Polycarbonate resin composition, its production method, and molded article containing the same

Abstract

The present invention relates to a polycarbonate resin composition, a production method thereof, and a molded article containing the same, and more specifically, to a polycarbonate resin composition containing A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min, B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) 2 to 12% by weight of a liquid phosphorus-based flame retardant, and E) 1 to 7% by weight of a phosphazene compound, a production method thereof, and a molded article containing the same. According to the present invention, there is an effect of providing a polycarbonate resin composition which contains a high content of post-consumer recycled polycarbonate, thereby increasing the recycling ratio, and is excellent in impact resistance, heat resistance and flame retardancy, a production method thereof, and a molded article containing the same.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0104189 filed on August 19, 2022, and Korean Patent Application No. 10-2023-0097211, refiled on July 26, 2023 based thereon, and all contents disclosed in the documents of said Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a polycarbonate resin composition, a method for producing the same, and a molded article containing the same. More specifically, the present invention relates to a polycarbonate resin composition that has excellent flame retardancy, impact resistance, and heat resistance even though it contains a high content of post-consumer recycled polycarbonate, which is made by recycling plastics discarded by end consumers after use, a method for producing the same, and a molded article containing the same. [Background technology]

[0003] Plastics have been used in a variety of fields for decades due to their many advantages, including excellent productivity, light weight, and thermal insulation. However, due to their structural characteristics, they do not decompose easily, which causes environmental pollution when they are disposed of in landfills. Various research efforts have been made to solve this problem, one of which is recycling. Recycling waste plastics can solve the problem of environmental pollution and also has a significant effect in terms of cost reduction.

[0004] In line with the trend toward environmental awareness, IT, electrical and electronics, and automobile manufacturers are trying to recycle plastics discarded by end consumers after use, but there are many restrictions on their use because the mechanical properties of these plastics are inferior to those of existing plastics.

[0005] Among various types of plastics, polycarbonate is an amorphous thermoplastic resin that has the advantages of high impact resistance at room temperature, excellent thermal stability and transparency, and high dimensional stability. Therefore, it is widely used as a resin for various industrial applications, including building materials, exterior materials and parts for electrical and electronic products, automotive parts, and optical components.

[0006] Although polycarbonate has many advantages, it has problems such as low impact resistance at low temperatures and the resin itself lacks flame retardancy, making it dangerous in the event of a fire when used in electrical, electronic, and automotive devices. To solve this problem, if a flame retardant is added to polycarbonate, problems arise in that mechanical properties such as impact resistance and heat resistance are reduced.

[0007] Furthermore, when post-consumer recycled polycarbonate is used in a thermoplastic resin composition, there is a problem that the impact resistance and heat resistance are further reduced, so it is used only in small amounts.

[0008] Therefore, there is a demand for the development of a thermoplastic resin composition that can increase the proportion of recycled resin by including a high content of post-consumer recycled polycarbonate in the thermoplastic resin composition, while still being able to impart excellent flame retardancy, impact resistance, and heat resistance. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Korean Patent Publication No. 10-2011-0126425 Summary of the Invention [Problem to be solved by the invention]

[0010] In order to solve the above-mentioned problems of the prior art, the present disclosure aims to provide a polycarbonate resin composition that has excellent flame retardancy, impact resistance, and heat resistance despite containing a high content of post-consumer recycled polycarbonate.

[0011] Another object of the present disclosure is to provide a method for producing the polycarbonate resin composition.

[0012] Another object of the present disclosure is to provide a molded article containing the polycarbonate resin composition.

[0013] The above and other objects of the present disclosure can all be achieved by the disclosure set forth below. [Means for solving the problem]

[0014] To achieve the above object, the present disclosure provides a polycarbonate resin composition comprising: A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min; B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; D) 2 to 12% by weight of a liquid phosphorus-based flame retardant; and E) 1 to 7% by weight of a phosphazene compound.

[0015] The polycarbonate resin composition preferably contains A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min, A-2) 0 to 50% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min, B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) 2 to 12% by weight of a liquid phosphorus-based flame retardant, and E) 1 to 7% by weight of a phosphazene compound.

[0016] The polycarbonate resin composition preferably contains A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min, A-2) 1 to 50% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min, B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) 2 to 12% by weight of a liquid phosphorus-based flame retardant, and E) 1 to 7% by weight of a phosphazene compound.

[0017] The A-1) polycarbonate may preferably be a post-consumer recycled polycarbonate, and the A-2) polycarbonate may preferably be a general polycarbonate.

[0018] The polysiloxane-polycarbonate copolymer B may preferably comprise an aromatic diol compound, a carbonate precursor, and a polysiloxane.

[0019] The polysiloxane-polycarbonate copolymer B preferably includes 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, or may include a repeating unit represented by the following Chemical Formula 3:

[0020] [ka] (In the above-mentioned Chemical Formula 1, R 1 ~R 4 are each independently hydrogen, C 1-10 Alkyl, C 1-10 alkoxy, and halogen; Z is unsubstituted or C 1-6 Alkyl or C 6-20 Aryl-substituted C 1-10 Alkylene; unsubstituted or C 1-10Alkyl-substituted C 3-15 cycloalkylene; oxygen; S; SO; SO; and CO.

[0021] [ka] (In the above Chemical Formula 2, X 1 and X 2 are each independently 1-10 is alkylene, and Y 1 and Y 2 are each independently hydrogen, C 1-6 Alkyl, halogen, hydroxy group, C 1-6 Alkoxy groups, and C 6-20 aryl groups, R 5 ~R 8 are each independently hydrogen; unsubstituted or substituted with oxiranyl, oxiranyl, C 1-10 Alkoxy group or C 6-20 Aryl-substituted C 1-15 Alkyl;Halogen;C 1-10 Alkoxy; Allyl; C 1-10 haloalkyl; and C 6-20 aryl, and n2 is an integer of 30 to 120.

[0022] [ka] (In the above Chemical Formula 3, X 3 and X 4 are each independently 1-10 alkylene, and R 9 ~R 12 are each 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 aryl, and n1 is an integer of 30 to 120.

[0023] The polysiloxane-polycarbonate copolymer (B) may preferably have an average siloxane domain size of 20 nm or more.

[0024] The C) glass fibers may preferably have an average length of 1 to 15 mm, an average horizontal length of the cross section of 15 to 45 μm, and an average vertical length of the cross section of 2 to 15 μm.

[0025] The liquid phosphorus-based flame retardant D) may preferably be at least one selected from the group consisting of bisphenol-A bis(diphenyl phosphate), triphenyl phosphate, and resorcinol bisdiphenyl phosphate.

[0026] The phosphazene compound (E) may preferably be at least one selected from the group consisting of a cyclic phosphazene compound, a chain phosphazene compound, and a crosslinked phosphazene compound.

[0027] The weight ratio (D:E) of the liquid phosphorus-based flame retardant (D) and the phosphazene compound (E) may preferably be 1.2:1 to 3.0:1.

[0028] The polycarbonate resin composition may preferably have an Izod impact strength of 11 kgf·cm / cm or more, measured at room temperature using a notched test piece with a thickness of 3.2 mm in accordance with ASTM D256.

[0029] The polycarbonate resin composition may preferably have a heat distortion temperature of 97° C. or higher, measured in accordance with ASTM D648 using a test piece having a thickness of 6.4 mm under a load of 18.6 kg.

[0030] The polycarbonate resin composition may preferably have a flame retardancy of V-0 or higher as measured on a test piece having a thickness of 0.8 mm in accordance with the UL94 V test.

[0031] The present disclosure also provides a method for producing a polycarbonate resin composition, comprising the steps of kneading and extruding, under conditions of 200 to 350°C and 100 to 400 rpm, A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min, A-2) 0 to 50% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min, B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) 2 to 12% by weight of a liquid phosphorus-based flame retardant, and E) 1 to 7% by weight of a phosphazene compound.

[0032] The method for producing the polycarbonate resin composition preferably includes the steps of kneading and extruding A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min, A-2) 1 to 50% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min, B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer, C) 5 to 45% by weight of glass fiber, D) 2 to 12% by weight of a liquid phosphorus-based flame retardant, and E) 1 to 7% by weight of a phosphazene compound under conditions of 200 to 350°C and 100 to 400 rpm.

[0033] The present disclosure also provides a molded article comprising the polycarbonate resin composition. [Effects of the Invention]

[0034] The present invention has the effect of providing a polycarbonate resin composition that is excellent in flame retardancy, heat resistance, and impact resistance despite containing a high content of post-consumer recycled polycarbonate.

[0035] Furthermore, the polycarbonate resin composition according to the present invention can increase the content of post-consumer recycled polycarbonate, thereby increasing the recycling rate of waste plastics, and providing the advantages of being environmentally friendly, reducing greenhouse gas emissions, and saving energy. BEST MODE FOR CARRYING OUT THE INVENTION

[0036] The polycarbonate resin composition of the present invention will be described in detail below.

[0037] The present inventors have confirmed that even when a polycarbonate resin composition contains a high content of post-consumer recycled polycarbonate, it exhibits excellent flame retardancy, heat resistance, and impact resistance when it contains a combination of a liquid phosphorus-based flame retardant and a phosphazene compound, a polysiloxane-polycarbonate copolymer, and glass fibers in specific amounts. Based on this, they have conducted further research and have completed the present invention.

[0038] The polycarbonate resin composition according to the present invention will be described in detail below.

[0039] The polycarbonate resin composition described herein is characterized by containing A-1) 20 to 75 wt % of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min, B) 5 to 25 wt % of a polysiloxane-polycarbonate copolymer, C) 5 to 45 wt % of glass fiber, D) 2 to 12 wt % of a liquid phosphorus-based flame retardant, and E) 1 to 7 wt % of a phosphazene compound.In this case, even though the polycarbonate contains a high content of recycled polycarbonate, the composition has excellent flame retardancy, impact resistance, and heat resistance, and is environmentally friendly.

[0040] (A-1) Polycarbonate with a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min) The A-1) polycarbonate may be, for example, 20 to 75% by weight, preferably 25 to 72% by weight, more preferably 28 to 72% by weight, and even more preferably 30 to 62% by weight, based on the total weight of the polycarbonate resin composition. Within this range, the recycle rate is high, which has the effect of being environmentally friendly, reducing water and energy consumption, while also providing excellent flame retardancy, heat resistance, and impact resistance.

[0041] The A-1) polycarbonate may have a melt index of preferably 17 to 22 g / 10 min, more preferably 19 to 21 g / 10 min, and within this range, it is effective in achieving excellent balance of physical properties and impact resistance.

[0042] In this description, the melt index is measured according to ASTM D1238 at 300° C. under a load of 1.2 kg.

[0043] The polycarbonate A-1) may have a polydispersity index of, for example, more than 2.75, preferably 2.8 or more, more preferably 2.8 to 3.2, and even more preferably 2.8 to 3.0. Within this range, the polycarbonate has the effect of exhibiting excellent mechanical properties and a good balance of physical properties.

[0044] In this description, the polydispersity index refers to the distribution of molecular weights, and is calculated by dividing the weight average molecular weight by the number average molecular weight. A high polydispersity index means that the standard deviation of the molecular weight distribution is large, and that there are more molecular weights that are larger or smaller than the weight average molecular weight.

[0045] In this description, unless otherwise specified, the weight average molecular weight and number average molecular weight can be measured using GPC (Gel Permeation Chromatography, water breeze). Specifically, they can be measured as relative values to a standard PS (standard polystyrene) sample through GPC using THF (tetrahydrofuran) as an eluent. In this case, as a specific measurement example, the solvent is THF, the column temperature is 40°C, the flow rate is 0.3 ml / min, the sample concentration is 20 mg / ml, the injection volume is 5 μL, the column model is 1×PLgel 10 μm MiniMix-B (250 × 4.6 mm) + 1×PLgel 10 μm MiniMix-B (250 × 4.6 mm) + 1×PLgel 10 μm MiniMix-B Guard (50 × 4.6 mm), the measuring equipment is an Agilent 1200 series system, the refractive index detector is an Agilent G1362 RID, the RI temperature is 35°C, the data is processed by Agilent ChemStation S / W, and the test method (Mn, Mw, and PDI) can be measured under the conditions of OECD TG 118.

[0046] The A-1) polycarbonate may have a weight average molecular weight of, for example, 20,000 g / mol or more but less than 28,000 g / mol, preferably 22,000 to 27,000 g / mol, and more preferably 24,000 to 27,000 g / mol. Within this range, the polycarbonate has the effect of exhibiting excellent mechanical properties and a good balance of physical properties.

[0047] The A-1) polycarbonate may have a heat distortion temperature measured in accordance with ASTM D648 of, for example, 124°C or higher, preferably 127°C or higher, more preferably 130°C or higher, and even more preferably 130 to 140°C. Within this range, the polycarbonate has the effect of exhibiting excellent mechanical properties and a good balance of physical properties.

[0048] In this description, the heat distortion temperature can be measured in accordance with ASTM D648 using a test piece having a thickness of 6.4 mm under a load of 18.6 kg.

[0049] The A-1) polycarbonate may be, for example, a post-consumer recycled polycarbonate. In this case, recycling waste plastics has the effect of being environmentally friendly, saving energy and water, and reducing carbon emissions.

[0050] In this description, the term "post-consumer recycled polycarbonate" refers to any polycarbonate generally recognized as a post-consumer recycled polycarbonate in the technical field to which the present invention pertains, without any particular limitations. For example, it refers to polycarbonate recycled from recovered waste plastics. Specifically, it refers to polycarbonate prepared in a usable raw material state after sorting, washing, and crushing recovered waste plastics. If necessary, it can also be processed into pellets through an extrusion process, which has the advantage of eliminating the need for additional processing such as purification. Because such post-consumer recycled polycarbonate has undergone one or more processes, it may contain additives such as colorants, lubricants, and / or mold release agents.

[0051] The post-consumer recycled polycarbonate can also be referred to as recycled polycarbonate or regenerated polycarbonate, for example.

[0052] The A-1) polycarbonate may be, for example, a resin obtained by polymerizing an aromatic diol compound and a carbonate precursor.

[0053] Examples of the aromatic diol compound include 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, and the like. The hydroxyphenyl ester may be one or more selected from the group consisting of bisphenol A, 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, and α,ω-bis[3-(ο-hydroxyphenyl)propyl]polydimethylsiloxane, and preferably bisphenol A.

[0054] The carbonate precursor may be, for example, at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformates. From the viewpoints of production efficiency and physical properties, it is preferable to use triphosgene, phosgene, or a mixture thereof.

[0055] As a specific example, the polycarbonate formed by polymerization of the aromatic diol compound and the carbonate precursor includes a repeating unit represented by the following chemical formula 4:

[0056] [ka]

[0057] In the above formula 4, R'1 to R'4 are each independently hydrogen, C 1-10 Alkyl, C 1-10 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 Alkyl-substituted C 3-15 It is cycloalkylene, O, S, SO, SO2, or CO.

[0058] Preferably, in the chemical formula 4, R'1 to R'4 are each independently hydrogen or C 1-3 alkyl, and Z' is unsubstituted or substituted with methyl or phenyl. 1-6 It may also be alkylene.

[0059] The A-1) polycarbonate may be, for example, at least one selected from the group consisting of linear polycarbonate, branched polycarbonate, and polyester carbonate copolymer, and preferably linear polycarbonate, which has the advantages of improved fluidity and excellent appearance properties.

[0060] The linear polycarbonate may be preferably, but is not limited to, a bisphenol A-based polycarbonate.

[0061] As the polycarbonate A-1), for example, commercially available products may be used as long as they comply with the definition of the present invention.

[0062] (A-2) Polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min The A-2) polycarbonate may have, for example, a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min, preferably 7 to 12 g / 10 min, and more preferably 9 to 11 g / 10 min. Within this range, the polycarbonate has the effect of exhibiting excellent mechanical properties and heat resistance.

[0063] The polycarbonate A-2) may have a polydispersity index of, for example, 2.75 or less, preferably 2.6 or less, more preferably 2.5 or less, and even more preferably 2.3 to 2.5. Within this range, the polycarbonate has the effect of exhibiting excellent mechanical properties and a good balance of physical properties.

[0064] The A-2) polycarbonate may have a weight average molecular weight of, for example, 28,000 g / mol or more, preferably 29,000 g / mol or more, more preferably 30,000 g / mol or more, and even more preferably 30,000 to 37,000 g / mol. Within this range, the polycarbonate has the effect of exhibiting excellent mechanical properties and a good balance of physical properties.

[0065] The A-2) polycarbonate may have a heat distortion temperature measured in accordance with ASTM D648 of, for example, 124°C or higher, preferably 127°C or higher, more preferably 130°C or higher, and even more preferably 130 to 140°C. Within this range, the polycarbonate has the effect of exhibiting excellent mechanical properties and a good balance of physical properties.

[0066] The A-2) polycarbonate may be, for example, a general polycarbonate.

[0067] In this description, the term "general polycarbonate" is not particularly limited as long as it is generally recognized as a general polycarbonate in the technical field to which the present invention pertains, as long as it complies with the definition of the present invention. In contrast to the post-consumer recycled polycarbonate described herein, the general polycarbonate may be a polycarbonate that has not undergone molding processes such as injection molding after being produced by polymerizing the monomers that constitute the polycarbonate, or a corresponding available polycarbonate.

[0068] The general polycarbonate may be referred to as, for example, virgin polycarbonate, new polycarbonate, fresh polycarbonate, or non-recycled polycarbonate.

[0069] The monomers constituting the A-2) polycarbonate may preferably be selected within the same range as those mentioned for the A-1) polycarbonate.

[0070] The A-2) polycarbonate may be, for example, 0 to 50% by weight, preferably 1 to 50% by weight, more preferably 7 to 45% by weight, even more preferably 10 to 42% by weight, and even more preferably 15 to 42% by weight, relative to the total weight of the polycarbonate resin composition. Within this range, there are advantages in that the impact resistance and heat resistance are excellent.

[0071] (B) Polysiloxane-polycarbonate copolymer The polysiloxane-polycarbonate copolymer B) may, for example, contain an aromatic diol compound, a carbonate precursor, and a polysiloxane, and in such a case, there is an advantage that impact resistance is improved.

[0072] In the present invention, B) polysiloxane-polycarbonate copolymer is distinguished from the above-mentioned A-1) polycarbonate in that polysiloxane is introduced into the main chain of polycarbonate.

[0073] The aromatic diol compound and carbonate precursor may be, for example, the same as those used in the production of the A-1) polycarbonate described above.

[0074] The polysiloxane-polycarbonate copolymer B 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.

[0075] The polysiloxane-polycarbonate copolymer B, for example, includes 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:

[0076] [ka]

[0077] In the above formula 1, R 1 ~R 4 are each independently hydrogen, C 1-10 Alkyl, C 1-10 alkoxy, and halogen; Z is unsubstituted or C 1-6 Alkyl or C 6-20 Aryl-substituted C 1-10 Alkylene; unsubstituted or C 1-10 Alkyl-substituted C 3-15 It is selected from cycloalkylene; oxygen; S; SO; SO2; and CO.

[0078] Preferably, in the formula 1, R 1 ~R 4 are each independently hydrogen or C 1-3 alkyl, and Z is unsubstituted or substituted with methyl or phenyl. 1-6 It may also be alkylene.

[0079] The first repeating unit represented by the chemical formula 1 is preferably a polymer of bisphenol A, an aromatic diol compound, and triphosgene, a carbonate precursor, and is represented by the following chemical formula 1-1.

[0080] [ka]

[0081] The first repeating unit represented by the chemical formula 1 may be contained in an amount of, for example, 20 to 95 mol %, preferably 30 to 85 mol %, and more preferably 40 to 80 mol %, relative to 100 mol % of all repeating units in the polysiloxane-polycarbonate copolymer.

[0082] [ka]

[0083] In the above Chemical Formula 2, X 1 and X 2 are each independently 1-10 is alkylene, and Y 1 and Y 2 are each independently hydrogen, C 1-6 Alkyl, halogen, hydroxy group, C 1-6 Alkoxy groups, and C 6-20 aryl groups, R 5 ~R 8 are each independently hydrogen; unsubstituted or substituted with oxiranyl, oxiranyl, C 1-10 Alkoxy group or C 6-20 Aryl-substituted C 1-15 Alkyl;Halogen;C 1-10 Alkoxy; Allyl; C 1-10 haloalkyl; and C 6-20 aryl, and n2 is an integer of 30 to 120.

[0084] Preferably, in the above Chemical Formula 2, X1 and X 2 are each independently 2-10 alkylene, more preferably C 2-6 alkylene, most preferably isobutylene; 1 and Y 2 may each independently be hydrogen.

[0085] More preferably, in the above-mentioned Chemical Formula 2, R 5 ~R 8 may each independently be hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.

[0086] More preferably, the R 5 ~R 8 are each independently 1-10 Alkyl or C 1-6 alkyl, more preferably C 1-3 It may be alkyl, and particularly preferably methyl.

[0087] In addition, in the above chemical formula 2, n2 may be an integer of 30 to 120, and preferably an integer of 34 to 110.

[0088] The second repeating unit represented by the above chemical formula 2 is preferably represented by the following chemical formula 2-1.

[0089] [ka]

[0090] In the above chemical formula 2-1, R 5 ~R 8 and n2 are as defined above.

[0091] The second repeating unit represented by the chemical formula 2 may be contained in an amount of, for example, 5 to 80 mol %, preferably 15 to 70 mol %, and more preferably 20 to 60 mol %, relative to 100 mol % of all repeating units in the polysiloxane-polycarbonate copolymer.

[0092] Preferably, the polysiloxane-polycarbonate copolymer may further include a third repeating unit represented by the following Chemical Formula 3:

[0093] [ka]

[0094] In the above Chemical Formula 3, X 3 and X 4 are each independently 1-10 alkylene, and R 9 ~R 12 are each 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 aryl, and n1 is an integer of 30 to 120.

[0095] Preferably, in the above Chemical Formula 3, X 3 and X 4 are each independently 2-10 It may be alkylene, preferably C 2-4 It may be alkylene, more preferably propane-1,3-diyl.

[0096] In the above formula 3, R 9 ~R 12may each independently be hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl.

[0097] Preferably, the R 9 ~R 12 are each independently 1-10 Alkyl or C 1-6 alkyl, more preferably C 1-3 It is preferably alkyl, and more preferably methyl.

[0098] In addition, in the above chemical formula 3, n1 may be an integer of 30 to 120, and preferably an integer of 34 to 110.

[0099] When the third repeating unit represented by Formula 3 is further included, the heat resistance and impact resistance of the composition can be further improved.

[0100] The third repeating unit represented by the above chemical formula 3 is preferably represented by the following chemical formula 3-1.

[0101] [ka]

[0102] In the above Chemical Formula 3-1, R 9 ~R 12 and n1 are as defined above.

[0103] The third repeating unit represented by Chemical Formula 3 may be further included in an amount of, for example, 1 to 30 mol %, preferably 3 to 25 mol %, and more preferably 5 to 20 mol %, based on 100 mol % in total of the first repeating unit and the second repeating unit.

[0104] The weight average molecular weight of the polysiloxane-polycarbonate copolymer B may be, 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. Within this range, the composition is easy to process and mold, while providing the advantages of simultaneously satisfying impact resistance and heat resistance.

[0105] The polysiloxane-polycarbonate copolymer B may have an average siloxane domain size of, for example, 20 nm or more, preferably 20 to 60 nm, and more preferably 30 to 60 nm. Within this range, the siloxane domains of the polysiloxane-polycarbonate copolymer act as an impact modifier like rubber, thereby significantly improving impact resistance.

[0106] The term "domain" used in the present invention refers to other unit chains dispersed within a matrix chain. Furthermore, the term "average size of siloxane domains" in the present invention refers to the average size of polysiloxane chains dispersed within polycarbonate chains, specifically the average size of polysiloxane chains dispersed within the polycarbonate chain matrix, more specifically the average size of polysiloxane aggregates or agglomerates.

[0107] In the present invention, the average size of the siloxane domains can be measured, for example, by analyzing the shape through a microscope, and specifically, measured at room temperature using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). Preferably, the average size of the siloxane domains is an average value calculated by randomly selecting, for example, 10 siloxane domains from a photograph taken with the microscope and measuring their sizes.

[0108] The polysiloxane-polycarbonate copolymer (B) may be, for example, 5 to 25% by weight, preferably 7 to 23% by weight, more preferably 9 to 20% by weight, and even more preferably 9 to 16% by weight, based on the total weight of the polycarbonate resin composition. Within this range, the balance of physical properties and impact resistance are improved.

[0109] (C) Glass fiber) The C) glass fiber may be, for example, 5 to 45% by weight, preferably 7 to 45% by weight, more preferably 7 to 40% by weight, and even more preferably 7 to 28% by weight, based on the total weight of the polycarbonate resin composition. Within this range, excellent heat resistance can be provided while maintaining high mechanical properties, processability, etc.

[0110] The C) glass fiber may have an average length of, for example, 1 to 15 mm, preferably 1 to 10 mm, more preferably 1 to 7 mm, and even more preferably 2 to 5 mm. Within this range, the mechanical strength with the resin is improved, and the appearance properties of the final product are excellent.

[0111] The C) glass fiber may have an average horizontal length of, for example, 15 to 45 μm, preferably 20 to 35 μm, and more preferably 25 to 30 μm in cross section, and within this range, it has the effect of providing excellent fluidity and mechanical properties.

[0112] The C) glass fiber may have an average longitudinal length of, for example, 2 to 15 μm, preferably 2 to 12 μm, and more preferably 4 to 10 μm in cross section, and within this range, it has the effect of providing excellent fluidity and mechanical properties.

[0113] The C) glass fiber may have a cross-sectional aspect ratio of, for example, 1.5 to 5, preferably 2 to 4.7, more preferably 2.5 to 4.5, even more preferably 3 to 4.5, and even more preferably 3.5 to 4.5. Within this range, the glass fiber has excellent fluidity and mechanical properties, and the final product has reduced twists and kinks, resulting in excellent dimensional stability.

[0114] In this description, the aspect ratio of a cross section is the ratio of the width to the length, and if the aspect ratio is 1, it is circular, and if it is greater than 1, it is elliptical.

[0115] The glass fiber C) may be, for example, chopped glass fiber, which has the advantage of excellent compatibility.

[0116] In this description, the chopped glass fiber is not particularly limited as long as it is chopped fiber glass commonly used in the technical field to which the present invention pertains.

[0117] In this description, the average length, horizontal length of the cross section, and vertical length of the cross section of the glass fiber can be measured by a measurement method commonly used in the technical field to which the present invention belongs. Specifically, 30 pieces can be measured by a microscopic analysis method and the average value can be calculated.

[0118] The C) glass fiber may be surface-treated, for example, with a silane-based compound or a urethane-based compound. Preferably, the C) glass fiber is surface-treated with one or more surface treatment agents selected from the group consisting of aminosilane-based compounds, epoxysilane-based compounds, and urethane-based compounds. More preferably, the C) glass fiber is surface-treated with an epoxysilane-based compound. In this case, the C) glass fiber has excellent dispersibility in the resin composition, resulting in improved mechanical strength.

[0119] For example, the surface treatment agent may be contained in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, even more preferably 0.1 to 0.8% by weight, and even more preferably 0.2 to 0.5% by weight, relative to a total of 100% by weight of the surface-treated glass fiber (glass fiber + surface treatment agent). Within this range, the effect of achieving excellent mechanical properties, balance of physical properties, and appearance of the final product is achieved.

[0120] The aminosilane compound is not particularly limited as long as it is an aminosilane that is generally used as a coating agent for glass fibers. For example, it may be at least one selected from the group consisting of γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, γ-acetoacetatepropyltrimethoxysilane, γ-acetoacetatepropyltriethoxysilane, γ-cyanoacetyltrimethoxysilane, γ-cyanoacetyltriethoxysilane, and acetoxyacetotrimethoxysilane. In this case, the compound has the effect of providing excellent mechanical properties and heat resistance, as well as excellent surface properties of the injection molded product.

[0121] The epoxy silane compound is not particularly limited as long as it is an epoxy silane that is generally used as a coating agent for glass fibers. For example, it may be at least one selected from the group consisting of 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In this case, it has the effect of providing excellent mechanical properties and heat resistance, as well as excellent surface properties of the extruded product.

[0122] The glass fibers C) can be appropriately selected and used within the range commonly used in the art, as long as they comply with the definition of the present invention.

[0123] (D) Liquid phosphorus-based flame retardant The D) liquid phosphorus-based flame retardant may be contained in an amount of, for example, 2 to 12 wt %, preferably 3 to 10 wt %, more preferably 3 to 8 wt %, and even more preferably 4 to 7 wt %, based on the total weight of the polycarbonate resin composition. Within this range, excellent impact resistance and heat resistance are obtained, and the resulting molded article has a beautiful appearance and exhibits excellent flame retardancy.

[0124] The liquid phosphorus-based flame retardant (D) refers to a flame retardant that remains liquid at room temperature. More specifically, it maintains a liquid state at room temperature under atmospheric pressure and simultaneously imparts flame retardancy to the resin composition according to the present invention and adjusts the melt index. As a result, even with the use of a minimum amount of flame retardant in the overall resin composition according to the present invention, flame retardancy is stably satisfied, while at the same time improving productivity and resolving problems with the appearance and processing of the obtained molded product. Furthermore, when combined with the phosphazene compound (E) described below), a synergistic effect is achieved in which flame retardancy of V-0 grade or higher is ensured and impact resistance and heat resistance are further improved.

[0125] In this description, normal temperature may be a point within the range of 20±5°C.

[0126] The liquid phosphorus-based flame retardant D) is, for example, at least one selected from the group consisting of bisphenol-A bis(diphenyl phosphate) (BPADP), triphenyl phosphate (TPP), and resorcinol bisdiphenyl phosphate (RDP), and is preferably bisphenol-A bis(diphenyl phosphate), which has the advantages of being excellent in impact resistance and heat resistance, as well as ensuring flame retardancy.

[0127] (E) Phosphazene Compounds The amount of the phosphazene compound (E) is, for example, 1 to 7% by weight, preferably 2 to 6% by weight, more preferably 2 to 5% by weight, and even more preferably 3 to 4% by weight, relative to the total weight of the polycarbonate resin composition. When the amount of the phosphazene compound (E) is within this range, the combination with the liquid phosphorus-based flame retardant (D) ensures flame retardancy, while providing the advantages of further improving impact resistance and heat resistance.

[0128] The phosphazene compound E is, for example, an organic compound having a -P=N- bond in the molecule, and may be preferably at least one selected from the group consisting of a cyclic phosphazene compound, a chain phosphazene compound, and a crosslinked phosphazene compound, and is preferably a cyclic phosphazene compound, which has the effect of providing excellent flame retardancy and mechanical properties.

[0129] The cyclic phosphazene compound may preferably be a compound represented by the following chemical formula 5.

[0130] [ka]

[0131] In the above Chemical Formula 5, m is an integer of 3 to 25, and R 13 and R 14 are the same or different and represent an aryl group or an alkylaryl group.

[0132] In the above chemical formula 5, m is preferably an integer of 3 to 5.

[0133] The cyclic phosphazene compound represented by the chemical formula 5 is more preferably R 13 and R 14 is a phenyl group, and more preferably, it may be one or more selected from the group consisting of phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decafenoxycyclopentaphosphazene.

[0134] The chain phosphazene compound may preferably be a compound represented by the following chemical formula 6.

[0135] [ka]

[0136] In the formula 6, n is an integer of 3 to 10,000, and X is -N=P(OR 15 )3 groups, or -N=P(O)OR 15 represents a group, and Y represents a -P(OR 16 ) 4 groups, or -P(O)(OR 16 )2 groups. R 15 and R 16 are the same or different and represent an aryl group or an alkylaryl group.

[0137] In the above chemical formula 6, n is preferably an integer of 3 to 100, and more preferably an integer of 3 to 25.

[0138] The chain phosphazene compound represented by the chemical formula 6 is preferably R 15 and R 16 is a chain phenoxyphosphazene in which the phenyl group is

[0139] The crosslinked phosphazene compound is, for example, one or more phosphazene compounds selected from the group consisting of cyclic phosphazene compounds and chain phosphazene compounds, crosslinked by a crosslinking group represented by the following chemical formula 7.

[0140] [ka]

[0141] In the above Chemical Formula 7, A is —C(CH 3 ) 2 —, —SO 2 —, —S—, or —O—, and I is an integer of 0 or 1.

[0142] In the above Chemical Formula 7, [ka] and [ka] The notation is to clarify that CH3 is not an omission but a bond.

[0143] The bridged phosphazene compound is preferably a compound represented by the formula 5, wherein R 13 and R 14 a bridged phenoxyphosphazene compound in which a cyclic phenoxyphosphazene compound in which R is a phenyl group is bridged by a bridge group represented by the chemical formula 7; 15 and R 16 is a phenyl group, may be a bridged phenoxyphosphazene compound in which the chain phenoxyphosphazene compound is crosslinked by the crosslinking group represented by the chemical formula 7, or a mixture thereof, or more preferably may be a bridged phenoxyphosphazene compound in which the cyclic phenoxyphosphazene compound is crosslinked by the crosslinking group represented by the chemical formula 7.

[0144] When the composition contains a combination of the liquid phosphorus-based flame retardant (D) and the phosphazene compound (E), the synergistic effect of the combination achieves flame retardancy of V-0 or higher, and has the advantage of significantly improving both impact resistance and heat resistance.

[0145] For example, the liquid phosphorus-based flame retardant (D) may be contained in a larger amount than the phosphazene compound (E). In this case, there is an advantage that even a small amount of the flame retardant can achieve better flame retardancy.

[0146] The weight ratio (D:E) of the D) liquid phosphorus-based flame retardant to the E) phosphazene compound may be, for example, 1.2:1 to 3.0:1, preferably 1.2:1 to 2.7:1, more preferably 1.2:1 to 2.4:1, even more preferably 1.2:1 to 2.2:1, still more preferably 1.3:1 to 2.1:1, particularly preferably 1.5:1 to 2.1:1, and particularly more preferably 1.7:1 to 2.1:1. Within this range, even a small content can achieve excellent flame retardancy, and there are advantages in that the content is excellent in impact resistance and heat resistance.

[0147] The sum of the D) liquid phosphorus-based flame retardant and E) phosphazene compound may be, for example, 4 to 14% by weight, preferably 5 to 13% by weight, more preferably 6 to 12% by weight, and even more preferably 7 to 11% by weight, relative to the total weight of the polycarbonate resin composition. Within this range, there is an advantage that the flame retardancy, impact resistance, and heat resistance are all significantly improved.

[0148] For example, the polycarbonate resin composition may be free of a core-shell impact modifier, and in this case, the combination of D) the liquid phosphorus-based flame retardant and E) the phosphazene compound provides excellent impact resistance and heat resistance, as well as further improved flame retardancy. For example, the core-shell impact modifier may be a core-shell impact modifier containing a methacrylate-butadiene rubber.

[0149] In this description, "core-shell impact modifier-free" means that no core-shell impact modifier is intentionally added during the production of the polycarbonate resin composition.

[0150] The polycarbonate resin composition may contain, for example, one or more additives selected from the group consisting of heat stabilizers, flame retardant aids, lubricants, processing aids, plasticizers, coupling agents, light stabilizers, mold release agents, dispersants, anti-dripping agents, weathering stabilizers, antioxidants, compatibilizers, pigments, dyes, antistatic agents, anti-wear agents, fillers, and antibacterial agents. In such cases, the desired physical properties are effectively achieved without deteriorating the inherent physical properties of the polycarbonate resin composition described herein.

[0151] The additives can be contained in an amount of 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, based on 100 parts by weight of the total polycarbonate resin composition. In such a case, the required physical properties can be effectively achieved without impairing the inherent physical properties of the polycarbonate resin composition described herein.

[0152] The heat stabilizer may be, for example, at least one 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 is preferably a hindered phenol-based heat stabilizer, a phosphorus-based heat stabilizer, or a mixture thereof. In this case, it has the effect of preventing oxidation due to heat during the extrusion process and providing excellent mechanical properties.

[0153] The hindered phenol-based heat stabilizer 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 pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

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

[0155] The sulfur-based heat stabilizer may be, for example, at least one selected from the group consisting of 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 pentaerythritol tetrakis(3-laurylthiopropionic acid ester), but is not limited thereto.

[0156] Examples of the phosphorus-based heat stabilizer include tris(mixed, mono, and dinonylphenyl)phosphite, tris(2,3-di-t-butylphenyl)phosphite, 4,4'-butylidenebis(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'-biphenylenephosphonate, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, 2,2'-ethylidenebis The phosphate may be one or more selected from the group consisting of (4,6-di-t-butylphenyl)-2-ethylhexyl-phosphite, bis(2,4,6-di-t-butylphenyl)pentaerythritol-di-phosphite, triphenyl phosphite, diphenyldecyl phosphite, didecylphenyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trisnonylphenyl phosphite, and tridodecyl trithiophosphite, and is preferably bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-di-phosphite, but is not limited thereto.

[0157] The lubricant may be, for example, one or more selected from the group consisting of modified montanic acid wax, long chain ester of pentaerythritol, and fatty acid ester of neopentylpolyol.

[0158] The ultraviolet absorber may be, for example, one or more selected from the group consisting of triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.

[0159] Examples of the triazine-based ultraviolet absorber include 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, and 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine. )-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 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.

[0160] The benzophenone-based ultraviolet absorber may be, for example, at least one selected from the group consisting of 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone.

[0161] Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole, 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-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)-

[0033] The compound may be one or more selected from the group consisting of 2-(2'-hydroxy-3'-tert-butyl-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, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-5-chlorobenzotriazole.

[0162] The 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.

[0163] (Polycarbonate resin composition) The polycarbonate resin composition may preferably have an Izod impact strength of 11 kgf·cm / cm or more, more preferably 13 kgf·cm / cm or more, even more preferably 15 kgf·cm / cm or more, and even more preferably 15 to 25 kgf·cm / cm, as measured at room temperature using a notched test piece with a thickness of 3.2 mm in accordance with ASTM D256, and the composition exhibits an excellent balance of physical properties within this range.

[0164] The polycarbonate resin composition may preferably have a heat distortion temperature of 97°C or higher, more preferably 105°C or higher, even more preferably 110°C or higher, still more preferably 113°C or higher, particularly preferably 115°C or higher, and particularly preferably 115 to 125°C, as measured in accordance with ASTM D648 on a 6.4 mm thick test piece under a load of 18.6 kg. Within this range, the composition has an excellent balance of physical properties.

[0165] The polycarbonate resin composition may preferably have a flame retardancy of V-0 or higher as measured on a 0.8 mm thick test piece in accordance with the UL94 V test (Vertical Burning Test). Within this range, the polycarbonate resin composition has the effect of being excellent in impact resistance and heat resistance as well as being imparted with high flame retardancy.

[0166] (Method for producing polycarbonate resin composition) The present invention relates to a method for producing a polycarbonate resin composition, which comprises the steps of kneading and extruding, under conditions of 200 to 350°C and 100 to 400 rpm, A-1) 20 to 75 wt% of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min, A-2) 0 to 50 wt% of a polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more but less than 15 g / 10 min, B) 5 to 25 wt% of a polysiloxane-polycarbonate copolymer, C) 5 to 45 wt% of glass fiber, D) 2 to 12 wt% of a liquid phosphorus-based flame retardant, and E) 1 to 7 wt% of a phosphazene compound. This method provides excellent impact resistance, heat resistance, and flame retardancy.

[0167] The method for producing the polycarbonate resin composition shares all the technical features of the polycarbonate resin composition described above, and therefore, a description of the overlapping parts will be omitted.

[0168] The kneading and extrusion may be carried out, for example, using a single-screw extruder, a twin-screw extruder, or a Banbury mixer, which can provide the effect of uniformly dispersing the composition and achieving excellent compatibility.

[0169] The kneading and extrusion may be carried out, for example, at a barrel temperature in the range of 200 to 350°C, preferably 220 to 330°C, and more preferably 240 to 310°C. In this case, the processing amount per unit time is appropriate, sufficient melt-kneading is possible, and problems such as thermal decomposition of the resin component are not caused.

[0170] The kneading and extrusion may be carried out under conditions where the screw rotation speed is, for example, 100 to 400 rpm, preferably 150 to 350 rpm, and more preferably 200 to 300 rpm. In this case, the processing amount per unit time is appropriate, and therefore, the process efficiency is excellent while the effect of suppressing excessive cutting of the glass fibers is achieved.

[0171] (molded product) The molded article described herein is characterized by containing the polycarbonate resin composition described herein. In this case, the molded article contains a high content of post-consumer recycled polycarbonate, which has the effects of being environmentally friendly and having excellent impact resistance, heat resistance, and flame retardancy.

[0172] The molded article may be, for example, an electrical or electronic part, an automotive part, or an industrial material.

[0173] The method for producing a molded article according to the present invention preferably comprises: A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min; A-2) 0 to 50% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min; B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; and D) a liquid phosphorus-based The method includes the steps of kneading and extruding 2 to 12 wt % of a flame retardant and 1 to 7 wt % of an E) phosphazene compound under conditions of 200 to 350°C and 100 to 400 rpm to produce pellets, and injecting the produced pellets to produce a molded product. In this case, the high content of post-consumer recycled polycarbonate provides environmental friendliness and excellent impact resistance, heat resistance, and flame retardancy.

[0174] The prepared pellets may be manufactured by, for example, sufficiently drying them using a dehumidifying dryer or a hot air dryer, and then injection molding them.

[0175] In the above description, the total weight of the polycarbonate resin composition means the combined total weight of A-1) polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min, B) polysiloxane-polycarbonate copolymer, C) glass fiber, D) liquid phosphorus-based flame retardant, and E) phosphazene compound. When the polycarbonate resin composition contains A-2) polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min, the total weight of the polycarbonate resin composition means the combined total weight of the A-1), A-2), B), C), D), and E).

[0176] The method for producing the molded article described herein is not particularly limited, provided that it complies with the definition of the present invention and uses conditions, methods, apparatus, etc. that are commonly used in the technical field to which the present invention pertains.

[0177] In the description of the polycarbonate resin composition, its production method, and molded articles herein, other conditions, equipment, etc. not explicitly described can be appropriately selected within the range commonly used in the art, and are not particularly limited.

[0178] Below, preferred examples are presented to help understand the present description, but the following examples are merely illustrative of the present description, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and technical idea of the present description, and it is natural that such changes and modifications also fall within the scope of the appended claims.

[0179] The materials used in the examples and comparative examples are as follows. *A-1) Polycarbonate with a melt index (300°C, 1.2 kg) of 20 g / 10 min according to ASTM D1238: Post-consumer recycled polycarbonate (PCR-PC) *A-2) Polycarbonate having a melt index (300°C, 1.2 kg) of 10 g / 10 min according to ASTM D1238: General polycarbonate (General PC; PC1300-10 from LG Chemical) *B-1) Polysiloxane-polycarbonate copolymer (Si-PC): SPC8100-02 (LG Chemical, average size of polyorganosiloxane domains is 50nm to 60nm) *B-2) Core-shell structure impact modifier (MBS): Core-shell structure impact modifier containing methyl methacrylate-butadiene rubber (LG Chemical, EM538) *C) Glass fiber: Glass fiber surface-treated with a silane compound (average length 3 mm, average cross-sectional width 28 μm, average cross-sectional length 7 μm) *D) Liquid phosphorus-based flame retardant (BPADP): Bisphenol A bis(diphenyl phosphate) (ADEKA, FP600) *E) Phosphazene compound: Phenoxyphosphazene (Weihai Jinwei Chem Industry, HPC TP-JW01)

[0180] [Example] The compositions and amounts shown in Tables 1 to 3 below were mixed and then homogeneously mixed in a mixer. The mixture was melted and kneaded in a twin-screw extruder (screw diameter 26 mm, L / D = 40), and then extruded at an extrusion temperature of 250 to 300°C and a screw rotation speed of 250 rpm to prepare polycarbonate resin composition pellets. The mixture was dried at 80°C for at least 4 hours and then injected into an injection molding machine (ENGEL, 80MT) at a nozzle temperature of 260°C to prepare test pieces for measuring physical properties. The test pieces were then left for at least 48 hours, after which the physical properties were measured.

[0181] [Table 1]

[0182] [Table 2]

[0183] [Table 3] V-NOT * : It is impossible to evaluate the flame retardancy grade because it does not meet the flammability standards according to the UL94 V test. In other words, the burning time of the test specimen is exceeded or it burns out.

[0184] As shown in Tables 1 to 3, the polycarbonate resin compositions of the present invention (Examples 1 to 10) were confirmed to be superior in impact strength, flame retardancy, and heat distortion temperature compared to Comparative Examples 1 to 13. Furthermore, even when A-1) PCR-PC was contained at a high content, the compositions exhibited excellent impact strength, flame retardancy, and heat distortion temperature, which had the advantage of enabling an increased recycling rate. In particular, Examples 1 to 8, in which the weight ratio (D:E) of D) liquid phosphorus-based flame retardant to E) phosphazene compound was 1.2:1 to 3.0:1, exhibited even more excellent flame retardancy.

[0185] Specifically, Comparative Example 1, which did not contain B-1) Si-PC and E) phosphazene, had very low impact strength, while Comparative Example 2, which further contained B-2) MBS impact modifier in addition to Comparative Example 1, had slightly increased impact strength but decreased flame retardancy.

[0186] Furthermore, Comparative Example 3, which did not contain B-1) Si-PC but contained B-2) MBS impact modifier, had reduced flame retardancy and impact strength, and Comparative Example 4, which did not contain both D) BDADP and E) phosphazene, had low impact strength and very poor flame retardancy.

[0187] Furthermore, Comparative Example 5, which contained B-2) MBS impact modifier instead of B-1) Si-PC and used D) BDADP alone, had low flame retardancy and heat distortion temperature, Comparative Example 6, which contained B-2) MBS impact modifier instead of B-1) Si-PC, had low flame retardancy and heat distortion temperature, and Comparative Example 7, which used D) BDADP alone, had reduced flame retardancy and heat distortion temperature.

[0188] Furthermore, in Comparative Examples 8 and 9, in which the content of B-1) Si-PC was outside the range of the present invention, the flame retardancy was reduced, and in Comparative Example 9, the impact strength was also low.

[0189] Furthermore, C) Comparative Examples 10 and 11, in which the glass fiber content was outside the range of the present invention, had poor flame retardancy.

[0190] Furthermore, Comparative Example 12, which did not contain D) BDADP, had poor flame retardancy to the extent that it was impossible to measure the flame retardancy, and Comparative Example 13, which contained E) phosphazene beyond the range of the present invention, had reduced impact strength.

[0191] In conclusion, the polycarbonate resin composition according to the present invention, which contains A-1) post-consumer recycled polycarbonate, B) polysiloxane-polycarbonate copolymer, C) glass fiber, and a combination of D) liquid phosphorus-based flame retardant and E) phosphazene compound in specified amounts, was confirmed to have excellent impact resistance, heat resistance, and flame retardancy. Furthermore, despite using a high content of A-1) post-consumer recycled polycarbonate, the impact resistance, heat resistance, and flame retardancy were all improved.

Claims

1. A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min; B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; D) 2 to 12 wt % of a liquid phosphorus-based flame retardant; E) 1 to 7% by weight of a phosphazene compound.

2. The polycarbonate resin composition according to claim 1, characterized in that it contains A-2) 1 to 50 wt% of a polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min.

3. 2. The polycarbonate resin composition according to claim 1, wherein the A-1) polycarbonate is a post-consumer recycled polycarbonate.

4. 2. The polycarbonate resin composition according to claim 1, wherein the polysiloxane-polycarbonate copolymer (B) is obtained by polymerizing an aromatic diol compound, a carbonate precursor, and a polysiloxane.

5. 2. The polycarbonate resin composition according to claim 1, wherein the polysiloxane-polycarbonate copolymer B comprises 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, or comprises a repeating unit represented by the following Chemical Formula 3: 【Chemical 1】 (In the above-mentioned Chemical Formula 1, R 1 ~R 4 are each independently hydrogen, C 1-10 Alkyl, C 1-10 alkoxy, and halogen; Z is unsubstituted or selected from C 1-6 Alkyl or C 6-20 Aryl-substituted C 1-10 alkylene; unsubstituted or C 1-10 Alkyl-substituted C 3-15 Cycloalkylene; oxygen; S; SO; SO 2 and CO. 【Chemistry 2】 (In the above Chemical Formula 2, X 1 and X 2 are each independently C 1-10 is alkylene, and Y 1 and Y 2 are each independently hydrogen, C 1-6 Alkyl, halogen, hydroxy group, C 1-6 Alkoxy groups, and C 6-20 aryl groups, R 5 ~R 8 are each independently hydrogen; unsubstituted or oxiranyl, oxiranyl-substituted C 1-10 Alkoxy group or C 6-20 Aryl-substituted C 1-15 Alkyl; halogen; C 1-10 Alkoxy; Allyl; C 1-10 haloalkyl; and C 6-20 aryl, and n2 is an integer from 30 to 120. 【Chemistry 3】 (In the above Chemical Formula 3, X 3 and X 4 are each independently C 1-10 alkylene, and R 9 ~R 12 are each independently hydrogen; unsubstituted or oxiranyl, oxiranyl-substituted 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 aryl, and n1 is an integer from 30 to 120.

6. 2. The polycarbonate resin composition according to claim 1, wherein the polysiloxane-polycarbonate copolymer B) has an average siloxane domain size of 20 nm or more.

7. 2. The polycarbonate resin composition according to claim 1, wherein the C) glass fiber has an average length of 1 to 15 mm, an average horizontal length of the cross section of 15 to 45 μm, and an average vertical length of the cross section of 2 to 15 μm.

8. 2. The polycarbonate resin composition according to claim 1, wherein the liquid phosphorus-based flame retardant D) is at least one selected from the group consisting of bisphenol-A bis(diphenyl phosphate), triphenyl phosphate, and resorcinol bisdiphenyl phosphate.

9. 2. The polycarbonate resin composition according to claim 1, wherein the phosphazene compound (E) is at least one selected from the group consisting of a cyclic phosphazene compound, a chain phosphazene compound, and a crosslinked phosphazene compound.

10. 2. The polycarbonate resin composition according to claim 1, wherein the weight ratio (D:E) of the liquid phosphorus-based flame retardant (D) to the phosphazene compound (E) is 1.2:1 to 3.0:

1.

11. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition has an Izod impact strength of 11 kgf cm / cm or more, measured at room temperature using a notched test piece having a thickness of 3.2 mm in accordance with ASTM D256.

12. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition has a heat distortion temperature of 97°C or higher, as measured under a load of 18.6 kg on a 6.4 mm thick test piece in accordance with ASTM D648.

13. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition has a flame retardancy of V-0 or higher as measured on a 0.8 mm thick test piece in accordance with the UL94 V test.

14. A method for producing a polycarbonate resin composition, comprising the steps of kneading and extruding under conditions of 200 to 350°C and 100 to 400 rpm: A-1) 20 to 75% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 15 to 25 g / 10 min; A-2) 0 to 50% by weight of a polycarbonate having a melt index (300°C, 1.2 kg) of 5 g / 10 min or more and less than 15 g / 10 min; B) 5 to 25% by weight of a polysiloxane-polycarbonate copolymer; C) 5 to 45% by weight of glass fiber; D) 2 to 12% by weight of a liquid phosphorus-based flame retardant; and E) 1 to 7% by weight of a phosphazene compound.

15. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 13.

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