Polycarbonate resin composition, method for preparing the same and molding products comprising the same

Abstract

The present invention relates to a polycarbonate resin composition, a method for manufacturing the same, and a molded article comprising the same, and more specifically, to a polycarbonate resin composition having excellent mechanical properties and heat resistance while achieving high flame retardancy in a thin thickness, comprising (A) 51 to 80 weight% of a polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2; (B) 5 to 37 weight% of a polycarbonate-polysiloxane copolymer; (C) 0.6 to 10 weight% of an impact modifier; and (D) a phosphate ester-based flame retardant and (E) a total of 6 to 17 weight% of a phosphazene-based flame retardant; a method for manufacturing the same, and a molded article comprising the same.

Description

Technology Field

[0001] The present invention relates to a polycarbonate resin composition, a method for manufacturing the same, and a molded article including the same. More specifically, the invention relates to a polycarbonate resin composition that includes a granular type polycarbonate having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2, which achieves high flame retardancy at a thin thickness while having excellent mechanical properties and heat resistance, a method for manufacturing the same, and a molded article including the same. Background Technology

[0003] Polycarbonate (hereinafter referred to as 'PC') resin is transparent and has excellent flame retardancy, heat resistance, and impact strength, so it is widely used as a resin for various industries, including electrical and electronic components.

[0004] Recently, with the growth of the smart home market and the increasing use of electronic devices, the applications of high-heat-resistant flame-retardant polycarbonate resins are expanding beyond components such as charging parts and adapters to include housings for home electronic devices. Furthermore, as electrical and electronic products become thinner, there is an increasing demand for high flame retardancy at thin thicknesses, as well as mechanical properties such as impact resistance and tensile strength to prevent breakage when dropped during daily use.

[0005] Conventionally, to solve this problem, methods have been known to i) incorporate a metal-based flame retardant into polycarbonate, ii) combine an impact modifier such as an acrylic or styrene-based one with a metal salt-based flame retardant, or iii) combine an impact modifier with a phosphorus-based flame retardant.

[0006] However, it was difficult to sufficiently secure the required physical properties simultaneously by only incorporating metal-based flame retardants, and when combining impact modifiers and metal salt-based flame retardants, it was difficult to secure flame retardancy, and when combining impact modifiers and phosphate-based flame retardants, there was a problem that an excessive amount of flame retardant had to be incorporated to secure sufficient flame retardancy, and there was a problem that high flame retardancy was difficult to achieve in thin thicknesses and heat resistance or mechanical strength was reduced.

[0007] Therefore, there is a need to develop polycarbonate resin compositions with excellent flame retardancy, mechanical properties, and heat resistance at thin thicknesses. Prior art literature

[0009] Korean Published Patent No. 10-2000-0041993 A The problem to be solved

[0010] In order to solve the problems of the conventional technology described above, the present invention aims to provide a polycarbonate resin composition that ensures high flame retardancy at a thin thickness while satisfying both mechanical properties and heat resistance, and is applicable to high-quality components of electrical and electronic products, industrial uses, and housings of household electronic devices.

[0011] In addition, the present invention aims to provide a method for manufacturing the above-mentioned polycarbonate resin composition.

[0012] In addition, the present invention aims to provide a molded article comprising the above-mentioned polycarbonate resin composition.

[0014] The above objectives and other objectives of this description can all be achieved by the present invention described below. means of solving the problem

[0016] To achieve the above objective, the present invention provides a polycarbonate resin composition characterized by comprising: (A) 51 to 80 weight% of a polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2; (B) 5 to 37 weight% of a polycarbonate-polysiloxane copolymer; (C) 0.6 to 10 weight% of an impact modifier; and (D) a phosphate ester-based flame retardant and (E) a total of 6 to 17 weight% of a phosphazene-based flame retardant.

[0018] In addition, the present invention provides a method for manufacturing a polycarbonate resin composition, comprising the steps of kneading and extruding under conditions of 200 to 300°C and 100 to 300 rpm, wherein the composition comprises: (A) 51 to 80 weight% of a polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2; (B) 5 to 37 weight% of a polycarbonate-polysiloxane copolymer; (C) 0.6 to 10 weight% of an impact modifier; and (D) 6 to 17 weight% of a total of a phosphate ester-based flame retardant and (E) a phosphazene-based flame retardant.

[0020] In addition, the present invention provides a molded article characterized by comprising the above-mentioned polycarbonate resin composition. Effects of the invention

[0022] According to the present invention, a granular type polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2 is uniformly dispersed with a powder type flame retardant, and when fed into an extruder hopper, the mixture is uniformly blended without causing layer separation, thereby achieving high flame retardancy at a thin thickness of 0.5 mm, and the combination of a phosphate ester-based flame retardant and a phosphazene-based flame retardant provides a polycarbonate resin composition with significantly improved mechanical properties such as impact strength and tensile strength, as well as heat resistance.

[0023] Furthermore, since the resin composition according to the present invention satisfies flame retardancy, mechanical properties, and heat resistance at a thin thickness, it offers the advantage of being applicable with high quality to components of electrical and electronic products or housings of household electronic devices, in addition to industrial applications. Brief explanation of the drawing

[0025] Figure 1 is a photograph showing a pellet-type polycarbonate (left) and a granule-type polycarbonate (right) of the same amount (1g). Figure 2 is a photograph of granular polycarbonate taken with an optical microscope to measure particle size (magnification x 20). Figure 3 is a photograph of pellet-type polycarbonate taken with an optical microscope to measure particle size (magnification x 20). Specific details for implementing the invention

[0026] The polycarbonate resin composition of the present invention will be described in detail below.

[0027] The inventors confirmed that in a polycarbonate resin composition containing a conventional flame retardant, when the polycarbonate resin is changed to a granular type polycarbonate and a combination of a phosphate ester-based flame retardant and a phosphazene-based flame retardant is included as a flame retardant system, high flame retardancy is secured at a thin thickness of 0.5 mm due to the synergistic effect of these combinations, while also having excellent mechanical properties and heat resistance. Based on this, they further devoted themselves to research and completed the present invention.

[0029] The polycarbonate resin composition according to the present description is described in detail as follows.

[0031] The polycarbonate resin composition of the present invention is characterized by comprising (A) 51 to 80 weight% of a polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2; (B) 5 to 37 weight% of a polycarbonate-polysiloxane copolymer; (C) 0.6 to 10 weight% of an impact modifier; and (D) a phosphate ester-based flame retardant and (E) a total of 6 to 17 weight% of a phosphazene-based flame retardant; and in this case, high flame retardancy is achieved at a thin thickness of 0.5 mm, while excellent mechanical properties such as tensile strength, flexural strength, and impact strength, as well as heat resistance, are achieved.

[0033] (A) Polycarbonate resin having an average particle size of 0.1 to 2 mm

[0034] The above polycarbonate resin (A), having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2, may be, for example, 51 to 80 weight%, preferably 51 to 70 weight%, more preferably 53 to 65 weight%, and even more preferably 58 to 63 weight% with respect to the total weight of the above components (A), (B), (C), (D), and (E), and within this range, there is an effect of excellent mechanical properties and balance of properties.

[0036] The above polycarbonate resin may, for example, have an average particle size of 0.1 to 5 mm with a standard deviation of 0.8 to 1.2, preferably an average particle size of 0.3 to 4 mm with a standard deviation of 0.85 to 1.15, more preferably an average particle size of 0.5 to 3 mm with a standard deviation of 0.9 to 1.1, and even more preferably an average particle size of 0.7 to 2.5 mm with a standard deviation of 0.95 to 1. Within this range, it is uniformly mixed with a powder-type flame retardant to have excellent flame retardancy, mechanical properties, and heat resistance. Furthermore, when the compositions of (A) to (E) are mixed and fed into the extruder hopper, layer separation does not occur, and the resin is uniformly mixed, which has the advantage of not causing a variation in physical properties within a single batch.

[0037] In this description, the average particle size and its standard deviation can be measured by selecting 10 granule particles from each of 10 randomly selected zones using optical microscope images, measuring the length of the major axis of the selected granule particles, and calculating the average value and its standard deviation.

[0039] The above polycarbonate resin has, for example, a bulk density of 1 to 1.12 g / cm³ as measured according to ASTM D1895. 3 , preferably 1.05 to 1.1 g / cm³ 3 , more preferably 1.07 to 1.09 g / cm³ 3 It can be, and within this range, it is uniformly mixed with a powder-type flame retardant, offering the advantage of excellent flame retardancy, mechanical properties, and heat resistance.

[0041] The above (A) polycarbonate resin may preferably be of the granule type, and the granule-type polycarbonate resin has a variety of particle sizes and a lower bulk density compared to the pellet-type polycarbonate resin, so that layer separation does not occur when mixed with a powder-type flame retardant, which has the advantage of improving flame retardancy, mechanical properties, and heat resistance.

[0042] The above pellet-type polycarbonate resin has an average particle size of 3 to 6 mm and a standard deviation of 0.03 to 0.1, having a more uniform particle size compared to the above granule-type polycarbonate resin, and has a bulk density of 1.18 g / cm³ as measured according to ASTM D1895. 3 Above, it is larger than granular type polycarbonate resin.

[0044] In this description, the granular-type polycarbonate resin undergoes a series of purification processes to remove impurities present in the polymer solution after the polycarbonate polymerization process. The polycarbonate polymer, having undergone the purification process, takes on a granular shape while undergoing a solvent removal process. This is then thermally extruded to form a pellet type.

[0045] As another example, granular polycarbonate resins can be manufactured by interfacial condensation polymerization. Polycarbonate resins are generally manufactured in three stages: raw material preparation and polymerization, polymer washing and solvent recovery, and post-treatment. However, granular polycarbonate is manufactured without undergoing a post-treatment process. Specifically, bisphenolate, in which bisphenol A is dissolved in an aqueous NaOH solution with a concentration of 5 to 10 wt%, is mixed with methylene chlorite (MDC) as a solvent and phosgene, and then a condensation polymerization reaction is carried out at the interface between the aqueous solution and the organic solvent. After the reaction, granular polycarbonate can be manufactured by neutralizing the resin in an emulsion state, washing, centrifuging, and / or adding a precipitating agent.

[0047] The above (A) polycarbonate resin may be a polymerized resin including, for example, an aromatic diol compound and a carbonate precursor.

[0048] The above aromatic diol compounds are, for example, 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, 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A; BPA), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane (Bisphenol Z; BPZ), 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, It may be one or more selected from the group consisting of 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, and α,ω-bis[3-(ο-hydroxyphenyl)propyl]polydimethylsiloxane, and preferably bisphenol A.

[0049] The above carbonate precursor may be, for example, one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate, and it may be preferable to use triphosgene, phosgene, or a mixture thereof in terms of manufacturing efficiency and physical properties.

[0050] As a specific example, the polycarbonate formed by the polymerization of the above aromatic diol compound and carbonate precursor includes a repeating unit represented by the following chemical formula 4.

[0051] [Chemical Formula 4]

[0052]

[0053] (In the above chemical formula 4, R'1 to R'4 are each independently hydrogen, C 1-10 Alkyl, C 1-10 It is an alkoxy or halogen, and Z' is unsubstituted or C 1-6 alkyl or C 6-20 Aryl-substituted C 1-10 Alkylene, unsubstituted, or C 1-10 C substituted with alkyl 3-15 It is cycloalkylene, O, S, SO, SO2, or CO.

[0054] Preferably, in the above formula 4, R'1 to R'4 are each independently hydrogen or C 1-3 It is alkyl, and Z' is unsubstituted or substituted with methyl or phenyl C 1-6 It can be an alkylene.

[0056] The above (A) polycarbonate resin may, for example, have a weight average molecular weight of 15,000 to 100,000 g / mol on the absolute PC molecular weight scale, preferably 20,000 to 80,000 g / mol, more preferably 30,000 to 60,000 g / mol, and even more preferably 30,000 to 50,000 g / mol, and within this range, it has the effect of having excellent mechanical properties.

[0058] In this description, the absolute PC molecular weight is measured by gel permeation chromatography using a traceable polycarbonate molecular weight standard. Specifically, it can be measured as a relative molecular weight distribution value for a polycarbonate sample via Gel Permeation Chromatography (GPC) using THF (tetrahydrofuran) as the eluent. Specifically, the measurement can be performed under the following conditions: solvent: THF, column temperature: 40℃, flow rate: 0.3 ml / min, sample concentration: 1 mg / ml, injection volume: 10 µl, column model: 1xPLgel 10 µm MiniMix-Bx2, equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S / W, test method (Mn, Mw, and PDI): OECD TG 118.

[0060] (B) Polycarbonate-polysiloxane copolymer

[0061] The above polycarbonate-polysiloxane copolymer (B) may be, for example, 5 to 37 weight%, preferably 10 to 35 weight%, more preferably 15 to 30 weight%, and even more preferably 20 to 30 weight% with respect to the total weight of components (A), (B), (C), (D) and (E), and within this range, there is an advantage of excellent mechanical properties, particularly impact resistance.

[0063] It is specified that the above polysiloxane-polycarbonate copolymer may be prepared, for example, by condensation polymerization of polycarbonate and polysiloxane, or by interfacial polymerization of an aromatic diol compound, a carbonate precursor, and polysiloxane, but is not limited thereto.

[0064] The above polysiloxane-polycarbonate copolymer comprises, for example, an aromatic polycarbonate-based first repeating unit represented by the following chemical formula 1; and an aromatic polycarbonate-based second repeating unit having one or more siloxane bonds represented by the following chemical formula 2.

[0066] [Chemical Formula 1]

[0067]

[0068] (In the above chemical formula 1, R 1 to R 4 are independently hydrogen, C 1-10 Alkyl, C 1-10 Selected from alkoxy and halogen, where Z is unsubstituted or C 1-6 alkyl or C 6-20 Aryl-substituted C 1-10 Alkylene; unsubstituted or C 1-10 C substituted with alkyl 3-15 Cycloalkylene; oxygen; sulfur; selected from SO, SO2 or CO.

[0069] Preferably, in the above Formula 1, R1 to R4 are each independently hydrogen or C 1-3 C is alkyl, where Z is unsubstituted or substituted with methyl or phenyl. 1-6 It can be an alkylene.

[0070] As another example, the first repeating unit represented by the above chemical formula 1 is represented by the following chemical formula 1-1, in the case where bisphenol A, an aromatic diol compound, and triphosgene, a carbonate precursor, are polymerized.

[0071] [Chemical Formula 1-1]

[0072]

[0074] [Chemical Formula 2]

[0075]

[0076] (In the above chemical formula 2, X 2 C each independently 1-10 It is an alkylene, and Y 1Each independently hydrogen, C 1-6 Alkyl, halogen, hydroxyl group, C 1-6 Alkoxy group or C 6-20 Selected from among the aryl groups, R 5 to R 8 Each is independently hydrogen; unsubstituted or substituted with oxiranyl, oxiranyl C 1-10 Alkoxy group, C 6-20 Aryl-substituted C 1-15 Alkyl; Halogen; C 1-10 Alkoxy; allyl; C 1-10 haloalkyl; or C 6-20 Selected from Aryl, and n2 is an integer from 30 to 120.)

[0077] Preferably, X in the above chemical formula 2 2 C each independently 2-10 It is an alkylene, and more preferably C 2-6 It is an alkylene, most preferably isobutylene, and the above Y 1 It can be hydrogen.

[0078] More preferably, R in Formula 2 above 5 to R 8 Each may independently be 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.

[0079] More preferably, the above R 5 to R 8 C each independently 1-10 alkyl or C 1-6 It is alkyl, and more preferably C 1-3 It is alkyl, and most preferably can be methyl.

[0080] In addition, in the above chemical formula 2, n2 may be an integer from 30 to 120, and preferably an integer from 34 to 110.

[0081] The repeating unit represented by the above chemical formula 2 is preferably represented by the following chemical formula 2-1.

[0082] [Chemical Formula 2-1]

[0083]

[0084] (In the above chemical formula 2-1, R 5 to R 8 and n2 are the same as defined above.)

[0086] As another example, the above polysiloxane-polycarbonate copolymer may further include repeating units represented by the following chemical formula 3.

[0087] [Chemical Formula 3]

[0088]

[0089] In the above chemical formula 3, X 1 C each independently 1-10 It is an alkylene, and R 9 to R 12 Each is independently hydrogen; unsubstituted or substituted with oxiranyl, oxiranyl C 1-10 Alkoxy, or C 6-20 Aryl-substituted C 1-15 Alkyl; Halogen; C 1-10 Alkoxy; allyl; C 1-10 haloalkyl; or C 6-20 It is an aryl, and n1 is an integer from 30 to 120.

[0090] Preferably, X in the above chemical formula 3 1 C each independently 2-10 It may be an alkylene, preferably C 2-4 It can be an alkylene, more preferably propane-1,3-diyl.

[0091] R in the above chemical formula 3 9 to R 12Each may independently be 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.

[0092] Preferably, the above R 9 to R 12 C each independently 1-10 alkyl or C 1-6 It is alkyl, and more preferably C 1-3 It is alkyl, and most preferably methyl.

[0093] In addition, in the above chemical formula 3, n1 may be an integer from 30 to 120, and preferably an integer from 34 to 110.

[0094] If the composition further includes repeating units represented by the above chemical formula 3, it may provide the advantage of further improving the heat resistance and impact resistance of the composition.

[0095] The repeating unit represented by the above chemical formula 3 is preferably represented by the following chemical formula 3-1.

[0096] [Chemical Formula 3-1]

[0097]

[0098] (In the above chemical formula 3-1, R 9 to R 12 and n1 are the same as defined above.)

[0100] The above polysiloxane-polycarbonate copolymer may have a weight-average molecular weight of, for example, 1,000 to 100,000 g / mol, preferably 5,000 to 70,000 g / mol, and more preferably 5,000 to 50,000 g / mol, and within this range, it provides the advantage of being easy to process and mold the composition while simultaneously satisfying impact resistance and heat resistance.

[0101] Unless otherwise defined, the weight-average molecular weight in this description can be measured using Gel Permeation Chromatography (GPC, waters breeze). Specifically, it can be measured as the relative molecular weight distribution value for a polysiloxane-polycarbonate sample via Gel Permeation Chromatography (GPC, waters breeze) using THF (tetrahydrofuran) as the eluent. In this case, as a specific measurement example, the measurement can be performed under the following conditions: solvent: THF, column temperature: 40℃, flow rate: 0.3ml / min, sample concentration: 1mg / ml, injection volume: 10µl, column model: 1xPLgel 10µm MiniMix-Bx2 (250x4.6mm), equipment name: Agilent 1200 series system, Refractive index detector: Agilent G1362 RID, RI temperature: 35℃, data processing: Agilent ChemStation S / W, test method (Mn, Mw and PDI): OECD TG 118.

[0103] (C) Impact reinforcement

[0104] The above impact modifier (C) may be, for example, 0.6 to 10 weight%, preferably 0.6 to 7 weight%, more preferably 1 to 5 weight%, and even more preferably 1 to 4 weight% with respect to the total weight of components (A), (B), (C), (D), and (E), and within this range, there is an effect of excellent mechanical properties while maintaining a balance of physical properties.

[0106] The above (C) impact modifier is, for example, an alkyl ester compound-diene rubber-unsaturated aromatic compound graft copolymer, preferably a methyl methacrylate-butadiene-styrene copolymer, in which case it has the effect of having excellent mechanical properties while having an excellent balance of physical properties.

[0108] Unless otherwise noted, the above (meth)acrylate alkyl ester compound means that both alkyl acrylate esters and alkyl methacrylate esters are possible, and may be one or more selected from the group consisting of (meth)acrylate methyl ester, (meth)acrylate ethyl ester, (meth)acrylate propyl ester, (meth)acrylate 2-ethylhexyl ester, (meth)acrylate decyl ester, and (meth)acrylate lauryl ester, and preferably may be methyl methacrylate.

[0110] The above diene-based rubber may be, for example, one or more selected from butadiene polymer, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, and polymers derived therefrom, and preferably may be a butadiene polymer.

[0112] The above unsaturated aromatic compound may be one or more selected from the group consisting of styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brovostyrene, ρ-bromostyrene, m-bromostyrene, ο-chlorostyrene, ρ-chlorostyrene, m-chlorostyrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, and preferably may be styrene.

[0114] (D) Phosphate ester-based flame retardant

[0115] The above (D) phosphate ester-based flame retardant may be, for example, 3 to 12 weight%, preferably 4 to 10 weight%, more preferably 4 to 7 weight% with respect to the total weight of components (A), (B), (C), (D) and (E), and within this range, excellent heat resistance and flame retardancy are achieved.

[0117] The above (D) phosphate ester-based flame retardant may be, for example, one or more selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresylphenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, bisphenol A tetraphenyl diphosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetraxylyl diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetracresyl diphosphate, hydroquinone tetraxylyl diphosphate, resorcinol tetraphenyl diphosphate, and resorcinol bisdixyleneyl phosphate, and in this case, there is an advantage of ensuring the flame retardancy of the composition as well as having superior heat resistance of the composition.

[0119] (E) Phosphazene-based flame retardant

[0120] The above phosphazene-based flame retardant (E) may be present in an amount of, for example, 1.5 to 12 weight%, preferably 2 to 10 weight%, more preferably 4 to 10 weight%, and even more preferably 6 to 9 weight% with respect to the total weight of components (A), (B), (C), (D) and (E), and within this range, flame retardancy is ensured while having excellent mechanical properties.

[0121] The above (E) phosphazene-based flame retardant is, for example, an organic compound having -P=N- bonds in its molecule, and preferably one or more selected from the group consisting of cyclic phosphazene compounds, chain-type phosphazene compounds, and cross-linked phosphazene compounds, and preferably a cyclic phosphazene compound, in which case it has excellent flame retardancy and mechanical properties.

[0123] The above-mentioned cyclic phosphazene compound is preferably a compound represented by the following chemical formula 5.

[0124] [Chemical Formula 5]

[0125]

[0126] (In the above chemical formula 5, m is an integer from 3 to 25, and R 1 and R 2 is identical or different and represents an aryl group or an alkylaryl group)

[0127] In the above chemical formula 5, m is preferably an integer from 3 to 5.

[0129] The cyclic phosphazene compound represented by the above chemical formula 5 is more preferably, R 1 and R 2 The phenyl group is a cyclic phenoxyphosphazene, and more preferably, it may be one or more selected from the group consisting of phenoxycyclotriphosphazene, octafenoxycyclotetraphosphazene, and decafexycyclopentaphosphazene.

[0131] The above-mentioned chain-type phosphazene compound is preferably a compound represented by the following chemical formula 6.

[0132] [Chemical Formula 6]

[0133]

[0134] (In the above chemical formula 6, n is an integer from 3 to 10,000, and X is -N=P(OR 1 )3rd term or -N=P(O)OR 1 It represents Qi, and Y is -P(OR 1 )4th term or -P(O)(OR 1 ) Represents period 2. R 3 and R 4 is identical or different and represents an aryl group or an alkylaryl group.

[0135] In the above chemical formula 6, n is preferably an integer from 3 to 100, more preferably an integer from 3 to 25.

[0136] The chain-type phosphazene compound represented by the above chemical formula 6 is preferably R 3 and R 4 It is a chain-type phenoxphosphazene with a phenyl group.

[0138] The above-mentioned cross-linked phosphazene compound is formed by cross-linking one or more phosphazene compounds selected from the group consisting of cyclic phosphazene compounds and chain-type phosphazene compounds by a cross-linking group represented by the following chemical formula 7.

[0139] [Chemical Formula 7]

[0140]

[0141] (In the above Chemical Formula 7, A is -C(CH3)2-, -SO2-, -S-, or -O-, and l is 0 or 1.)

[0143] The above cross-linked phosphazene compound is preferably, in Formula 5, R 1 and R 2 A cross-linked phenoxyphosphazene compound formed by cross-linking a cyclic phenoxyphosphazene compound in which g is a phenyl group by a cross-linking group represented by Chemical Formula 7, wherein in Chemical Formula 6, R 3 and R 4 The phenyl group may be a chain-type phenoxyphosphazene compound formed by crosslinking a phenyl group with a crosslinking group represented by Chemical Formula 7, or a mixture thereof, and more preferably, the cyclic phenoxyphosphazene compound formed by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by Chemical Formula 7.

[0145] When the combination of the above (D) phosphate ester-based flame retardant and (E) phosphazene-based flame retardant is included, there is an advantage that flame retardancy, impact resistance, and heat resistance are all significantly improved due to the synergistic effect resulting from the combination.

[0147] The total amount of the above (D) phosphate ester-based flame retardant and (E) phosphazene-based flame retardant may be, for example, 6 to 17 weight%, preferably 8 to 17 weight%, more preferably 10 to 15 weight%, and even more preferably 10 to 13 weight% with respect to the total weight of components (A), (B), (C), (D) and (E), and within this range, flame retardancy is ensured while excellent mechanical properties and heat resistance are achieved.

[0148] The weight ratio of the above (D) phosphate ester-based flame retardant and (E) phosphazene-based flame retardant may be, for example, 1:1 to 1:3, preferably 1:1.5 to 1:2.7, more preferably 1:1.7 to 1:2.5, and within this range, flame retardancy is ensured while having excellent impact resistance and heat resistance.

[0150] additives

[0151] The above polycarbonate resin composition may include, for example, one or more selected from the group consisting of heat stabilizers, UV stabilizers, and lubricants.

[0152] The above heat stabilizer may be, for example, one or more selected from the group consisting of hindered phenol-based heat stabilizers, diphenylamine-based heat stabilizers, sulfur-based heat stabilizers, and phosphorus-based heat stabilizers, and preferably may be a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, or a mixture thereof, in which case it has the effect of preventing oxidation by heat during the extrusion process and having excellent mechanical properties.

[0153] The hindered phenolic heat stabilizer mentioned above may be, for example, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene or a mixture thereof, and preferably may be pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0154] The above diphenylamine-based heat stabilizer may be, for example, one or more selected from the group consisting of phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and 4-isopropoxydiphenylamine.

[0155] The above-mentioned sulfur-based heat stabilizer may be, for example, one or more selected from dilauryl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, and pentaerythrityl tetrakis (3-laurylthiopropion ester), but is not limited thereto.

[0156] The above-mentioned phosphorus-based heat stabilizers are, for example, tris(mixed, mono- and ginoylphenyl)phosphite, tris(2,3-di-t-butylphenyl)phosphite, 4,4'-butylidene bis(3-methyl-6-t-butylphenyl-di-tridecyl)phosphite, 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-t-butylphenyl)butane, bis(2,4-di-t-butylphenyl)pentaerythritol-di-phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenephosphanite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythrityl-di-phosphite, and 2,2'-ethylidene It may be one or more selected from bis(4,6-di-t-butylphenyl)-2-ethylhexyl-phosphite, bis(2,4,6-di-t-butylphenyl) pentaerythritol-di-phosphite, triphenylphosphite, diphenyldecyl phosphite, didecylphenyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonirphenir phosphite, and tridodecyl trithiophosphite, and preferably bis(2,6-di-t-butyl-4-methylphenyl) pentaerythrityl-di-phosphite, but is not limited thereto.

[0157] The above heat stabilizer may be, for example, 0.01 to 5 weight%, preferably 0.1 to 4 weight%, more preferably 0.5 to 3 weight% with respect to the total weight of components (A), (B), (C), (D) and (E), and has the effect of preventing oxidation by heat during the extrusion process and having excellent mechanical properties.

[0159] The above lubricant may be one or more selected from the group consisting of modified montanic acid wax, long chain ester of pentaerythritol, and fatty acid ester of neopentylpolyol.

[0160] The above lubricant may be, for example, 0.01 to 5 weight%, preferably 0.1 to 4 weight%, more preferably 0.5 to 3 weight% with respect to the total weight of components (A), (B), (C), (D) and (E), and in this case, there is an advantage of inducing smooth flow during extrusion and injection processes.

[0162] The above-mentioned ultraviolet absorber may be one or more selected from the group consisting of, for example, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.

[0163] The above triazine-based ultraviolet absorbers are, for example, 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-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, It may be one or more selected from the group consisting of 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-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.

[0164] The above benzophenone-based ultraviolet absorber may be, for example, one or more selected from the group consisting of 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy4-n-octoxy-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.

[0165] The above-mentioned benzotriazole-based ultraviolet absorbers are, for example, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)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-benzotriazole-2-yl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, It may be one or more selected from the group consisting of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole and (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole.

[0166] The above cyanoacrylate-based ultraviolet absorber may be, for example, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate, or a mixture thereof.

[0167] The above-mentioned UV absorber may be, for example, 0.01 to 5 weight%, preferably 0.1 to 4 weight%, more preferably 0.5 to 3 weight% with respect to the total weight of components (A), (B), (C), (D), and (E), and in this case, there is an effect of improving light resistance while maintaining an excellent balance of physical properties.

[0169] The above polycarbonate composition may optionally further include one or more additives selected from anti-dropping agents, processing aids, plasticizers, coupling agents, light stabilizers, release agents, dispersants, anti-dropping agents, weather stabilizers, antioxidants, compatibilizers, pigments, dyes, antistatic agents, wear-resistant agents, fillers, and antimicrobial agents, as needed.

[0171] Polycarbonate resin composition

[0172] The above polycarbonate resin composition preferably has a flame retardancy of V-0 grade or higher when measured with a specimen of 0.5 mm thickness according to the UL 94 V measurement method (Vertical Burning Test), and in this case, there is an effect of ensuring high flame retardancy at a thin thickness of 0.5 mm while having an excellent balance of physical properties.

[0174] The above polycarbonate resin composition may preferably have a heat distortion temperature of 90°C or higher, more preferably 93°C or higher, even more preferably 93 to 100°C, and even more preferably 95 to 100°C, measured at 18.6 kgf according to ASTM D648, and within this range, it has the effect of having excellent heat resistance while having an excellent balance of physical properties.

[0176] The above polycarbonate resin composition may preferably have an impact strength of 8 kgf·cm / cm or more, more preferably 30 kgf·cm / cm or more, even more preferably 50 kgf·cm / cm or more, even more preferably 50 to 80 kgf·cm / cm, and particularly preferably 55 to 75 kgf·cm / cm, measured at room temperature (20 to 25°C) by making a notch in a specimen with a thickness of 1 / 8" according to ASTM D256, and within this range, the balance of physical properties is excellent.

[0178] The above polycarbonate resin composition preferably has a tensile strength of 600 kgf / cm² measured according to ASTM D638 at a specimen thickness of 1 / 8" and a crosshead speed of 50 mm / min. 2 Ideally, 650 kgf / cm² 2 Ideally, 650 to 720 kgf / cm² 2 , more preferably 650 to 700 kgf / cm² 2 It can be, and within this range, there is an effect where the balance of physical properties is excellent.

[0180] The above polycarbonate resin composition preferably has a flexural strength of 950 kgf / cm² measured according to ASTM D790 at a specimen thickness of 1 / 8", a span of 50 mm, and a speed of 10 mm / min. 2 Ideally, 1000 kgf / cm² 2 Above, more preferably 1000 to 1100 kgf / cm² 2 It can be, and within this range, there is an effect where the balance of physical properties is excellent.

[0182] Method for manufacturing a polycarbonate resin composition

[0183] The method for manufacturing a polycarbonate resin composition according to the present invention is characterized by comprising the step of mixing and extruding under conditions of 200 to 300°C and 100 to 300 rpm, including (A) 51 to 80 weight% of a polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2; (B) 5 to 37 weight% of a polycarbonate-polysiloxane copolymer; (C) 0.6 to 10 weight% of an impact modifier; and (D) 6 to 17 weight% of a total of a phosphate ester-based flame retardant and (E) a phosphazene-based flame retardant. In this case, high flame retardancy is achieved at a thin thickness of 0.5 mm, while excellent mechanical properties such as tensile strength, flexural strength, and impact strength, as well as heat resistance, are achieved.

[0185] The method for manufacturing the above polycarbonate resin composition shares all the technical features of the aforementioned polycarbonate resin composition. Therefore, the description of the overlapping parts will be omitted.

[0187] The above mixing and extrusion can be performed, for example, through a single-screw extruder, a twin-screw extruder, or a Banbury mixer, in which case the composition is uniformly dispersed, resulting in excellent compatibility.

[0189] The above mixing and extrusion can preferably be performed within a barrel temperature range of 220 to 280°C, more preferably 240 to 260°C, in which case sufficient melt mixing can be achieved while the throughput per unit time is appropriate, and there is an effect of not causing problems such as thermal decomposition of the resin components.

[0190] The above mixing and extrusion can preferably be performed under conditions where the screw rotation speed is 150 to 300 rpm, more preferably 150 to 250 rpm, in which case the throughput per unit time is appropriate, resulting in excellent process efficiency and the effect of suppressing excessive cutting.

[0192] Molded product

[0193] The molded article of the present invention is characterized by comprising the polycarbonate resin composition of the present invention, and in this case, while achieving high flame retardancy at a thin thickness of 0.5 mm, it has excellent mechanical properties such as tensile strength, flexural strength, and impact strength, as well as heat resistance, and has the advantage of being utilized for various applications such as housings for household electronic devices as well as electrical and electronic components and industrial applications.

[0195] The above-mentioned molded product may be, for example, a component of an electrical and electronic product, a housing of an electronic device, a laptop bezel, an automotive interior material, or an automotive exterior material.

[0197] The method for manufacturing a molded article according to the present invention preferably comprises the steps of: (A) 51 to 80 weight% of a polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2; (B) 5 to 37 weight% of a polycarbonate-polysiloxane copolymer; (C) 0.6 to 10 weight% of an impact modifier; and (D) 6 to 17 weight% of a total of a phosphate ester-based flame retardant and (E) a phosphazene-based flame retardant; and kneading and extruding the mixture under conditions of 200 to 300°C and 100 to 300 rpm to produce pellets; and injecting the produced pellets to manufacture a molded article. In this case, the method has the effect of providing a molded article with excellent mechanical properties and heat resistance while achieving high flame retardancy at a thin thickness of 0.5 mm.

[0199] The above-mentioned pellets can be manufactured by sufficiently drying them using, for example, a dehumidifying dryer or a hot air dryer, and then performing injection molding.

[0201] The method for manufacturing the molded article described herein is not particularly limited as long as it follows the definition of the present invention, provided that conditions, methods, and devices commonly used in the technical field to which the present invention belongs are utilized.

[0203] In describing the polycarbonate resin composition, the method of manufacturing the same, and the molded article described herein, it is specified that other conditions or equipment not explicitly described may be appropriately selected within the scope of practices ordinarily carried out in the industry and are not particularly limited.

[0205] The polycarbonate resin having an average particle size of 0.1 to 2 mm and the pellet-type polycarbonate resin of the present invention will be described below with reference to the drawings.

[0206] Figure 1 below shows 1g of pellet-type polycarbonate resin (left) and granule-type polycarbonate resin (right). From the photograph, it can be seen that the pellet-type polycarbonate resin has a larger average particle size and angular edges compared to the granule-type polycarbonate resin. Additionally, it can be seen that the pellet-type polycarbonate resin has a higher density compared to the granule-type polycarbonate resin.

[0207] Figure 2 below is a photograph of a granular type polycarbonate resin taken with an optical microscope at 20x magnification to measure the average particle size.

[0208] Figure 3 below is a photograph of a pellet-type polycarbonate resin taken with an optical microscope at 20x magnification to measure the average particle size.

[0210] Hereinafter, preferred embodiments are presented to aid in understanding the description; however, the following embodiments are merely illustrative of the description, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the description, and that such variations and modifications fall within the scope of the appended claims.

[0212] The materials used in the examples and comparative examples are as follows.

[0213] A-1) Granular type polycarbonate: Weight-average molecular weight of 40,000 g / mol on the absolute PC molecular weight scale (average particle size 1 mm, standard deviation 0.98, bulk density 1.084 g / cm³) 3 )

[0214] A-2) Pellet-type polycarbonate: Weight-average molecular weight of 40,000 g / mol on the absolute PC molecular weight scale (average particle size 3 mm, standard deviation 0.056, bulk density 1.187 g / cm³) 3 )

[0215] B) Polysiloxane-polycarbonate copolymer: Si-PC ((LG Chem)

[0216] C) Impact modifier: Methyl methacrylate-butadiene-styrene copolymer (LG Chem's EM538)

[0217] D) Phosphate ester-based flame retardant: FP-600 (ADEKE)

[0218] E) Phosphazene-based flame retardant: Hexaphenoxycyclotriphosphazene (HPCTP) (Fushimi Pharmaceutical Co. Ltd, JINWEI CHEM)

[0219] F) Additives

[0220] f-1) Heat stabilizer: IR-1076 (Songwon Industrial)

[0221] f-2) UV absorber: UV-329 (BASF)

[0222] f-3) Lubricant: PETS-L348 (FACI)

[0224] [Example]

[0225] The composition and content listed in Tables 1 and 2 below were mixed and then uniformly mixed using a mixer. The mixture was then melted and kneaded in a twin-screw extruder under conditions of 220–290°C, and then extruded to produce polycarbonate resin composition pellets. These pellets were dried at 80°C for at least 4 hours, then injected using an injection molding machine to produce specimens for measuring physical properties. After being left for at least 48 hours, the physical properties were measured.

[0226] The additives were 0.4 wt% heat stabilizer, 0.1 wt% ultraviolet absorber, and 0.5 wt% lubricant.

[0228] [Test Example]

[0229] The characteristics of the specimens prepared in Examples 1 to 10 and Comparative Examples 1 to 9 were measured by the following method, and the results are shown in Tables 1 and 2 below.

[0231] measurement method

[0232] * Tensile strength (kgf / cm²) 2 Tensile strength was measured according to ASTM D638 with a specimen thickness of 1 / 8" at a crosshead speed of 50 mm / min.

[0233] * Flexural strength (kgf / cm²) 2 According to ASTM D790, flexural strength was measured with a specimen thickness of 1 / 8", a span of 50 mm, and a speed of 10 mm / min.

[0234] * Impact strength (kgf·cm / cm): According to ASTM D256, a notch was made in a 1 / 8" thick specimen and the impact strength was measured at room temperature (20~25℃).

[0235] * Flame Retardancy: The flame retardancy rating was evaluated as follows for a specimen with a thickness of 0.5 mm based on the UL 94 V measurement method (Vertical Burning Test).

[0236] First, a flame 20 mm high was applied to the specimen for 10 seconds, the combustion time (t1) of the specimen was measured, and the combustion pattern was recorded. Subsequently, after the combustion ended following the first application of the flame, the specimen was applied again for 10 seconds, the combustion time (t2) and the glowing time (t3) were measured, and the combustion pattern was recorded. After performing this five times using specimens of the same specifications, the results were evaluated according to the criteria shown in Table 3 below.

[0237] division V-0 V-1 V-2 Individual combustion time (t1 or t2 of individual specimen) 10 seconds or less 30 seconds or less 30 seconds or less Total combustion time of 5 specimens (sum of t1 and t2 of 5 specimens) 50 seconds or less 250 seconds or less 250 seconds or less Time of combustion and spark formation after secondary flame contact (sum of t2 and t3 of individual specimens) 30 seconds or less 60 seconds or less 60 seconds or less Whether or not it drops flame-emitting particles doesn't exist doesn't exist is

[0238] * Heat distortion temperature (HDT, °C): The heat distortion temperature was measured according to ASTM D648 with a specimen thickness of 1 / 4" and under 18.6 kg.

[0239] * Flow index (g / 10min): Measured for 10 minutes at 260℃ under a load of 2.16 Kgf according to ASTM D1238.

[0241] Classification (Weight%) Examples 1 2 3 3 4 5 6 7 9 10 A-1) 58 58 58 58 56 58 63 53 54 78 A-2) B) 25 25 25 25 25 30 20 30 25 5 C) 3 3 3 3 3 1 3 3 5 3 D) 11 8 6 4 5 4 6 6 6 6 E) 2 5 7 9 10 6 7 7 9 7 additives 1 1 1 1 1 1 1 1 1 1 Physical properties HDT(°C) 91 94 95 99 92 99 96 95 91 95 Tensile strength (kgf / cm²) 2 ) 680 660 620 625 600 610 610 605 610 630 Flexural strength (kgf / cm²) 2 ) 1050 1030 1006 980 1000 1010 1000 980 990 1010 Impact strength (kgf·cm / cm) 8 10 60 61 53 58 52 70 54 9 Flame retardancy (0.5 mm) V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0

[0242] (In Table 1 above, the content of each component is in weight% based on the total weight of the composition.)

[0243] Classification (Weight%) Comparative example 1 2 3 4 5 6 7 8 9 A-1) 58 58 82 38 60.9 46 69 51 A-2) 58 B) 25 25 25 1 45 25 25 25 25 C) 3 3 3 3 3 0.1 15 3 3 D) 6 13 6 6 6 6 1 10 E) 7 13 7 7 7 7 1 10 additives 1 1 1 1 1 1 1 1 1 Physical properties HDT(°C) 94 106 89 95 95 95 95 120 60 Tensile strength (kgf / cm²) 2 ) 620 590 680 650 600 625 610 560 630 Flexural strength (kgf / cm²) 2 ) 990 940 1070 1050 950 1005 990 900 990 Impact strength (kgf·cm / cm) 48 75 7 8 80 6 70 65 5 Flame retardancy (0.5 mm) V-2 V-1 V-0 V-1 V-1 V-0 V-2 V-2 V-0

[0244] (In Table 2 above, the content of each component is in weight% based on the total weight of the composition.)

[0245] As shown in Tables 1 and 2 above, the polycarbonate resin compositions of the present invention (Examples 1 to 10) demonstrated excellent effects in impact strength, tensile strength, flexural strength, and heat resistance, while achieving high flame retardancy of V-0 grade or higher at a thin thickness of 0.5 mm compared to Comparative Examples 1 to 9.

[0246] Specifically, Examples 1 to 10, which include granular type polycarbonate resin, showed excellent flame retardancy, impact strength, tensile strength, flexural strength, and heat resistance when the components (A) to (E) blended during the mixing and extrusion steps were fed into the extruder hopper, particularly without the phenomenon of separation between the polycarbonate and the flame retardant.

[0247] As a notable result, it was confirmed that the impact strength was further improved in Examples 3 to 10, in which (E) a phosphazene-based flame retardant was included in a larger amount than (D) a phosphate ester-based flame retardant.

[0248] On the other hand, Comparative Example 1, which included a pellet-type polycarbonate resin, showed a layer separation phenomenon when the components (A) to (E) blended during the mixing and extrusion steps were fed into the extruder hopper, causing the flame retardancy to drop to V-2, and Comparative Example 2, which used phosphazene flame retardant alone, also showed a flame retardancy of only V-1.

[0249] In addition, (D) Comparative Example 3, which used a phosphate ester-based flame retardant alone, had poor heat distortion temperature and impact strength, and (B) Comparative Example 4, which used a small amount of polycarbonate-polysiloxane copolymer, had reduced flame retardancy.

[0250] In addition, Comparative Example 5, which contains a small amount of (A-1) polycarbonate resin and an excess amount of (B) polycarbonate-polysiloxane carbonate, showed reduced flame retardancy and flexural strength.

[0251] In addition, Comparative Example 6, in which (C) an impact reinforcing agent was used in a small amount, had reduced impact strength, and Comparative Example 7, in which (C) an impact reinforcing agent was used in an excessive amount, had reduced flame retardancy.

[0252] In addition, Comparative Example 8, in which the total amount of (D) phosphate ester-based flame retardant and (E) phosphazene-based flame retardant was small, showed reduced flame retardancy, while Comparative Example 9, in which the amount was excessive, showed lower heat distortion temperature and impact strength.

[0254] [Additional Examples]

[0255] In the step of manufacturing polycarbonate resin composition pellets by melting and kneading the mixture with the composition and content described in Example 3 of Table 1 and Comparative Example 1 of Table 2, and then extruding it in a twin-screw extruder under conditions of 220–290°C, the pellets produced at the feed rate of one batch of the extruder at the initial (30% point), middle (50% point), and final (80% point) stages, respectively, were injected into an injection molding machine to produce specimens for measuring physical properties. After leaving the specimens for at least 48 hours, the physical properties were measured in the same manner as described above. This is shown in Table 4 below.

[0257] division Example 3 Comparative Example 1 beginning Mid-term last period beginning Mid-term last period HDT(°C) 94 95 95 92 93 98 Tensile strength (kgf / cm²) 2 ) 630 630 630 600 610 650 Flexural strength (kgf / cm²) 2 ) 1000 1010 1010 960 980 1040 Impact strength (kgf·cm / cm) 58 60 61 36 38 68 Flame retardancy (0.5 mm) V-0 V-0 V-0 V-1 V-2 V-2 Flow index (g / 10min) 20 21 21 32 31 14

[0258] As shown in Table 4 above, Example 3, which contains a polycarbonate resin in granular form, was found to have excellent mechanical properties, heat resistance, and flame retardancy without change during the initial, middle, and final stages in one batch.

[0259] On the other hand, Comparative Example 1, which contained a pellet-type polycarbonate resin, showed severe deviations in mechanical properties, heat resistance, and flame retardancy in the initial, middle, and final stages of one batch. This was attributed to the layer separation phenomenon when the pellet-type polycarbonate resin and flame retardant were fed into the hopper during the mixing and extrusion stages.

[0260] For reference, the physical property values ​​listed in Example 3 of Table 1 and Comparative Example 1 of Table 2 are the average values ​​of the initial, middle, and final stages, and for the Examples and Comparative Examples excluding Comparative Example 1, since there is no difference in physical properties between the initial, middle, and final stages of the extrusion step using granular polycarbonate resin, the values ​​are measured at any point.

Claims

Claim 1 A polycarbonate resin composition characterized by comprising: (A) 51 to 80 weight% of a polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2; (B) 5 to 37 weight% of a polycarbonate-polysiloxane copolymer; (C) 0.6 to 10 weight% of an impact modifier; and (D) a phosphate ester-based flame retardant and (E) a total of 6 to 17 weight% of a phosphazene-based flame retardant. Claim 2 A polycarbonate resin composition according to claim 1, characterized in that the (A) polycarbonate resin is of the granule type. Claim 3 In claim 1, the above (B) polycarbonate-polysiloxane copolymer is the following chemical formula 1 [Chemical Formula 1] (In the above chemical formula 1, R 1 to R 4 are independently hydrogen, C 1-10 Alkyl, C 1-10 Selected from alkoxy and halogen, where Z is unsubstituted or C 1-6 alkyl or C 6-20 Aryl-substituted C 1-10 Alkylene; unsubstituted or C 1-10 C substituted with alkyl 3-15 An aromatic polycarbonate-based first repeating unit represented by cycloalkylene; oxygen; sulfur; selected from SO, SO2 or CO; and the following chemical formula 2 [Chemical Formula 2] (In the above chemical formula 2, X 2 C each independently 1-10 It is an alkylene, and Y 1 Each independently hydrogen, C 1-6 Alkyl, halogen, hydroxyl group, C 1-6 Alkoxy group or C 6-20 Selected from among the aryl groups, R 5 to R 8 Each is independently hydrogen; unsubstituted or substituted with oxiranyl, oxiranyl C 1-10 Alkoxy group, C 6-20 Aryl-substituted C 1-15 Alkyl; Halogen; C 1-10 Alkoxy; allyl; C 1-10 haloalkyl; or C 6-20 A polycarbonate resin composition characterized by comprising an aromatic polycarbonate-based second repeating unit having one or more siloxane bonds, represented as (selected from aryls, where n2 is an integer from 30 to 120). Claim 4 In paragraph 3, the above (B) polysiloxane-polycarbonate copolymer is the following chemical formula 3 [Chemical Formula 3] (In the above chemical formula 3, X 1 C each independently 1-10 It is an alkylene, and R 9 to R 12 Each is independently hydrogen; unsubstituted or substituted with oxiranyl, oxiranyl C 1-10 Alkoxy, or C 6-20 Aryl-substituted C 1-15 Alkyl; Halogen; C 1-10 Alkoxy; allyl; C 1-10 haloalkyl; or C 6-20 A polycarbonate resin composition characterized by including a repeating unit represented as an aryl, where n1 is an integer from 30 to 120. Claim 5 A polycarbonate resin composition according to claim 1, characterized in that the impact reinforcing agent (C) is an (meth)acrylate alkyl ester compound-diene rubber-unsaturated aromatic compound graft copolymer. Claim 6 A polycarbonate resin composition according to claim 1, characterized in that the weight ratio of the (D) phosphate ester-based flame retardant and the (E) phosphazene-based flame retardant is 1:1 to 1:

3. Claim 7 A polycarbonate resin composition according to claim 1, wherein the (D) phosphate ester-based flame retardant is one or more selected from the group consisting of trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresylphenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, bisphenol A tetraphenyl diphosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetraxyl diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetracresyl diphosphate, hydroquinone tetraxyl diphosphate, resorcinol tetraphenyl diphosphate, and resorcinol bisdixyleneyl phosphate. Claim 8 A polycarbonate resin composition according to claim 1, characterized in that the (E) phosphazene-based flame retardant is one or more selected from the group consisting of cyclic phosphazene compounds, chain-type phosphazene compounds, and cross-linked phosphazene compounds. Claim 9 A polycarbonate resin composition according to claim 8, wherein the cyclic phosphazene compound is a compound represented by the following chemical formula 5, the chain-type phosphazene compound is a compound represented by the following chemical formula 6, and the cross-linked phosphazene compound is a compound formed by cross-linking one or more phosphazene compounds selected from the group consisting of cyclic phosphazene compounds and chain-type phosphazene compounds by a cross-linking group represented by the following chemical formula 7. [Chemical Formula 5] (In the above chemical formula 5, m is an integer from 3 to 25, and R 1 and R 2 (which is identical or different and represents an aryl group or an alkylaryl group)[Chemical Formula 6] (In the above chemical formula 6, n is an integer from 3 to 10,000, and X is -N=P(OR 1 )3rd term or -N=P(O)OR 1 It represents Qi, and Y is -P(OR 1 )4th term or -P(O)(OR 1 ) Represents period 2. R 3 and R 4 is identical or different and represents an aryl group or an alkylaryl group. [Chemical Formula 7] (In the above Chemical Formula 7, A is -C(CH3)2-, -SO2-, -S-, or -O-, and l is 0 or 1.) Claim 10 A polycarbonate resin composition according to claim 1, characterized in that the polycarbonate resin composition comprises one or more selected from the group consisting of a heat stabilizer, a UV absorber, and a lubricant. Claim 11 The polycarbonate resin composition according to claim 1 is characterized in that the polycarbonate resin composition has an Izod impact strength of 7.5 kgf·cm / cm or higher, measured at room temperature (20~25℃) with a specimen thickness of 1 / 8" according to ASTM D256, and a flame retardancy of V-0 grade or higher, measured at a specimen thickness of 0.5 mm according to UL 94V. Claim 12 A polycarbonate resin composition according to claim 1, characterized in that the polycarbonate resin composition has a heat distortion temperature of 90°C or higher as measured under an 18.6 kgf load in accordance with ASTM D648. Claim 13 A method for manufacturing a polycarbonate resin composition, characterized by comprising the step of kneading and extruding under conditions of 200 to 300°C and 100 to 300 rpm, wherein the composition comprises (A) 51 to 80 weight% of a polycarbonate resin having an average particle size of 0.1 to 5 mm and a standard deviation of 0.8 to 1.2, (B) 5 to 37 weight% of a polycarbonate-polysiloxane copolymer, (C) 0.6 to 10 weight% of an impact modifier, and (D) a phosphate ester-based flame retardant and (E) a phosphazene-based flame retardant, totaling 6 to 17 weight%. Claim 14 A molded article characterized by comprising a polycarbonate resin composition according to any one of claims 1 to 12.

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