Polycarbonate resin composition and molded article comprising the same

Abstract

To provide a fire retardant polycarbonate resin composition having low environmental load and excellent in stiffness, fire resistance, water and fire resistance, and wet heat resistance.SOLUTION: A polycarbonate resin composition comprises (A) 100 pts.wt. of an aromatic polycarbonate resin (component A) containing a polycarbonate block represented by formula [1], (B) 0.01-0.25 pts.wt. of a fluoroalkyl group-free aromatic sulfonic acid alkali(earth) metal salt (component B) having a water solubility of 500 g / L or less at 80°C, (C) 0.1-2 pts.wt. of an alkylsilane-surface-unmodified hydrophilic fumed silica (component C) having a specific surface area by BET adsorption method of 50-250 m2 / g and a saturated water absorption coefficient of 0.3% or more and less than 2.0% at 23°C / 50%RH, (D) 0.05-1.2 pts.wt. of a fluorine-containing anti-dripping agent (component D), and (E) 1-80 pts.wt. of an inorganic filler (component E).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition and a molded article made thereof. More specifically, the present invention relates to a polycarbonate resin composition containing an aromatic polycarbonate resin, a specific alkali (earth) metal salt of an aromatic sulfonate, hydrophilic fumed silica not surface-modified with a specific alkylsilane, a fluorinated anti-dripping agent, and an inorganic filler, and the polycarbonate resin composition has a low environmental impact and is excellent in rigidity, flame retardancy, water-resistant flame retardancy, and moist heat resistance, and a molded article made thereof. [Background technology]

[0002] Polycarbonate resins are used in a wide range of applications, including machine parts, automotive parts, electrical and electronic components, and office equipment, thanks to their excellent properties, such as mechanical strength, dimensional stability, and flame retardancy. Their excellent flame retardancy and impact resistance have led to their use as housings and exterior components for a variety of electronic devices. In recent years, not only have they become thinner and more compact, but their expanded applications have also led to demands for high flame retardancy and sufficient performance in outdoor environments, as exemplified by the UL746C standard. However, currently, polycarbonate resins have not achieved sufficient performance as materials for applications requiring extremely high impact resistance, such as outdoor electrical and electronic storage boxes, such as telecommunications boxes, and solar power generation junction boxes. Furthermore, due to environmental concerns, the flame retardancy of polycarbonate resins has shifted from brominated flame retardants to phosphorus-based and organometallic flame retardants. However, the widely used perfluoroalkanesulfonic acid metal salts have become a concern due to their persistent biodegradability, and their use must also be considered.

[0003] Furthermore, alkali (earth) metal sulfonates are known as organic metal salts that do not contain fluoroalkyl groups. However, they suffer from the problem of insufficient flame retardancy. While there are cases where inorganic fine particles are used in combination as a flame retardant aid (Patent Documents 1 and 2), the flame retardancy is insufficient despite the use of perfluorobutanesulfonic acid metal salts. Furthermore, there is no disclosure of long-term water resistance and moist heat resistance that can withstand the UL746C water exposure test and high-temperature moist heat treatment, which are standards for long-term properties for thin-walled products of 1 mm or less. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-045910 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-156031 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a flame-retardant polycarbonate resin composition which has a low environmental impact and is excellent in rigidity, flame retardancy, water-resistant flame retardancy, and moist heat resistance, and to provide a molded article made from the same. [Means for solving the problem]

[0006] As a result of extensive research to solve the above problems, the present inventors have discovered that the above problems can be solved by the following configuration, and have arrived at the present invention.

[0007] (Configuration 1) (A) 100 parts by weight of an aromatic polycarbonate resin (component A) containing a polycarbonate block represented by the following general formula [1], (B) 0.01 to 0.25 parts by weight of an aromatic sulfonic acid alkali (earth) metal salt (component B) containing no fluoroalkyl group and having a solubility in water of 500 g / L or less at 80°C, (C) a specific surface area of ​​50 to 250 m by BET adsorption 2A polycarbonate resin composition comprising 0.1 to 2 parts by weight of hydrophilic fumed silica (component C) that has not been surface-modified with alkylsilane and has a water absorption of 0.3% or more and less than 2.0% at 23°C / 50%RH, 0.05 to 1.2 parts by weight of (D) a fluorine-containing anti-dripping agent (component D), and 1 to 80 parts by weight of (E) an inorganic filler (component E). [ka] (In the above general formula [1], R 1 and R 2 each independently represents a 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 18 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 14 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 carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]: [ka] (In the above general formula [2], R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents a 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 19 and R 20each independently represents a 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 carboxy group; when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0008] (Configuration 2) Component C has a specific surface area of ​​120 to 220 m2 in BET adsorption. 2 / g and a saturated water absorption rate at 23°C / 50% RH of 0.5% or more and less than 1.5%. (Configuration 3) 3. The polycarbonate resin composition according to claim 1, wherein component B is an alkali (earth) metal salt of an aromatic sulfonate containing no fluoroalkyl group, the alkali (earth) metal salt having a solubility in water at 80°C of 100 g / L or less. (Configuration 4) 4. The polycarbonate resin composition according to any one of Aspects 1 to 3, wherein Component B is at least one selected from the group consisting of dipotassium diphenylsulfide-4,4'-disulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, and mixtures thereof. (Configuration 5) 5. The polycarbonate resin composition according to any one of configurations 1 to 4, wherein the content of component B is 0.03 to 0.15 parts by weight per 100 parts by weight of component A. (Configuration 6) 6. The polycarbonate resin composition according to any one of configurations 1 to 5, wherein component A has a viscosity average molecular weight of 15,000 to 25,000. (Configuration 7) 7. The polycarbonate resin composition according to any one of configurations 1 to 6, wherein the polycarbonate block represented by the formula [1] is a polycarbonate block derived from 2,2-bis(4-hydroxyphenyl)propane. (Configuration 8) 8. The polycarbonate resin composition according to any one of configurations 1 to 7, wherein the content of component C is 0.3 to 1.0 part by weight per 100 parts by weight of component A. (Configuration 9) 9. The polycarbonate resin composition according to any one of configurations 1 to 8, wherein the content of component D is 0.15 to 0.5 parts by weight per 100 parts by weight of component A. (Configuration 10) 10. The polycarbonate resin composition according to any one of configurations 1 to 9, wherein component E is at least one inorganic filler selected from the group consisting of (E-1) glass fiber (component E-1), (E-2) plate-like glass filler (component E-2), (E-3) fibrous carbon filler (component E-3), (E-4) non-fibrous carbon filler (component E-4), and (E-5) silicate mineral (component E-5). (Configuration 11) 11. The polycarbonate resin composition according to any one of configurations 1 to 10, wherein the content of component E is 5 to 45 parts by weight per 100 parts by weight of component A. (Configuration 12) 12. The polycarbonate resin composition according to any one of configurations 1 to 11, comprising 0.01 to 1 part by weight of (F) an ultraviolet absorber (Component F) per 100 parts by weight of Component A. (Configuration 13) 13. The polycarbonate resin composition according to any one of configurations 1 to 12, comprising 0.01 to 0.5 parts by weight of (G) a heat stabilizer (Component G) per 100 parts by weight of Component A. (Configuration 14) 14. The polycarbonate resin composition according to any one of configurations 1 to 13, wherein component C is compounded as a masterbatch obtained by extrusion mixing in advance 95 to 20 parts by weight of component A and 5 to 80 parts by weight of component C, each having a viscosity average molecular weight of 15,000 to 25,000. (Configuration 15) (A) 100 parts by weight of an aromatic polycarbonate resin (component A) containing a polycarbonate block represented by the following general formula [1], (B) 0.01 to 0.25 parts by weight of an aromatic sulfonic acid alkali (earth) metal salt (component B) containing no fluoroalkyl group and having a solubility in water of 500 g / L or less at 80°C, (C) a specific surface area of ​​50 to 250 m by BET adsorption 2 A method for producing a polycarbonate resin composition, comprising melt-kneading 0.1 to 2 parts by weight of hydrophilic fumed silica (component C) that has not been surface-modified with alkylsilane and has a water absorption of 0.3% or more and less than 2.0% at 23°C / 50%RH, 0.05 to 1.2 parts by weight of (D) a fluorine-containing anti-dripping agent (component D), and 1 to 80 parts by weight of (E) an inorganic filler (component E). [ka] (In the above general formula [1], R 1 and R 2 each independently represents a 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 18 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 14 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 carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]: [ka] (In the above general formula [2], R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18each independently represents a 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 19 and R 20 each independently represents a 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 carboxy group; when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0009] (Configuration 16) A molded article made from the polycarbonate resin composition according to any one of aspects 1 to 14. [Effects of the Invention]

[0010] The polycarbonate resin composition of the present invention has low environmental impact and is excellent in rigidity, flame retardancy, water-resistant flame retardancy, and moist heat resistance, specifically, in flame retardancy that can withstand the UL746C water exposure test and high-temperature moist heat treatment, and is therefore suitable for use as a material for outdoor structural members, various housing members, and automobile-related parts. It is also useful for various electronic and electrical device parts, camera parts, office automation device parts, precision machinery parts, machinery parts, vehicle parts, and other applications such as agricultural materials, transport containers, play equipment, and miscellaneous goods, and its industrial effects are exceptional. DETAILED DESCRIPTION OF THE INVENTION

[0011] (Component A: aromatic polycarbonate resin) The aromatic polycarbonate resin in the present invention contains a polycarbonate block represented by the following general formula [1].

[0012] [ka]

[0013] (In the above general formula [1], R 1 and R 2 each independently represents a 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 18 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 14 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 carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]:

[0014] [ka]

[0015] (In the above general formula [2], R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents a 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 19 and R 20each independently represents a 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 carboxy group; when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0016] The dihydric phenols from which the polycarbonate blocks are derived include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, and 2,2-bis(4-hydroxyphenyl)methane. Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)propane, 4,4'-dihydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane. Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable, as it has excellent strength and good durability. These may be used alone or in combination.

[0017] The viscosity average molecular weight of component A is preferably 10,000 to 30,000, more preferably 13,000 to 27,000, even more preferably 15,000 to 25,000, and particularly preferably 18,000 to 23,000. If the viscosity average molecular weight of component A is below the lower limit, it may be difficult to obtain practical mechanical strength in many fields, while if it exceeds the upper limit, the melt viscosity will be high and high molding processing temperatures will generally be required, which may lead to problems such as thermal degradation of the resin.

[0018] (Component B: Alkali (earth) metal salt of aromatic sulfonic acid that does not contain a fluoroalkyl group) The polycarbonate resin composition of the present invention contains an aromatic alkali (earth) metal sulfonate salt containing no fluoroalkyl group as component B. Alkali (earth) metal sulfonates are extremely useful in that they allow the heat resistance of the polycarbonate resin to be largely maintained. Although alkali (earth) metal sulfonates include fluorine-substituted organic alkali (earth) metal sulfonates, the alkali (earth) metal aromatic sulfonate salt containing no fluoroalkyl group is used as component B of the present invention in consideration of environmental impact.

[0019] The content of Component B is 0.01 to 0.25 parts by weight, preferably 0.03 to 0.15 parts by weight, and more preferably 0.04 to 0.12 parts by weight, per 100 parts by weight of Component A. If the content of Component B is less than 0.01 part by weight, flame retardancy cannot be maintained, and if it exceeds 0.25 part by weight, flame retardancy and moist heat resistance become poor.

[0020] The solubility of component B in water at 80°C is 500 g / L or less, more preferably 100 g / L or less, and even more preferably 75 g / L or less. If the solubility exceeds 500 g / L, component B will flow out or re-aggregate upon exposure to hot water, making it impossible to maintain water-resistant flame retardancy and resulting in poor moist heat resistance. The lower limit of the solubility is not particularly limited, but is preferably 5 g / L or more. The solubility was evaluated by placing 100 parts (100 mL) of ion-exchanged water in a glass container equipped with a stirrer, allowing the container to stand for a sufficient period in a hot bath maintained at 80°C, and then slowly adding component B with stirring. The component B was then added to the container, and the amount of component B that remained undissolved was determined based on the limit of addition amount.

[0021] Examples of such metal salts include alkali metal salts of aromatic sulfonic acids and alkaline earth metal salts of aromatic sulfonic acids (neither of which contain fluorine atoms). These can be used alone or in combination of two or more. (Here, the term "alkali (earth) metal salt" is used to mean both alkali metal salts and alkaline earth metal salts.) Among these, alkali (earth) metal salts of aromatic sulfonic acids are preferred, and potassium salts are particularly preferred.

[0022] The aromatic sulfonic acid used in the alkali (earth) metal salt of aromatic sulfonate may be at least one acid selected from the group consisting of sulfonic acids of monomeric or polymeric aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters, sulfonic acids of monomeric or polymeric aromatic ethers, sulfonic acids of aromatic sulfonates, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfone sulfonic acids, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates of aromatic sulfonic acids with methylene bonds, and these may be used alone or in combination of two or more.

[0023] Specific examples of the alkali (earth) metal salt of aromatic sulfonate include disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, lithium poly(2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, and benzenesulfonate. Examples of the diphenylsulfonate include magnesium diphenylsulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-4-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, dipotassium diphenylsulfone-3,4'-disulfonate, sodium α,α,α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, a formalin condensate of sodium naphthalenesulfonate, and a formalin condensate of sodium anthracenesulfonate. Among these, dipotassium diphenylsulfide-4,4'-disulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, and mixtures thereof are particularly preferred.

[0024] (Component C: Hydrophilic fumed silica without alkylsilane surface modification treatment) The polycarbonate resin composition of the present invention contains hydrophilic fumed silica that has not been surface-modified with alkylsilane as component C. By including this hydrophilic fumed silica that has not been surface-modified with alkylsilane, it is possible to achieve good flame retardancy that can withstand the UL746C water exposure test.

[0025] The fumed silica used in the present invention is amorphous silicon dioxide synthesized by a dry method, and is synthesized by high-temperature hydrolysis of silicon halide in an oxyhydrogen flame. Generally, fumed silica is surface-modified with hydrophobic silanes such as chlorosilanes, alkoxysilanes, hydrosilanes, silylamines, silane coupling agents, and polyorganosiloxanes to improve dispersibility and functionality. However, in the present invention, it is necessary to use hydrophilic fumed silica without alkylsilane surface modification. Hydrophilic fumed silica without alkylsilane surface modification exhibits flame retardancy by improving strength through strong interaction with polycarbonate resin, while hydrophobic fumed silica with alkylsilane surface modification exhibits poor dispersion in polycarbonate resin, resulting in poor moist heat resistance, and the flammability of the surface-modifying components prevents improved flame retardancy.

[0026] The specific surface area of ​​component C in BET adsorption is 50 to 250 m 2 / g, preferably 100 to 230m 2 / g, more preferably 120 to 220m 2 / g. The specific surface area of ​​component C in BET adsorption is 50m 2 / g or less, 250m 2 / g, the flame retardancy deteriorates. The specific surface area by BET adsorption is measured by the following method: Using a fully automatic specific surface area measuring device (Macsorb, manufactured by Mountec Co., Ltd.), the sample is pretreated at 100°C for 10 minutes, and then the surface area of ​​the sample is calculated from the amount of nitrogen adsorbed and desorbed by the BET single-point method, and the specific surface area is calculated by dividing the surface area by the weight.

[0027] The saturated water absorption of component C at 23°C / 50% RH is 0.3% or more and less than 2.0%, preferably 0.5% or more and less than 1.5%, and more preferably 0.7% or more and less than 1.2%. Since alkylsilane surface modification is required to achieve a saturated water absorption of less than 0.3% at 23°C / 50% RH, there is no hydrophilic fumed silica without alkylsilane surface modification that has a saturated water absorption of less than 0.3% at 23°C / 50% RH. On the other hand, if the saturated water absorption at 23°C / 50% RH is 2.0% or more, the flame retardancy is insufficient. The fumed silica used in the present invention exhibits a combustion-suppressing effect due to surface adsorbed water, but if the adsorbed water is excessive, hydrolysis may be promoted, increasing flammability. Therefore, it is considered important to maintain the appropriate range. The saturated water absorption was measured using a TA-instruments Hi-Res TGA2950 Thermogravimetric Analyzer, in which fumed silica that had been sufficiently conditioned at 23°C / 50% RH for 168 hours or more was heated from room temperature to 900°C at a rate of 10°C / min in an air atmosphere, and the weight loss of the sample from room temperature to 220°C was measured as the saturated water absorption.

[0028] The content of Component C is 0.1 to 2.0 parts by weight, preferably 0.2 to 1.5 parts by weight, and more preferably 0.3 to 1.0 parts by weight, per 100 parts by weight of Component A. If the content of Component C is less than 0.1 part by weight, the flame retardancy becomes insufficient, and if it exceeds 2.0 parts by weight, the moist heat resistance and flame retardancy deteriorate.

[0029] The method for producing the fumed silica used in the present invention is not particularly limited. 2Any manufacturing method can be used as long as the saturation water absorption at 23°C / 50%RH is 0.3% or more but less than 2.0% and the saturation water absorption is not an alkylsilane surface modification treatment. Specifically, a method in which a silane compound is supplied to a reactor and then burned or hydrolyzed in a flame can be used. For example, the methods described in Japanese Patent Publication Nos. 47-46274, 58-54085, 59-169922, 59-184721, and 60-011218 can be referenced.

[0030] Fumed silica is produced by feeding a raw material gas containing a silane compound into a flame in a reaction step, and burning or hydrolyzing the silane compound in the flame. The fumed silica produced in the reaction step is cooled in a cooling step and then sent to a separation and recovery step. In this step, the solid content is separated from the reaction gas and recovered, and then, if necessary, deoxidized in a deoxidation step. The fumed silica obtained in this manner has a bulk density of about 0.02 g / cm. 3 It is a very small powder, and if it were to be packaged and used as is, the packaging and transportation costs would be high, and the powder has a tendency to scatter, making handling the powder a major problem. Therefore, it is possible to adjust the bulk density significantly during the compression process.

[0031] In the present invention, Component C can be added as a masterbatch in advance extrusion mixed with Component A. By using a masterbatch, powder scattering of Component C is suppressed, improving handling, and further improving dispersibility, which may result in stable flame retardancy.

[0032] When component C is used as a masterbatch, the ratio of components A and C is preferably component A:component C=95-20 parts by weight:5-80 parts by weight, more preferably component A:component C=95-40 parts by weight:5-60 parts by weight, and even more preferably component A:component C=90-60 parts by weight:10-40 parts by weight. If the ratio of component C is less than the lower limit, the economic viability of the masterbatch is impaired, and if the ratio of component C exceeds the upper limit, the extrusion mixing processability of the masterbatch may be poor.

[0033] When Component C is used as a masterbatch, the viscosity average molecular weight of Component A is preferably 15,000 to 25,000, more preferably 15,000 to 23,000, and even more preferably 15,000 to 20,000. If the viscosity average molecular weight is below the lower limit, extrusion productivity will be poor, and if it exceeds the upper limit, the extrusion processing temperature will become extremely high, which will lead to deterioration of Component A and may cause problems with flame retardancy and color appearance.

[0034] Examples of component C in the present invention include "Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 150, Aerosi 200, Aerosil 1200V (trade names) manufactured by Nippon Aerosil Co., Ltd.," "Reolosil QS-09, QS-10, QS-102, CP-102, QS-20, QS-20L (trade names) manufactured by Tokuyama Corporation," and "CAB-O-SIL L-90, LM-150, LM-150D, M-5 (trade names) manufactured by Cabot Corporation."

[0035] (Component D: Fluorine-containing anti-drip agent) The polycarbonate resin composition of the present invention contains a fluorinated anti-dripping agent as component D. By including this fluorinated anti-dripping agent, good flame retardancy can be achieved without impairing the physical properties of the molded article.

[0036] Examples of the fluorinated anti-dripping agent include fluorine-containing polymers capable of forming fibrils, such as polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers), partially fluorinated polymers such as those disclosed in U.S. Patent No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Of these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0037] Fibril-forming PTFE has an extremely high molecular weight and tends to bond PTFE molecules together to form fibers under external influences such as shear force. Its molecular weight, calculated from the standard specific gravity, is 1 million to 10 million, more preferably 2 million to 9 million, in number average molecular weight. Such PTFE can be used in solid form or in the form of an aqueous dispersion. Furthermore, such fibril-forming PTFE can be used in a PTFE mixture with other resins to improve dispersibility in resins and to obtain even better flame retardancy and mechanical properties.

[0038] Commercially available PTFE products having such fibril-forming ability include, for example, Teflon® 6J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L manufactured by Daikin Industries, Ltd. Representative examples of commercially available aqueous PTFE dispersions include Fluon AD-1 and AD-936 manufactured by Asahi ICI Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Teflon® 30J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.

[0039] The mixed form of PTFE can be obtained by (1) mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitation to obtain a co-aggregated mixture (methods described in Japanese Patent Application Laid-Open Nos. 60-258263 and 63-154744, etc.), (2) mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Application Laid-Open No. 4-272957), or (3) uniformly mixing an aqueous dispersion of PTFE with an organic polymer particle solution and simultaneously extracting each medium from the mixture. (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous PTFE dispersion (method described in JP-A-06-220210, JP-A-08-188653, etc.), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, and then polymerizing a vinyl monomer in the mixed dispersion to obtain a mixture (method described in JP-A-11-29679, etc.). Commercially available PTFE blends include "Metablen A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

[0040] The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, of 100% by weight of the PTFE mixture. When the proportion of PTFE is within this range, good dispersibility of PTFE can be achieved. Note that the proportion of the above-mentioned D component indicates the net amount of anti-drip agent, and in the case of mixed PTFE, it indicates the net amount of PTFE.

[0041] The content of component D is 0.05 to 1.2 parts by weight, preferably 0.1 to 1.0 part by weight, more preferably 0.1 to 0.8 parts by weight, and even more preferably 0.15 to 0.5 parts by weight, per 100 parts by weight of component A. If the content of component D is less than 0.05 part by weight, the flame retardancy becomes insufficient, whereas if it exceeds 1.2 parts by weight, the moist heat resistance and flame retardancy deteriorate, leading to an increase in the cost of the resin composition.

[0042] (Component E: inorganic filler) The polycarbonate resin composition of the present invention contains an inorganic filler as component E. The inclusion of this inorganic filler enables the composition to achieve high rigidity.

[0043] As such fillers, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, fibrous fillers are fillers that have a fibrous shape (including rod-like, needle-like, or shapes with axes extending in multiple directions), and plate-like fillers are fillers that have a plate-like shape (including those with an uneven surface or curved plates). Granular fillers are fillers with shapes other than these, including irregular shapes. The fibrous and plate-like shapes are often clear from observing the shape of the filler, but the difference between them and so-called irregular shapes is that those with an aspect ratio of 3 or more can be said to be fibrous or plate-like.

[0044] Preferred examples of plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-like fillers obtained by surface-coating these fillers with a different material, such as a metal or metal oxide. The particle size is preferably in the range of 0.1 to 300 μm. This particle size refers to the median diameter (D50) of the particle size distribution measured by X-ray transmission, a type of liquid-phase precipitation method, in the range up to about 10 μm; the median diameter (D50) of the particle size distribution measured by laser diffraction / scattering in the range 10 to 50 μm; and the value measured by vibrating sieving in the range 50 to 300 μm. These particle sizes are those in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based, or may be in the form of a granule that has been bundled or compressed with various resins such as olefin-based resins, styrene-based resins, acrylic resins, polyester-based resins, epoxy-based resins, and urethane-based resins, or higher fatty acid esters.

[0045] The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 13 μm, and even more preferably 10 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm. The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is a value calculated from images obtained by observing with a scanning electron microscope the residue collected after dissolving the molded product in a solvent or decomposing the resin with a basic compound, and the ashing residue collected after ashing in a crucible. Examples of such fibrous fillers include glass fiber, flat cross-section glass fiber, milled glass fiber, carbon fiber, milled carbon fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whiskers, boron whiskers, aluminum borate whiskers, calcium carbonate whiskers, titanium oxide whiskers, wollastonite, xonotlite, palygorskite (attapulgite), and sepiolite, and other fibrous inorganic fillers; fibrous heat-resistant organic fillers, such as aramid fiber, polyimide fiber, and polybenzthiazole fiber, are also examples. Examples of fillers coated with a different material include metal-coated glass fiber, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fiber. The method for coating the surface of a different material is not particularly limited, and examples include various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition, ion plating, CVD methods (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD, and sputtering. Here, the term "fibrous filler" refers to a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, and more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is the value in the resin composition.Furthermore, flat cross section glass fibers are glass fibers having an average major axis of the fiber cross section of 10 to 50 μm, preferably 15 to 40 μm, and more preferably 20 to 35 μm, and an average ratio of major axis to minor axis (major axis / minor axis) of 1.5 to 8, preferably 2 to 6, and even more preferably 2.5 to 5. Like the plate-like filler, the fibrous filler may also be surface-treated with various coupling agents, bundled with various resins, and granulated by compression.

[0046] It is preferable that component E is at least one inorganic filler selected from the group consisting of (E-1) glass fiber (component E-1), (E-2) plate-like glass filler (component E-2), (E-3) fibrous carbon filler (component E-3), (E-4) non-fibrous carbon filler (component E-4), and (E-5) silicate mineral (component E-5), and it is more preferable that component E is at least one inorganic filler selected from the group consisting of (E-1) glass fiber (component E-1), (E-2) plate-like glass filler (component E-2), and (E-5) silicate mineral (component E-5).

[0047] The content of component E is 1 to 80 parts by weight, preferably 5 to 45 parts by weight, more preferably 5 to 30 parts by weight, and particularly preferably 5 to 20 parts by weight, per 100 parts by weight of component A. If the content of component E is less than 1 part by weight, rigidity will be insufficient, and if it exceeds 80 parts by weight, flame retardancy will deteriorate.

[0048] (Component F: UV absorber) The polycarbonate resin composition of the present invention can contain an ultraviolet absorber as component F to suppress ultraviolet degradation in outdoor applications. Specific examples of the ultraviolet absorber include benzophenone-based absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.Specific examples of the ultraviolet absorber include benzotriazole-based ones, such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, Examples of the 2-hydroxyphenyl-2H-benzotriazole skeleton include 2-(2-hydroxy-5-acryloxyethylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomers, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomers.Specific examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol. Further examples include compounds in which the phenyl group of the above-mentioned compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Specific examples of cyclic iminoester-based ultraviolet absorbers include 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), and 2,2'-p,p'-diphenylenebis(3,1-benzoxazin-4-one). Specific examples of cyanoacrylate-based ultraviolet absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene. Furthermore, the ultraviolet absorber may be a polymeric ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and / or a photostable monomer with a monomer such as an alkyl (meth)acrylate by adopting a structure of a radically polymerizable monomer compound. Suitable examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.Among these, benzotriazole-based and hydroxyphenyltriazine-based compounds are preferred in terms of UV absorption ability, and cyclic iminoester-based and cyanoacrylate-based compounds are preferred in terms of heat resistance and color. Specific examples include "Chemisorb 79" from Chemipro Kasei Co., Ltd. and "Tinuvin 234" from BASF Japan Ltd. The UV absorbents may be used alone or in combination of two or more.

[0049] The content of component F is preferably 0.01 to 1 part by weight, more preferably 0.01 to 0.8 parts by weight, even more preferably 0.05 to 0.6 parts by weight, and particularly preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of component A. If the content is less than 0.01 part by weight, the weather resistance may be insufficient, and if it exceeds 1 part by weight, the flame retardancy may be insufficient.

[0050] (Component G: Heat stabilizer) The polycarbonate resin composition of the present invention may contain a heat stabilizer to suppress thermal and oxidative degradation as Component G. The content of Component G is preferably 0.01 to 0.5 parts by weight, more preferably 0.02 to 0.4 parts by weight, and even more preferably 0.03 to 0.3 parts by weight per 100 parts by weight of Component A.

[0051] (i) Phosphorus-based stabilizers Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphines.

[0052] Specific examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert- butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

[0053] Other phosphite compounds that can be used include those that react with dihydric phenols to form a cyclic structure, such as 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

[0054] Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred are triphenyl phosphate and trimethyl phosphate.

[0055] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl ... Examples include (2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. Such phosphonite compounds can be used in combination with, and are preferred for, the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups.

[0056] Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0057] Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

[0058] The phosphorus-based stabilizers can be used singly or in combination of two or more. Among the phosphorus-based stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula [3] are preferred.

[0059] [ka]

[0060] (In the above general formula [3], R and R′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different.)

[0061] As described above, the phosphonite compound is preferably tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite, and stabilizers containing this phosphonite as a main component are commercially available as Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P-EPQ (trademark, manufactured by BASF Japan Ltd.), either of which may be used.

[0062] Among the phosphite compounds of the above formula [3], more preferred are distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite.

[0063] Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of these can be used. Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite is commercially available as ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes Chemical Industry Co., Ltd.), Ultranox P626 (trademark, manufactured by Accu Standard Inc.), Doverphos S-9432 (trademark, manufactured by Dover Chemical Co.), and Irgaofos 126 and 126FF (trademarks, manufactured by BASF Japan Ltd.), and any of these can be used. Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and is readily available. Bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite is commercially available as ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark, manufactured by Dover Chemical Co.), and either can be used.

[0064] (ii) Hindered phenolic antioxidants The hindered phenol compound may be any of various compounds that are usually incorporated into resins, such as α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, and 3,5-di-tert-butyl-4-hydroxybenzyl. Phosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4 -methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9- Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate nurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3- Examples include {(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene, and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate.

[0065] Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferred in the present invention. 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane is particularly preferred. The above hindered phenol antioxidants can be used alone or in combination of two or more.

[0066] It is preferable to use either a phosphorus-based stabilizer or a hindered phenol-based antioxidant, and more preferably to use them in combination.When using them in combination, it is more preferable to use 0.01 to 0.3 parts by weight of a phosphorus-based stabilizer and 0.01 to 0.3 parts by weight of a hindered phenol-based antioxidant per 100 parts by weight of component A.

[0067] (iii) Other heat stabilizers The resin composition of the present invention may also contain other heat stabilizers in addition to the phosphorus-based stabilizer and hindered phenol-based antioxidant. Such other heat stabilizers are preferably used in combination with either one of these stabilizers and antioxidants, and particularly preferably in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160). This compound is commercially available under the trade name Irganox HP-136 (trademark, manufactured by BASF Japan Ltd.), and this compound can be used. Furthermore, stabilizers containing this compound mixed with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the same company is a suitable example. Such premixed stabilizers can also be used in the present invention.

[0068] Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the resin composition is used for rotational molding.

[0069] (Other additives) The polycarbonate resin composition of the present invention is preferably blended with the additives described below according to the intended use.

[0070] (i) Mold release agent The polycarbonate resin composition of the present invention preferably further contains a mold release agent for the purposes of improving productivity during molding and reducing distortion of molded articles. Known mold release agents can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymers, etc.; those modified with functional group-containing compounds such as acid-modified waxes can also be used), silicone compounds, fluorine compounds (fluorinated oils typified by polyfluoroalkyl ethers), paraffin wax, and beeswax. Fatty acid esters are particularly preferred mold release agents. Fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohols may be monohydric alcohols or polyhydric alcohols (dihydric or higher). The carbon number of the alcohol is in the range of 3 to 32, more preferably 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerols (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in the fatty acid ester of the present invention.

[0071] On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably has 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, icosanoic acid, and docosanoic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferred. Among these, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred.

[0072] The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are usually produced from natural fats and oils, such as animal fats and oils typified by beef tallow and lard, and vegetable fats and oils typified by palm oil and sunflower oil, and therefore these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids, particularly stearic acid and palmitic acid, which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used.

[0073] The fatty acid ester of the present invention may be either a partial ester or a full ester (full ester). However, partial esters usually have a high hydroxyl value, which can easily induce decomposition of the resin at high temperatures, so full esters are more preferred. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. The iodine value is preferably 10 or less. The iodine value can be substantially 0. These properties can be determined by the method specified in JIS K 0070.

[0074] The content of the mold release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and even more preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of Component A. Within this range, the polycarbonate resin composition may have good mold and roll releasability. In particular, such an amount of fatty acid ester provides a flame-retardant resin composition having good mold and roll releasability without impairing good color.

[0075] (ii) Dyes and pigments The polycarbonate resin composition of the present invention can further contain various dyes and pigments to provide molded articles with diverse design properties. Examples of dyes and pigments that can be used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain better metallic colors. Aluminum powder is preferred as a metallic pigment. Furthermore, blending with a fluorescent brightener or other fluorescent dye that emits light can provide even better design effects that take advantage of the emitted light color.

[0076] (iii) Fluorescent whitening agents The fluorescent brightener used in the resin composition of the present invention is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white. Examples include stilbene-based, benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples include CI Fluorescent Brightener 219:1, Eastman Chemical Company's EASTOBRITE OB-1, and Showa Chemical Co.'s Hakkol PSR. The fluorescent brightener absorbs ultraviolet energy from light and radiates it in the visible region. The content of the fluorescent brightener is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of Component A. Even if the amount exceeds 0.1 part by weight, the effect of improving the color tone of the composition may be small.

[0077] (iv) Compounds capable of absorbing heat rays The polycarbonate resin composition of the present invention may contain a compound capable of absorbing heat rays. Suitable examples of such compounds include phthalocyanine-based near-infrared absorbers; metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, ruthenium oxide, immonium oxide, and titanium oxide; various metal compounds with excellent near-infrared absorption, such as metal boride-based and tungsten oxide-based near-infrared absorbers such as lanthanum boride, cerium boride, and tungsten boride; and carbon fillers. Examples of such phthalocyanine-based near-infrared absorbers include MIR-362 manufactured by Mitsui Chemicals, Inc., and are readily available commercially. Examples of carbon fillers include carbon black, graphite (both natural and synthetic), and fullerenes, with carbon black and graphite being preferred. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and even more preferably 0.001 to 0.07 parts by weight, based on 100 parts by weight of the resin component. The contents of the metal oxide-based near-infrared absorber, metal boride-based near-infrared absorber, and carbon filler are preferably in the range of 0.1 to 200 ppm (weight ratio), more preferably 0.5 to 100 ppm, in the polycarbonate resin composition of the present invention.

[0078] (v) Light diffusing agent The polycarbonate resin composition of the present invention can contain a light diffusing agent to impart a light diffusing effect. Examples of such light diffusing agents include polymeric fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymeric fine particles are already known as light diffusing agents for polycarbonate resins. More preferred examples include acrylic crosslinked particles with a particle size of several micrometers and silicone crosslinked particles such as polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include spherical, discoidal, cylindrical, and irregular shapes. Such spherical shapes do not necessarily need to be perfect spheres and include deformed ones, and such cylindrical shapes include cubes. Preferred light diffusing agents are spherical, and the more uniform their particle size, the better. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 3 parts by weight per 100 parts by weight of Component A. Two or more light diffusing agents can be used in combination.

[0079] (vi) Highly reflective white pigments The polycarbonate resin composition of the present invention can contain a highly light-reflecting white pigment to impart a light-reflecting effect. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as such a white pigment. The content of such highly light-reflecting white pigment is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, per 100 parts by weight of component A. Two or more types of highly light-reflecting white pigments can be used in combination.

[0080] (vii) antistatic agents The polycarbonate resin composition of the present invention may require antistatic properties. In such cases, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonate phosphonium salts, such as arylsulfonate phosphonium salts (e.g., dodecylbenzenesulfonate phosphonium salt) and alkylsulfonate phosphonium salts, as well as borate phosphonium salts, such as tetrafluoroborate phosphonium salt. The content of the phosphonium salt is preferably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and even more preferably 1.5 to 3 parts by weight, per 100 parts by weight of the resin component. Examples of antistatic agents include (2) organic sulfonate alkali (earth) metal salts, such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. As mentioned above, such metal salts are also used as flame retardants. More specifically, examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the alkali (earth) metal organic sulfonate is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, and more preferably 0.005 to 0.2 parts by weight, per 100 parts by weight of component A. In particular, alkali metal salts such as potassium, cesium, and rubidium are suitable.

[0081] Examples of antistatic agents include (3) organic ammonium sulfonates such as ammonium alkylsulfonates and ammonium arylsulfonates. The amount of the ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of the resin component. Examples of antistatic agents include (4) polymers containing a poly(oxyalkylene) glycol component as a constituent component, such as polyetheresteramide. The amount of the polymer is suitably 5 parts by weight or less based on 100 parts by weight of the resin component.

[0082] (viii) Other resins and elastomers In the polycarbonate resin composition of the present invention, a small proportion of other resins or elastomers can be used in place of part of the resin component of Component A, as long as the effects of the present invention are achieved. The amount of other resins or elastomers blended is preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, based on 100% by weight of the total including Component A. Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, and epoxy resins. Examples of elastomers include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and core-shell elastomers such as MBS (methyl methacrylate / styrene / butadiene) rubber, MB (methyl methacrylate / butadiene) rubber, and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

[0083] (ix) Other additives The polycarbonate resin composition of the present invention may also contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents, and the like.

[0084] <Production of Resin Composition> Any method can be used to produce the polycarbonate resin composition of the present invention, for example, by thoroughly mixing components A, B, C, D, E, and optionally other components using a premixing device such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, followed by granulation using an extrusion granulator or a briquetting machine as needed, followed by melt-kneading in a melt kneader such as a vented twin-screw extruder, and pelletizing using equipment such as a pelletizer.

[0085] <Molded product manufacturing> The polycarbonate resin composition of the present invention can be injection molded from such pellets to obtain a molded article. Such injection molding can be carried out not only by a conventional cold runner molding method, but also by a hot runner, which allows for runnerless production. In addition to conventional molding methods, other molding methods can be used, including gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (including those using supercritical fluids), rapid heating and cooling mold molding, adiabatic mold molding, in-mold remelt molding, and molding methods consisting of combinations of these.

[0086] Furthermore, the polycarbonate resin composition of the present invention can be melt-kneaded in an extruder and directly formed into sheets, films, profile extrusion molded products, direct blow molded products, and injection molded products without going through pelletization. The polycarbonate resin composition of the present invention can also be used in the form of various profile extrusion molded products, sheets, films, etc. by extrusion molding. Sheets and films can also be formed using inflation methods, calendaring methods, casting methods, etc. Furthermore, the composition can be molded into heat-shrinkable tubes by subjecting it to a specific stretching operation, or into molded products by rotational molding, blow molding, etc.

[0087] Furthermore, molded articles formed from resin compositions can be subjected to various surface treatments, such as decorative painting, hard coating, water-repellent / oil-repellent coating, hydrophilic coating, ultraviolet absorbing coating, infrared absorbing coating, electromagnetic wave absorbing coating, heat-generating coating, antistatic coating, antistatic coating, conductive coating, and metallizing (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.).

[0088] (Flame retardant) The flame retardancy of the polycarbonate resin composition of the present invention was evaluated by conducting a vertical flame test on UL test specimens (13 mm wide x 125 mm long x 1.8 mm and 1.5 mm thick) prepared in accordance with the UL94 flame test, and classifying the maximum burning time, total burning time, and number of drips accompanying cotton ignition (number of drips) into V-0, V-1, V-2, or Not-V according to the standard. A V-0 rating at a thickness of 1.8 mm is preferred, indicating excellent flame retardancy.

[0089] (Water-resistant and flame-retardant) The weather-resistant flame retardancy of the polycarbonate resin composition of the present invention was evaluated in accordance with the UL746C weather resistance test. The UL test specimens were subjected to a hot water exposure test followed by a vertical flame test. The maximum flame time, total flame time, and number of drips (number of drips) associated with cotton ignition were measured and classified into V-0, V-1, V-2, and Not-V according to the standard. The hot water exposure test involved immersing a molded article in ion-exchanged water heated to 82°C for 168 hours. Conditioning between the hot water exposure test and the vertical flame test involved holding the article in an environment of 23°C / 50% RH for at least 48 hours. A V-0 rating after the hot water exposure test is preferred, as it indicates excellent water-resistance and flame retardancy.

[0090] (Heat and humidity resistance) The moist heat resistance of the polycarbonate resin composition of the present invention was evaluated by treating a 2 mm thick plate molded by injection molding for 500 hours in a constant temperature and humidity chamber maintained at 90°C / 95% RH, and then measuring the light transmittance in accordance with JIS K 7361 using an HM-150N manufactured by Murakami Color Research Laboratory Co., Ltd. A light transmittance value of 15% or more is preferred in view of excellent appearance stability over long-term use, and a light transmittance value of 30% or more is more preferred.

[0091] (rigidity) The rigidity of the polycarbonate resin composition of the present invention was evaluated by the flexural modulus measured at 2 mm / min in accordance with ISO 178. For use as an outdoor exterior material, the flexural modulus is preferably 2,500 MPa or more, more preferably 3,000 MPa or more, even more preferably 4,000 MPa or more, and particularly preferably 5,000 MPa or more. [Example]

[0092] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. Unless otherwise specified, parts in the examples are parts by weight and % is % by weight. Evaluations were made according to the following methods.

[0093] (1) Viscosity average molecular weight (Mv) The viscosity average molecular weight of Component A of the present invention was calculated as follows. Resin composition pellets were mixed with 20 to 30 parts by weight of methylene chloride to dissolve the soluble components in Component A. The soluble components were collected by filtration through Celite to remove the insoluble components. The solvent in the resulting solution was then removed by heating and thoroughly dried to obtain the solid components of Component A that were soluble in methylene chloride.

[0094] The specific viscosity (η SP ) was measured using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of the obtained solid in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0095] (2) Flame retardancy (UL94 vertical flame test) The resin composition pellets were dried with hot air at 120°C for 5 hours, and then an injection molding machine was used to produce UL test specimens (13 mm wide x 125 mm long x 1.8 mm and 1.5 mm thick) at a molding temperature of 300-320°C, a mold temperature of 70°C, and a molding cycle of 30 seconds. A vertical combustion test was conducted using the obtained UL test specimens in accordance with UL94.

[0096] (3) Water resistance and flame retardancy (UL746C hot water exposure test) The UL test specimen obtained in (2) above was placed in a sealed glass container and ion-exchanged water was poured into it until the UL test specimen was fully immersed. It was then transferred to a thermostatic chamber maintained at 80°C and subjected to a hot water exposure treatment for 168 hours. After the test period, the test specimen was removed and kept in an environment of 23°C / 50% RH for at least 48 hours to condition it, after which a vertical flame test was performed in accordance with UL94.

[0097] (4) Moisture and heat resistance The resin composition pellets were dried with hot air at 120°C for 5 hours, and then molded using an injection molding machine at a molding temperature of 280°C, a mold temperature of 70°C, and a molding cycle of 30 seconds to produce molded plates (50 mm wide x 100 mm long x 2.0 mm thick). The resulting plates were then treated for 500 hours in a constant temperature and humidity chamber maintained at 90°C / 95% RH. The light transmittance of the molded plates before and after treatment was measured using a Murakami Color Research Laboratory HM-150N in accordance with JIS K 7361.

[0098] (5) Rigidity (flexural modulus) The resin composition pellets were dried with hot air at 120°C for 5 hours, and then molded using an injection molding machine at a molding temperature of 280°C and a mold temperature of 80°C to give test specimens (length 80 mm x width 10 mm x thickness 4 mm). The flexural modulus was measured in accordance with ISO178.

[0099] [Ingredients used] (Component A: aromatic polycarbonate resin) A-1: Linear aromatic polycarbonate resin powder with a viscosity-average molecular weight of 19,700 and a repeating structure of 2,2-bis(4-hydroxyphenyl)propane (Panlite L-1225WX, manufactured by Teijin Limited) A-2: Linear aromatic polycarbonate resin powder with a viscosity average molecular weight of 14,700 and a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane (manufactured by Teijin Limited) A-3: Linear aromatic polycarbonate resin powder with a viscosity average molecular weight of 28,000 and a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane (manufactured by Teijin Limited)

[0100] (Component B: Alkali (earth) metal salt of aromatic sulfonic acid that does not contain a fluoroalkyl group) B-1: Potassium diphenylsulfone-3-sulfonate (solubility in water at 80°C: 50 g / L) B-2: Polystyrene-Polystyrene Sulfonic Acid Potassium Copolymer (PSS-K, manufactured by Sony Chemical & Information Devices Corporation, insoluble in water at 80°C) B-3 (Comparative Example): Sodium p-toluenesulfonate (NATS-FR manufactured by ARiCHEM, LCC, solubility in water at 80°C > 500 g / L)

[0101] (Component C: Hydrophilic fumed silica without alkylsilane surface modification treatment) C-1: Aerosil 50 (manufactured by Nippon Aerosil Co., Ltd., no alkylsilane surface modification, BET specific surface area 50 m 2 / g,23℃ / 50%RH saturated water absorption rate 0.9%) C-2: QS-10 (Tokuyama Corporation, no alkylsilane surface modification, BET specific surface area 145 m) 2 / g,23℃ / 50%RH saturated water absorption rate 1.0%) C-3: Aerosil 200 (Nippon Aerosil Co., Ltd., no alkylsilane surface modification, BET specific surface area 200 m 2 / g,23℃ / 50%RH saturated water absorption rate 1.1%) C-4: QS-20 (Tokuyama Corporation, no alkylsilane surface modification, BET specific surface area 219 m)2 / g,23℃ / 50%RH saturated water absorption rate 1.1%) C-5 (comparison): Nipsil (manufactured by Tosoh Silica Corporation, no alkylsilane surface modification, BET specific surface area 20 m 2 / g,23℃ / 50%RH saturated water absorption rate 4%) C-6 (comparison): QS-30 (manufactured by Tokuyama Corporation, no alkylsilane surface modification, BET specific surface area 300 m 2 / g,23℃ / 50%RH saturated water absorption rate 2.0%) C-7 (comparison): Aerosil RY200 (manufactured by Nippon Aerosil Co., Ltd., surface modified with polydimethylsilane, BET specific surface area 200 m 2 / g,23℃ / 50%RH saturated water absorption rate 0.1%)

[0102] (Component D: Fluorine-containing anti-drip agent) D-1: SN3307PF (styrene-acrylonitrile copolymer coated polytetrafluoroethylene, polytetrafluoroethylene content 50% by weight, manufactured by Shine Polymers)

[0103] (Component E: inorganic filler) E-1: Glass fiber (product name: 3PE455FB, manufactured by Nitto Boseki Co., Ltd.) E-2: Glass flakes (product name: MEG160FYX, manufactured by Nippon Sheet Glass Co., Ltd.) E-3: Talc (Victorite TK-RC (product name) manufactured by Shokoyama Mining Co., Ltd.)

[0104] (Component F: UV absorber) F-1: UV absorber (ADEKA Corporation, Adekastab LA-31 (product name))

[0105] (Component G: Heat stabilizer) G-1: stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (manufactured by BASF Japan Ltd.: Irganox 1076 (trade name)) G-2: Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos168 (trade name) manufactured by BASF Japan Ltd.)

[0106] [Examples 1 to 15, Comparative Examples 1 to 12] (Production of polycarbonate resin composition) Components A to E and various additives were weighed according to the compositions shown in Tables 1 and 2, mixed uniformly in a blender, and melt-kneaded in a vented twin-screw extruder to obtain pellets. The content of component D listed in Tables 1 and 2 is the net polytetrafluoroethylene content in component D. The various additives used were premixed with polycarbonate resin at concentrations approximately 10 to 100 times the blending amount, and then the entire mixture was mixed in the blender. A Kobe Steel KTX-30 vented twin-screw extruder (30 mm diameter) was used. Strands were extruded under conditions of barrel and die temperatures of 300°C, screw rotation speed of 150 rpm, discharge rate of 20 kg / h, and vent suction of 3 kPa. After cooling in a water bath, the strands were cut in a pelletizer and pelletized. Various evaluation results are shown in Tables 1 and 2. In Example 12, component C-3 was added as masterbatch pellets obtained by extrusion mastering a linear aromatic polycarbonate resin powder (Panlite CM-1000, manufactured by Teijin Limited) with a viscosity average molecular weight of 16,000 and a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane and component C-3 in a ratio of 80:20 parts by weight using a vented twin-screw extruder TEX30α manufactured by The Japan Steel Works, Ltd. at a cylinder temperature of 270°C. Component A in Example 12 includes the polycarbonate resin contained in the masterbatch.

[0107] [Table 1]

[0108] [Table 2]

[0109] As is clear from the above table, the compositions of Examples 1 to 15 achieved V-0 in the UL94 vertical flame test at a thickness of 1.8 mm, and further maintained V-0 at 1.8 mm in water-resistant flame retardancy after exposure to hot water, and also exhibited excellent moist heat resistance and rigidity at 90°C / 95% RH / 500 h. [Industrial Applicability]

[0110] The polycarbonate resin composition of the present invention has low environmental impact and is excellent in rigidity, flame retardancy, water-resistant flame retardancy, and moist heat resistance, specifically, in flame retardancy that can withstand the UL746C water exposure test and high-temperature moist heat treatment, making it suitable for use as a material for outdoor structural members, various housing members, and automobile-related parts.It is also useful for various electronic and electrical device parts, camera parts, office automation device parts, precision machine parts, machine parts, vehicle parts, and other various applications such as agricultural materials, transport containers, play equipment, and miscellaneous goods.

Claims

1. (A) 100 parts by weight of an aromatic polycarbonate resin (component A) containing a polycarbonate block represented by the following general formula [1], (B) 0.01 to 0.25 parts by weight of an aromatic sulfonic acid alkali (earth) metal salt (component B) containing no fluoroalkyl group and having a solubility in water of 500 g / L or less at 80°C, (C) a specific surface area by BET adsorption of 50 to 250 m ２ / g and having a saturated water absorption rate at 23°C / 50% RH of 0.3% or more but less than 2.0%, the polycarbonate resin composition containing 0.1 to 2 parts by weight of hydrophilic fumed silica (component C) that has not been surface-modified with alkylsilane, 0.05 to 1.2 parts by weight of (D) a fluorine-containing anti-dripping agent (component D), and 1 to 80 parts by weight of (E) an inorganic filler (component E). 【Chemical 1】 (In the above general formula [1], R １ and R ２ each independently represents a 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 18 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 14 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 carboxy group; when there are a plurality of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]: 【Chemistry 2】 (In the above general formula [2], R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represents a 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 １９ and R ２０ each independently represents a 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 carboxy group; when there are a plurality of groups, they may be the same or different; g is an integer from 1 to 10, and h is an integer from 4 to 7.

2. Component C has a specific surface area of ​​120 to 220 m2 in BET adsorption. ２ 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition is a hydrophilic fumed silica that has not been surface-modified with an alkylsilane, has a water absorption of 0.5% or more and less than 1.5% at 23°C / 50% RH, and has a water saturation absorption of 0.5% or more and less than 1.5% at 23°C / 50% RH.

3. 2. The polycarbonate resin composition according to claim 1, wherein component B is an aromatic sulfonic acid alkali (earth) metal salt containing no fluoroalkyl group, the solubility of which in water at 80°C is 100 g / L or less.

4. 2. The polycarbonate resin composition according to claim 1, wherein component B is at least one selected from the group consisting of dipotassium diphenylsulfide-4,4'-disulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, and mixtures thereof.

5. 2. The polycarbonate resin composition according to claim 1, wherein the content of component B is 0.03 to 0.15 parts by weight per 100 parts by weight of component A.

6. 2. The polycarbonate resin composition according to claim 1, wherein the viscosity average molecular weight of component A is 15,000 to 25,000.

7. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate block represented by the formula [1] is a polycarbonate block derived from 2,2-bis(4-hydroxyphenyl)propane.

8. 2. The polycarbonate resin composition according to claim 1, wherein the content of Component C is 0.3 to 1.0 part by weight per 100 parts by weight of Component A.

9. 2. The polycarbonate resin composition according to claim 1, wherein the content of component D is 0.15 to 0.5 parts by weight per 100 parts by weight of component A.

10. 2. The polycarbonate resin composition according to claim 1, wherein component E is at least one inorganic filler selected from the group consisting of (E-1) glass fiber (component E-1), (E-2) plate-like glass filler (component E-2), (E-3) fibrous carbon filler (component E-3), (E-4) non-fibrous carbon filler (component E-4), and (E-5) silicate mineral (component E-5).

11. 2. The polycarbonate resin composition according to claim 1, wherein the content of component E is 5 to 45 parts by weight per 100 parts by weight of component A.

12. 2. The polycarbonate resin composition according to claim 1, further comprising 0.01 to 1 part by weight of an ultraviolet absorber (F) (Component F) per 100 parts by weight of Component A.

13. 2. The polycarbonate resin composition according to claim 1, further comprising 0.01 to 0.5 parts by weight of a heat stabilizer (G) (Component G) per 100 parts by weight of Component A.

14. 2. The polycarbonate resin composition according to claim 1, wherein Component C is compounded as a masterbatch obtained by previously extrusion mixing 95 to 20 parts by weight of Component A and 5 to 80 parts by weight of Component C, both of which have a viscosity average molecular weight of 15,000 to 25,000.

15. (A) 100 parts by weight of an aromatic polycarbonate resin (component A) containing a polycarbonate block represented by the following general formula [1], (B) 0.01 to 0.25 parts by weight of an aromatic sulfonic acid alkali (earth) metal salt (component B) containing no fluoroalkyl group and having a solubility in water of 500 g / L or less at 80°C, (C) a specific surface area by BET adsorption of 50 to 250 m ２ A method for producing a polycarbonate resin composition comprising melt-kneading 0.1 to 2 parts by weight of hydrophilic fumed silica (component C) that has not been surface-modified with alkylsilane and has a water absorption of 0.3% or more and less than 2.0% at 23°C / 50% RH, 0.05 to 1.2 parts by weight of (D) a fluorine-containing anti-dripping agent (component D), and 1 to 80 parts by weight of (E) an inorganic filler (component E). 【Chemistry 3】 (In the above general formula [1], R １ and R ２ each independently represents a 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 18 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 14 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 carboxy group; when there are a plurality of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]: 【Chemistry 4】 (In the above general formula [2], R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represents a 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 １９ and R ２０ each independently represents a 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 carboxy group; when there are a plurality of groups, they may be the same or different; g is an integer from 1 to 10, and h is an integer from 4 to 7.

16. A molded article made from the polycarbonate resin composition according to any one of claims 1 to 14.

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