Polycarbonate resin composition and molded article made therefrom

Abstract

To provide a polycarbonate resin composition with excellent strength, impact resistance, fluidity, and flame retardancy. [Solution] A polycarbonate resin composition comprising (A) 100 parts by weight of polycarbonate resin (component A), (B) 5 to 100 parts by weight of carbon fibers (component B) having a number-average fiber length variation coefficient of 0.4 or more, and (C) 0.01 to 2 parts by weight of a metal salt-based flame retardant (component C).

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin composition containing carbon fibers having a coefficient of variation in number-average fiber length of 0.4 or more and a metal salt-based flame retardant, and a molded product made therefrom.

Background Art

[0002] Polycarbonate resin is excellent in transparency, impact resistance, heat resistance and dimensional stability, and is used as an engineering plastic in a wide range of fields such as casings for electric and electronic equipment, interior and exterior parts of automobiles, building materials, furniture, musical instruments and sundries. In particular, polycarbonate resin compositions containing carbon fibers are excellent in mechanical properties, impact resistance, dimensional stability and conductivity, and are used in camera parts, notebook computer parts and mobile phone parts, etc. (For example, Patent Document 1) To improve the mechanical properties of a polycarbonate resin composition containing carbon fibers, the content of carbon fibers can be increased, but increasing the content of carbon fibers improves strength and rigidity but has the problem that impact resistance and fluidity decrease. On the other hand, it is disclosed that high flame retardancy can be obtained by adding a flame retardant to a polycarbonate resin composition containing carbon fibers. (For example, Patent Document 2) However, these polycarbonate resin compositions exhibit high flame retardancy but have the problem that mechanical properties decrease. Also, from the viewpoint of effectively utilizing limited resources, the development of materials using recycled carbon fibers recovered from end materials generated during carbon fiber production is desired.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The object of the present invention is to provide a polycarbonate resin composition and a molded article made therefrom that has excellent strength, impact resistance, fluidity, and flame retardancy. [Means for solving the problem]

[0005] As a result of diligent research to achieve the above objectives, the inventors have discovered that a polycarbonate resin composition containing carbon fibers having a specific coefficient of variation in fiber length and a metal salt-based flame retardant, and molded articles made therefrom, can solve the above objectives, leading to the present invention. That is, according to the present invention, the following 1 to 10 are provided.

[0006] 1. A polycarbonate resin composition comprising (A) 100 parts by weight of polycarbonate resin (component A), (B) 5 to 100 parts by weight of carbon fibers (component B) having a number-average fiber length variation coefficient of 0.4 or more, and (C) 0.01 to 2 parts by weight of a metal salt-based flame retardant (component C). 2. The polycarbonate resin composition according to item 1 above, wherein component A is a polycarbonate resin having a terminal OH group content of 0.35% or more. 3. The polycarbonate resin composition according to item 1 or 2 above, wherein component B is carbon fiber obtained by recycling process scraps from the carbon fiber manufacturing process. 4. A polycarbonate resin composition according to any one of items 1 to 3 above, wherein component C is an organic sulfonic acid metal salt. 5. A polycarbonate resin composition according to any one of items 1 to 4 above, comprising 0.01 to 50 parts by weight of (D) drip inhibitor (component D) per 100 parts by weight of component A. 6. A polycarbonate resin composition according to any one of items 1 to 5 above, comprising 0.001 to 1 part by weight of (E) phosphorus-based stabilizer (component E) per 100 parts by weight of component A. 7. A polycarbonate resin composition according to any one of items 1 to 6 above, comprising 0.01 to 10 parts by weight of (F) mold release agent (F component) per 100 parts by weight of component A. 8. The fluidity of the polycarbonate resin composition according to the preceding paragraph 1 is greater than that of the polycarbonate resin composition in which the B component is carbon fiber with a coefficient of variation in number average fiber length of less than 0.4. The polycarbonate resin composition according to any one of the preceding paragraphs 1 to 7. 9. The flame retardancy at a thickness of 0.8 mm measured according to the UL94 standard is V-2 or higher. The polycarbonate resin composition according to any one of the preceding paragraphs 1 to 8. 10. A molded product made of the polycarbonate resin composition according to any one of the preceding paragraphs 1 to 9.

Advantages of the Invention

[0007] The polycarbonate resin composition of the present invention and the molded product made therefrom are excellent in strength, impact resistance, fluidity and flame retardancy, and are therefore particularly suitable for use as camera parts, notebook computer parts and mobile phone parts. Therefore, the industrial effect achieved is remarkable.

Modes for Carrying Out the Invention

[0008] Hereinafter, the details of the present invention will be described.

[0009] <Component A: Polycarbonate Resin> The polycarbonate resin used as the component A of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of a carbonate prepolymer, and ring-opening polymerization of a cyclic carbonate compound.

[0010] Typical examples of divalent phenols used here include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, and 4,4'-(p-phenyl Examples include bis(4-hydroxyphenyl)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred divalent phenols are bis(4-hydroxyphenyl)alkanes, among which bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0011] The polycarbonate resin of the present invention may further contain other copolymerization units, as long as they do not impair the effects of the present invention. Examples of dihydroxy compounds that induce other copolymerization units include hydroquinone, resorcinol, orsinol, 2,2-bis(4-hydroxyphenyl)norbornene, 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 10,10-bis(4-hydroxyphenyl)-9-antrone, and 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentaenebisphenoxyethanolfluorene.

[0012] Diol compounds that induce other copolymerization units include isosorbide:1,4:3,6-dianhydro-D-sorbitol, tricyclodecanedimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, and cyclohex-1,4-yl Examples include dicyclodimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis-1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol).

[0013] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0014] When producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, an end-terminating agent, an antioxidant to prevent oxidation of the divalent phenol, etc., may be used as needed. The polycarbonate resin of the present invention also includes a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with both such bifunctional carboxylic acid and bifunctional alcohol. Furthermore, a mixture of two or more of the obtained polycarbonate resins may also be used.

[0015] Branched polycarbonate resins can impart properties such as drip prevention to the polycarbonate resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1,1-bis(4- Examples include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0016] In the production of the polycarbonate resin composition of the present invention, the amount of terminal OH groups in the polycarbonate resin is preferably 0.35% or more, more preferably 0.40% or more, still more preferably 0.45% or more, and particularly preferably 0.45% or more and 5.0% or less. When the amount of terminal OH groups is less than 0.35%, good flexural strength may not be obtained. On the other hand, when the amount of terminal OH groups is 5.0% or more, the thermal stability may decrease. The amount of terminal OH groups is measured according to the method described in the examples.

[0017] In the production of the polycarbonate resin composition of the present invention, the polycarbonate resin may be a recycled polycarbonate resin. By using a recycled polycarbonate resin, it becomes possible to provide a composition with a reduced environmental load. The recycled polycarbonate resin is derived from bottles, disks, pachinko machines, sheets, semiconductor transport containers, etc.

[0018] <Component B: Carbon fiber> The carbon fiber used as the component B of the present invention has a coefficient of variation in number-average fiber length of 0.4 or more, preferably 0.4 to 1.0, and more preferably 0.4 to 0.8. When the coefficient of variation in number-average fiber length is less than 0.4, the improvement in fluidity is insufficient. On the other hand, when it exceeds 1.0, the supply of carbon fiber becomes unstable during melt kneading, so the carbon fiber content in the resin composition may become non-uniform. The coefficient of variation in number-average fiber length is measured according to the method described in the examples.

[0019] The content of component B is 5 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 5 to 60 parts by weight, still more preferably 5 to 𝟓𝟎 parts by weight, and particularly preferably 5 to 40 parts by weight with respect to 100 parts by weight of component A. When the content of component B is less than 5 parts by weight, good flexural strength cannot be obtained. On the other hand, when it exceeds 100 parts by weight, the strands during melt kneading become unstable, resulting in deteriorated productivity and difficulty in pellet formation.

[0020] The carbon fiber used as component B of the present invention preferably has a sizing agent attached thereto, more preferably the attached amount of the sizing agent is 0.5 to 5.0% by weight, and even more preferably 1.0 to 3.0% by weight. If the attached amount of the sizing agent is less than 0.5% by weight, productivity or molding processability may decrease, and if it exceeds 5.0% by weight, mold deposit properties may deteriorate.

[0021] In producing the polycarbonate resin composition of the present invention, the carbon fiber is preferably recycled carbon fiber, more preferably any one of carbon fiber obtained by recycling market return products of molded articles made of the polycarbonate resin composition, carbon fiber obtained by recycling process end materials during the production of molded articles made of the polycarbonate resin composition, and carbon fiber obtained by recycling process end materials during the production of carbon fiber, and even more preferably any one of carbon fiber obtained by recycling process end materials during the production of molded articles made of the polycarbonate resin composition and carbon fiber obtained by recycling process end materials during the production of carbon fiber, and particularly preferably carbon fiber obtained by recycling process end materials during the production of carbon fiber. By using recycled carbon fiber, it becomes possible to provide a composition with reduced environmental load.

[0022] <Component C: Metal salt-based flame retardant> The polycarbonate resin composition of the present invention contains a metal salt-based flame retardant as component C. The content of component C is 0.01 to 2 parts by weight, preferably 0.05 to 2 parts by weight, more preferably 0.05 to 1 part by weight, and even more preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight of component A. If the content of component C is less than 0.01 part by weight, the improvement of flame retardancy is insufficient, and if it exceeds 2 parts by weight, the flame retardancy and impact resistance deteriorate.

[0023] Examples of metal salt-based flame retardants include metal salts of organic sulfonic acids and metal salts of phosphinates, with metal salts of organic sulfonic acids being preferred. Examples of metal salts of organic sulfonic acids include lithium alkyl sulfonates having 1 to 50 carbon atoms, sodium alkyl sulfonates having 1 to 50 carbon atoms, potassium alkyl sulfonates having 1 to 50 carbon atoms, lithium aralkyl sulfonates having 6 to 60 carbon atoms, sodium aralkyl sulfonates having 6 to 60 carbon atoms, potassium aralkyl sulfonates having 6 to 60 carbon atoms, lithium perfluoroalkanesulfonates having 1 to 50 carbon atoms, sodium perfluoroalkanesulfonates having 1 to 50 carbon atoms, and perfluoroalkanesulfonates having 1 to 50 carbon atoms. Potassium bis(alkylsulfone)imide lithium with 2 to 100 carbon atoms, sodium bis(alkylsulfone)imide with 2 to 100 carbon atoms, potassium bis(alkylsulfone)imide with 2 to 100 carbon atoms, lithium bis(aralkylsulfone)imide with 12 to 120 carbon atoms, sodium bis(aralkylsulfone)imide with 12 to 120 carbon atoms, potassium bis(aralkylsulfone)imide with 12 to 120 carbon atoms, lithium bis(perfluoroalkylsulfone)imide with 2 to 100 carbon atoms, 2 to 100 bis(perfluoroalkylsulfone)imide sodium, 2-100 bis(perfluoroalkylsulfone)imide potassium, lithium diphenylsulfonate, sodium diphenylsulfonate, potassium diphenylsulfonate, dilithium diphenylsulfonate, disodium diphenylsulfonate, dipotassium diphenylsulfonate, lithium polystyrenesulfonate, sodium polystyrenesulfonate, potassium polystyrenesulfonate, lithium alkylnaphthalenesulfonate (10-100 carbon atoms), sodium alkylnaphthalenesulfonate (10-100 carbon atoms), potassium alkylnaphthalenesulfonate (10-100 carbon atoms), lithium alkyldiphenylethersulfonate (12-100 carbon atoms), sodium alkyldiphenylethersulfonate (12-100 carbon atoms), potassium alkyldiphenylethersulfonate (12-100 carbon atoms), lithium alkyldiphenylethersulfonate (12-100 carbon atoms),Examples include sodium alkyldiphenyl ether disulfonate with 12 to 100 carbon atoms, potassium alkyldiphenyl ether disulfonate with 12 to 100 carbon atoms, lithium benzenesulfonate formalin condensate, sodium benzenesulfonate formalin condensate, potassium benzenesulfonate formalin condensate, lithium naphthalenesulfonate formalin condensate, sodium naphthalenesulfonate formalin condensate, potassium naphthalenesulfonate formalin condensate, sodium alkylsulfonate with 1 to 50 carbon atoms, and alkylsulfonate with 1 to 50 carbon atoms. Potassium sulfonate, sodium aralkylsulfonate with 6-60 carbon atoms, potassium aralkylsulfonate with 6-60 carbon atoms, sodium perfluoroalkanesulfonate with 1-50 carbon atoms, potassium perfluoroalkanesulfonate with 1-50 carbon atoms, lithium bis(alkylsulfone)imide with 2-100 carbon atoms, sodium bis(alkylsulfone)imide with 2-100 carbon atoms, potassium bis(alkylsulfone)imide with 2-100 carbon atoms, lithium bis(aralkylsulfone)imide with 12-120 carbon atoms, bis(aralkyl Sodium bis(aralkylsulfone)imide, potassium bis(aralkylsulfone)imide with 12-120 carbon atoms, lithium bis(perfluoroalkylsulfone)imide with 2-100 carbon atoms, sodium bis(perfluoroalkylsulfone)imide with 2-100 carbon atoms, potassium bis(perfluoroalkylsulfone)imide with 2-100 carbon atoms, sodium diphenylsulfonate, potassium diphenylsulfonate, disodium diphenylsulfonate, dipotassium diphenylsulfonate, sodium polystyrenesulfonate Um, potassium polystyrene sulfonate, sodium alkylnaphthalene sulfonate with 10 to 100 carbon atoms, potassium alkylnaphthalene sulfonate with 10 to 100 carbon atoms, sodium alkyldiphenyl ether sulfonate with 12 to 100 carbon atoms, potassium alkyldiphenyl ether sulfonate with 12 to 100 carbon atoms, lithium alkyldiphenyl ether disulfonate with 12 to 100 carbon atoms, sodium alkyldiphenyl ether disulfonate with 12 to 100 carbon atoms, potassium alkyldiphenyl ether disulfonate with 12 to 100 carbon atoms,Examples include sodium benzenesulfonate formalin condensate, potassium benzenesulfonate formalin condensate, sodium naphthalenesulfonate formalin condensate, potassium naphthalenesulfonate formalin condensate, etc. Sodium alkyl sulfonate with 1 to 50 carbon atoms, potassium alkyl sulfonate with 1 to 50 carbon atoms, sodium aralkyl sulfonate with 6 to 60 carbon atoms, potassium aralkyl sulfonate with 6 to 60 carbon atoms, sodium perfluoroalkane sulfonate with 1 to 50 carbon atoms, potassium perfluoroalkane sulfonate with 1 to 50 carbon atoms, lithium bis(alkylsulfone)imide with 2 to 100 carbon atoms, sodium bis(alkylsulfone)imide with 2 to 100 carbon atoms, potassium bis(alkylsulfone)imide with 2 to 100 carbon atoms, lithium bis(aralkylsulfone)imide with 12 to 120 carbon atoms, sodium bis(aralkylsulfone)imide with 12 to 120 carbon atoms, potassium bis(aralkylsulfone)imide with 12 to 120 carbon atoms, lithium bis(perfluoroalkylsulfone)imide with 2 to 100 carbon atoms, sodium bis(perfluoroalkylsulfone)imide with 2 to 100 carbon atoms, potassium bis(perfluoroalkylsulfone)imide with 2 to 100 carbon atoms, sodium diphenylsulfone sulfonate, potassium diphenylsulfone sulfonate, disodium diphenylsulfone disulfonate, dipotassium diphenylsulfone disulfonate, sodium alkyl naphthalenesulfonate with 10 to 100 carbon atoms, potassium alkyl naphthalenesulfonate with 10 to 100 carbon atoms are preferred.

[0024] <Component D: Anti-dripping agent> From the viewpoint of flame retardancy, it is preferable that an anti-dripping agent is used in the polycarbonate resin composition of the present invention within a range that does not impair the object of the present invention. The content of Component D is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 50 parts by weight, still more preferably 0.05 to 25 parts by weight, and particularly preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of Component A. When the content of Component D is less than 0.01 part by weight, the improvement of flame retardancy may be insufficient, and when it exceeds 50 parts by weight, the fluidity may deteriorate.

[0025] Examples of the anti-drip agent used as component D include polytetrafluoroethylene (PTFE) and modified PTFE.

[0026] <Component E: Phosphorus-based stabilizer> In the polycarbonate resin composition of the present invention, from the viewpoints of heat resistance and molding stability, it is preferable to use a phosphorus-based stabilizer within a range that does not impair the object of the present invention.

[0027] As phosphorus-based stabilizers, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-bis(2,6-ditatobutyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 2,2'-methylenebis(4,6-ditatobutylphenyl)2-ethylhexyl phosphite, tris(2,4-ditatobutylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra-C12-C15-alkyl(propane N-2,2-diylbis(4,1-phenylene))bisphosphite, 2-ethylhexyldiphenylphosphite, isodecyldiphenylphosphite, triisodecylphosphite, triphenylphosphite, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, alkyl (C12,C14,C16,C18) acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, Diylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, dibutyl phosphate, bis(2-ethylhexyl) phosphate, ethyl diethyl phosphonoacetate, dibutylbutyl phosphonate, dimethyl octadecyl phosphonate, dimethylmethyl phosphonate, diethyl hydroxymethyl phosphonate, diethylphenyl phosphonate, diethylphosphonoacetic acid, diethyl(p-methylbenzyl) phosphonate, diethylbenzyl phosphonate, diethyl(p-chlorobenzyl) phosphonate, diethyl Examples include tyloctadecylphosphonate, diethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, nitrilotris(methylenephosphonic acid), triphenylphosphine, and stearyl acid phosphate zinc salt, as well as 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-bis(2,6-ditatobutyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, and 2,2'-methylenebis(4,6-ditert-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, ethyl diethylphosphonoacetate, dibutyl butylphosphonate, dimethyl octadecylphosphonate, dimethyl methylphosphonate, diethyl hydroxymethylphosphonate, diethyl phenylphosphonate, diethyl phosphonoacetic acid, diethyl (p-methylbenzyl) phosphonate, diethyl benzylphosphonate, diethyl (p-chlorobenzyl) phosphonate, diethyl octadecylphosphonate, diethyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, nitrilotris (methylenephosphonic acid), triphenylphosphine, zinc stearyl acid phosphate are preferred, and ethyl diethylphosphonoacetate, dibutyl butylphosphonate, dimethyl octadecylphosphonate, dimethyl methylphosphonate, diethyl hydroxymethylphosphonate, diethyl phenylphosphonate, diethyl phosphonoacetic acid, diethyl (p-methylbenzyl) phosphonate, diethyl benzylphosphonate, diethyl (p-chlorobenzyl) phosphonate, diethyl octadecylphosphonate, diethyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, nitrilotris (methylenephosphonic acid), triphenylphosphine, zinc stearyl acid phosphate are more preferred.,

[0028] The content of Component E is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and even more preferably 0.01 to 0.5 part by weight with respect to 100 parts by weight of Component A. When the content of Component E is less than 0.001 part by weight, the thermal stability may be insufficient, while when it exceeds 1 part by weight, the mechanical properties may deteriorate.,

[0029] <Component F: Release agent> In the polycarbonate resin composition of the present invention, from the viewpoint of improving the mold release property from the mold during melt molding, it is preferred that a release agent is used within a range that does not impair the object of the present invention.,

[0030] Examples of mold release agents include olefin waxes, olefin waxes containing carboxyl groups and / or carboxylic acid anhydride groups, silicone oils, organopolysiloxanes, higher fatty acid esters of monohydric or polyhydric alcohols, paraffin waxes, and beeswax.

[0031] The content of component F is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 10 parts by weight, and even more preferably 0.05 to 5 parts by weight, per 100 parts by weight of component A. If the content of component F is less than 0.01 parts by weight, the release properties from the mold during injection molding may be insufficient, while if it exceeds 10 parts by weight, the mechanical properties may deteriorate.

[0032] <Other ingredients> The polycarbonate resin composition of the present invention may contain, to the extent that it does not impair the objectives of the present invention, heat stabilizers other than component E, ultraviolet absorbers, bluing agents, antistatic agents, flame retardants other than component C, heat shielding agents, fluorescent dyes (including fluorescent whitening agents), colorants, pigments, light diffusing agents, reinforcing fillers, sliding modifiers, and other resins and elastomers.

[0033] <Method for producing polycarbonate resin composition> In the present invention, it is preferable to blend components A, B, and C in a molten state in the polycarbonate resin composition. As a method of blending in a molten state, an extruder is generally used, and it is preferable to knead and pelletize at a molten resin temperature of 200 to 400°C. This yields a polycarbonate resin composition in which components A, B, and C are uniformly blended. The configuration of the extruder and the screw configuration are not particularly limited.

[0034] (Liquidity) In the present invention, the fluidity of the polycarbonate resin composition is preferably greater than that of a polycarbonate resin composition in which component B is carbon fiber with a number-average fiber length variation coefficient of less than 0.4. The fluidity was measured by injection molding the polycarbonate resin composition using an injection molding machine (Sumitomo Heavy Industries, Ltd., all-electric small injection molding machine SE130EV-A) with a channel thickness of 2 cm and a channel width of 8 mm, under the conditions of a cylinder temperature of 290°C, a mold temperature of 100°C, and an injection pressure of 118 MPa.

[0035] (Flame retardant) In this invention, the flame retardancy is preferably V-2 or higher at a thickness of 0.8 mm. The flame retardancy is measured according to the UL94 standard using a 125 mm × 13 mm × 0.8 mm thick test specimen molded from a polycarbonate resin composition. [Examples]

[0036] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the present invention. The evaluation was carried out according to the following method. (1) Terminal OH group amount (%) 40 mg of polycarbonate resin was dissolved in 0.6 mL of deuterated chloroform, and the amount of terminal OH groups was calculated from the integral ratio of the constituent units and terminal OH groups using proton NMR with a JEOL JNM-AL400. (2) Number-average coefficient of variation of fiber length Several grams of polycarbonate resin composition were weighed and dissolved in dichloromethane. The carbon fibers were then filtered and separated. The separated carbon fibers were suspended in water, and the length of 5000 fibers was measured using a JASCO International SC-2micro analyzer. The number-average fiber length and standard deviation of the fiber length were then calculated. Using these values, the coefficient of variation of the number-average fiber length was calculated using the following formula. (Coefficient of variation of number-mean fiber length) = (Standard deviation of fiber length) / (Number-mean fiber length) (3) Liquidity The flow length of an Archimedes spiral flow channel with a channel thickness of 2 cm and a channel width of 8 mm was measured by injection molding a polycarbonate resin composition using an injection molding machine (Sumitomo Heavy Industries, Ltd., all-electric small injection molding machine SE130EV-A) under the conditions of cylinder temperature 290°C, mold temperature 100°C, and injection pressure 118 MPa. In addition, the ratio of fluidity to comparative examples was calculated based on the fluidity measurement results. Specifically, Examples 1 to 7 were compared with Comparative Example 1, Examples 8 to 14 with Comparative Example 2, Examples 15 to 24 with Comparative Example 3, Examples 25 to 34 with Comparative Example 4, and Examples 35 to 44 with Comparative Example 5. When the fluidity of the comparison target was set to 100, the relative value of the fluidity of each was taken as the ratio of fluidity. (4) Flame retardant A 125mm x 13mm x 0.8mm thick test specimen molded from a polycarbonate resin composition was subjected to a combustion test in accordance with the UL94 standard. Based on the test results, the specimens were evaluated as one of the following grades: V-0, V-1, V-2, or not-V. (5) Bending strength A flat test specimen measuring 80 mm x 10 mm x 4 mm in thickness, molded from a polycarbonate resin composition, was subjected to a bending test in accordance with ISO 178, and its bending strength was measured. (6) Charpy impact strength (without notch) Using a flat test specimen measuring 80 mm × 10 mm × 4 mm in thickness, molded from a polycarbonate resin composition, the Charpy impact strength (without notches) at 23°C was measured according to ISO 179.

[0037] [Examples 1-4, 6-11, 13-19, 21-29, 31-39, 41-44, Comparative Examples 1-9] Each component other than the carbon fiber, as shown in Tables 1 to 6, was weighed and uniformly mixed using a tumbler. A polycarbonate resin composition was prepared by feeding this mixture through the main feeder of an extruder and the carbon fiber through the side feeder. The extruder used was a vented twin-screw extruder, model TEX-30XSST, manufactured by Japan Steel Works Ltd. (fully meshed, co-rotating, double-threaded screw). The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 180 rpm, and a vent vacuum of 3 kPa. The extrusion was performed at an extrusion temperature of 280°C.

[0038] [Examples 5, 12, 20, 30, 40] Each component other than the carbon fiber, as shown in Tables 1 to 5, was weighed and uniformly mixed using a tumbler. A polycarbonate resin composition was prepared by feeding this mixture through the main feeder of an extruder and the carbon fiber through the side feeder. The extruder used was a vented twin-screw extruder, model TEX-30XSST, manufactured by Japan Steel Works Ltd. (full meshing, co-direction rotation, double-threaded screw). The extrusion conditions were a discharge rate of 15 kg / h, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa. The extrusion was performed at a temperature of 300°C.

[0039] The components of the compositions shown in Tables 1 to 6 are as follows: (Component A: Polycarbonate resin) A-1: Aromatic polycarbonate resin (manufactured by Teijin Limited; a polycarbonate resin polymerized from bisphenol A and phosgene by interfacial polymerization, with a viscosity-average molecular weight of 19,700 and a terminal OH group content of 0.25%). A-2: Recycled polycarbonate resin (polycarbonate resin with a viscosity-average molecular weight of 20,500 and terminal OH group content of 1.0%, obtained by recycling polycarbonate headlamp lenses) (Component B: Carbon fiber) B-1: DSZ6-PA3(2) (Manufactured by Varetga Inc., carbon fiber obtained by recycling process scraps from carbon fiber manufacturing) B-2: HT C422 (manufactured by Teijin Limited, virgin carbon fiber) (Component C: Metal salt-based flame retardant) C-1: F-Top PFBS (manufactured by Mitsubishi Materials Corporation, potassium perfluorobutanesulfonate) C-2: KSS-FR (AriChem Inc., potassium diphenylsulfonate) (Component D: Drip prevention agent) D-1: Polyflon MPA FA-500H (manufactured by Daikin Industries, Ltd., high molecular weight PTFE) (Component E: Phosphorus-based stabilizer) E-1: JC-224 (manufactured by Johoku Chemical Industry Co., Ltd., ethyl diethyl phosphonoacetate) (Component F: Release agent) F-1: HW405MP (Manufactured by Mitsui Chemicals, Inc., polyethylene wax) (Other ingredients) G-1: ROYAL BLACKRB90003S (Manufactured by Koshigaya Kasei, polystyrene resin master containing 50% carbon black)

[0040] [Table 1]

[0041] [Table 2]

[0042] [Table 3]

[0043] [Table 4]

[0044] [Table 5]

[0045] [Table 6] [Industrial applicability]

[0046] The polycarbonate resin composition and molded articles made therefrom of the present invention are excellent in strength, impact resistance, fluidity, and flame retardancy, and can therefore be used in camera parts, laptop computer parts, mobile phone parts, and the like.

Claims

1. A polycarbonate resin composition comprising (A) 100 parts by weight of polycarbonate resin (component A), (B) 5 to 100 parts by weight of carbon fibers (component B) having a number-average fiber length variation coefficient of 0.4 or more, and (C) 0.01 to 2 parts by weight of a metal salt-based flame retardant (component C).

2. The polycarbonate resin composition according to claim 1, wherein component A is a polycarbonate resin having a terminal OH group content of 0.35% or more.

3. The polycarbonate resin composition according to claim 1 or 2, wherein component B is carbon fiber obtained by recycling process scraps from the production of carbon fiber.

4. The polycarbonate resin composition according to claim 1 or 2, wherein component C is an organic sulfonic acid metal salt.

5. The polycarbonate resin composition according to claim 1 or 2, comprising 0.01 to 50 parts by weight of (D) drip inhibitor (component D) per 100 parts by weight of component A.

6. The polycarbonate resin composition according to claim 1 or 2, comprising 0.001 to 1 part by weight of (E) phosphorus-based stabilizer (component E) per 100 parts by weight of component A.

7. The polycarbonate resin composition according to claim 1 or 2, comprising 0.01 to 10 parts by weight of (F) a mold release agent (component F) per 100 parts by weight of component A.

8. The polycarbonate resin composition according to claim 1 or 2, wherein the fluidity of the polycarbonate resin composition according to claim 1 is greater than the fluidity of the polycarbonate resin composition in which component B is carbon fiber having a number-average fiber length variation coefficient of less than 0.

4.

9. A polycarbonate resin composition according to claim 1 or 2, wherein the flame retardancy at a thickness of 0.8 mm, as measured according to the UL94 standard, is V-2 or higher.

10. A molded article comprising the polycarbonate resin composition according to claim 1 or 2.

Images