristics.

[0067] The heat stabilizer is more preferably formed by coating a fatty acid on a material composed of sodium organic phosphate, phosphoric acid, and pentaerythritol stearate. At this time, the heat stabilizer is uniformly dispersed in the polycarbonate resin composition. Therefore, even when exposed to high temperatures for a long time, it has excellent flow characteristics and impact resistance characteristics.

[0068] The fatty acid preferably has 8 - 20 carbon atoms, more preferably 14 - 20 carbon atoms, and even more preferably 16 - 18 carbon atoms. At this time, it has the advantage of being uniformly dispersed in the polycarbonate resin composition, thereby improving flow characteristics and impact resistance characteristics.

[0069] With respect to 100 parts by weight of the polycarbonate resin, the content of the heat stabilizer can be 0.01 - 5.5 parts by weight, preferably 0.01 - 1 part by weight, and more preferably 0.01 - 0.5 part by weight. Within this range, even when exposed to high temperatures for a long time, it has excellent flow characteristics and impact resistance characteristics.

[0070] Metal salt flame retardant

[0071] When using the metal salt flame retardant, there are advantages of not only ensuring the flame retardant properties of the polycarbonate resin composition, but also making the heat resistance of the polycarbonate resin composition more excellent.

[0072] As an example, the metal salt flame retardant may be one or more selected from perfluoroalkyl sulfonates, diphenyl sulfone sulfonates, alkyl sulfonates, benzene sulfonates, sulfosulfonates, and alkyl benzene sulfonates, and preferably contains perfluoroalkyl sulfonates or sulfosulfonates.

[0073] As an example, the metal ion of the salt may be lithium, sodium or potassium.

[0074] As an example, the perfluoroalkyl sulfonate may be sodium perfluorobutane sulfonate, potassium perfluorobutane sulfonate, etc. At this time, it is possible to maintain high impact resistance or heat resistance of the polycarbonate resin composition, etc., and ensure the flame retardant properties at the target level.

[0075] Preferably, the content of the metal salt flame retardant may be 0.01 to 3 parts by weight, 0.01 to 1 part by weight, or 0.01 to 0.5 part by weight based on 100 parts by weight of the polycarbonate resin. In this range, there are advantages of not only ensuring the flame retardant properties of the polycarbonate resin composition, but also making the heat resistance of the polycarbonate resin composition more excellent.

[0076] Drip retardant

[0077] The polycarbonate resin composition may contain a drip retardant, and its content may be 0.1 to 5 parts by weight, 0.1 to 3 parts by weight, or 0.1 to 1 part by weight based on 100 parts by weight of the polycarbonate resin. In this range, there are advantages of maintaining physical properties such as high heat resistance, impact resistance, and flow properties of the polycarbonate resin composition, and further improving the flame retardant properties.

[0078] As an example, a mixed drip retardant, a coated drip retardant, or a combination thereof may be used as the drip retardant.

[0079] The mixed drip retardant is not limited thereto. For example, it may be a fluorine-containing compound mixed with an ethylenic compound, etc. At this time, the dispersibility of the drip retardant can be improved, thereby further improving the flame retardant properties.

[0080] The coated drip retardant is not particularly limited as long as it is a commonly used coated drip retardant in the art. For example, it may be a fluorine-containing compound using the ethylenic compound or a polymer containing one or more of the ethylenic compounds as a coating agent, etc.

[0081] As an example, the ethylenic compound may be methyl methacrylate, styrene, acrylonitrile, etc.

[0082] As an example, the fluorine-containing compound may be polytetrafluoroethylene or the like.

[0083] Additive

[0084] According to requirements, the polycarbonate resin composition may optionally further contain one or more additives selected from flame retardant aids, lubricants, processing aids, plasticizers, coupling agents, light stabilizers, mold release agents, dispersants, weather stabilizers, antioxidants, compatibilizers, pigments, dyes, antistatic agents, wear-resistant agents, fillers, ultraviolet absorbers, and fungicides.

[0085] With respect to 100 parts by weight of the polycarbonate resin, the content of the additive may be 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight. At this time, there is an effect of neither reducing the original physical properties of the polycarbonate resin composition of the present invention nor well achieving the required physical properties.

[0086] The lubricant may be one or more selected from modified montanic acid wax, long chain ester of pentaerythritol, and fatty acid ester of neopentylpolyol.

[0087] As an example, the ultraviolet absorber may be one or more selected from triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers.

[0088] As an example, the triazine ultraviolet absorber may be one or more selected from 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, and 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-triazine.

[0089] As an example, the benzophenone ultraviolet absorber may be one or more selected from 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octyloxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, and 2,2',4,4'-tetrahydroxy-benzophenone.

[0090] As an example, the benzotriazole ultraviolet absorber may be one or more selected from 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole.

[0091] As an example, the cyanoacrylate ultraviolet absorber may be 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate, or a mixture thereof.

[0092] Polycarbonate resin composition

[0093] The polycarbonate resin composition of the present invention provides a polycarbonate resin composition comprising 100 parts by weight of a polycarbonate resin, 0.01 to 5.5 parts by weight of a heat stabilizer, 0.01 to 3 parts by weight of a metal salt flame retardant, and 0.1 to 5 parts by weight of a drip inhibitor, wherein the melting point of the heat stabilizer is higher than the melting point of the polycarbonate resin.

[0094] Preferably, the flame retardancy of the polycarbonate resin composition measured according to UL94 is, for example, V-0 or higher within one day after injection molding. As a preferred example, the flame retardancy measured according to UL94 is V-0 or higher two days after injection molding, and the flame retardancy and stability are excellent.

[0095] Preferably, according to the ASTM D1238 (300 °C, 1.2 kg) standard, the melt flow index difference between the melt flow index measured after the polycarbonate resin composition has been retained at 300 °C for 5 minutes and the melt flow index measured after being retained for 10 minutes may be 0.1 to 5 g / 10 min, preferably 0.1 to 3 g / 10 min, more preferably 1 to 2 g / 10 min.

[0096] Among them, according to the ASTM D1238 (300 °C, 1.2 kg) standard, the melt flow index measured after being retained at 300 °C for 5 minutes may be 7 g / 10 min or more, preferably 8 g / 10 min or more, more preferably 8 to 24 g / 10 min, even more preferably 9 to 20 g / 10 min. Within this range, there is an excellent effect of balanced physical properties.

[0097] In addition, according to the ASTM D1238 (300 °C, 1.2 kg) standard, the melt flow index measured after being retained at 300 °C for 10 minutes may be 8 g / 10 min or more, preferably 10 to 30 g / 10 min, more preferably 10 to 22 g / 10 min. Within this range, there is an excellent effect of balanced physical properties.

[0098] Preferably, the difference in impact strength measured according to the ASTM D256 standard between the specimen (with a thickness of 1 / 8 inch) of the polycarbonate resin composition retained at 300 °C for 5 minutes and the specimen (with a thickness of 1 / 8 inch) retained at 300 °C for 10 minutes may be 5 kgf·cm / cm or less, preferably 3 kgf·cm / cm or less, more preferably 0 to 3 kgf·cm / cm.

[0099] Among them, the impact strength measured according to the ASTM D256 standard of the specimen (with a thickness of 1 / 8 inch) retained at 300 °C for 5 minutes may be 78 kgf·cm / cm or more, preferably 78 to 90 kgf·cm / cm, more preferably 80 to 90 kgf·cm / cm. Within this range, there is an excellent effect of balanced physical properties.

[0100] In addition, the impact strength measured according to the ASTM D256 standard of the specimen (with a thickness of 1 / 8 inch) retained at 300 °C for 10 minutes may be 70 kgf·cm / cm or more, preferably 70 to 90 kgf·cm / cm, more preferably 75 to 90 kgf·cm / cm. Within this range, there is an excellent effect of balanced physical properties.

[0101] Hereinafter, the method for preparing the polycarbonate resin composition of the present invention will be described.

[0102] The preparation method of the present invention includes all the technical features of the above polycarbonate resin composition, and the repeated descriptions thereof are omitted.

[0103] The polycarbonate resin composition of the present invention includes a step of kneading and extruding a mixture containing 100 parts by weight of polycarbonate resin, 0.01 to 5.5 parts by weight of heat stabilizer, 0.01 to 3 parts by weight of metal salt flame retardant, and 0.1 to 5 parts by weight of anti-dripping agent, wherein the melting point of the heat stabilizer is higher than the melting point of the polycarbonate resin. At this time, even when exposed to high temperature for a long time, it has excellent flow characteristics and impact resistance characteristics.

[0104] As an example, the kneading and extrusion can be carried out under the conditions of 200 - 330 °C and 100 - 400 rpm, or 220 - 300 °C and 200 - 400 rpm, 260 - 300 °C and 200 - 300 rpm, but not limited thereto, and can be appropriately selected within the scope of conventional implementation in the art for implementation.

[0105] As an example, the kneading and extrusion can be carried out using a Banbury mixer, a single-screw extruder, a twin-screw extruder, a kneading reactor, etc. At this time, the polycarbonate resin composition is uniformly dispersed, and thus has an excellent compatibility effect.

[0106] As an example, the kneading and extrusion can be carried out within the range where the barrel temperature is 200 - 330 °C, preferably 220 - 320 °C, more preferably 240 - 280 °C. At this time, it has the advantages that the processing amount per unit time is appropriate, sufficient melt kneading can be carried out, and problems such as thermal decomposition of resin components are not caused.

[0107] As an example, the kneading and extrusion can be carried out under the condition that the screw rotation speed is 100 - 400 rpm, preferably 150 - 300 rpm, more preferably 150 - 250 rpm. At this time, the processing amount per unit time is appropriate, and thus has excellent process efficiency and physical properties of the polycarbonate resin composition.

[0108] As an example, the polycarbonate resin composition obtained by the extrusion can be made into pellets using a granulator.

[0109] The present invention provides a molded article comprising the polycarbonate resin composition.

[0110] As described above, the polycarbonate resin composition of the present invention does not contain existing impact enhancers, but mixes a heat stabilizer whose melting point is higher than that of the polycarbonate resin, and thus can simultaneously satisfy heat resistance characteristics, flow characteristics, impact resistance characteristics, flame retardant characteristics, etc.

[0111] Furthermore, the molded article of the present invention can be used for a variety of purposes such as household electronic devices, chargers, adapter housings, etc. in addition to electrical and electronic parts or industrial uses.

[0112] Preferably, the method for preparing the molded article of the present invention may include: kneading and extruding a mixture containing 100 parts by weight of a polycarbonate resin, 0.01 - 5.5 parts by weight of a heat stabilizer, 0.01 - 3 parts by weight of a metal salt flame retardant, and 0.1 - 5 parts by weight of a drip inhibitor at 200 - 330 °C and 100 - 400 rpm to form pellets; and injection molding the formed pellets to produce a molded article. At this time, it has the effect of providing a molded article with excellent flow characteristics and impact resistance even when exposed to high temperatures for a long time.

[0113] As an example, the formed pellets can be fully dried using a dehumidifying dryer or a hot air dryer and then used for injection molding.

[0114] The method for preparing the molded article of the present invention is not particularly limited, as long as it follows the definition of the present invention and uses the conditions, methods, and devices commonly used in the art, etc.

[0115] When explaining the polycarbonate resin composition of the present invention, its preparation method, and the molded article, other conditions or equipment, etc. not explicitly described can be appropriately selected within the scope of routine implementation in the art, and there is no particular limitation.

[0116] Hereinafter, preferred embodiments are presented to help understand the present invention. However, the following embodiments are only used to illustrate the present invention, and those skilled in the art can make various changes and modifications within the scope and technical concept of the present invention, and such variations and modifications fall within the scope of the appended claims.

[0117] The materials used in the examples and comparative examples are as follows.

[0118] A) Polycarbonate resin (PC)

[0119] a - 1) A bisphenol A polycarbonate resin with a melt index (at 300 °C and a load of 1.2 kg) of 10 g / 10 min according to ASTM D1238 standard was used.

[0120] a - 2) A bisphenol A polycarbonate resin with a melt index (at 300 °C and a load of 1.2 kg) of 22 g / 10 min according to ASTM D1238 standard was used.

[0121] B) Heat stabilizer

[0122] b-1) Sodium phosphate compounds containing fatty acids (TOV Company, Korea, HDT-S, melting point 1500 °C)

[0123] b-2) Tris(2,4-di-t-butylphenyl)phosphite (BASF Company, IF-168, melting point 181 - 184 °C)

[0124] C) Flame retardant

[0125] c-1) Potassium perfluorobutanesulfonate as a metal salt flame retardant, using HES2-FR from Arichem Company.

[0126] c-2) Bisphenol A bis(diphenyl phosphate) as a phosphorus-based flame retardant, using FP600 from ADEKA Company.

[0127] D) Hybrid anti-dripping agent

[0128] Polytetrafluoroethylene (PTFE) using the product Metablen A-3800 mixed with methyl methacrylate was used.

[0129] E) Additive

[0130] The product named FACI L348 from FACI ASIAPACIFIC Company was used as a lubricant.

[0131] [Examples]

[0132] After mixing according to the components and contents recorded in Table 1 and uniformly mixing using a mixer, it was melted and kneaded in a twin-screw extruder (screw diameter 26 mm, L / D = 40), and then extruded under the conditions of an extrusion temperature of 260 °C and a screw rotation speed of 200 rpm to prepare polycarbonate resin composition pellets. After drying at 80 °C for 4 hours or more, injection molding was carried out using an injection molding machine (ENGEL Company, 80MT) at a nozzle temperature of 260 °C to manufacture specimens for physical property measurement, and then left at room temperature for 48 hours or more, and the physical properties were measured.

[0133] [Experimental Examples]

[0134] The characteristics of the specimens prepared in Examples 1 to 2 and Comparative Examples 1 to 4 were measured by the following method, and the results are shown in Table 2.

[0135] Measurement method

[0136] *Melt flow index (g / 10 min) after 5-minute residence: The melt flow index after 5-minute residence at 300 °C was measured in accordance with ASTM D1238 (300 °C, 1.2 kg).

[0137] *Izod impact strength (kgf·cm / cm) after 5-minute residence: The Izod impact strength was measured at room temperature after notching a specimen with a thickness of 1 / 8 inch and 5-minute residence in accordance with ASTM D256.

[0138] *Melt flow index (g / 10 min) after 10-minute residence: The melt flow index after 10-minute residence at 300 °C was measured in accordance with ASTM D1238 (300 °C, 1.2 kg).

[0139] *Izod impact strength (kgf·cm / cm) after 10-minute residence: The Izod impact strength was measured at room temperature after notching a specimen with a thickness of 1 / 8 inch and 10-minute residence in accordance with ASTM D256.

[0140] *Flame retardancy: The flame retardancy of a specimen with a thickness of 1 / 16 inch was evaluated in accordance with the UL94 measurement method as follows. First, after contacting the specimen with a 20-mm high flame for 10 seconds, the burning time (t1) of the specimen was measured and the burning pattern was recorded. Then, after the first contact, when the burning stopped, it was contacted again for 10 seconds, and then, the burning time (t2) and glowing time (t3) of the specimen were measured and the burning pattern was recorded. After performing five times with specimens of the same specifications, the evaluation was carried out according to the criteria shown in Table 1.

[0141] Table 1:

[0142]

[0143] Table 2:

[0144]

[0145]

[0146] As shown in Table 1, it can be confirmed that the polycarbonate resin compositions of the present invention (Examples 1 to 2) have excellent flow characteristics and impact resistance even after long-term exposure at high temperatures as compared with Comparative Examples 1 to 4.

[0147] In particular, based on the physical property result values of Example 1 and Comparative Example 3, Example 1 of the present invention, which contains a heat stabilizer with a melting point higher than that of the polycarbonate resin in the polycarbonate resin composition, has the effect of improved flow characteristics and impact resistance characteristics when exposed at high temperature for a long time, compared with Comparative Example 3, which contains a heat stabilizer with a melting point lower than that of the polycarbonate resin.

[0148] Specifically, it can be confirmed that Examples 1 to 2, which contain a polycarbonate resin, a heat stabilizer, a metal salt flame retardant, and a drip retardant and the melting point of the heat stabilizer is higher than the melting point of the polycarbonate resin, have excellent flow characteristics and impact resistance characteristics compared with Comparative Examples 1, 2, and 4, which do not contain the combination of the heat stabilizer, the metal salt flame retardant, and the drip retardant.

[0149] In summary, it can be confirmed that when a heat stabilizer, a metal salt flame retardant, and a drip retardant are contained in the polycarbonate resin of the present invention in a predetermined content and a heat stabilizer with a melting point higher than the melting point of the polycarbonate resin is mixed, it has more excellent heat resistance characteristics, impact resistance characteristics, and flame retardant characteristics than the known polycarbonate resin composition level. In particular, even when staying at high temperature, the high flow characteristics and impact resistance characteristics can be significantly improved.

Claims

1. A polycarbonate resin composition, characterized in that it comprises a polycarbonate resin, a heat stabilizer, a metal salt flame retardant, and a drip inhibitor, wherein the melting point of the heat stabilizer is higher than that of the polycarbonate resin.

2. The polycarbonate resin composition according to claim 1, characterized in that the heat stabilizer is an organic basic phosphate containing fatty acids.

3. The polycarbonate resin composition according to claim 1 or 2, characterized in that the melting point of the heat stabilizer is 350 °C or higher.

4. The polycarbonate resin composition according to claim 1 or 2, characterized in that relative to 100 parts by weight of the polycarbonate resin, the content of the heat stabilizer is 0.01 to 5.5 parts by weight.

5. The polycarbonate resin composition according to claim 1, characterized in that the metal salt flame retardant is one or more selected from perfluoroalkyl sulfonates, diphenyl sulfone sulfonates, alkyl sulfonates, benzene sulfonates, sulfosulfonates, and alkyl benzene sulfonates.

6. The polycarbonate resin composition according to claim 1 or 5, characterized in that relative to 100 parts by weight of the polycarbonate resin, the content of the metal salt flame retardant is 0.01 to 3 parts by weight.

7. The polycarbonate resin composition according to claim 1, characterized in that the drip inhibitor is a mixed drip inhibitor, a coated drip inhibitor, or a combination thereof.

8. The polycarbonate resin composition according to claim 1 or 7, characterized in that relative to 100 parts by weight of the polycarbonate resin, the content of the drip inhibitor is 0.1 to 5 parts by weight.

9. The polycarbonate resin composition according to claim 1, characterized in that according to the ASTM D1238 standard at 300 °C under a load of 1.2 kg, the difference in melt flow index between the melt flow index measured after the polycarbonate resin composition has been retained at 300 °C for 5 minutes and the melt flow index measured after being retained for 10 minutes is 0.1 to 5 g / 10 min.

10. The polycarbonate resin composition according to claim 1, characterized in that the difference in impact strength between the impact strength measured according to the ASTM D256 standard for a specimen of the polycarbonate resin composition with a thickness of 1 / 8 inch retained at 300 °C for 5 minutes and the impact strength measured according to the ASTM D256 standard for a specimen of the polycarbonate resin composition with a thickness of 1 / 8 inch retained at 300 °C for 10 minutes is 5 kgf·cm / cm or less.

11. A polycarbonate resin composition, characterized in that it comprises 100 parts by weight of a polycarbonate resin, 0.01 to 5.5 parts by weight of a heat stabilizer, 0.01 to 3 parts by weight of a metal salt flame retardant, and 0.1 to 5 parts by weight of a drip inhibitor, wherein the melting point of the heat stabilizer is higher than that of the polycarbonate resin.

12. A method for preparing a polycarbonate resin composition, characterized in that It includes the steps of kneading and extruding a mixture containing 100 parts by weight of a polycarbonate resin, 0.01 to 5.5 parts by weight of a heat stabilizer, 0.01 to 3 parts by weight of a metal salt flame retardant, and 0.1 to 5 parts by weight of a drip inhibitor. Among them, the melting point of the heat stabilizer is higher than that of the polycarbonate resin.

13. A method for preparing a polycarbonate resin composition, characterized in that it includes the steps of kneading and extruding a mixture containing a polycarbonate resin, a heat stabilizer, a metal salt flame retardant, and a drip inhibitor under the conditions of 200 to 330 °C and 100 to 400 rpm. Among them, the melting point of the heat stabilizer is higher than that of the polycarbonate resin.

14. A molded article, characterized in that it contains the polycarbonate resin composition according to any one of claims 1, 2, 5, 9, 10, and 11.

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