Polycarbonate resin composition and molded article made therefrom

Abstract

To provide a polycarbonate resin composition with excellent rigidity, heat resistance, 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) 1 to 50 parts by weight of a phosphorus-based flame retardant (component C).

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition containing carbon fibers having a number-average fiber length variation coefficient of 0.4 or higher and a phosphorus-based flame retardant, and a molded article made therefrom. [Background technology]

[0002] Polycarbonate resin is used as an engineering plastic in a wide range of fields, including electrical and electronic equipment housings, automotive interior and exterior parts, building materials, furniture, musical instruments, and general merchandise, due to its excellent transparency, impact resistance, heat resistance, and dimensional stability. In particular, polycarbonate resin compositions containing carbon fibers are used in camera parts, laptop computer parts, and mobile phone parts because of their excellent mechanical properties, impact resistance, dimensional stability, and conductivity. (For example, Patent Document 1) To improve the mechanical properties of a polycarbonate resin composition containing carbon fibers, the carbon fiber content can be increased, but this increases strength and rigidity but decreases impact resistance. On the other hand, it has been 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 suffer from reduced mechanical properties. Furthermore, from the perspective of effectively utilizing limited resources, there is a desire for the development of materials using recycled carbon fibers recovered from scraps generated during carbon fiber manufacturing. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2001-49109 [Patent Document 2] Japanese Patent Publication No. 2022-139199 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The object of the present invention is to provide a polycarbonate resin composition and a molded article made therefrom that has excellent rigidity, heat resistance, 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 phosphorus-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 13 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) 1 to 50 parts by weight of a phosphorus-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 a phosphate ester-based flame retardant. 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 0.01 to 50 parts by weight of (E) a silicone-based compound (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 0.1 to 100 parts by weight of (F) inorganic filler (component F) per 100 parts by weight of component A. 8. A polycarbonate resin composition according to any one of items 1 to 7 above, comprising 0.01 to 50 parts by weight of (G) compatibilizer (G component) per 100 parts by weight of component A. The polycarbonate resin composition according to any one of the preceding items 1 to 8, which contains 0.001 to 1.0 parts by weight of (H) phosphorus stabilizer (H component) with respect to 100 parts by weight of component A. The polycarbonate resin composition according to any one of the preceding items 1 to 9, which contains 0.01 to 10 parts by weight of (I) mold release agent (I component) with respect to 100 parts by weight of component A. The polycarbonate resin composition according to any one of the preceding items 1 to 10, wherein the flexural modulus of the polycarbonate resin composition according to claim 1 is greater than the flexural modulus of the polycarbonate resin composition in which component B 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 items 1 to 11, wherein the flame retardancy at a thickness of 0.8 mm measured according to the UL94 standard is V-2 or higher. A molded article made of the polycarbonate resin composition according to any one of the preceding items 1 to 12.

Effect of the Invention

[0007] The polycarbonate resin composition of the present invention and a molded article made therefrom are excellent in rigidity, heat resistance 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.

Mode 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 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 method, melt transesterification method, solid-phase transesterification method of carbonate prepolymer, and ring-opening polymerization method of 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.

[0012] Examples of the dihydroxy compound for inducing other copolymer units include hydroquinone, resorcinol, orcinol, 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-anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentene bisphenoxyethanol fluorene, and the like.

[0013] Examples of the diol compound for inducing other copolymer units include isosorbide: 1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl) tricyclodecane, tetramethylcyclobutane diol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexane dimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, cyclohex-1,4-ylenedimethanol, trans-1,4-cyclohexane dimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane, cis-1,4-cyclohexane dimethanol (cCHDM), cis-1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexane dimethanol, 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol), and the like.

[0014] As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate, or the like is used, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, or the like is included.

[0015] In the production of a polycarbonate resin by interfacial polymerization of the above-mentioned dihydric phenol and a carbonate precursor, a catalyst, a terminal stopper, an antioxidant for preventing oxidation of the dihydric phenol, etc. may be used as necessary. Further, the polycarbonate resin of the present invention includes a branched polycarbonate resin obtained by copolymerizing a polyfunctional aromatic compound having trifunctionality or higher, a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid, a copolymer polycarbonate resin obtained by copolymerizing a difunctional alcohol (including alicyclic), and a polyester carbonate resin obtained by copolymerizing both such a difunctional carboxylic acid and a difunctional alcohol. Further, a mixture obtained by mixing two or more of the obtained polycarbonate resins may also be used.

[0016] The branched polycarbonate resin can impart properties such as drip prevention performance to the polycarbonate resin composition of the present invention. Examples of the polyfunctional aromatic compound having trifunctionality or higher used in such a branched polycarbonate resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)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, 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol and other tris-phenols, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their acid chlorides, etc. Among them, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and particularly 1,1,1-tris(4-hydroxyphenyl)ethane is preferred.

[0017] 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 bending 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.

[0018] 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 reduced environmental impact. The recycled polycarbonate resin is derived from materials such as bottles, disks, pachinko machines, sheets, and semiconductor transport containers.

[0019] <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 flexural modulus is insufficient. On the other hand, when it exceeds 1.0, the supply of carbon fiber becomes unstable during melt kneading, and 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.

[0020] 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 modulus 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.

[0021] 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. When the attached amount of the sizing agent is less than 0.5% by weight, productivity or molding processability may decrease, and when it exceeds 5.0% by weight, mold deposit properties may deteriorate.

[0022] In producing the polycarbonate resin composition of the present invention, the carbon fiber is preferably recycled carbon fiber, more preferably any one of carbon fibers obtained by recycling market return products of molded articles made of the polycarbonate resin composition, carbon fibers obtained by recycling process edge materials during the production of molded articles made of the polycarbonate resin composition, and carbon fibers obtained by recycling process edge materials during the production of carbon fibers, and even more preferably any one of carbon fibers obtained by recycling process edge materials during the production of molded articles made of the polycarbonate resin composition and carbon fibers obtained by recycling process edge materials during the production of carbon fibers, and particularly preferably carbon fibers obtained by recycling process edge materials during the production of carbon fibers. By using recycled carbon fiber, it becomes possible to provide a composition with reduced environmental impact.

[0023] <Component C: Phosphorus-based flame retardant> The polycarbonate resin composition of the present invention contains a phosphorus-based flame retardant as Component C. The content of Component C is 1 to 50 parts by weight, preferably 1 to 45 parts by weight, more preferably 1 to 40 parts by weight, even more preferably 5 to 40 parts by weight, and particularly preferably 5 to 35 parts by weight with respect to 100 parts by weight of Component A. When the content of Component C is less than 1 part by weight, the improvement in flame retardancy is insufficient, and when it exceeds 50 parts by weight, the heat resistance deteriorates.

[0024] Phosphorus-based flame retardants used as component C include phosphate ester-based flame retardants, red phosphorus-based flame retardants, phosphazenes, etc. Among them, phosphate ester-based flame retardants and phosphazenes are preferred, and phosphate ester-based flame retardants are more preferred. Examples of phosphate ester-based flame retardants include cresyl diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), and 1,3-phenylene-bis(2,6-dimethylphenyl phosphate), etc. It may also be an oligomer with about 2 to 20 repeating units or a polymer with 20 or more repeating units containing the above as constituent components.

[0025] <Component D: Dripping inhibitor> In the polycarbonate resin composition of the present invention, from the viewpoint of flame retardancy, it is preferable to use a dripping inhibitor 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.

[0026] Dripping inhibitors used as component D include polytetrafluoroethylene (PTFE) and modified PTFE, etc.

[0027] <Component E: Silicone-based compound> From the viewpoint of flame retardancy, it is preferable that a silicone-based compound is used in the polycarbonate resin composition of the present invention, to the extent that it does not impair the objective of the present invention. The content of component E is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 50 parts by weight, even more preferably 0.05 to 40 parts by weight, and particularly preferably 0.1 to 40 parts by weight, per 100 parts by weight of component A. If the content of component E is less than 0.01 parts by weight, the improvement in flame retardancy may be insufficient, and if it exceeds 50 parts by weight, the mechanical properties may deteriorate.

[0028] Silicone compounds used as component E include polyorganosiloxanes and polycarbonate-polyorganosiloxane copolymers. Polyorganosiloxanes contain at least one constituent unit selected from the group consisting of the following formula (1), and are oligomers with approximately 2 to 20 repeating units or polymers with 20 or more repeating units.

[0029] [ka]

[0030] (In formula (1), R1, R2, and R3 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.) Polycarbonate-polyorganosiloxane copolymers are compounds consisting of structural units represented by the following formula (2) and structural units represented by the following formula (4).

[0031] [ka]

[0032] (In formula (2), R4 and R5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; a and b each independently represent an integer of 1 to 4; and X is a single bond or at least one group selected from the group consisting of the following formula (3).)

[0033]

Chemical formula

[0034] (In formula (3), R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 each independently represent at least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 14 and R 15 each independently represent at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group; when there are a plurality of them, they may be the same or different; c is an integer of 1 to 10; and d is an integer of 4 to 7.)

[0035]

Chemical formula

[0036] (In formula (4), R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R22 and R 23 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a vinyl group, Y and Z each independently represents a single bond or a divalent aliphatic group having 1 to 10 carbon atoms, e and f each independently represents an integer of 1 to 4, and g and h represent 0 or a natural number.)

[0037] <F component: Inorganic filler> In the polycarbonate resin composition of the present invention, from the viewpoints of flame retardancy and mechanical properties, it is preferable that an inorganic filler is used within a range not impairing the object of the present invention. The content of the F component is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 100 parts by weight, still more preferably 0.5 to 80 parts by weight, and particularly preferably 1 to 80 parts by weight with respect to 100 parts by weight of the A component. When the content of the F component is less than 0.1 part by weight, the improvement of flame retardancy and mechanical properties may be insufficient, and when it exceeds 100 parts by weight, the strands during melt kneading may not be stable, so the productivity may deteriorate.)

[0038] Examples of the inorganic filler include talc, mica, kaolin, clay, wollastonite, alumina, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, graphite, glass fiber, potassium titanate fiber, metal fiber, etc., and talc, mica, wollastonite, graphite, and glass fiber are preferable.)

[0039] <G component: Compatibilizer> In the polycarbonate resin composition of the present invention, from the viewpoint of mechanical properties, it is preferable to use a compatibilizer within a range that does not impair the object of the present invention. The content of the G component is preferably 0.01 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, still more preferably 0.01 to 30 parts by weight, and particularly preferably 0.05 to 30 parts by weight with respect to 100 parts by weight of the A component. When the content of the G component is less than 0.01 part by weight, the improvement of mechanical properties may be insufficient, and when it exceeds 50 parts by weight, the flame retardancy may deteriorate.

[0040] Examples of the compatibilizer include compounds having an epoxy group, an oxazoline group, an oxazine group, a carboxy group, a hydroxy group, an ester bond, a carbodiimide bond, a urethane bond, a urea bond, an amide bond, an imide bond, etc. Compounds having an epoxy group, an oxazoline group, an oxazine group, a hydroxy group, an ester bond, a carbodiimide bond, a urethane bond, an imide bond are preferred.

[0041] <H component: 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.

[0042] 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 - ditertbutylphenyl)2 - ethylhexyl phosphite, tris(2,4 - ditertbutylphenyl) phosphite, tris(nonylphenyl) phosphite, ethyldiethylphosphonoacetate, dibutylbutyl phosphonate, dimethyloctadecyl phosphonate, dimethylmethyl phosphonate, diethylhydroxymethyl phosphonate, diethylphenyl phosphonate, diethylphosphonoacetic acid, diethyl(p - methylbenzyl) phosphonate, diethylbenzyl phosphonate, diethyl(p - chlorobenzyl) phosphonate, diethyloctadecyl phosphonate, diethyl(3,5 - di - t - butyl - 4 - hydroxybenzyl) phosphonate, nitrilotris(methylenephosphonic acid), triphenylphosphine, zinc stearyl acid phosphate salt are preferred, and ethyldiethylphosphonoacetate, dibutylbutyl phosphonate, dimethyloctadecyl phosphonate, dimethylmethyl phosphonate, diethylhydroxymethyl phosphonate, diethylphenyl phosphonate, diethylphosphonoacetic acid, diethyl(p - methylbenzyl) phosphonate, diethylbenzyl phosphonate, diethyl(p - chlorobenzyl) phosphonate, diethyloctadecyl phosphonate, diethyl(3,5 - di - t - butyl - 4 - hydroxybenzyl) phosphonate, nitrilotris(methylenephosphonic acid), triphenylphosphine, zinc stearyl acid phosphate salt are more preferred.,

[0043] The content of Component H is preferably 0.001 to 1.0 parts by weight, more preferably 0.005 to 0.5 parts by weight, and even more preferably 0.01 to 0.5 parts by weight with respect to 100 parts by weight of Component A. When the content of Component H is less than 0.001 parts by weight, the thermal stability may be insufficient, while when it exceeds 1.0 parts by weight, the mechanical properties may deteriorate.,

[0044] <Component I: 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 preferable to use a release agent within a range that does not impair the object of the present invention., 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.

[0045] The content of component I is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.05 to 1 part by weight, per 100 parts by weight of component A. If the content of component I 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.

[0046] <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 H, ultraviolet absorbers, bluing agents, antistatic agents, heat shielding agents, fluorescent dyes (including fluorescent whitening agents), colorants, pigments, light diffusing agents, reinforcing fillers other than component F, sliding modifiers, and other resins and elastomers.

[0047] <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. (Flexural modulus) In the present invention, the flexural modulus 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 flexural modulus is measured according to ISO 178 using an 80 mm × 10 mm × 4 mm thick flat test specimen molded from the polycarbonate resin composition. (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]

[0048] 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) Flexural modulus Using 80mm x 10mm x 4mm thick flat test specimens molded from a polycarbonate resin composition, bending tests were conducted according to ISO 178, and the flexural modulus was measured. Based on the measurement results, the ratio of the flexural modulus to the comparative examples was calculated. Specifically, Examples 1-3 were compared with Comparative Example 1, Examples 4-6 with Comparative Example 2, Examples 7-13 with Comparative Example 3, Examples 14-20 with Comparative Example 4, Examples 21-27 with Comparative Example 5, and Examples 28-31 with Comparative Example 6. When the flexural modulus of the comparison subjects was set to 100, the relative values ​​of each flexural modulus were used as the ratio of bending strength. (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) HDT The temperature of deflection (HDT) was measured according to ISO 75-1 using a flat test specimen measuring 80 mm × 10 mm × 4 mm in thickness, molded from a polycarbonate resin composition. The test load was 1.80 MPa.

[0049] [Examples 1-11, 13-18, 20-25, 27-31, Comparative Examples 1-10] Each component other than the carbon fiber, as shown in Tables 1 to 7, 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.

[0050] [Examples 12, 19, 26] Each component other than the carbon fiber, as shown in Tables 3 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 an extrusion temperature of 300°C.

[0051] The components of the compositions shown in Tables 1 to 7 are as follows: (Component A: Polycarbonate resin) A-1: Aromatic polycarbonate resin (manufactured by Teijin Limited, a polycarbonate resin with a viscosity-average molecular weight of 20,900 polymerized from bisphenol A and phosgene by interfacial polymerization, with terminal OH groups of 0.20%) A-2: Aromatic polycarbonate resin (manufactured by Teijin Limited, a polycarbonate resin with a viscosity-average molecular weight of 19,700 polymerized from bisphenol A and phosgene by interfacial polymerization, with terminal OH groups of 0.25%) A-3: Recycled polycarbonate resin (polycarbonate resin with a viscosity-average molecular weight of 20,500 obtained by recycling polycarbonate headlamp lenses, with 1.0% terminal OH groups) A-4: Recycled polycarbonate resin (polycarbonate resin with a viscosity-average molecular weight of 20,400, obtained by recycling polycarbonate headlamp lenses, with 1.2% terminal OH groups) (Component B: Carbon fiber) B-1: HT C422 (manufactured by Teijin Limited, virgin carbon fiber) B-2: DSZ6-PA3(2) (Manufactured by Varetga Inc., carbon fiber obtained by recycling process scraps from carbon fiber manufacturing) (Component C: Phosphorus-based flame retardant) C-1: CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd., bisphenol A-bis(diphenyl phosphate)) C-2:PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd., 1,3-phenylene-bis(2,6-dimethylphenyl phosphate)) (Component D: Drip prevention agent) D-1: Polyflon MPA FA-500H (manufactured by Daikin Industries, Ltd., high molecular weight PTFE) (Component E: Silicone-based compound) E-1: Polycarbonate-polyorganosiloxane copolymer (manufactured by Teijin Limited, a polycarbonate-polyorganosiloxane copolymer with a viscosity-average molecular weight of 19,800, polymerized by interfacial polymerization from 89 parts by weight of bisphenol A, 11 parts by weight of a dihydroxyaryl-terminated polyorganosiloxane represented by the following formula (5), and phosgene)

[0052] [ka]

[0053] (Component F: Inorganic filler) F-1: Victorilite TK-RC (manufactured by Katsumitsuyama Mining Co., Ltd., talc) F-2: PFE-301S (manufactured by Nitto Boseki Co., Ltd., cut glass fiber) (Component G: Compatibilizer) G-1: jER1256 (Manufactured by Mitsubishi Chemical Corporation, bisphenol A type phenoxy resin with epoxy equivalent of 7,500-8,500) (Component H: Phosphorus-based stabilizer) H-1: JC-224 (manufactured by Johoku Chemical Industry Co., Ltd., ethyl diethyl phosphonoacetate) H-2: ADEKA Stab PEP-36 (manufactured by ADEKA Corporation, 3,9-bis(2,6-ditatobutyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane) (Component I: Release agent) I-1: HW405MP (Manufactured by Mitsui Chemicals, Inc., polyethylene wax) (Other ingredients) J-1: ROYAL BLACKRB90003S (Manufactured by Koshigaya Kasei, polystyrene resin master containing 50% carbon black)

[0054] [Table 1]

[0055] [Table 2]

[0056] [Table 3]

[0057] [Table 4]

[0058] [Table 5]

[0059] [Table 6]

[0060] [Table 7] [Industrial applicability]

[0061] The polycarbonate resin composition and molded articles made therefrom of the present invention have excellent rigidity, heat resistance, 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) 1 to 50 parts by weight of a phosphorus-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 a phosphate ester-based flame retardant.

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 0.01 to 50 parts by weight of (E) a silicone-based compound (component E) per 100 parts by weight of component A.

7. The polycarbonate resin composition according to claim 1 or 2, comprising 0.1 to 100 parts by weight of (F) inorganic filler (component F) per 100 parts by weight of component A.

8. The polycarbonate resin composition according to claim 1 or 2, comprising 0.01 to 50 parts by weight of (G) compatibilizer (component G) per 100 parts by weight of component A.

9. The polycarbonate resin composition according to claim 1 or 2, comprising 0.001 to 1.0 parts by weight of (H) phosphorus-based stabilizer (component H) per 100 parts by weight of component A.

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

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

4.

12. 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.

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

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