Polycarbonate resin composition and molded article formed therefrom

Abstract

A polycarbonate resin composition of the present invention comprises: about 100 parts by weight of a base resin comprising about 30 to about 95 wt% of a polycarbonate resin and about 5 to about 70 wt% of a polysiloxane-polycarbonate copolymer resin; about 5 to about 50 parts by weight of a glass fiber; about 1 to about 20 parts by weight of a phosphorus-based flame retardant; and about 0.1 to about 2 parts by weight of a polydimethylsiloxane with a terminal reactive group having a kinematic viscosity of about 5 to about 200 cSt, measured at 40°C in accordance with ASTM D445. The polycarbonate resin composition exhibits excellent impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, balance thereof and the like.

Description

Polycarbonate resin composition and molded article formed therefrom

[0001] The present invention relates to a polycarbonate resin composition and a molded article formed therefrom. More specifically, the present invention relates to a polycarbonate resin composition having excellent impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and a balance of these physical properties, and to a molded article formed therefrom.

[0002]

[0003] Polycarbonate resins boast excellent mechanical strength, heat resistance, and transparency, making them useful in a wide range of applications, including office automation equipment, electrical and electronic products, and building materials. Recent trends in mobile electrical and electronic products, such as cell phones, are increasingly shifting to metal-based, battery-integrated products, aiming for superior design, reduced weight, and water resistance. However, demand for plastic-based batteries and rear covers remains, necessitating lower prices and greater stability. Plastic materials, particularly for rear covers, require high rigidity as well as impact resistance to prevent LCD damage. Clear coating or post-injection painting is essential for a variety of colors and to prevent scratches. Furthermore, the trend toward faster charging, higher-capacity batteries, and slimmer designs in mobile electrical and electronic products is driving demand for thin-film, flame-retardant materials.

[0004] To improve the rigidity of plastic materials, polycarbonate materials reinforced with inorganic fillers such as glass fibers are being used. However, if glass fibers are used in excessive amounts, there is a risk that impact resistance and appearance characteristics may deteriorate, and this may cause a decrease in the efficiency and effectiveness of the painting process.

[0005] Therefore, there is a need for the development of a polycarbonate resin composition having excellent impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and a balance of these properties.

[0006] The background technology of the present invention is disclosed in Korean Patent Publication No. 10-2022-0056273, etc.

[0007]

[0008] The purpose of the present invention is to provide a polycarbonate resin composition having excellent impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and a balance of these physical properties.

[0009] Another object of the present invention is to provide a molded article formed from the polycarbonate resin composition.

[0010] The above and other objects of the present invention can all be achieved by the present invention described below.

[0011]

[0012] 1. One aspect of the present invention relates to a thermoplastic resin composition. The polycarbonate resin composition comprises: about 100 parts by weight of a base resin comprising about 30 to about 95 wt% of a polycarbonate resin and about 5 to about 70 wt% of a polysiloxane-polycarbonate copolymer resin; about 5 to about 50 parts by weight of glass fiber; about 1 to about 20 parts by weight of a phosphorus-based flame retardant; and about 0.1 to about 2 parts by weight of a polydimethylsiloxane having a terminal reactive group and having a kinematic viscosity of about 5 to about 200 cSt as measured at 40° C. according to ASTM D445.

[0013] 2. In the above 1 specific example, the polycarbonate resin may have a weight average molecular weight of about 10,000 to about 200,000 g / mol as measured by GPC (gel permeation chromatography).

[0014] 3. In the above 1 or 2 specific examples, the polycarbonate-polysiloxane copolymer resin may include about 70 to about 99 wt% of a polycarbonate block and about 1 to about 30 wt% of a polysiloxane block.

[0015] 4. In the above 1 to 3 specific examples, the polycarbonate-polysiloxane copolymer resin may have a weight average molecular weight of about 10,000 to about 50,000 g / mol as measured by GPC (gel permeation chromatography).

[0016] 5. In the above 1 to 4 specific examples, the terminal reactive group of the polydimethylsiloxane having the terminal reactive group may include at least one of a hydroxyl group, an epoxy group, and a maleic anhydride group.

[0017] 6. In the above 1 to 5 specific examples, the phosphorus flame retardant may include at least one of a phosphazene compound, a phosphate compound, a phosphonate compound, a phosphinate compound, and a phosphine oxide compound.

[0018] 7. In the above 1 to 6 specific examples, the weight ratio of the polysiloxane-polycarbonate copolymer resin and the glass fiber may be about 1:0.1 to about 1:3.

[0019] 8. In the above specific examples 1 to 7, the weight ratio of the polysiloxane-polycarbonate copolymer resin and the polydimethylsiloxane having the terminal reactive group may be about 1:0.005 to about 1:0.1.

[0020] 9. In the above 1 to 8 specific examples, the weight ratio of the glass fiber and the polydimethylsiloxane having the terminal reactive group may be about 1:0.01 to about 1:0.3.

[0021] 10. In the above 1 to 9 specific examples, the weight ratio of the phosphorus flame retardant and the polydimethylsiloxane having the terminal reactive group may be about 1:0.01 to about 1:0.5.

[0022] 11. In the above 1 to 10 specific examples, the polycarbonate resin composition may have a notched Izod impact strength of about 8 to about 30 kgf·cm / cm of a 1 / 8" thick specimen measured according to ASTM D256.

[0023] 12. In the above 1 to 11 specific examples, the polycarbonate resin composition has a flexural modulus of about 23,000 to about 80,000 kgf / cm of a 1 / 4" thick specimen measured under conditions of 2.8 mm / min according to ASTM D790. 2 It could be.

[0024] 13. In the above 1 to 12 specific examples, the polycarbonate resin composition may be such that the height at which the specimen is destroyed is about 30 cm or more, as measured by immersing a 2 mm thick specimen in a thinner solution for 2 minutes and 30 seconds, drying at 80°C for 20 minutes, leaving it at room temperature for 24 hours, and then impacting it with a drop weight evaluation device using a Dupont drop test method using a 2 kg weight.

[0025] 14. In the above 1 to 13 specific examples, the polycarbonate resin composition may have a flame retardancy of V-0 or higher in a 0.6 mm thick specimen measured by the UL-94 vertical test method.

[0026] 15. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from a polycarbonate resin composition according to any one of 1 to 14.

[0027]

[0028] The present invention has the effect of providing a polycarbonate resin composition having excellent impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and a balance of these physical properties, and a molded article formed therefrom.

[0029]

[0030] Hereinafter, the present invention will be described in detail as follows.

[0031] The polycarbonate resin composition according to the present invention is characterized by comprising (A) a polycarbonate resin; (B) a polysiloxane-polycarbonate copolymer resin; (C) glass fiber; (D) a phosphorus-based flame retardant; and (E) polydimethylsiloxane having a terminal reactive group.

[0032] In this specification, “a to b” indicating a numerical range is defined as “≥a and ≤b”.

[0033]

[0034] (A) Polycarbonate resin

[0035] According to one specific example of the present invention, a polycarbonate resin used in a conventional thermoplastic resin composition may be used. For example, an aromatic polycarbonate resin produced by reacting a diphenol (aromatic diol compound) with a carbonate precursor such as phosgene, halogen formate, or carbonic diester may be used.

[0036] In specific examples, the diphenols may include, but are not limited to, 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, etc. For example, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane can be used, and specifically, 2,2-bis(4-hydroxyphenyl)propane, also called bisphenol-A, can be used.

[0037] In specific examples, examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, carbonyl chloride (phosgene), diphosgene, triphosgene, carbonyl bromide, bishaloformate, etc. These may be used alone or in combination of two or more.

[0038] The above polycarbonate resin may be used with a branched chain, and may be manufactured by adding, for example, about 0.05 to about 2 mol% of a trivalent or higher polyfunctional compound, specifically, a compound having a trivalent or higher phenol group, to the total diphenols used for polymerization.

[0039] The above polycarbonate resin can be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the above polycarbonate resin can be partially or entirely replaced with an aromatic polyester-carbonate resin obtained by polymerization in the presence of an ester precursor, for example, a difunctional carboxylic acid.

[0040] In a specific example, the polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 200,000 g / mol, for example, about 15,000 to about 100,000 g / mol. Within this range, the thermoplastic resin composition may have excellent mechanical properties, heat resistance, etc.

[0041] In a specific example, the polycarbonate resin may be included in an amount of about 30 to about 95 wt%, for example, about 40 to about 90 wt%, of 100 wt% of the base resin (A+B) including the polycarbonate resin and the polysiloxane-polycarbonate copolymer resin. When the content of the polycarbonate resin is less than about 30 wt%, of 100 wt% of the base resin, there is a concern that the (thin film) flame retardancy, etc. of the polycarbonate resin composition may be reduced, and when it exceeds about 95 wt%, there is a concern that the chemical resistance, appearance characteristics, etc. of the polycarbonate resin composition may be reduced.

[0042]

[0043] (B) Polysiloxane-polycarbonate copolymer resin

[0044] A polysiloxane-polycarbonate copolymer resin according to one specific example of the present invention is applied together with a polycarbonate resin, glass fiber, a phosphorus-based flame retardant, and polydimethylsiloxane having a terminal reactive group, and can improve the impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and the balance of these physical properties of a polycarbonate resin composition, and includes a polycarbonate block and a polysiloxane block. For example, the polysiloxane-polycarbonate copolymer may be a triblock copolymer of a polycarbonate block / polysiloxane block / polycarbonate block, but is not limited thereto.

[0045] In a specific example, the polysiloxane-polycarbonate copolymer resin may be a polysiloxane-polycarbonate copolymer resin produced by reacting a siloxane compound represented by the following chemical formula 1, an aromatic dihydroxy compound, and a carbonate precursor.

[0046] [Chemical Formula 1]

[0047]

[0048] In the above chemical formula 1, R1 and R2 are each independently a C1-C10 alkyl group, a C6-C18 aryl group, or a C1-C10 alkyl group or a C6-C18 aryl group having a halogen atom or an alkoxy group, A is each independently a substituted or unsubstituted C2-C20 hydrocarbon group, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, Y is each independently a hydrogen atom, a halogen atom, a C1-C18 halogenated alkyl group, a cyano group (-CN), or an ester group, and m may be 2 to 1,000, for example, 4 to 120, specifically 10 to 100.

[0049] In a specific example, the aromatic dihydroxy compound (diphenol) may be an aromatic dihydroxy compound used in the production of a conventional polycarbonate resin, and examples thereof include, but are not limited to, 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, and the like. Specifically, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, etc. can be used, and preferably, 2,2-bis(4-hydroxyphenyl)propane, also called bisphenol A, can be used.

[0050] In specific examples, examples of the carbonate precursor include phosgene, triphosgene, diaryl carbonate, and mixtures thereof. In addition, examples of the diaryl carbonate include, but are not limited to, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. These may be used singly or in combination of two or more, and for example, diphenyl carbonate may be used.

[0051] In a specific example, the polycarbonate-polysiloxane copolymer may comprise about 70 to about 99 wt%, for example, about 80 to about 97 wt%, of a polycarbonate block derived from the aromatic dihydroxy compound, and about 1 to about 30 wt%, for example, about 3 to about 25 wt%, of a polysiloxane block derived from the siloxane compound. Within this range, the polycarbonate resin composition may exhibit excellent impact resistance, chemical resistance, flame retardancy, and the like.

[0052] In a specific example, the polycarbonate-polysiloxane copolymer may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 50,000 g / mol, for example, about 15,000 to about 40,000 g / mol. Within this range, the polycarbonate resin composition may have excellent impact resistance, chemical resistance, flame retardancy, moldability, and the like.

[0053] In a specific example, the polycarbonate-polysiloxane copolymer can be prepared by a conventional method. For example, the aromatic dihydroxy compound, carbonate precursor, and siloxane compound can be copolymerized using interfacial polycondensation, emulsion polymerization, or the like. In addition, the polycarbonate-polysiloxane copolymer can be a commercially available product.

[0054] In a specific example, the polysiloxane-polycarbonate copolymer resin may be included in an amount of about 5 to about 70 wt%, for example, about 10 to about 60 wt%, of 100 wt% of the base resin (A+B) including the polycarbonate resin and the polysiloxane-polycarbonate copolymer resin. When the content of the polysiloxane-polycarbonate copolymer resin is less than about 5 wt%, of 100 wt% of the base resin, there is a concern that the chemical resistance, appearance properties, etc. of the polycarbonate resin composition may be deteriorated, and when it exceeds about 70 wt%, there is a concern that the (thin film) flame retardancy, etc. of the polycarbonate resin composition may be deteriorated.

[0055]

[0056] (C) Glass fiber

[0057] According to one specific example of the present invention, glass fiber can be applied together with a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, a phosphorus-based flame retardant, and a polydimethylsiloxane having a terminal reactive group, thereby improving the impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and the balance of these physical properties of a polycarbonate resin composition. Glass fibers used in conventional thermoplastic resin compositions can be used.

[0058] In specific embodiments, the glass fibers may be in the form of fibers and may have various cross-sections such as circular, oval, rectangular, etc. For example, it may be preferable in terms of mechanical properties to use fibrous glass fibers having circular and / or rectangular cross-sections.

[0059] In a specific example, the glass fiber having a circular cross-section may have a cross-sectional diameter of about 5 to about 20 ㎛ as measured using a Scanning Electron Microscope (SEM) and a length before processing of about 2 to about 20 mm, and the glass fiber having a rectangular (flat) cross-section may have a cross-sectional aspect ratio (major axis of the cross-section / minor axis of the cross-section) as measured using a Scanning Electron Microscope (SEM) of about 1.5 to about 10, a minor axis of about 2 to about 10 ㎛, and a length before processing of about 2 to about 20 mm. In the above range, the rigidity, moldability, etc. of the thermoplastic resin composition may be improved.

[0060] In a specific example, the glass fiber may be treated with a conventional surface treatment agent. The surface treatment agent may include, but is not limited to, a silane compound, a urethane compound, an epoxy compound, or the like.

[0061] In a specific example, the glass fiber may be included in an amount of about 5 to about 50 parts by weight, for example, about 5 to about 35 parts by weight, and specifically about 5 to about 30 parts by weight, relative to about 100 parts by weight of the base resin. If the content of the glass fiber is less than about 5 parts by weight relative to about 100 parts by weight of the base resin, there is a concern that the rigidity, etc. of the polycarbonate resin composition may be reduced, and if it exceeds about 50 parts by weight, there is a concern that the chemical resistance, etc. of the polycarbonate resin composition may be reduced.

[0062] In a specific example, the weight ratio of the polysiloxane-polycarbonate copolymer resin and the glass fiber may be from about 1:0.1 to about 1:3, for example from about 1:0.15 to about 1:2. In this range, the chemical resistance, rigidity, appearance characteristics, etc. of the polycarbonate resin composition may be more excellent.

[0063]

[0064] (D) Inherent flame retardant

[0065] A phosphorus-based flame retardant according to one specific example of the present invention can be applied together with a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, glass fiber, and polydimethylsiloxane having a terminal reactive group, and can improve the impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and the balance of these physical properties of a polycarbonate resin composition, and can include a phosphorus-based flame retardant used in a typical thermoplastic resin composition.

[0066] In a specific example, the phosphorus flame retardant may include a phosphazene compound, a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, a metal salt thereof, etc. These may be used alone or in combination of two or more.

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

[0068] [Chemical Formula 2]

[0069]

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

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

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

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

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

[0075] In a specific example, the phosphorus flame retardant may include an aromatic phosphoric acid ester compound represented by the following chemical formula 3.

[0076] [Chemical Formula 3]

[0077]

[0078] In the above chemical formula 3, R1, R2, R4 and R5 are each independently a hydrogen atom, a C6-C20 (carbon number 6 to 20) aryl group, or a C6-C20 aryl group substituted with a C1-C10 alkyl group, R3 is a C6-C20 arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group, for example, derived from a dialcohol such as resorcinol, hydroquinone, bisphenol-A, or bisphenol-S, and n is an integer of 0 to 10, for example, 0 to 4.

[0079] As the aromatic phosphate ester compound represented by the above chemical formula 3, when n is 0, examples thereof include diaryl phosphates such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(2,6-dimethylphenyl)phosphate, tri(2,4,6-trimethylphenyl)phosphate, tri(2,4-ditertiarybutylphenyl)phosphate, tri(2,6-dimethylphenyl)phosphate, etc., and when n is 1, examples thereof include bisphenol-A bis(diphenylphosphate), resorcinol bis(diphenylphosphate), resorcinol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol bis[bis(2,4-ditertiarybutylphenyl)phosphate], hydroquinone bis[bis(2,6-dimethylphenyl)phosphate], and hydroquinone. Examples include, but are not limited to, bis[bis(2,4-ditertiarybutylphenyl)phosphate]. These may be applied singly or in the form of a mixture of two or more.

[0080] In a specific example, the phosphorus-based flame retardant may be included in an amount of about 1 to about 20 parts by weight, for example, about 5 to about 15 parts by weight, and specifically about 6 to about 12 parts by weight, relative to about 100 parts by weight of the base resin. If the content of the phosphorus-based flame retardant is less than about 1 part by weight relative to about 100 parts by weight of the base resin, there is a concern that the (thin film) flame retardancy, etc. of the polycarbonate resin composition may be reduced, and if it exceeds about 20 parts by weight, there is a concern that the impact resistance, chemical resistance, (thin film) flame retardancy, etc. of the polycarbonate resin composition may be reduced.

[0081] In a specific example, the weight ratio of the polysiloxane-polycarbonate copolymer resin and the phosphorus-based flame retardant may be from about 1:0.1 to about 1:1, for example from about 1:0.12 to about 1:0.8. In this range, the (thin film) flame retardancy, impact resistance, chemical resistance, etc. of the polycarbonate resin composition may be more excellent.

[0082]

[0083] (E) Polydimethylsiloxane having a terminal reactive group

[0084] According to one specific example of the present invention, a polydimethylsiloxane having a terminal reactive group can be applied together with a polycarbonate resin, a polysiloxane-polycarbonate copolymer resin, glass fiber, and a phosphorus-based flame retardant, thereby improving the impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and the balance of these physical properties of a polycarbonate resin composition. A polydimethylsiloxane having a terminal reactive group having a kinematic viscosity of about 5 to about 200 cSt measured at 40°C according to ASTM D445 can be used.

[0085] In a specific example, the polydimethylsiloxane having the terminal reactive group may have a kinematic viscosity of about 5 to about 200 cSt, for example, about 10 to about 100 cSt, measured at 40°C according to ASTM D445. When the kinematic viscosity of the polydimethylsiloxane having the terminal reactive group is less than about 5 cSt, there is a concern that the thermal stability, moldability, impact resistance, etc. of the polycarbonate resin composition may be reduced, and when it exceeds about 200 cSt, there is a concern that the transparency, moldability, etc. of the polycarbonate resin composition may be reduced.

[0086] In a specific example, the terminal reactive group of the polydimethylsiloxane having the terminal reactive group may include at least one of a hydroxyl group, an epoxy group, and a maleic anhydride group.

[0087] In a specific example, the polydimethylsiloxane having the terminal reactive group may be included in an amount of about 0.1 to about 2 parts by weight, for example, about 0.2 to about 1.5 parts by weight, relative to about 100 parts by weight of the base resin. If the content of the polydimethylsiloxane having the terminal reactive group is less than about 0.1 parts by weight relative to about 100 parts by weight of the base resin, there is a concern that the (thin film) flame retardancy, etc. of the polycarbonate resin composition may be reduced, and if it exceeds about 2 parts by weight, there is a concern that the appearance characteristics, etc. of the polycarbonate resin composition may be reduced.

[0088] In a specific example, the weight ratio of the polysiloxane-polycarbonate copolymer resin and the polydimethylsiloxane having the terminal reactive group may be from about 1:0.005 to about 1:0.1, for example from about 1:0.007 to about 1:0.08. In this range, the impact resistance, chemical resistance, appearance characteristics, etc. of the polycarbonate resin composition may be more excellent.

[0089] In a specific example, the weight ratio of the glass fiber and the polydimethylsiloxane having the terminal reactive group may be from about 1:0.01 to about 1:0.3, for example from about 1:0.015 to about 1:0.2. In this range, the (thin film) flame retardancy, appearance characteristics, etc. of the polycarbonate resin composition may be more excellent.

[0090] In a specific example, the weight ratio of the above-described flame retardant and the polydimethylsiloxane having the terminal reactive group may be about 1:0.01 to about 1:0.5, for example, about 1:0.01 to about 1:0.3, specifically about 1:0.02 to about 1:0.2. In this range, the (thin film) flame retardancy, chemical resistance, impact resistance, etc. of the polycarbonate resin composition may be more excellent.

[0091]

[0092] A polycarbonate resin composition according to one embodiment of the present invention may further include conventional additives, if necessary. Examples of such additives include antioxidants, release agents, lubricants, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. When the additives are used, the content may be about 0.001 to about 20 parts by weight relative to about 100 parts by weight of the base resin, but is not limited thereto.

[0093]

[0094] A polycarbonate resin composition according to one specific example of the present invention can be manufactured using a known polycarbonate resin composition manufacturing method. For example, after mixing the above components and, if necessary, other additives, the composition can be manufactured into pellets by melt extrusion at about 200 to about 300°C, for example, about 250 to about 280°C, using a conventional twin-screw extruder.

[0095] In a specific example, the polycarbonate resin composition may have a notched Izod impact strength of about 8 to about 30 kgf·cm / cm, for example, about 8 to about 25 kgf·cm / cm, of a 1 / 8" thick specimen measured according to ASTM D256.

[0096] In a specific example, the polycarbonate resin composition has a flexural modulus of about 23,000 to about 80,000 kgf / cm for a 1 / 4" thick specimen measured under conditions of 2.8 mm / min according to ASTM D790. 2 , for example, about 25,000 to about 75,000 kgf / cm 2 It could be.

[0097] In a specific example, the polycarbonate resin composition is subjected to a height of destruction of the specimen measured by immersing a 2 mm thick specimen in a thinner solution for 2 minutes and 30 seconds, drying at 80°C for 20 minutes, leaving it at room temperature for 24 hours, and then impacting it with a drop weight evaluation device using a Dupont drop test method using a 2 kg weight, of about 30 cm or more, for example, about 30 to about 95 cm.

[0098] In a specific example, the polycarbonate resin composition may have a flame retardancy of V-0 or higher on a 0.6 mm thick specimen measured by the UL-94 vertical test method.

[0099]

[0100] The molded article according to the present invention is formed from the polycarbonate resin composition. For example, the polycarbonate resin composition can be used to manufacture various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention pertains. The molded article has excellent impact resistance, rigidity, chemical resistance, appearance characteristics, (thin film) flame retardancy, and a balance of these properties, and is therefore particularly useful as an interior or exterior material for mobile electrical / electronic products.

[0101]

[0102] Hereinafter, the structure and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, these are presented as preferred examples of the present invention and should not be construed as limiting the present invention in any way.

[0103]

[0104] Example

[0105] The specifications of each component used in the following examples and comparative examples are as follows.

[0106] (A) Polycarbonate resin

[0107] Bisphenol-A polycarbonate resin (weight average molecular weight (Mw): approximately 22,000 g / mol) was used.

[0108] (B) Polysiloxane-polycarbonate copolymer resin

[0109] A polysiloxane-polycarbonate copolymer resin having a polydimethylsiloxane (PDMS) content of 6 wt% and a weight average molecular weight (Mw) of approximately 22,000 g / mol was used.

[0110] (C) Glass fiber

[0111] (C1) Flat cross-section glass fiber (Manufacturer: Nittobo, Product name: CSG 3PA-832) was used.

[0112] (C2) Round cross-section glass fiber (Manufacturer: Owenscorning, Product name: 183F) was used.

[0113] (D) Inherent flame retardant

[0114] (D1) A cyclic phosphazene compound (Manufacturer: Pharmicell Co. Ltd., Product name: Phoretar 201) was used.

[0115] (D2) Oligomeric bisphenol-A bis(diphenylphosphate) (Manufacturer: DAIHACHI, Product name: CR-741) was used.

[0116] (D3) Oligomeric resorcinol bis(diphenylphosphate) (Manufacturer: DAIHACHI, Product name: PX-200) was used.

[0117] (E) polydimethylsiloxane

[0118] (E1) Polydimethylsiloxane (kinematic viscosity: approximately 40 cSt) having a terminal reactive group (hydroxyl group) was used.

[0119] (E2) Polydimethylsiloxane (manufacturer: Momentive, product name: PDMS-200, kinematic viscosity: approximately 40 cSt) was used.

[0120]

[0121] Examples 1 to 14 and Comparative Examples 1 to 9

[0122] Each of the above components was added in the amounts shown in Tables 1, 2, 3, and 4 below, and then extruded at about 260°C to produce pellets. The extrusion was performed using a twin-screw extruder with an L / D of 36 and a diameter of 45 mm. The manufactured pellets were dried at 80°C for more than 5 hours, and then injected using a 6 oz injection molding machine (molding temperature: about 320°C) to produce test pieces. The physical properties of the manufactured test pieces were evaluated using the following methods, and the results are shown in Tables 1, 2, 3, and 4 below.

[0123]

[0124] Method of measuring physical properties

[0125] (1) Notched Izod impact strength (unit: kgf·cm / cm): The notched Izod impact strength of a 1 / 8" thick specimen was measured according to ASTM D256.

[0126] (2) Flexural modulus (unit: kgf / cm) 2 ): According to ASTM D790, the flexural modulus of a 1 / 4" thick specimen was measured under the condition of 2.8 mm / min.

[0127] (3) Evaluation of chemical resistance (impact resistance after painting): A 2 mm thick specimen was immersed in a thinner solution for 2 minutes and 30 seconds, dried at 80°C for 20 minutes, left at room temperature for 24 hours, and then impacted using a drop test device using a 2 kg weight, and the height at which the specimen was destroyed (unit: cm) was measured.

[0128] (4) Flame retardancy: The flame retardancy of a 0.8 mm thick specimen was measured using the UL-94 vertical test method.

[0129] (5) Appearance evaluation: After injecting a pin-gate structured injection molded product at an injection molding machine barrel temperature of 320℃, the occurrence of phase separation or gas marks near the gate was visually checked. (○: No occurrence, ×: Occurrence)

[0130]

[0131] Example 1234567(A) (% by weight)40809080808080(B) (% by weight)60201020202020(C1) (parts by weight)101010530-10(C2) (parts by weight)-----10-(D1) (parts by weight)8888886(D2) (parts by weight)-------(D3) (parts by weight)-------(E1) (parts by weight)0.50.50.50.50.50.50.5(E2) (parts by weight)-------Notched Izod impact strength (kgf·cm / cm)14141522131517Flexural modulus (kgf / cm) 2 )31,90032,50033,20027,00073,00033,80033,500Specimen fracture height (cm)62685792326772FlammabilityV-0V-0V-0V-0V-0V-0V-0Appearance evaluation○○○○○○○

[0132] * Weight parts: Weight parts per 100 weight parts of base resin (A+B)

[0133]

[0134] Example 891011121314(A) (Wt%)80808080808080(B) (Wt%)20202020202020(C1) (Wt)10101010101010(C2) (Wt)-------(D1) (Wt)12----88(D2) (Wt)-612----(D3) (Wt)---612--(E1) (Wt)0.50.50.50.50.50.21.5(E2) (Wt)-------Notched Izod Impact Strength (kgf·cm / cm)121491481314Flexural Modulus (kgf / cm) 2)34,20033,40033,20033,20033,90033,20032,500Specimen fracture height (cm)51584055426065FlammabilityV-0V-0V-0V-0V-0V-0V-0Appearance evaluation○○○○○○○

[0135] * Weight parts: Weight parts per 100 weight parts of base resin (A+B)

[0136]

[0137] Comparative Example 1234 (A) (% by weight) 20998080 (B) (% by weight) 8012020 (C1) (parts by weight) 1010240 (C2) (parts by weight) ---- (D1) (parts by weight) 8888 (D2) (parts by weight) ---- (D3) (parts by weight) ---- (E1) (parts by weight) 1111 (E2) (parts by weight) ---- Notched Izod impact strength (kgf·cm / cm) 14152210 Flexural modulus (kgf / cm) 2 )29,00032,20019,50090,500Specimen fracture height (cm)48258210 or lessFlame retardancyV-2V-0V-0V-0Appearance evaluation○×○○

[0138] * Weight parts: Weight parts per 100 weight parts of base resin (A+B)

[0139]

[0140] Comparative Example 56789 (A) (Wt%) 8080808080 (B) (Wt%) 2020202020 (C1) (Wt%) 1010101010 (C2) (Wt%) ----- (D1) (Wt%) 0.5 25888 (D2) (Wt%) ----- (D3) (Wt%) ----- (E1) (Wt%) 0.5 0.5 0.013- (E2) (Wt%) ---- 0.5 Notch Izod Impact Strength (kgf cm / cm) 185 14 11 13 Flexural Modulus (kgf / cm) 2 )31,00032,00033,50028,50029,500Specimen fracture height (cm)7510 or less386442FlammabilityHBV-2V-1V-0V-1Appearance evaluation○○○××

[0141] * Weight parts: Weight parts per 100 weight parts of base resin (A+B)

[0142]

[0143] From the above results, it can be seen that the polycarbonate resin composition according to the present invention is excellent in impact resistance (notched Izod impact strength), rigidity (flexural modulus), chemical resistance (specimen fracture height), (thin film) flame retardancy (flame retardancy), appearance characteristics (appearance evaluation), and the balance of these physical properties.

[0144] On the other hand, in the case of Comparative Example 1, where the content of the polycarbonate resin is less than the range of the present invention and the content of the polysiloxane-polycarbonate copolymer resin exceeds the range of the present invention, it can be seen that (thin film) flame retardancy, etc. are deteriorated, and in the case of Comparative Example 2, where the content of the polycarbonate resin exceeds the range of the present invention and the content of the polysiloxane-polycarbonate copolymer resin is less than the range of the present invention, it can be seen that chemical resistance, appearance characteristics, etc. are deteriorated. In the case of Comparative Example 3, where the content of the glass fiber is less than the range of the present invention, it can be seen that rigidity, etc. are deteriorated, and in the case of Comparative Example 4, where the content of the glass fiber exceeds the range of the present invention, it can be seen that chemical resistance, etc. are deteriorated. In the case of Comparative Example 5, where the content of the phosphorus-based flame retardant is less than the range of the present invention, it can be seen that (thin film) flame retardancy, etc. are deteriorated, and in the case of Comparative Example 6, where the content of the phosphorus-based flame retardant exceeds the range of the present invention, it can be seen that impact resistance, chemical resistance, (thin film) flame retardancy, etc. are deteriorated. In addition, in the case of Comparative Example 7, where the content of polydimethylsiloxane having a terminal reactive group is less than the range of the present invention, it can be seen that (thin film) flame retardancy, etc. are reduced, and in the case of Comparative Example 8, where the content of polydimethylsiloxane having a terminal reactive group is more than the range of the present invention, it can be seen that appearance characteristics, etc. are reduced, and in the case of Comparative Example 9, where polydimethylsiloxane (D2) is applied instead of the polydimethylsiloxane having a terminal reactive group of the present invention, it can be seen that (thin film) flame retardancy, appearance characteristics, etc. are reduced.

[0145]

[0146] The present invention has been described with reference to exemplary embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. About 100 parts by weight of a base resin comprising about 30 to about 95 wt% of a polycarbonate resin and about 5 to about 70 wt% of a polysiloxane-polycarbonate copolymer resin; About 5 to about 50 parts by weight of glass fiber; About 1 to about 20 parts by weight of a phosphorus flame retardant; and A polycarbonate resin composition comprising about 0.1 to about 2 parts by weight of a polydimethylsiloxane having a terminal reactive group having a kinematic viscosity of about 5 to about 200 cSt as measured at 40° C. according to ASTM D445.

2. A polycarbonate resin composition according to claim 1, characterized in that the polycarbonate resin has a weight average molecular weight of about 10,000 to about 200,000 g / mol as measured by GPC (gel permeation chromatography).

3. A polycarbonate resin composition according to claim 1 or 2, characterized in that the polycarbonate-polysiloxane copolymer resin comprises about 70 to about 99 wt% of a polycarbonate block and about 1 to about 30 wt% of a polysiloxane block.

4. A polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate-polysiloxane copolymer resin has a weight average molecular weight of about 10,000 to about 50,000 g / mol as measured by gel permeation chromatography (GPC).

5. A polycarbonate resin composition according to any one of claims 1 to 4, wherein the terminal reactive group of the polydimethylsiloxane having the terminal reactive group includes at least one of a hydroxyl group, an epoxy group, and a maleic anhydride group.

6. In any one of claims 1 to 5, the phosphorus flame retardant may include at least one of a phosphazene compound, a phosphate compound, a phosphonate compound, a phosphinate compound, and a phosphine oxide compound.

7. A polycarbonate resin composition according to any one of claims 1 to 6, characterized in that the weight ratio of the polysiloxane-polycarbonate copolymer resin and the glass fiber is about 1:0.1 to about 1:

3.

8. A polycarbonate resin composition according to any one of claims 1 to 7, characterized in that the weight ratio of the polysiloxane-polycarbonate copolymer resin and the polydimethylsiloxane having a terminal reactive group is about 1:0.005 to about 1:0.

1.

9. A polycarbonate resin composition according to any one of claims 1 to 8, wherein the weight ratio of the glass fiber and the polydimethylsiloxane having a terminal reactive group is about 1:0.01 to about 1:0.

3.

10. A polycarbonate resin composition according to any one of claims 1 to 9, characterized in that the weight ratio of the phosphorus flame retardant and the polydimethylsiloxane having a terminal reactive group is about 1:0.01 to about 1:0.

5.

11. A polycarbonate resin composition according to any one of claims 1 to 14, wherein the polycarbonate resin composition has a notched Izod impact strength of about 8 to about 30 kgf·cm / cm on a 1 / 8" thick specimen measured according to ASTM D256.

12. In any one of claims 1 to 11, the polycarbonate resin composition has a flexural modulus of about 23,000 to about 80,000 kgf / cm of a 1 / 4" thick specimen measured under conditions of 2.8 mm / min according to ASTM D790. 2 A polycarbonate resin composition characterized by:

13. A polycarbonate resin composition according to any one of claims 1 to 12, characterized in that the height at which the specimen is destroyed is about 30 cm or more, as measured by immersing a 2 mm thick specimen in a thinner solution for 2 minutes and 30 seconds, drying at 80° C. for 20 minutes, leaving it at room temperature for 24 hours, and then impacting it with a drop weight evaluation device using a Dupont drop test method using a 2 kg weight.

14. A polycarbonate resin composition according to any one of claims 1 to 13, characterized in that the polycarbonate resin composition has a flame retardancy of V-0 or higher on a 0.6 mm thick specimen measured by the UL-94 vertical test method.

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

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